AU664426B2 - N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide thereof for high pH scale control - Google Patents
N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide thereof for high pH scale control Download PDFInfo
- Publication number
- AU664426B2 AU664426B2 AU35582/93A AU3558293A AU664426B2 AU 664426 B2 AU664426 B2 AU 664426B2 AU 35582/93 A AU35582/93 A AU 35582/93A AU 3558293 A AU3558293 A AU 3558293A AU 664426 B2 AU664426 B2 AU 664426B2
- Authority
- AU
- Australia
- Prior art keywords
- acid
- scale
- calcium
- hydroxyethyl
- bis
- 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.)
- Ceased
Links
- 239000002253 acid Substances 0.000 title claims description 54
- 150000001204 N-oxides Chemical class 0.000 title claims description 46
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 100
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 46
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 40
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 25
- 230000005764 inhibitory process Effects 0.000 claims description 25
- 230000002401 inhibitory effect Effects 0.000 claims description 22
- 229910021532 Calcite Inorganic materials 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 17
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 13
- 239000001506 calcium phosphate Substances 0.000 claims description 11
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 11
- 235000011010 calcium phosphates Nutrition 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 159000000003 magnesium salts Chemical class 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 11
- OMAAXMJMHFXYFY-UHFFFAOYSA-L calcium trioxidophosphanium Chemical compound [Ca+2].[O-]P([O-])=O OMAAXMJMHFXYFY-UHFFFAOYSA-L 0.000 claims description 10
- GVHLBLKTDYODFL-UHFFFAOYSA-N calcium;(2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound [Ca].OCC(P(O)(O)=O)P(O)(O)=O GVHLBLKTDYODFL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- -1 hydroxy propyl Chemical group 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 6
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 4
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 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 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 229910001868 water Inorganic materials 0.000 description 31
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 150000001342 alkaline earth metals Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000003139 biocide Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 229920000867 polyelectrolyte Polymers 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000002455 scale inhibitor Substances 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000003352 sequestering agent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical class O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002169 ethanolamines Chemical class 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 125000000815 N-oxide group Chemical group 0.000 description 1
- GWASTCVCPXFIQT-UHFFFAOYSA-N NC1OP(=O)O1 Chemical class NC1OP(=O)O1 GWASTCVCPXFIQT-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
664426
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
S F Ref: 235596 0* C S *0 0 *e 0
CS
C
S
S
S
C
C
C
Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Calgon Corporation Route 60 Campbell's Run Road Robinson Township Pennsylvania UNITED STATES OF AMERICA Shih-Ruey Thomas Chen, Raymond 3. Schaper and Gary F.
Matz Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia N-(2-Hydroxyethyl)-N-bis(Methylenephosphonic Acid) and Corresponding N-oxide Thereof for High pH Scale Control The following statement is a full description of this invention, including the best method of performing it known to me/us:i845/5 2811H C-1573 TITLE OF THE INVENTION N-(2-HYDROXYETHYL)-N-BIS(METHYLENEPHOSPHONIC ACID) AND CORRESPONDING N-OXIDE THEREOF FOR HIGH pH SCALE
CONTROL
BACKGROUND OF THE INVENTION 1. Field of the Invention 20 The present invention relates to compositions and methods for inhibiting the formation, deposition and adherence of alkaline earth metal scale deposits, especially calcium carbonate (CaCO3) scale deposits, on metallic surfaces of aqueous systems, 25 especially under conditions of high pH and high calcite concentration, those found in cycled up cooling tower systems, where those compositions are 2811H 2 C-1573 N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide thereof.
Generally, calcium carbonate scale deposits are incrustation coatings which accumulate on the metallic surfaces of a water-carrying system through a number of different causes.
Various industrial and commercial water-carrying systems are subject to calcium carbonate scale formation problems. Calcium carbonate scale is of particular concern in heat exchange systems employing water, such as, for example, boiler systems, and once-through and open recirculating water cooling systems. Cooling towers are especially significant, particularly where severe conditions, including high pH and high calcite concentrations are encountered.
The water employed in these systems ordinarily will contain a number of dissolved salts, and the alkaline earth metal cation calcium is usually prevalent, as is the anion carbonate. The combination product of calcium cation and carbonate anion will precipitate from the water in which they •are carried to form scale deposits when the concentration of the anion and cation comprising the reaction product, i. calcium carbonate, exceeds the solubility of the reaction product itself. Thus, when the concentrations of calcium ion and carbonate ion exceed the solubility of the calcium carbonate reaction product, a solid phase of calcium carbonate will form as a precipitate. Precipitation of the reaction product will continue until the solubility product concentrations of the constituent ions are no longer exceeded.
