JP6126841B2 - Scale adhesion prevention method and scale adhesion prevention agent - Google Patents
Scale adhesion prevention method and scale adhesion prevention agent Download PDFInfo
- Publication number
- JP6126841B2 JP6126841B2 JP2012285345A JP2012285345A JP6126841B2 JP 6126841 B2 JP6126841 B2 JP 6126841B2 JP 2012285345 A JP2012285345 A JP 2012285345A JP 2012285345 A JP2012285345 A JP 2012285345A JP 6126841 B2 JP6126841 B2 JP 6126841B2
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- Prior art keywords
- phenol resin
- water
- resin
- phenol
- scale adhesion
- 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.)
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- 238000000034 method Methods 0.000 title claims description 24
- 230000002265 prevention Effects 0.000 title claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 57
- 239000000498 cooling water Substances 0.000 claims description 42
- 230000003405 preventing effect Effects 0.000 claims description 30
- 150000002989 phenols Chemical class 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 21
- 239000003814 drug Substances 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 229940079593 drug Drugs 0.000 claims description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 125000000129 anionic group Chemical group 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 11
- 229920003169 water-soluble polymer Polymers 0.000 claims description 11
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- 229920003986 novolac Polymers 0.000 claims description 10
- 150000003009 phosphonic acids Chemical class 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000006683 Mannich reaction Methods 0.000 claims description 5
- 229920003987 resole Polymers 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 46
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 28
- 239000000377 silicon dioxide Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000011575 calcium Substances 0.000 description 13
- 229910052791 calcium Inorganic materials 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 12
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229930003836 cresol Natural products 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
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- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 7
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 7
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 7
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 7
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000008235 industrial water Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 5
- 101150054854 POU1F1 gene Proteins 0.000 description 5
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
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- 150000003016 phosphoric acids Chemical class 0.000 description 5
- 238000010517 secondary reaction Methods 0.000 description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 239000002552 dosage form Substances 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
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- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 2
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
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- -1 metaxylenediamine Chemical compound 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
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- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- AXLHVTKGDPVANO-UHFFFAOYSA-N methyl 2-amino-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoate Chemical compound COC(=O)C(N)CNC(=O)OC(C)(C)C AXLHVTKGDPVANO-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、ビル空調、一般工場、石油化学コンビナート、鉄鋼プロセスの直接冷却水系等に設置されている熱交換器を備えた冷却水系（冷却水装置）にて発生するスケール付着を防止し、熱交換器の安定運転を効率的に達成することができるスケール付着防止方法及びスケール付着防止剤に関するものである。 The present invention prevents scale adhesion that occurs in a cooling water system (cooling water device) equipped with a heat exchanger installed in a building cooling system, a general factory, a petrochemical complex, a direct cooling water system of a steel process, etc. The present invention relates to a scale adhesion preventing method and a scale adhesion preventing agent capable of efficiently achieving stable operation of an exchanger.
冷却水系、ボイラ水系などの水と接触する伝熱面、配管内ではスケール障害が発生する。特に省資源省エネルギーの立場から、冷却水の系外への排棄(ブロー)を少なくして高濃縮運転を行う場合、溶解する塩類が濃縮されて、伝熱面が腐食しやすくなるとともに、難溶性の塩となってスケール化する。生成したスケールは熱効率の低下、配管の閉塞、水質計測機器のセンサー部への付着による障害等、ボイラや熱交換器の運転に重大な障害を引き起こす。 Scale failure occurs in heat transfer surfaces and piping that come into contact with water such as cooling water systems and boiler water systems. In particular, from the standpoint of resource conservation and energy conservation, when highly concentrated operation is performed with less cooling water drainage (blow), the dissolved salts are concentrated and the heat transfer surface is likely to be corroded and difficult. Scales as soluble salt. The generated scale causes serious obstacles to the operation of boilers and heat exchangers, such as deterioration in thermal efficiency, blockage of piping, and obstacles due to adhesion to the sensor part of water quality measurement equipment.
生成するスケールは種々存在するが、そのうち炭酸カルシウム、硫酸カルシウム、亜硫酸カルシウム、リン酸カルシウム、水酸化マグネシウム、リン酸亜鉛、水酸化亜鉛、塩基性炭酸亜鉛等の非シリカ系スケールの防止のためには、一般にマレイン酸、アクリル酸、イタコン酸等のカルボキシル基を有するモノマー由来の構成単位を持つポリマーが有効である。また、これら非シリカ系スケールの防止のためには、上記のカルボキシル基を有するモノマーとビニルスルホン酸、アリルスルホン酸、２−アクリルアミド２−メチルプロパンスルホン酸等のスルホン酸基を有するビニルモノマーとのコポリマー；上記のカルボキシル基を有するモノマーとアクリルアミド等のノニオン性ビニルモノマーとのコポリマー；ヘキサメタリン酸ソーダやトリポリリン酸ソーダ等の無機ポリリン酸類；ヒドロキシエチリデンジホスホン酸やホスホノブタントリカルボン酸等のホスホン酸類等が一般的に使用されている。
また、シリカ、ケイ酸カルシウム、ケイ酸マグネシウム等のシリカ系スケールの防止のためには、アクリルアミド系ポリマー（特許文献１)、カチオン系ポリマー(特許文献２)、ポリエチレングリコール（特許文献３)等のスケール防止剤が提案されており、スケール種に応じてポリマーが使い分けられている。
There are various scales to be produced, but among them, to prevent non-silica scales such as calcium carbonate, calcium sulfate, calcium sulfite, calcium phosphate, magnesium hydroxide, zinc phosphate, zinc hydroxide, basic zinc carbonate, etc. In general, a polymer having a structural unit derived from a monomer having a carboxyl group such as maleic acid, acrylic acid, and itaconic acid is effective. In order to prevent these non-silica scales, a monomer having the above carboxyl group and a vinyl monomer having a sulfonic acid group such as vinyl sulfonic acid, allyl sulfonic acid, 2-acrylamido 2-methylpropane sulfonic acid, etc. Copolymers; Copolymers of the above-mentioned monomers having a carboxyl group and nonionic vinyl monomers such as acrylamide; inorganic polyphosphoric acids such as sodium hexametaphosphate and sodium tripolyphosphate; phosphonic acids such as hydroxyethylidene diphosphonic acid and phosphonobutane tricarboxylic acid Is commonly used.
In order to prevent silica-based scales such as silica, calcium silicate, and magnesium silicate, acrylamide polymers (Patent Document 1), cationic polymers (Patent Document 2), polyethylene glycol (Patent Document 3), etc. Scale inhibitors have been proposed, and polymers are properly used depending on the scale type.
冷却水系において使用される補給水は、通常、工業用水、水道水、地下水等であるため、水中に様々なイオン種が存在する。したがって、特に高濃縮運転を行う場合には、全てのスケール種に効果的に対応できるスケール防止剤が必要であるが、現状ではまだ無い。特に、シリカ系スケールの付着防止に有効なポリマーが無いのが現状である。
例えば、特許文献１のアクリルアミド系ポリマーは、シリカ濃度が低い場合にはスケールの防止効果はあるものの、水質の変動つまりシリカ濃度の変動には効果が十分追随できない。
特許文献２のカチオン系ポリマーは、四級アンモニウム塩であり、カチオン性が非常に強いため、水中のシリカや微生物由来の汚れ（スライム）とゲル状の反応物をつくりやすく、配管内でつまり等のトラブルを起こしやすいという欠点がある。また、このカチオン系ポリマーは、カチオン性であるために配管の金属材料に吸着しやすく、系内でのポリマーの消耗が著しいという欠点もある。
特許文献３のポリエチレングリコールは、シリカ濃度が低い場合にはスケールの付着を抑える効果はあるが、共存イオンの影響を受けやすく効果が安定しない等の問題がある。
Since the makeup water used in the cooling water system is usually industrial water, tap water, ground water, etc., various ionic species exist in the water. Therefore, in particular, when performing highly concentrated operation, a scale inhibitor that can effectively cope with all scale species is necessary, but it is not yet available. In particular, there is no polymer that is effective in preventing adhesion of silica-based scales.
For example, although the acrylamide polymer of Patent Document 1 has a scale prevention effect when the silica concentration is low, the effect cannot sufficiently follow the change in water quality, that is, the change in silica concentration.
The cationic polymer of Patent Document 2 is a quaternary ammonium salt and has a very strong cationic property, so it is easy to produce silica-like soil or slime (slime) derived from water and a gel-like reaction product. There is a drawback that it is easy to cause trouble. In addition, since this cationic polymer is cationic, it easily adsorbs to the metal material of the pipe, and there is a drawback that the polymer is consumed significantly in the system.
The polyethylene glycol of Patent Document 3 has an effect of suppressing scale adhesion when the silica concentration is low, but has a problem that the effect is not stable because it is easily influenced by coexisting ions.