Numerous factors may be responsible for producing a condition of supersaturation for the reaction 281111 3 C-1573 product calcium carbonate. Among such factors are changes in the pH of the water system, evaporation of the water phase, rate of heat transfer, amount of dissolved solids, and changes in the temperature or pressure of the system.
For cooling systems and similar heat exchange systems including cooling towers, the mechanism of scale formation is apparently one of crystallization of scale-forming salts from a solution which is locally supersaturated in the region adjacent the heating surface of the system. The thin viscous film of water in this region tends to become more concentrated than the remainder of the solution outside this region. Precipitation is also favored on the heat transfer surface because of the inverse solubility relationship of calcium carbonate. As a result, the solubility of the scale-forming calcium 0 15 carbonate salt reaction product is first exceeded in ~this thin film, and crystallization of calcium carbonate scale results directly on the heating or *heat exchange surface.
In addition to this, a common source of scale in S 20 boiler systems is the breakdown of calcium bicarbonate to form calcium carbonate, water and carbon dioxide under the influence of heat. For open recirculating cooling water systems, in which a cooling tower, spray pond, evaporative condenser, and S 25 the like serve to dissipate heat by evaporation of water, the chief factor which promotes calcium carbonate scale formation is concentration of solids dissolved in the water by repeated evaporation of portions of the water phase. Thus, even a water which is not scale forming on a once-through basis usually will become scale forming when concentrated 2811H 4 C-1573 two, four, or six times. Moreover, alkalinity of the makeup water, vith evaporative cycles over time results in an increasing alkalinity of the water in the overall system, often reaching pH's of 8.5 and even higher. Conventional scale inhibiting compositions typically fail in systems having such severe conditions.
The formation of calcium carbonate scale deposits poses a serious problem in a number of regards. The calcium carbonate scale which is formed possesses a low degree of heat conductivity. Thus, a calcium carbonate scale deposit is essentially an insulating layer imposed across the path of heat travel from whatever source to the water of the system. In the case of a cooling system, the retarded heat transfer causes a loss in cooling efficiency. In addition to this problem, calcium carbonate scale formation facilitates underdeposit corrosive processes, and a substantial calcium carbonate scale deposit will interfere materially with fluid flow. Consequently, o calcium carbonate scale is an expensive problem in many industrial water systems, causing delays and shutdowns for cleaning and removal.
Although the present invention is directed primarily to preventing or inhibiting the deposition of calcium carbonate scale, the most prevalent type of scale deposit, it is also applicable to inhibiting 25 the deposition of other types of alkaline earth metal scales, especially where those are associated with calcium carbonate scale under the severe conditions described herein. For example, most industrial and commercial water contains alkaline earth metal cations, such as calcium and magnesium, and several anions such as bicarbonate, carbonate, and 2811H 5 C-1573 phosphate. When combinations of these anions and cations are present in concentrations which exceed the solubility of their reaction products, precipitates form until their product solubility concentrations are no longer exceeded. These precipitates are alkaline earth metal scales. Thus, by alkaline earth metal scales is meant scales including but not limited to calcium carbonate, magnesium carbonate, and calcium phosphate. These scales form frequently in the tubes of heat exchangers and on other heat exchange surfaces, such as those in cooling towers. Particular systems or applications areas where severe conditions lead to exceptional buildup of calcium carbonate and related scales, in addition to cycled up cooling towers, include reverse osmosis systems, sugar refining evaporators, and certain types of gas scrubbers.
The N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide of the present invention are used in the same range of amounts as threshold inhibitors in the scale inhibition method of the present invention, rather than as sequestering 20 or chelating agents, although the compositions of the present invention have dispersant properties as well and significantly reduce the adherency of any scale deposit which is formed, facilitating its easy removal.
Scale-forming compounds can be prevented from precipitating by inactivating their cations with chelating or sequestering agents, so that the S. solubility of their reaction products is not exceeded. Generally, this requires many times as much chelating or sequestering agent as cation, since chelation is a stoichiometric reaction, and these 2811H 6 C-1573 amounts are not always desirable or economical.
However, several decades ago, it was discovered that certain inorganic polyphosphates would prevent such precipitation when added in amounts far less than the concentrations needed for sequestering or chelating.
When a precipitation inhibitor is present in a potentially scale-forming system at a markedly lower concentration than that required for sequestering the scale-forming cation (stoichiometric), it is said to be present in "threshold" amounts. See, for example, Hatch and Rice, Indust. Eng. Chem., 321, 51-53 (1939); Reitemeier and Buehrer, J. Phys. Chem., 44 535-536 (1940); Fink and Richardson U.S. Pat. No.
2,358,222; and Hatch, U.S. Pat. No. 2,539,305.
Similarly, anioic and cationic polymers can be used as dispersants in accordance with methods known in the art, but the dosage levels necessary to achieve dispersion are in the range of 0.5 1.0% by weight of the system being treated, which is many orders of magnitude higher that the dosage levels used for the compositions of the present invention.
Thus, it is a unique aspect of the present invention 20 that it is possible to achieve essentially non-adherent scale using only threshold inhibitor dosage levels of the compositions of the present invention.
Recently, attention has been focused on 25 controlling scaling under severe conditions, where conventional treatments such as those described above do not provide complete scale control. Current technology in scale control can be used to inhibit CaCO 3 scale up to 100 to 120 times calcite saturation, a water containing Ca 2 and
CO
2 present at 100 times (100 X) their 3hi 2811H 7 C-1573 solubility limit. However, what is desired are inhibitors effective in greater than 150X water, especially in greater than 250X water, and more especially in greater than 300 X water, where the calcite ions can be prevented from precipitating as calcium carbonate scale using substoichiometric amounts of an inhibitor. The compositions of the present invention are especially useful under severe conditions characterized by a calcite saturation level of 150 X and above, especially 250X and above, and more especially 300X and above, as defined in the paragraph immediately below.
Severity of the scaling tendency of a water sample is measured using the saturation index, which may be derived in accordance with the following equation: SI [Ca 2+][C03 2 K spCaCO 3 where SI is the saturation index for calcium .ar Ca2+ 2carbonate, [Ca]J is the concentration of free calcium ions, [COO is the concentration of 3 K Sfree carbonate ions, and spCaCO 3 is the conditional solubility product constant for CaC03.
All of the quantities on the right side of the above equation are adjusted for pH, temperature and ionic strength.
5 Calculation and use of the saturation index, and generation of the data from which it is derived, are matters within the skill of the art. See, for example, Critical Stability Constants, Vol. 4: "Inorganic Complexes", Smith Mantell (1976), Plenum Press; and Aquatic Chemistry, Chap. 5, 2nd ed., Stumm 2811H 8 C-1573 Morgan (1981), Wiley Sons.
Another characteristic feature of the severe conditions under which the scale controlling compositions of the present invention are especially useful is high pH, i.e. a pH of 8.5 and higher, particularly a pH of 9 or 10 or even higher. A related feature of such severe conditions is high alkalinity.
ne of the particular advantages of the scale inhibiting compositions of the present invention is the exceptional calcium tolerances which they exhibit. Calcium tolerance is a measure of a chemical compound's ability to remain soluble in the presence of calcium ions (Ca 2 One of the parameters of scale control under severe conditions is pH. As pH increases, calcium tolerance decreases rapidly for traditional CaCO 3 threshold inhibitors, 1-hydroxy ethylidene 1,1-diphosphonic acid (HEDP) and amino tri(methylene phosphonic acid) (AMP). These inhibitors precipitate with calcium at alkaline pH's, rendering them useless as threshold scale inhibitors. While it is common practice to use 20 an acid feed to the water of, a cooling tower system in order to lower pH and thus avoid the calcium tolerance problem for conventional C inhibitors, the danger to handlers which such acid feeding poses makes it all the more important to find 25 scale inhibitors which operate at high pH's.
An advantage of the scale inhibiting composition of the present invention which is an N-oxide is its ability to maintain a level of resistance to degradation by oxidizing biocides which is sufficient to ensure adequate scale inhibition at dosing levels within the ranges herein described. This is of 2811H 9 C-1573 particular importance in cooling systems such as tlose using cycled up'cooling towers. Such systems maintain a large body of water for a considerable length of time exposed to the atmosphere under conditions which do not include sufficient aeration and exposure to sunlight' to provide control of microbial, especially bacterial and fungal, growth.
Unchecked, such microorganisms flourish and produce colonies extensive enough to give rise to problems of biofilm blockage of heat exchange surfaces, and clogging of the components of the water transporting apparatus used in operating the cooling system.
Such problems of unwanted microbial growth in a cooling system are usually solved by use of an oxidizing biocide, especially chlorine or bromine, since these are inexpensive, effective, and produce minimal environmental impact. However, as is well known, such oxidizing biocides also tend to degrade scale inhibitors containing a N,N-bis(phosphonomethylene) group, presumably by oxidative attack on the nitrogen atom of the group.