また、近年排水の再利用化が進んでおり、排水の凝集処理水を補給水とするケースが増えている。また、湖沼や河川水由来の工業用水を用いる場合は、用水処理として凝集処理が行われることが一般的である。その結果、これらの凝集処理水中に凝集剤由来のアルミニウムが残留する場合がある。これらを補給水として用いた場合に、カルシウムやシリカ以外にアルミニウムも成分として含まれるスケールの付着が起こる。アルミニウム含有スケールの防止のためには、冷却水系循環水の濃縮管理、カルシウム系スケールの防止に有効なカルボキシル基を有するポリマーやホスホン酸類の添加、などの対策をとっているが、決め手となる有効な方法がないのが現状である。 In recent years, wastewater has been reused, and there are an increasing number of cases where wastewater is treated with agglomerated water. Moreover, when using industrial water derived from lakes and rivers, agglomeration is generally performed as the water treatment. As a result, the flocculant-derived aluminum may remain in these flocculated water. When these are used as make-up water, adhesion of scale containing aluminum as a component in addition to calcium and silica occurs. In order to prevent aluminum-containing scales, measures such as the concentration management of cooling water circulating water and the addition of carboxyl-containing polymers and phosphonic acids, which are effective in preventing calcium-based scales, have been taken. There is no current method.
本発明は上述した事情に鑑み、ビル空調、一般工場、石油化学コンビナート、鉄鋼プロセスの直接冷却水系等の熱交換器を備えた冷却水系内で発生するスケールの付着防止に極めて有効であり、特にシリカ系及びアルミニウム系のスケールの付着防止効果が高く、熱交換器の安定運転に大きく寄与できるスケール付着防止方法及びスケール付着防止剤を提供することを目的とする。 In view of the circumstances described above, the present invention is extremely effective for preventing adhesion of scales generated in a cooling water system including a heat exchanger such as a building cooling system, a general factory, a petrochemical complex, and a direct cooling water system of a steel process. An object of the present invention is to provide a scale adhesion preventing method and a scale adhesion preventing agent that are highly effective in preventing adhesion of silica-based and aluminum-based scales and can greatly contribute to stable operation of a heat exchanger.
本発明者らは上記目的を達成するために鋭意検討した結果、冷却水系の冷却水に、フェノール樹脂及び／又は変性フェノール樹脂（１）と、アニオン性官能基を有する水溶性ポリマー、ホスホン酸類及びその塩、並びにリン酸類及びその塩の少なくとも１種からなる薬剤（２）とを併用することにより、上記目的が達成されることを見いだし、本発明を完成した。
本発明は、次の［１］〜［５］を提供するものである。
［１］フェノール樹脂及び／又は変性フェノール樹脂（１）と、アニオン性官能基を有する水溶性ポリマー、ホスホン酸類及びその塩、並びにリン酸類及びその塩の少なくとも１種からなる薬剤（２）とを、冷却水系の冷却水に併用することを特徴とするスケール付着防止方法。
［２］前記フェノール樹脂及び／又は変性フェノール樹脂（１）の前記冷却水中における含有量を０．１〜１００ｍｇ／Ｌとする［１］に記載のスケール付着防止方法。
［３］前記薬剤（２）の前記冷却水中における含有量を０．１〜２００ｍｇ／Ｌとする［１］又は［２］に記載のスケール付着防止方法。
［４］フェノール樹脂及び／又は変性フェノール樹脂（１）と、アニオン性官能基を有する水溶性ポリマー、ホスホン酸類及びその塩、並びにリン酸類及びその塩の少なくとも１種からなる薬剤（２）とを含むことを特徴とするスケール付着防止剤。
［５］前記フェノール樹脂及び／又は変性フェノール樹脂（１）と前記薬剤（２）とが一剤化されることなく独立している［４］に記載のスケール付着防止剤。
As a result of intensive studies to achieve the above object, the present inventors have found that the cooling water in the cooling water system includes a phenol resin and / or a modified phenol resin (1), a water-soluble polymer having an anionic functional group, phosphonic acids, and The inventors have found that the above object can be achieved by using the salt, and phosphoric acid and the drug (2) comprising at least one of the salts, and thus the present invention has been completed.
The present invention provides the following [1] to [5].
[1] A phenol resin and / or a modified phenol resin (1), a water-soluble polymer having an anionic functional group, a phosphonic acid and its salt, and a drug (2) comprising at least one of phosphoric acid and its salt A method for preventing scale adhesion, which is used in combination with cooling water in a cooling water system.
[2] The scale adhesion preventing method according to [1], wherein the content of the phenol resin and / or the modified phenol resin (1) in the cooling water is 0.1 to 100 mg / L.
[3] The scale adhesion preventing method according to [1] or [2], wherein the content of the drug (2) in the cooling water is 0.1 to 200 mg / L.
[4] A phenol resin and / or a modified phenol resin (1), a water-soluble polymer having an anionic functional group, a phosphonic acid and its salt, and a drug (2) comprising at least one of phosphoric acid and its salt A scale adhesion inhibitor characterized by containing.
[5] The scale adhesion preventing agent according to [4], wherein the phenol resin and / or the modified phenol resin (1) and the drug (2) are independent without being unified.
本発明によると、ビル空調、一般工場、石油化学コンビナート、鉄鋼プロセスの直接冷却水系等に設置されている熱交換器を備えた冷却水系内で発生するスケールの付着防止に極めて有効であり、特にシリカ系及びアルミニウム系のスケールの付着防止効果が高く、熱交換器の安定運転に大きく寄与できるスケール付着防止方法及びスケール付着防止剤を提供することができる。 According to the present invention, it is extremely effective in preventing adhesion of scale generated in a cooling water system equipped with a heat exchanger installed in a building cooling system, a general factory, a petrochemical complex, a direct cooling water system of a steel process, etc. It is possible to provide a scale adhesion preventing method and a scale adhesion preventing agent that have a high adhesion preventing effect on silica-based and aluminum-based scales and can greatly contribute to stable operation of a heat exchanger.
以下、本発明を実施形態に基づいて詳細に説明する。
本発明のスケール付着防止方法は、フェノール樹脂及び／又は変性フェノール樹脂（１）（以下「成分（１）」ということがある）と、アニオン性官能基を有する水溶性ポリマー、ホスホン酸類及びその塩、並びにリン酸類及びその塩の少なくとも１種からなる薬剤（２）（以下「成分（２）」ということがある）とを、冷却水系の冷却水に併用することを特徴とする。また、本発明のスケール付着防止剤は、フェノール樹脂及び／又は変性フェノール樹脂（１）と、アニオン性官能基を有する水溶性ポリマー、ホスホン酸類及びその塩、並びにリン酸類及びその塩の少なくとも１種からなる薬剤（２）とを含むことを特徴とする。
本発明によると、冷却水系内で発生するスケールの付着を良好に防止することができ、特にシリカ系及びアルミニウム系のスケールの付着防止効果が高く、冷却水系の安定運転が可能である。その理由の詳細は不明であるが、フェノール樹脂及び／又は変性フェノール樹脂（１）中の水酸基が、脂肪族樹脂中の水酸基よりも、アルミニウム系スケールの水酸基及びシリカ系スケールの水酸基と強く作用し、シリカ系及びアルミニウム系のスケールの付着を良好に防止したものと考えられる。
Hereinafter, the present invention will be described in detail based on embodiments.
The scale adhesion preventing method of the present invention comprises a phenol resin and / or a modified phenol resin (1) (hereinafter sometimes referred to as “component (1)”), a water-soluble polymer having an anionic functional group, phosphonic acids and salts thereof. And a drug (2) (hereinafter sometimes referred to as “component (2)”) comprising at least one of phosphoric acids and salts thereof is used in combination with cooling water in a cooling water system. Moreover, the scale adhesion preventing agent of the present invention includes at least one of a phenol resin and / or a modified phenol resin (1), a water-soluble polymer having an anionic functional group, phosphonic acids and salts thereof, and phosphoric acids and salts thereof. It contains the chemical | medical agent (2) which consists of.
ADVANTAGE OF THE INVENTION According to this invention, the adhesion of the scale which generate | occur | produces in a cooling water system can be prevented favorably, especially the adhesion prevention effect of a silica type and aluminum type scale is high, and the stable operation of a cooling water system is possible. Although the details of the reason are unclear, the hydroxyl group in the phenolic resin and / or modified phenolic resin (1) acts more strongly on the aluminum scale hydroxyl group and silica scale hydroxyl group than the hydroxyl group in the aliphatic resin. It is considered that the adhesion of silica-based and aluminum-based scales was prevented satisfactorily.