It has been found that the N-oxide of the present invention offers significant resistance to such degradation; and it will continue to provide scale inhibition when dosed in accordance with the ranges set out herein.
It is also a surprising attribute of the 25 compounds, including N-oxide of the present invention that, even though they provide unacceptably low scale inhibition with aqueous systems having normal conditions and scaling tendencies, they provide an unexpectedly high level of scale inhibition protection in aqueous systems characterized by the severe conditions of high pH, high calcite e 2811H 10 C-1573 concentration, etc., and having sever, caling tendencies, as described in detail further herein.
It was wholly unexpected that compounds having that attribute, would also provide resistance to degradation by oxidizing biocides as well, under the severe conditions and scaling tendencies just described.
2. Brief Description of the Prior Art Early efforts to reduce scale formation in water-carrying systems employed compounds such as tannins, modified lignins, algins, and other similar materials. Chelating or sequestering agents have also been employed to prevent precipitation or crystallization of scale-forming calcium carbonate.
Another type of agent which has been actively explored heretofore as a calcium carbonate scale inhibiting material is the threshold active inhibitor. Such materials are effective as scale inhibitors in amounts considerably less than that stoichiometrically required, and this amount, as 20 already mentioned, is termed the threshold amount.
Inorganic polyphosphates have long been used as such threshold active inhibitors. For examples of such materials, see Fink US 2,358,222; Hatch US 2,539,305; and Ralston US 3,434,969. Certain water 25 soluble polymers, including groups derived from acrylamide and acrylic acid have been used to condition water containing scale-forming calcium carbonate. For example, see US 2,783,200; 3,514,476; 2,980,610; 3,285,886; 3,463,730; 3,518,204; 30 3,928,196; 3,965,027; and 4,936,987. In particular, there has been employed anionic polyelectrolytes such 2811H 11 C-1573 as polyacrylateE, polymaleic anhydrides, copolymers of acrylates and sulfonates, and polymers of sulfonated styrenes. See, for example, US 4,640,793; 4,650,591; 4,457,847 and 4,671,888. However, when used as threshold alkaline earth metal scale inhibitors, large dosages of these polymers are required, which in turn increases operating costs.
While various polycarboxylates, including polyacrylic acid, have been used as scale inhibiting agents, as described above, no similar use has been made of polycationic agents, apparently because of the difference in electronic charge and the conventional theories of the mechanisms of action for polymeric threshold inhibitors and dispersants.
While both the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) and the corresponding N-oxide, which comprise the active ingredient of the compositions of the present invention are known, their use for the control of alkaline earth metal scale, particularly calcium carbonate scale, under severe conditions which include elevated pH and high calcium carbonate saturation levels, with enhanced 20 resistance to degradation by oxidizing biocides, has not heretofore been suggested.
For example, US 4,080,375 discloses methylene phosphonates of amino-terminated oxyalkylates for use as scale inhibitors, but these compositions are not 25 the same as those of the present invention, nor is there any suggestion that such compositions would be useful under severe conditions as defined herein, where phosphonates such as HEDP and AMP give poor results. US 4,931,189 discloses aminomethylene phosphonates for inhibiting oil field scale formation :involving a high brine environment susceptible to 2811H 12 C-1573 gypsum or barite scale formation. Such use in no way suggests the control of scale under the severe conditions described herein under which the compositions and methods of the present invention operate with surprising success.
A particular phosphonate which has been marketed for scale control, but not suggested for use under the severe conditions defined he'ein, is ethanolamine N,N-dimethylene phosphonic acid, or N-(2-hydroxyethyl)-N-(methylenephosphonic acid), sold under such trademarks as WAYPLEX 61-A and BRIQUEST 221-50A, and described in EP-A-O 384 779; US 2,917,528; and US 2,964,549.
US 4,973,744; 4,977,292; and 5,051,532, as well as EP-A 432 664 and 437 722, all disclose methylene phosphonates which are N-oxides, including N-(2-hydroxyethyl)-N-(methylenephosphonic acid) N-oxide, useful for preventing scale and/or corrosion. There is no teaching or suggestion in any of these references, however, of their particular usefulness for controlling scale under severe conditions.