＜対象装置（冷却水系）＞
本発明は、ビル空調、一般工場、石油化学コンビナート、鉄鋼プロセスの直接冷却水系等の熱交換器を有する冷却水系に設置されている、冷却水系の熱交換器本体、循環水のピット、冷却塔等の装置及び配管内に付着するスケールを防止するために好適に適用される。
<Target device (cooling water system)>
The present invention relates to a cooling water system heat exchanger body, a circulating water pit, a cooling tower installed in a cooling water system having a heat exchanger such as a building air conditioning system, a general factory, a petrochemical complex, and a direct cooling water system of a steel process. It is suitably applied to prevent scales adhering in the apparatus and piping.
図１は冷却水系の一例を示す模式図である。循環水ピット１内の循環水は、循環ポンプ２によって抜き出され、熱交換器４内で熱交換されて加温された後、循環水ピット１内の上部から散布されることによって冷却される。なお、図１では、循環ポンプ２と熱交換器４との間に非伝熱チューブ３が設置されているが、これは後述する実施例で用いるものであり、通常は設置しないことが好ましい。この循環水ピット１内には、水面の高さを測定するレベルセンサー５と、循環水の導電率を測定する導電率計６が設けられている。
循環水ピット１内の循環水の一部をブロー配管７から連続的に又は断続的にブローすると共に、補給水槽１３から補給水ポンプ１０を用いて補給することにより、前記のレベルセンサー５及び導電率計６の測定値が所定範囲内になるように調整される。また、第１の槽１１及び第２の槽１２から薬注ポンプ８，９を介して循環水ピット１内に、成分（１）及び成分（２）、並びに必要に応じて他の薬剤が注入される。なお、第１の槽１１に成分（１）を貯蔵するとともに第２の槽に成分（２）を貯蔵してもよく、更に第１の槽１１及び第２の槽１２の少なくとも１つに他の薬剤を混合させて貯蔵してもよい。また、第１の槽１１に成分（１）及び成分（２）の混合物を貯蔵するとともに第２の槽１２に他の薬剤を貯蔵してもよい。なお、薬剤の種類だけ槽を用意し、薬剤ごとに別々の槽で貯蔵してもよい。
FIG. 1 is a schematic diagram showing an example of a cooling water system. The circulating water in the circulating water pit 1 is extracted by the circulating pump 2, heat-exchanged in the heat exchanger 4 and heated, and then cooled by being sprayed from the upper part in the circulating water pit 1. . In FIG. 1, the non-heat transfer tube 3 is installed between the circulation pump 2 and the heat exchanger 4, but this is used in the examples described later, and it is preferable not to install it normally. In the circulating water pit 1, a level sensor 5 for measuring the height of the water surface and a conductivity meter 6 for measuring the conductivity of the circulating water are provided.
A part of the circulating water in the circulating water pit 1 is blown continuously or intermittently from the blow pipe 7 and is replenished by using the makeup water pump 10 from the makeup water tank 13. The measured value of the rate meter 6 is adjusted to be within a predetermined range. In addition, the component (1) and the component (2) and other chemicals are injected into the circulating water pit 1 from the first tank 11 and the second tank 12 through the chemical injection pumps 8 and 9, respectively. Is done. The component (1) may be stored in the first tank 11 and the component (2) may be stored in the second tank. In addition, at least one of the first tank 11 and the second tank 12 may be used. These drugs may be mixed and stored. Further, the first tank 11 may store the mixture of the component (1) and the component (2), and the second tank 12 may store other chemicals. In addition, a tank may be prepared for each type of medicine, and each medicine may be stored in a separate tank.
＜対象となるスケール＞
本発明は、炭酸カルシウム、硫酸カルシウム、亜硫酸カルシウム、リン酸カルシウム、水酸化マグネシウムなどのカルシウムやマグネシウム系スケール；リン酸亜鉛、水酸化亜鉛、塩基性炭酸亜鉛などの亜鉛を成分とするスケール；重合シリカ、ケイ酸カルシウム、ケイ酸マグネシウムなどのシリカ系スケール；水酸化アルミニウム、ケイ酸アルミニウムなどのアルミニウムを成分とするスケールに好適に適用される。このように、一般に冷却水系で問題となるスケール種全般が対象であることが本発明の特徴であり、特にアルミニウム含有スケール及びシリカ含有スケールに対して有効であることが、従来技術と大きく異なる特徴である。
<Target scale>
The present invention includes calcium carbonate, calcium sulfate, calcium sulfite, calcium phosphate, magnesium hydroxide, and other calcium and magnesium-based scales; scales containing zinc phosphate, zinc hydroxide, basic zinc carbonate, and other components; polymerized silica, It is suitably applied to silica-based scales such as calcium silicate and magnesium silicate; scales containing aluminum such as aluminum hydroxide and aluminum silicate. As described above, it is a feature of the present invention that the general scale species which are generally problematic in the cooling water system are targets, and particularly effective for aluminum-containing scales and silica-containing scales. It is.
＜フェノール樹脂及び／又は変性フェノール樹脂（１）＞
フェノール樹脂には、酸性触媒の存在下でフェノール類とアルデヒド類とを反応させて得られるノボラック型フェノール樹脂、塩基性触媒の存在下でフェノール類とアルデヒド類とを反応させて得られるレゾール型フェノール樹脂がある。なお、レゾール型フェノール樹脂には、ノボラック型フェノール樹脂をアルカリ水溶液としたものに、さらにアルデヒド類を加えて二次反応を行うことによりレゾール化した樹脂も含まれる。これらは夫々を単独に又は混合して使用してもよい。
さらには、フェノール類やフェノール樹脂を原料として各種変性剤により二次反応を行った変性フェノール樹脂を使用することが出来る。例えば、フェノール類やフェノール樹脂にアミン類とアルデヒド類を反応させることにより得られるマンニッヒ反応物等が挙げられる。
<Phenolic resin and / or modified phenolic resin (1)>
Phenol resins include novolak-type phenol resins obtained by reacting phenols and aldehydes in the presence of acidic catalysts, and resol-type phenols obtained by reacting phenols and aldehydes in the presence of basic catalysts. There is resin. The resol type phenol resin also includes a resin that has been resolated by adding a aldehyde to a novolac type phenol resin in an alkaline aqueous solution and performing a secondary reaction. These may be used alone or in combination.
Furthermore, modified phenolic resins that have been subjected to secondary reactions with various modifiers using phenols or phenolic resins as raw materials can be used. For example, a Mannich reaction product obtained by reacting phenols or phenol resins with amines and aldehydes can be used.
フェノール樹脂及び／又は変性フェノール樹脂の製造に用いるフェノール類としては、例えばフェノール；クレゾール各異性体、エチルフェノール各異性体、キシレノール各異性体、ブチルフェノールなどのアルキルフェノール類；カルダノールなどの不飽和アルキルフェノール類；α，βの各ナフトールなどの多芳香環フェノール類；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ピロガロール、レゾルシン、カテコールなどの多価フェノール類；ハイドロキノンなどが挙げられるが、何らこれらに限定されるものではない。これらのフェノール類は１種を単独で用いてもよく、２種以上を混合して用いてもよい。
フェノール樹脂又は変性フェノール樹脂の製造に用いるアルデヒド類としては、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ベンズアルデヒド、サリチルアルデヒド、グリキオキザールなどが挙げられるが、何らこれらに限定されるものではない。これらのアルデヒド類は１種を単独で用いてもよく、２種以上を混合して用いてもよい。
マンニッヒ反応を行うアミン類としては、例えばイソホロンジアミン、メタキシレンジアミン、ジエチレントリアミン、ジエタノールアミン、Ｎ-メチルエタノールアミンなどが挙げられるが、何らこれらに限定されるものではない。これらのアミン類は１種を単独で用いてもよく、２種以上を混合して用いてもよい。
Examples of the phenols used in the production of the phenol resin and / or the modified phenol resin include phenol; cresol isomers, ethylphenol isomers, xylenol isomers, alkylphenols such as butylphenol; unsaturated alkylphenols such as cardanol; Examples include polyaromatic phenols such as α and β naphthols; polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, pyrogallol, resorcin, and catechol; and hydroquinone, but are not limited thereto. Absent. These phenols may be used individually by 1 type, and 2 or more types may be mixed and used for them.
Examples of the aldehydes used for the production of the phenol resin or the modified phenol resin include, but are not limited to, formaldehyde, paraformaldehyde, acetaldehyde, propyl aldehyde, benzaldehyde, salicylaldehyde, glyoxal and the like. These aldehydes may be used individually by 1 type, and may mix and use 2 or more types.
Examples of amines that perform the Mannich reaction include, but are not limited to, isophoronediamine, metaxylenediamine, diethylenetriamine, diethanolamine, N-methylethanolamine, and the like. These amines may be used individually by 1 type, and may mix and use 2 or more types.
上記のフェノール樹脂及び変性フェノール樹脂としては、フェノールとホルムアルデヒドを重縮合してなるノボラック型フェノール樹脂；これにホルムアルデヒドをレゾール型二次反応させてなるレゾール型二次反応フェノール樹脂；クレゾールとホルムアルデヒドを重縮合してなるノボラック型クレゾール樹脂；これにジエタノールアミンを変性させてなるジエタノールアミン変性ノボラック型クレゾール樹脂；フェノール、カルダノール及びホルムアルデヒドを反応させてなるノボラック型カルダノール・フェノール樹脂；ビスフェノールＡ及びホルムアルデヒドを重縮合してなるノボラック型ビスフェノールＡ樹脂等が挙げられる。
フェノール樹脂及び変性フェノール樹脂の重量平均分子量は、冷却水のブロー水中のＣＯＤの上昇を抑制する観点および水溶液の高粘度化によるハンドリング性の悪化を防ぐ観点から、好ましくは１０００以上であり、より好ましくは３０００〜２００００である。
Examples of the phenol resin and modified phenol resin include a novolac type phenol resin obtained by polycondensation of phenol and formaldehyde; a resol type secondary reaction phenol resin obtained by reacting formaldehyde with a resol type secondary reaction; a mixture of cresol and formaldehyde. Novolak-type cresol resin obtained by condensation; diethanolamine-modified novolak-type cresol resin obtained by modifying diethanolamine; novolak-type cardanol / phenol resin obtained by reacting phenol, cardanol and formaldehyde; and polycondensation of bisphenol A and formaldehyde Novolak type bisphenol A resin and the like.
The weight average molecular weight of the phenolic resin and the modified phenolic resin is preferably 1000 or more, more preferably from the viewpoint of suppressing an increase in COD in the blow water of cooling water and preventing deterioration of handling properties due to an increase in viscosity of the aqueous solution. Is 3000-20000.
＜アニオン性官能基を有する水溶性ポリマー＞
アニオン性官能基を有する水溶性ポリマーとしては、一般にスケール防止剤として用いられているアニオン性ポリマーが使用できる。ポリマーを構成するモノマーとしては、マレイン酸、(メタ)アクリル酸、イタコン酸等のカルボキシル基を有するビニルモノマー；ビニルスルホン酸、アリルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、２−ヒドロキシ−３−アリロキシプロパンスルホン酸等のスルホン酸基を有するビニルモノマー；(メタ)アクリルアミド等のノニオン性ビニルモノマー等が挙げられる。これらのモノマーのホモポリマーやコポリマーを実際に用いることができるが、これらに限定されるものではない。これらのポリマーとして、例えば（メタ）アクリル酸と２−アクリルアミド−２−メチルプロパンスルホン酸とのコポリマー等が好適である。
アニオン性官能基を有する水溶性ポリマーの重量平均分子量は、スケール付着防止効果を向上させる観点から、好ましくは１０００〜５００００であり、より好ましくは５０００〜２００００である。
<Water-soluble polymer having an anionic functional group>
As the water-soluble polymer having an anionic functional group, an anionic polymer generally used as a scale inhibitor can be used. As monomers constituting the polymer, vinyl monomers having a carboxyl group such as maleic acid, (meth) acrylic acid, itaconic acid; vinyl sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-hydroxy And vinyl monomers having a sulfonic acid group such as -3-allyloxypropane sulfonic acid; and nonionic vinyl monomers such as (meth) acrylamide. Homopolymers and copolymers of these monomers can actually be used, but are not limited thereto. As these polymers, for example, a copolymer of (meth) acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid is suitable.
The weight average molecular weight of the water-soluble polymer having an anionic functional group is preferably 1000 to 50000, more preferably 5000 to 20000, from the viewpoint of improving the scale adhesion preventing effect.
＜ホスホン酸類及びその塩、並びにリン酸類及びその塩＞
ホスホン酸類及びその塩、並びにリン酸類及びその塩としては、ヘキサメタリン酸ソーダやトリポリリン酸ソーダ等の無機ポリリン酸類、ヒドロキシエチリデンジホスホン酸やホスホノブタントリカルボン酸等のホスホン酸など、一般的に使用されているものが使用できるが、これらに限定されるものではない。
<Phosphonic acids and salts thereof, and phosphoric acids and salts thereof>
Phosphonic acids and their salts, and phosphoric acids and their salts are generally used as inorganic polyphosphoric acids such as sodium hexametaphosphate and sodium tripolyphosphate, and phosphonic acids such as hydroxyethylidene diphosphonic acid and phosphonobutanetricarboxylic acid. However, the present invention is not limited to these.
＜添加方法＞
成分（１）及び成分（２）は、予め混合してから冷却水系の循環水及び／又は補給水に添加してもよく、混合することなく別々に循環水及び／又は補給水に添加してもよい。例えば、
添加方法（１）：成分（１）及び成分（２）を別々のタンクに準備し、別々に冷却水の循環水及び／又は補給水に添加する、
添加方法（２）：成分（１）及び成分（２）を別々のタンクに準備し、添加時にこれらを混合してから冷却水の循環水及び／又は補給水に添加する、
添加方法（３）：成分（１）及び成分（２）を同じタンク内で混合し混合物としておき、添加時に当該混合物を冷却水の循環水及び／又は補給水に添加する、
等の添加方法を適用することができる。
添加方法（１）及び添加方法（２）のように、成分（１）及び成分（２）を別々に添加する場合、冷却水の性状に応じて、成分（１）と成分（２）の冷却水中における含有比率を任意に調整することができる。
添加方法（３）のように、成分（１）及び成分（２）を同じタンク内で混合し混合物としておく場合、タンクの個数を少なくすることができる。
なお、成分（１）及び／又は成分（２）は、必要に応じて水にて希釈して濃度調整を行って用いてよい。また、必要に応じて、他の水処理薬品と混合して用いてもよい。
<Addition method>
Component (1) and component (2) may be added in advance to the circulating water and / or make-up water in the cooling water system after being mixed in advance, or added separately to the circulating water and / or make-up water without mixing. Also good. For example,
Addition method (1): Prepare component (1) and component (2) in separate tanks and add them separately to the circulating water and / or make-up water of cooling water.
Addition method (2): Component (1) and component (2) are prepared in separate tanks, mixed at the time of addition, and then added to circulating water and / or makeup water of cooling water.
Addition method (3): Component (1) and component (2) are mixed in the same tank to form a mixture, and at the time of addition, the mixture is added to circulating water and / or make-up water.
An addition method such as the above can be applied.
When component (1) and component (2) are added separately as in addition method (1) and addition method (2), cooling of component (1) and component (2) depends on the properties of the cooling water. The content ratio in water can be arbitrarily adjusted.
When the component (1) and the component (2) are mixed in the same tank as the addition method (3) to prepare a mixture, the number of tanks can be reduced.
In addition, the component (1) and / or the component (2) may be diluted with water as necessary to adjust the concentration. Moreover, you may mix and use other water treatment chemicals as needed.
＜添加濃度＞
成分（１）は、冷却水系の循環水中における濃度が、好ましくは０．１〜１００ｍｇ／Ｌ、より好ましくは１〜８０ｍｇ／Ｌ、更に好ましくは５〜５０ｍｇ／Ｌ、より更に好ましくは１０〜３０ｍｇ／Ｌとなるように添加する。０．１ｍｇ／Ｌ以上であるとスケール付着防止効果に優れ、１００ｍｇ／Ｌ以下であると経済的である。
成分（２）は、冷却水系の循環水中における濃度が、好ましくは０．１〜２００ｍｇ／Ｌ、より好ましくは１〜１００ｍｇ／Ｌ、更に好ましくは２〜５０ｍｇ／Ｌ、より更に好ましくは３〜１５ｍｇ／Ｌ、より更に好ましくは３〜１０ｍｇ／Ｌとなるように添加する。０．１ｍｇ／Ｌ以上であるとスケール付着防止効果に優れ、２００ｍｇ／Ｌ以下であると経済的である。
上記添加濃度は目安であり、水質よって好適な添加濃度は変化するため上記範囲に限定されるものではないが、例えば下記の水質のときに上記濃度範囲が好ましく適用される。
<Additional concentration>
The concentration of component (1) in the circulating water of the cooling water system is preferably 0.1 to 100 mg / L, more preferably 1 to 80 mg / L, still more preferably 5 to 50 mg / L, and still more preferably 10 to 30 mg. / L to add. When it is 0.1 mg / L or more, the scale adhesion preventing effect is excellent, and when it is 100 mg / L or less, it is economical.
The concentration of component (2) in the circulating water of the cooling water system is preferably 0.1 to 200 mg / L, more preferably 1 to 100 mg / L, still more preferably 2 to 50 mg / L, still more preferably 3 to 15 mg. / L, more preferably 3 to 10 mg / L. When it is 0.1 mg / L or more, the scale adhesion preventing effect is excellent, and when it is 200 mg / L or less, it is economical.
The above-mentioned concentration of addition is a standard, and the suitable concentration of addition varies depending on the water quality and is not limited to the above range. For example, the above concentration range is preferably applied when the following water quality is present.