SUMMARY OF THE INVENTION .e 0 25 The present invention relates to a composition useful as a deposit control agent to control the formation, deposition and adherency of scale imparting compounds selected from the group consisting essentially of calcium carbonate; calcium 30 phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the 2811H 13 C-1573 corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, COMPRISING N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) of the following formula:
CH
2 P03M2
HO-CH
2
-CH
2
-N
I
CH
2 P0 3 M2 where M is hydrogen or a suitable cation.
OPTIONALLY, the compound of the above formula may be N-oxide, in which event it has the following formula:
CH
2 P0 3
M
2
I
HO-CH
2
-CH
2 -N-+0
CH
2 P0 3
M
2 where M is as defined above; preferably, M is hydrogen, The present invention also relates to a 20 composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds selected from the group S"consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, COMPRISING, IN COMBINATION, 30 N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or *0 0o 14corresponding N-oxide of the formulas above, together with one or more members selected from the group consisting of homo- and copolymers including terpolymers comprising one or more of itaconic acid polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MAH), maleic acid t-butyl acrylamide (TBAM), sodium styrene sulfonate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulfonic acid (AHPS) sodium salt, and vinyl phosphonic acid, wherein the weight average molecular weight for such polymer additives is in the range of from about 500 to 250,000.
The invention also includes certain combinations involving acrylic acid (AA), methacrylic acid (MAA), acrylamide and 2-acrylamide-methyl propane sulfonic acid (AMPSA).
In particular, the present invention relates to combinations where the polymer additive is a member selected from the group consisting essentially of 50/50 and 75/25 SSS/MA; 75/25 AA/AHPS; 33/33/34 AA/MAA/IA; 70/20/10 AA/AMPSA/TBAM.
More particularly, the present invention relates to such a combination where the polymer additive is 50/50 or 75/25 SSS/MA; or 70/20/10 The present invention further relates to a method of inhibiting the formation, 20 deposition and adherence 41 o *oo 2811H 15 C-1573 of scale-forming salts selected from the group consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, COMPRISING THE STEP of adding to said system an amount sufficient to establish a concentration of from 1 to 100 mg/L of N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) or corresponding N-oxide of the formulas above. In particular, the present invention relates to such a method in which calcium carbonate is the scale-forming salt, the aqueous system comprises a cooling tower, and said compound is added to the aqueous system being treated in an amount sufficient to establish a concentration of from 10 to 50 mg/L.
The present invention further relates to a method of inhibiting the formation, deposition and adherence of scale-forming salts selected from the group consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, 25 COMPRISING THE STEP of adding to said system an amount sufficient to establish a concentration of from 1 to 100 mg/L of a composition comprising N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or corresponding N-oxide of the formulas above, together 6: 2811H 16 C-1573 with one or more members selected from the group consisting of: homo- and copolymers including terpolymers comprising one or more of acrylamide acrylic acid (AA), 2-acrylamide--methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol c monomethacrylate (PGM), maleic anhydride 4 maleic acid t-butyl acrylamide (TBAM), sodium styrene sulfonate, sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulfonic acid (AHPS), sodium salt, and vinyl phosphonic acid, wherein the weight average molecular weight for such polymer additives is in the range of from about 500 to 250,000. In particular, the present invention relates to such a method in which calcium carbonate is the scale-forming salt, the aqueous system comprises a cooling tower, said composition is added 20 to the aqueous system being treated in an amount sufficient to establish a concentration of from 10 to 50 mg/L, and said polymer additive is a member selected from the group consisting essentially of 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 25 AA/AMPSA; 100 AA; 50/50 and 75/25 SSS/MA; 75/25 AA/AHPS; 33/33/34 AA/MAA/IA; 50/50 AA/AM; 70/20/10 10 and 20 (having 5, 10 and repeating oxyethylene units, respectively); and AA/AMPSA/TBAM. More particularly, the present invention relates to such a method where the polymer 2811H 17 C-1573 additive is 75/25 or 60/40 AA/AMPSA; 100 AA; 50/50 or 75/25 SSS/MA; or 70/20/10 DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention useful as a deposit control agent to control the formation, deposition and adherency of scale imparting compounds selected from the group consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an.aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, comprises N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) of the formula:
CH
2 P03M2
HO-CH
2
-CH
2
-N
20
CH
2 P03M2 where M is hydrogen or a suitable cation.
OPTIONALLY, the compound of the above formula may Sbe N-oxide, in which event it has the following formula:
CH
2
PO
3
M
2
I
HO-CH
2
-CH
2 -N-0
CH
2 P03M2 where M is as defined above; preferably, M is 5 2811H 18 C-1573 hydrogen. This key feature of the compounds of the present invention confers significant resistance to degradation by oxidizing biocides, presumably by preventing oxidative attack on the nitrogen atom of the group.