＜本発明の適用に有効な水質＞
特に限定されるものではないが、例えば冷却水の循環水では、シリカ濃度はＳｉＯ2として５０ｍｇ／Ｌ以上、カルシウム濃度はカルシウム硬度で１００ｍｇ／Ｌ以上、アルミニウム濃度はＡｌとして０．５ｍｇ／Ｌ以上で、本発明の効果が好適に発揮される。また、冷却水系の腐食や故障の防止等の観点から、循環水において、シリカ濃度はＳｉＯ2として５００ｍｇ／Ｌ以下、カルシウム濃度はカルシウム硬度で１０００ｍｇ／Ｌ以下、アルミニウム濃度はＡｌとして５０ｍｇ／Ｌ以下であることが好ましい。
よって、上記シリカ濃度は、好ましくは５０〜５００ｍｇ／Ｌ、より好ましくは６０〜３００ｍｇ／Ｌ、更に好ましくは８０〜２５０ｍｇ／Ｌである。上記カルシウム硬度は、好ましくは１００〜１０００ｍｇ／Ｌ、より好ましくは１２０〜５００ｍｇ／Ｌ、更に好ましくは１２０〜４００ｍｇ／Ｌである。上記アルミニウム濃度は、好ましくは０．５〜５０ｍｇ／Ｌ、より好ましくは０．５〜２０ｍｇ／Ｌ、更に好ましくは０．５〜１０ｍｇ／Ｌである。
<Water quality effective for application of the present invention>
Although not particularly limited, for example, in circulating water of cooling water, the silica concentration is 50 mg / L or more as SiO 2 , the calcium concentration is 100 mg / L or more in calcium hardness, and the aluminum concentration is 0.5 mg / L or more as Al. Thus, the effects of the present invention are suitably exhibited. Further, from the viewpoint of preventing corrosion and failure of the cooling water system, in the circulating water, the silica concentration is 500 mg / L or less as SiO 2 , the calcium concentration is 1000 mg / L or less in calcium hardness, and the aluminum concentration is 50 mg / L or less as Al. It is preferable that
Therefore, the silica concentration is preferably 50 to 500 mg / L, more preferably 60 to 300 mg / L, and still more preferably 80 to 250 mg / L. The calcium hardness is preferably 100 to 1000 mg / L, more preferably 120 to 500 mg / L, and still more preferably 120 to 400 mg / L. The aluminum concentration is preferably 0.5 to 50 mg / L, more preferably 0.5 to 20 mg / L, and still more preferably 0.5 to 10 mg / L.
＜成分（１）及び成分（２）の剤型＞
成分（１）及び成分（２）ともに、水溶液の剤型が好ましいが、粉末やペレット状の固体でもよい。固体の場合は使用直前に溶解タンクにて溶解して水溶液状にして使用するのが好ましい。
成分（１）及び成分（２）は、各々独立した剤型でもよく、成分（１）及び成分（２）を混合して一剤化した剤型でもよい。各々独立した剤型の場合、循環水中の各成分の濃度を独立して調整することができる。一剤化した剤型の場合、保管スペースが小さくて済み、混合する手間を省くこともできる。
一剤化する場合には、アルミニウム系及びシリカ系のスケールの付着と、従来のカルシウム系、マグネシウム系及びリン酸系のスケールの付着とをバランスよく防止する観点から、成分（１）と成分（２）の質量比〔（１）／（２）〕は、好ましくは１／１０〜１０／１、より好ましくは１／５〜５／１、更に好ましくは１／２〜２／１である。
<Form of component (1) and component (2)>
Both the component (1) and the component (2) are preferably in the form of an aqueous solution, but may be a powder or a pellet-like solid. In the case of a solid, it is preferably used in the form of an aqueous solution by dissolving in a dissolution tank immediately before use.
Component (1) and component (2) may be independent dosage forms, or may be a dosage form obtained by mixing component (1) and component (2). In the case of independent dosage forms, the concentration of each component in the circulating water can be adjusted independently. In the case of a single dosage form, the storage space can be small, and the labor of mixing can be saved.
In the case of a single agent, from the viewpoint of preventing the adhesion of aluminum-based and silica-based scales and the conventional calcium-based, magnesium-based and phosphoric acid-based scales in a balanced manner, component (1) and component ( The mass ratio [(1) / (2)] of 2) is preferably 1/10 to 10/1, more preferably 1/5 to 5/1, and still more preferably 1/2 to 2/1.
＜他の薬剤との併用＞
成分（１）及び成分（２）とともに、必要に応じて、防食剤、スライムコントロール剤、消泡剤などを併用することができる。
防食剤としては、亜鉛塩、モリブデン酸塩、クロム酸塩、亜硝酸塩などの無機塩；メルカプトベンゾチアゾール、ベンゾトリアゾール、トリルトリアゾールなのどの有機防食剤；アミン類や界面活性剤などの被膜形成型材料などが挙げられる。なお、成分（２）の１種であるリン酸類及びホスホン酸類等のリン化合物はスケール防止作用とともに鉄や鋼材質の熱交換部の腐食防止の役割も果たす。
スライムコントロール剤としては、塩素、次亜塩素酸ソーダ、塩素化イソシアヌル酸、１，３−ジブロモ−５，５−ジメチルヒダントイン、１−ブロモ−３−クロロ−５，５−ジメチルヒダントインなどの塩素系、その他２，２−ジブロモ−３−ニトリロプロピオンアミド、２，２−ジブロモ−２−ニトロエタノール、ビス−１，４−ブロモアセトキシ−２−ブテン、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、４，５−ジクロロ−１，２−ジチオラン−３−オン、５−クロロ−２，４，６−トリフルオロイソフタロニトリル、ヘキサブロモジメチルスルホン、３，３，４，４−テトラクロロテトラヒドロチオフェン−１，１−ジオキシド、２−ブロモ−２−ニトロプロパン−１，３−ジオール、ベンゾイソチアゾリン−３−オン、グルタールアルデヒドなどが挙げられる。
消泡剤としては、シリコーン系（ジメチルポリシロキサンなど）、鉱物油（スピンドル油、ケロシンなど）、金属石鹸（炭素数１２〜２２、たとえばステアリン酸カルシウム、オレイン酸マグネシウム）などが挙げられる。
<Combination with other drugs>
An anticorrosive, a slime control agent, an antifoamer, etc. can be used together with a component (1) and a component (2) as needed.
Anticorrosives include inorganic salts such as zinc salts, molybdates, chromates and nitrites; organic anticorrosives such as mercaptobenzothiazole, benzotriazole and tolyltriazole; film-forming materials such as amines and surfactants Etc. It should be noted that phosphorus compounds such as phosphoric acids and phosphonic acids, which are one type of component (2), play a role of preventing corrosion and preventing corrosion of heat exchange parts made of iron or steel.
As a slime control agent, chlorine, sodium hypochlorite, chlorinated isocyanuric acid, 1,3-dibromo-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-dimethylhydantoin and other chlorine-based agents 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-nitroethanol, bis-1,4-bromoacetoxy-2-butene, 5-chloro-2-methyl-4-isothiazoline- 3-one, 4,5-dichloro-1,2-dithiolane-3-one, 5-chloro-2,4,6-trifluoroisophthalonitrile, hexabromodimethylsulfone, 3,3,4,4-tetra Chlorotetrahydrothiophene-1,1-dioxide, 2-bromo-2-nitropropane-1,3-diol, benzoisothiazoline-3- Emissions, such as glutaraldehyde, and the like.
Examples of antifoaming agents include silicones (such as dimethylpolysiloxane), mineral oils (such as spindle oil and kerosene), and metal soaps (having 12 to 22 carbon atoms such as calcium stearate and magnesium oleate).
以下、実施例及び比較例（参考例も含む。以下、同様。）に基づいてさらに詳述するが、本発明はこの実施例により何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples and comparative examples (including reference examples; hereinafter the same) , but the present invention is not limited to these examples.
＜重量平均分子量の測定方法＞
なお、実施例及び比較例において、各試料の重量平均分子量は、次のとおり、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した。
（分子量測定試料の調製）
試料がテトラヒドロフラン溶液に可溶の場合には、そのまま分子量測定試料とした。一方、試料がテトラヒドロフラン溶液に不溶の場合には、次の操作によって分子量測定試料を調製した。
すなわち、試料がアルカリ水溶液の場合はテトラヒドロフランに不溶のため、アルカリ金属イオンの除去と水分除去を樹脂中の低分子量成分を流出させずに行う必要がある。
そのため試料のアルカリ水溶液を０．１質量％程度に希釈し、塩酸をゆっくり滴下してｐＨを４．６に下げた懸濁液を調製した。次にこの懸濁液を透析チューブに入れて密閉し、連続で純水を通水できるようにしたバットにそのチューブを入れ、２４時間透析を行った。その後、透析チューブから取り出した懸濁液をガラスフィルターでろ過し、回収した樹脂を純水にて洗浄後、真空乾燥機にて４８時間室温で乾燥させることにより分子量測定試料とした。
（重量平均分子量の測定）
分子量測定試料をテトラヒドロフラン溶液とし、クロマトカラムとして東ソー製ＨＬＣ８０２２、溶媒としてテトラヒドロフランを用い、測定を行った。重量平均分子量は標準ポリスチレン換算により求めた。
<Measurement method of weight average molecular weight>
In Examples and Comparative Examples, the weight average molecular weight of each sample was measured by gel permeation chromatography (GPC) as follows.
(Preparation of molecular weight measurement sample)
When the sample was soluble in the tetrahydrofuran solution, it was used as a molecular weight measurement sample as it was. On the other hand, when the sample was insoluble in the tetrahydrofuran solution, a molecular weight measurement sample was prepared by the following operation.
That is, when the sample is an alkaline aqueous solution, it is insoluble in tetrahydrofuran, and thus it is necessary to remove alkali metal ions and remove moisture without causing low molecular weight components in the resin to flow out.
Therefore, the alkaline aqueous solution of the sample was diluted to about 0.1% by mass, and hydrochloric acid was slowly added dropwise to prepare a suspension whose pH was lowered to 4.6. Next, this suspension was put in a dialysis tube and sealed, and the tube was placed in a vat that was allowed to continuously pass pure water, and dialyzed for 24 hours. Thereafter, the suspension taken out from the dialysis tube was filtered through a glass filter, and the collected resin was washed with pure water and then dried at room temperature for 48 hours in a vacuum dryer to obtain a molecular weight measurement sample.
(Measurement of weight average molecular weight)
The measurement was performed using a tetrahydrofuran solution as the molecular weight measurement sample, HLC8022 manufactured by Tosoh as the chromatography column, and tetrahydrofuran as the solvent. The weight average molecular weight was determined by standard polystyrene conversion.
＜製造例１（ポリマー１）＞
原料樹脂として、群栄化学工業（株）製のレヂトップＰＳＭ−６３５８を使用した。本品は、フェノールとホルムアルデヒドを酸触媒の存在下に重縮合を行って得られたノボラック型フェノール樹脂（重量平均分子量：５４００）である。
ビーカーにＰＳＭ−６３５８ ４１．０ｇ、イオン交換水１４６．２ｇ、４８質量％水酸化ナトリウム水溶液１２．８ｇを入れ、マグネチックスターラにて攪拌溶解し、ＰＳＭ−６３５８を２０．５％含有するノボラック型フェノール樹脂アルカリ溶液２００ｇを得た。この溶液のｐＨは１２．４であった。
<Production Example 1 (Polymer 1)>
As a raw material resin, Resitop PSM-6358 manufactured by Gunei Chemical Industry Co., Ltd. was used. This product is a novolak type phenol resin (weight average molecular weight: 5400) obtained by polycondensation of phenol and formaldehyde in the presence of an acid catalyst.
A beaker is charged with 41.0 g of PSM-6358, 146.2 g of ion-exchanged water, and 12.8 g of a 48% by mass aqueous sodium hydroxide solution, dissolved by stirring with a magnetic stirrer, and a novolak type containing 20.5% of PSM-6358. 200 g of a phenol resin alkali solution was obtained. The pH of this solution was 12.4.
＜製造例２（ポリマー２）＞
共栓付三角フラスコに前記ノボラック型フェノール樹脂アルカリ溶液１００ｇを入れ、約６０℃に加温してから３７質量％のホルムアルデヒド水溶液４．４３ｇを加えた。コンデンサー、攪拌用窒素ガス吹き込み管、及び温度計を共栓に取り付け、オイルバスで、液温度８５℃に８時間保持することにより、レゾール型のホルムアルデヒド付加・重縮合反応を進行させた（レゾール型２次反応）。その後、これを冷却し、イオン交換水（濃度調整用）４．４６ｇを加えることにより、フェノール類２核体を含む低分子量成分含有率を低減し、重量平均分子量を１３４００に増加させた２次反応フェノール樹脂アルカリ溶液を得た。この溶液の樹脂成分濃度は１９．４質量％であった。
<Production Example 2 (Polymer 2)>
100 g of the novolac-type phenolic resin alkaline solution was placed in a conical stoppered Erlenmeyer flask, heated to about 60 ° C., and 4.43 g of a 37% by mass aqueous formaldehyde solution was added. A condenser, a nitrogen gas blowing tube for stirring, and a thermometer were attached to the stopper, and the resol-type formaldehyde addition / polycondensation reaction was advanced by holding at a liquid temperature of 85 ° C. for 8 hours with an oil bath (resol-type). Secondary reaction). Thereafter, this was cooled, and 4.46 g of ion-exchanged water (for concentration adjustment) was added to reduce the content of low molecular weight components including phenolic binuclear compounds and to increase the weight average molecular weight to 13400. A reaction phenol resin alkaline solution was obtained. The resin component concentration of this solution was 19.4% by mass.
＜製造例３（ポリマー３）＞
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコにクレゾール４５０．０ｇ、次いで３７質量％ホルムアルデヒド水溶液２００．０ｇを添加した。その後、触媒としてシュウ酸３．０ｇを添加し、系を攪拌しながらヒーターにより加熱を行い９５℃まで昇温し、温度を維持したまま４時間反応を行った。次に、常圧下で２００℃まで昇温しながら脱水濃縮を行い、２００℃に達したところで５．３ｋＰａの減圧下において未反応クレゾールの留去を行なった。こうして黄色透明なノボラック型クレゾール樹脂（重量平均分子量：２０００）３５０ｇを得た。
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコに得られたクレゾール樹脂１１０ｇ、エタノール１１０ｇを入れ、ヒーターで７０℃まで加熱を行い、２時間攪拌することにより、クレゾール樹脂をエタノールに溶解させて樹脂溶液を得た。次に樹脂溶液を４０℃以下に冷却した後、ジエタノールアミン５７．８ｇを添加し、次いで３７質量％ホルムアルデヒド水溶液４．５０ｇを添加した。その後系を攪拌しながら７０℃まで加熱し、１５時間保持することにより、クレゾール樹脂にジエタノールアミンを変性させた。次に系を冷却により４０℃以下とした後、３．６質量％塩酸５５．０ｇを添加した。よく攪拌を行い均一溶液とした後に、減圧下で加熱を行うことによりエタノールを留去し、最後にイオン交換水を所定量添加することで濃度調整を行った。これによりクレゾール樹脂のマンニッヒ反応物の水溶液を得た。この溶液の樹脂成分濃度は１５．８質量％であった。
<Production Example 3 (Polymer 3)>
To a separable flask equipped with a stirrer, a thermometer, and a reflux condenser, 450.0 g of cresol and then 200.0 g of a 37 mass% aqueous formaldehyde solution were added. Thereafter, 3.0 g of oxalic acid was added as a catalyst, heated with a heater while stirring the system, heated to 95 ° C., and reacted for 4 hours while maintaining the temperature. Next, dehydration concentration was performed while raising the temperature to 200 ° C. under normal pressure, and when the temperature reached 200 ° C., unreacted cresol was distilled off under a reduced pressure of 5.3 kPa. Thus, 350 g of a yellow transparent novolac cresol resin (weight average molecular weight: 2000) was obtained.
Place 110 g of cresol resin and 110 g of ethanol in a separable flask equipped with a stirrer, thermometer and reflux condenser, heat to 70 ° C. with a heater, and stir for 2 hours to dissolve the cresol resin in ethanol. Thus, a resin solution was obtained. Next, after cooling the resin solution to 40 ° C. or lower, 57.8 g of diethanolamine was added, and then 4.50 g of a 37 mass% formaldehyde aqueous solution was added. Thereafter, the system was heated to 70 ° C. with stirring, and maintained for 15 hours to modify the cresol resin with diethanolamine. Next, after cooling the system to 40 ° C. or lower, 55.0 g of 3.6 mass% hydrochloric acid was added. After thoroughly stirring to obtain a uniform solution, ethanol was distilled off by heating under reduced pressure, and finally the concentration was adjusted by adding a predetermined amount of ion-exchanged water. As a result, an aqueous solution of a Mannich reaction product of the cresol resin was obtained. The resin component concentration of this solution was 15.8% by mass.
＜製造例４（ポリマー４）＞
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコにフェノール２６３．５ｇ、カルダノール２９８．５ｇを添加し、次いで３７質量％ホルムアルデヒド水溶液２８０．７ｇを添加した。その後、触媒としてシュウ酸４．６７ｇを添加し、系を攪拌しながらヒーターにより加熱を行い９５℃まで昇温し、温度を維持したまま１２時間反応を行った。次に、常圧下で２００℃まで昇温しながら脱水濃縮を行い、２００℃に達したところで５．３ｋＰａの減圧下において未反応フェノールの留去を行なった。こうして褐色透明なノボラック型カルダノール・フェノール樹脂（重量平均分子量：１１０００）５９５ｇを得た。ビーカーにこのノボラック型カルダノール・フェノール樹脂４１．０ｇ、イオン交換水１４６．２ｇ、４８質量％水酸化ナトリウム水溶液１２．８ｇを入れ、マグネチックスターラにて攪拌溶解し、ノボラック型カルダノール・フェノール樹脂アルカリ溶液２００ｇを得た。この溶液の樹脂成分濃度は２０．５質量％であった。
<Production Example 4 (Polymer 4)>
263.5 g of phenol and 298.5 g of cardanol were added to a separable flask equipped with a stirrer, a thermometer, and a reflux condenser, and then 280.7 g of 37% by mass aqueous formaldehyde solution was added. Then, 4.67 g of oxalic acid was added as a catalyst, heated with a heater while stirring the system, heated to 95 ° C., and reacted for 12 hours while maintaining the temperature. Next, dehydration concentration was performed while raising the temperature to 200 ° C. under normal pressure, and when the temperature reached 200 ° C., unreacted phenol was distilled off under a reduced pressure of 5.3 kPa. Thus, 595 g of a brown transparent novolac-type cardanol / phenol resin (weight average molecular weight: 11000) was obtained. In a beaker, 41.0 g of this novolak-type cardanol / phenol resin, 146.2 g of ion-exchanged water, and 12.8 g of a 48% by mass aqueous sodium hydroxide solution were stirred and dissolved with a magnetic stirrer, and the novolac-type cardanol / phenolic resin alkaline solution 200 g was obtained. The resin component concentration of this solution was 20.5% by mass.
＜製造例５（ポリマー５）＞
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコに溶剤としてエチレングリコールモノエチルエーテル２４．０ｇ、ビスフェノールＡ２４０ｇを添加し、次いで５０質量％ホルムアルデヒド水溶液５１．８ｇを添加した。その後、触媒としてシュウ酸１．１０ｇを添加し、系を攪拌しながらヒーターにより加熱を行い１００℃まで昇温し、温度を維持したまま６時間反応を行った。次に、常圧下で２００℃まで昇温しながら脱水濃縮を行い、２００℃に達したところで５．３ｋＰａの減圧下において水分及び溶剤の留去を行なった。こうして褐色透明なノボラック型ビスフェノールＡ樹脂（重量平均分子量：６５００）２４０ｇを得た。ビーカーにこのノボラック型ビスフェノールＡ樹脂４１．０ｇ、イオン交換水１４６．２ｇ、４８質量％水酸化ナトリウム水溶液１２．８ｇを入れ、マグネチックスターラにて攪拌溶解し、ノボラック型ビスフェノールＡ樹脂アルカリ溶液２００ｇを得た。この溶液の樹脂成分濃度は２０．５質量％であった。
<Production Example 5 (Polymer 5)>
To a separable flask equipped with a stirrer, a thermometer, and a reflux condenser, 24.0 g of ethylene glycol monoethyl ether and 240 g of bisphenol A were added as a solvent, and then 51.8 g of a 50% by mass aqueous formaldehyde solution was added. Thereafter, 1.10 g of oxalic acid was added as a catalyst, heated with a heater while stirring the system, heated to 100 ° C., and reacted for 6 hours while maintaining the temperature. Next, dehydration concentration was performed while raising the temperature to 200 ° C. under normal pressure, and when the temperature reached 200 ° C., water and solvent were distilled off under a reduced pressure of 5.3 kPa. Thus, 240 g of a brown transparent novolac bisphenol A resin (weight average molecular weight: 6500) was obtained. In a beaker, 41.0 g of this novolac type bisphenol A resin, 146.2 g of ion-exchanged water, and 12.8 g of 48% by mass sodium hydroxide aqueous solution were stirred and dissolved with a magnetic stirrer. Obtained. The resin component concentration of this solution was 20.5% by mass.
＜実施例１〜１２、参考例１及び比較例１〜８＞
《評価試験装置》
評価試験装置として、図１に示す装置を用いた。
この装置の保有水量は１００Ｌであり、熱交換器４の伝熱面積は０．２５ｍ2である。熱交換器４の材質はＳＵＳ３０４であり、外径１９ｍｍのチューブを用いた。また、非伝熱チューブの材質はＳＵＳ３０４であり、外径１９ｍｍのチューブを用いた。
<Examples 1 to 12, Reference Example 1 and Comparative Examples 1 to 8>
<< Evaluation test equipment >>
As the evaluation test apparatus, the apparatus shown in FIG. 1 was used.
The amount of water held by this device is 100 L, and the heat transfer area of the heat exchanger 4 is 0.25 m 2 . The material of the heat exchanger 4 was SUS304, and a tube having an outer diameter of 19 mm was used. The material of the non-heat transfer tube was SUS304, and a tube with an outer diameter of 19 mm was used.
《使用したポリマー、工業用水、及び併用薬剤》
フェノール樹脂及び／又は変性フェノール樹脂、並びにその他のポリマーとして、表１に示すポリマー１〜９を用いた。
また、併用薬剤のうち、アニオン性官能基を有する水溶性ポリマーとして、アクリル酸（以下「Ｐ−ＡＡ」と略すことがある）と２−アクリルアミド−２−メチルプロパンスルホン酸（以下「ＡＭＰＳ」と略すことがある）とのモル比（Ｐ−ＡＡ／ＡＭＰＳ）が８０／２０(モル％)である、重量平均分子量９０００の共重合体(以下「Ｐ−ＡＡ／ＡＭＰＳ」と略すことがある)を用いた。
併用薬剤のうち、ホスホン酸類として、ヒドロキシエチリデンジホスホン酸（以下ＨＥＤＰと略すことがある）を用い、リン酸類として、ヘキサメタリン酸ソーダを用いた。
冷却水として、表２に示す水質の工業用水を用いた。なお、表２中、酸消費量（ｍｇ／Ｌとは、１Ｌの工業用水をｐＨ４．８まで下げるのに要した酸の量を、炭酸カルシウム量（ｍｇ）に換算した値である。濁度とは、ＪＩＳ Ｋ ０１０１の９．２に基づき測定した透過光濁度（濁度標準液としてカオリン標準液）で表される値である。
<Polymer used, industrial water, and concomitant drug>
As the phenol resin and / or modified phenol resin and other polymers, polymers 1 to 9 shown in Table 1 were used.
Among the concomitant drugs, as a water-soluble polymer having an anionic functional group, acrylic acid (hereinafter sometimes abbreviated as “P-AA”) and 2-acrylamido-2-methylpropanesulfonic acid (hereinafter referred to as “AMPS”) Copolymer having a weight average molecular weight of 9000 (hereinafter, may be abbreviated as “P-AA / AMPS”) having a molar ratio (P-AA / AMPS) of 80/20 (mol%). Was used.
Among the concomitant drugs, hydroxyethylidene diphosphonic acid (hereinafter sometimes abbreviated as HEDP) was used as the phosphonic acid, and sodium hexametaphosphate was used as the phosphoric acid.
Water for industrial use shown in Table 2 was used as the cooling water. In Table 2, acid consumption (mg / L is a value obtained by converting the amount of acid required to lower 1 L of industrial water to pH 4.8 into the amount of calcium carbonate (mg). Is a value represented by transmitted light turbidity (kaolin standard solution as a turbidity standard solution) measured based on 9.2 of JIS K 0101.
《評価試験操作（試験装置の運転）》
前述の工業用水を補給水とし、評価試験装置内の循環水の濃縮倍数が表３に示す倍率（５倍又は７倍）になるように循環水のカルシウム硬度を定期的に測定し、ブロー水量（循環水の系外排出）をコントロールしながら３０日間運転を行った。濃縮５倍となるようにコントロールした場合、カルシウム硬度の変動は１８６〜２４８ｍｇ／Ｌであり、濃縮７倍となるようにコントロールした場合、カルシウム硬度の変動は２６８〜３３０ｍｇ／Ｌであった。この間、循環水の熱交換器入口温度は３０℃、出口温度は４０℃に保った。また、循環水の熱交換器チューブ及び非伝熱チューブを通過する流速は０．５ｍ／ｓとした。
更に、各実施例及び比較例において、循環水中に、表３に示す種類のポリマー及び併用薬剤を表３に示す濃度にて連続添加した。
なお、表３中、ポリマーの濃度とは、循環水中におけるポリマーの固形分濃度のことをいう。Ｐ−ＡＡ／ＡＭＰＳの濃度とは、循環水中におけるＰ−ＡＡ／ＡＭＰＳの固形分濃度のことをいう。ＨＥＤＰの濃度とは、循環水中におけるＨＥＤＰのリン酸分子（ＰＯ4）換算濃度のことをいう。ヘキサメタリン酸ソーダの濃度とは、循環水中におけるヘキサメタリン酸ソーダのリン酸分子（ＰＯ4）換算濃度のことをいう。
また、すべての実施例及び比較例において、スライムコントロール処理として、次亜塩素酸ソーダを、循環水中の濃度が塩素分子（Ｃｌ2）換算で０．５〜１．０ｍｇ／Ｌになるように薬注ポンプを用いて連続添加した。
<< Evaluation test operation (operation of test equipment) >>
Using the above industrial water as make-up water, periodically measure the calcium hardness of the circulating water so that the concentration factor of circulating water in the evaluation test device is the magnification shown in Table 3 (5 times or 7 times). The operation was performed for 30 days while controlling (circulated water out of the system). When the concentration was controlled to be 5 times, the variation in calcium hardness was 186 to 248 mg / L, and when the concentration was controlled to be 7 times, the variation in calcium hardness was 268 to 330 mg / L. During this time, the inlet temperature of the circulating water heat exchanger was kept at 30 ° C., and the outlet temperature was kept at 40 ° C. Moreover, the flow rate which passes through the heat exchanger tube and non-heat-transfer tube of circulating water was 0.5 m / s.
Furthermore, in each Example and Comparative Example, the polymer of the type shown in Table 3 and the concomitant drug were continuously added to the circulating water at the concentrations shown in Table 3.
In Table 3, the polymer concentration means the solid content concentration of the polymer in the circulating water. The concentration of P-AA / AMPS refers to the solid content concentration of P-AA / AMPS in the circulating water. The concentration of HEDP refers to the concentration of HEDP converted to phosphoric acid molecules (PO 4 ) in the circulating water. The concentration of sodium hexametaphosphate refers to the phosphoric acid molecule (PO 4 ) equivalent concentration of sodium hexametaphosphate in the circulating water.
In all Examples and Comparative Examples, sodium hypochlorite is used as a slime control treatment so that the concentration in the circulating water is 0.5 to 1.0 mg / L in terms of chlorine molecules (Cl 2 ). Continuous addition was made using an injection pump.
《スケールの付着量の測定》
３０日間の試験終了後、熱交換器チューブ、非伝熱チューブを乾燥した後、付着したスケールを削り落として１０５℃で乾燥し、乾燥後の質量を測定してスケールの付着量とした。その結果を表３に示す。
《スケールの成分分析》
その後、スケールを６００℃で灰化することにより、スケール中の各金属を、その酸化物にした。この灰化処理により、スケール中のＣａ、Ａｌ、Ｍｇ及びＳｉは、ＣａＯ、Ａｌ2Ｏ3、ＭｇＯ及びＳｉＯ2になる。
この灰化したスケールを塩酸で溶解し、溶解液について高周波プラズマ発光分光分析装置（ＩＣＰ、アジレント社製、商品名：ＩＣＰ−４５００」）にて成分分析を行った。このようにしてＩＣＰで測定された各金属元素の質量を、その酸化物の質量に換算して評価した
また、実施例１と比較例１については、上記の灰化したスケールを塩酸で溶解したときの酸不溶解分をフッ酸で分解し、ＩＣＰにて成分分析した。その結果、実施例１及び比較例１の各スケールとも、成分分析で得られたＳｉの質量をＳｉＯ2の質量に換算すると、元の酸不溶解分の質量の９７〜９８％となった。この結果と、すべての実施例及び比較例において同じ工業用水を用いていることから、総ての実施例及び比較例において、酸不溶解分をＳｉＯ2として扱って問題ないことが判ったため、酸不溶解分の質量をＳｉＯ2の質量とみなして評価した。
上記のＩＣＰ測定の結果を、表３に示す。
<Measurement of scale adhesion>
After the test for 30 days was completed, the heat exchanger tube and the non-heat transfer tube were dried, the attached scale was scraped off and dried at 105 ° C., and the mass after drying was measured to obtain the amount of scale attached. The results are shown in Table 3.
<Scaling component analysis>
Thereafter, the scale was incinerated at 600 ° C. to convert each metal in the scale into its oxide. By this ashing treatment, Ca, Al, Mg and Si in the scale become CaO, Al 2 O 3 , MgO and SiO 2 .
This incinerated scale was dissolved with hydrochloric acid, and the dissolved solution was subjected to component analysis using a high-frequency plasma emission spectroscopic analyzer (ICP, product name: ICP-4500, manufactured by Agilent). Thus, the mass of each metal element measured by ICP was converted into the mass of the oxide and evaluated. In Example 1 and Comparative Example 1, the above-mentioned ashed scale was dissolved with hydrochloric acid. The acid-insoluble matter was decomposed with hydrofluoric acid and analyzed by ICP. As a result, in each scale of Example 1 and Comparative Example 1, when the mass of Si obtained by component analysis was converted to the mass of SiO 2 , it became 97 to 98% of the mass of the original acid-insoluble matter. Since this result and the same industrial water were used in all Examples and Comparative Examples, it was found that in all Examples and Comparative Examples, there was no problem in treating the acid insoluble matter as SiO 2. The mass of insoluble matter was evaluated as the mass of SiO 2 .
The results of the above ICP measurement are shown in Table 3.
《評価結果》
表３に示すとおり、本発明によると、スケール付着量の低減が可能であることが明らかになった。また本発明によると、灰化したスケールの成分中におけるシリカ等からなる酸不溶成分及びアルミナの割合が小さくなり、このことから、シリカ成分及びアルミニウム成分の付着が防止できることが明らかになった。
"Evaluation results"
As shown in Table 3, according to the present invention, it became clear that the amount of scale adhesion can be reduced. Further, according to the present invention, the ratio of the acid-insoluble component composed of silica or the like and the alumina in the components of the incinerated scale is reduced, and it has been clarified that the adhesion of the silica component and the aluminum component can be prevented.
１ 循環水ピット
２ 循環ポンプ
３ 非伝熱チューブ
４ 熱交換器
５ レベルセンサー
６ 導電率計
７ ブロー配管
８ 薬注ポンプ
９ 薬注ポンプ
１０ 補給水ポンプ
１１ 第１の槽
１２ 第２の槽
１３ 補給水槽
DESCRIPTION OF SYMBOLS 1 Circulating water pit 2 Circulating pump 3 Non-heat-transfer tube 4 Heat exchanger 5 Level sensor 6 Conductivity meter 7 Blow piping 8 Chemical injection pump 9 Chemical injection pump 10 Supplementary water pump 11 First tank 12 Second tank 13 Replenishment Aquarium
Claims (5)
前記フェノール樹脂は、フェノール類とアルデヒド類との反応生成物であるノボラック型フェノール樹脂及び／又はレゾール型フェノール樹脂であり、
前記変性フェノール樹脂は、フェノール類及び／又は前記フェノール樹脂とアミン類とアルデヒド類とのマンニッヒ反応物であり、
前記フェノール類は、フェノール、アルキルフェノール、不飽和アルキルフェノール及び多芳香環フェノールの少なくとも１種からなることを特徴とするスケール付着防止方法。 A cooling water system comprising a phenol resin and / or a modified phenol resin (1), a water-soluble polymer having an anionic functional group, a phosphonic acid and a salt thereof, and a drug (2) comprising at least one of a phosphoric acid and a salt thereof In combination with cooling water ,
The phenol resin is a novolac type phenol resin and / or a resol type phenol resin which is a reaction product of phenols and aldehydes,
The modified phenolic resin is a Mannich reaction product of phenols and / or the phenol resin, amines and aldehydes,
The scale adhesion preventing method , wherein the phenol is composed of at least one of phenol, alkylphenol, unsaturated alkylphenol, and polyaromatic phenol .
前記フェノール樹脂は、フェノール類とアルデヒド類との反応生成物であるノボラック型フェノール樹脂及び／又はレゾール型フェノール樹脂であり、
前記変性フェノール樹脂は、フェノール類及び／又は前記フェノール樹脂とアミン類とアルデヒド類とのマンニッヒ反応物であり、
前記フェノール類は、フェノール、アルキルフェノール、不飽和アルキルフェノール及び多芳香環フェノールの少なくとも１種からなることを特徴とするスケール付着防止剤。 A phenolic resin and / or modified phenol resin (1), seen containing water-soluble polymers, phosphonic acids and salts thereof, and a drug comprising at least one phosphorus acid and salts thereof (2) having an anionic functional group,
The phenol resin is a novolac type phenol resin and / or a resol type phenol resin which is a reaction product of phenols and aldehydes,
The modified phenolic resin is a Mannich reaction product of phenols and / or the phenol resin, amines and aldehydes,
The scale adhesion preventing agent characterized in that the phenol is composed of at least one of phenol, alkylphenol, unsaturated alkylphenol, and polyaromatic phenol .
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