In order to obtain high levels of control of scale deposits, especially under the severe conditions defined herein, it has been found that there are certain essential components of the structure of the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) and corresponding N-oxide of the present invention which are necessary to provide that performance, and thus clearly distinguish the compositions of the present invention from those of the prior art. For example, the N,N-bis(phosphonomethyl)amino portion of the structure is essential. Whether this group is present initially in the phosphonic acid form or as an alkali metal or other salt of the acid, has no critical bearing on the performance of the overall molecule. At the pH's under which the compositions of the present invention function, they are, and must 20 be, in their ionized form. Thus, it is not critical whether is hydrogen or a suitable cation, and the selection of an appropriate salt form is well within S•the skill of the art. Alkali metal salts are the most simple, and are preferred for that reason.
25 Overall, however, it is preferred that M is hydrogen.
a k% Another structural element of the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide to be considered is the S' terminal hydroxyl moiety: OH, which together with the ethylene group: -CH 2
-CH
2 bridging the terminal 2811H 19 C-1573 hydroxyl and the N-bis(methylenephosphonic acid) group, allows the overall molecule to provide a surprising degree of effectiveness in inhibiting scale in aqueous systems characterized by the severe conditions of high pH of at least about 9 and high calcite concentrations of about 250X and greater.
Finally, the optional structural feature of the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide of the present invention must be considered, the moiety. As has already been described, this feature of the overall structure confers resistance to degradation by oxidizing biocides which is sufficient to ensure adequate scale inhibition at dosing levels within the ranges herein described.
The N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) and corresponding N-oxide of the compositions and methods of the present invention are prepared by phosphonomethylation of the primary amine, ethanolamine. The ethanolamine starting material and its method of preparation are well known. The phosphonomethylation of the primary 20 amine is then carried out by a Mannich reaction such as that described in K. Moedritzer and R. Irani, Organic Chem. 31(5) 1603-7, "The Direct Synthesis of alpha-Aminomethyl Phosphonic Acids; Mannich-Type Reactions with Orthophosphorous Acid", May 1966. In S 25 a typical reaction, the ethanolamine is added to a mixture of phosphorous acid and water, and concentrated hydrochloric acid is then added slowly, after which the reaction mixture is heated to reflux with addition of aqueous formaldehyde. The harsh acidic conditions of this reaction usually result in 2811H 20 C-1573 partial dehydration of the desired final product, with formation of considerable amounts of a stable six-membered lactone ring, which possesses less scale inhibiting activity than the desired final product.
Production of this side product is basically unavoidable, but since it does possess scale inhibiting activity, and since conditions of use often result in its hydrolysis back to the desired final product, its formation is usually not a problem.
Although the general structural formula employed herein indicates that the nitrogen atom is completely phosphonomethylated, as a practical matter, preparation of the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) of the present invention, as described in detail further below, usually results in only about 80 to 90% phosphonomethylation. Other side products give N-substitution with H, CH 3 15 CH OH, etc. It is not practical, as a matter of simple production economics, however, to isolate and purify the completely phosphonomethylated compounds herein claimed, since the side products just described do not interfere with scale inhibition.
Such side products, are consequently, usually allowed to remain.
The optional N-oxide of the compositions and methods of the present invention is prepared first by phosphonomethylation of the ethanolamine, as described above, followed by an oxidation step which provides the N-oxide moietie. Once the desired phosphonomethylated ethanolamine has been prepared, the optional N-oxide final product of the present invention is then prepared by a step of oxidation, which may be accomplished, simply by adding 2811H 21 C-1573 hydrogen peroxide to a basic solution of the phosphonomethylated ethanolamine and heating the reaction mixture, which gives high yields of the N-oxide final product. Of course, it is also possible to use other well known techniques for carrying out such a step of oxidation, and any number of these may be successfully employed., When the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) or N-oxide compositions of the present invention are used to inhibit the precipitation, deposition, and .adherence of scale-forming salts in an aqueous system, they can be effectively 'employed for that purpose when added in amounts sufficient to establish a concentration in said aqueous system of from 1 to 100 mg/L.
Preferably, the amount added will be sufficient to establish a concentration of from 5 to 75 mg/L, and most preferably, the amount added will be sufficient to establish a concentration of from 10 to 50 mg/L of the composition. It is understood, however, that many factors, of the type which have been explained in detail with regard to the background to the 20 present invention, will determine the actual amount of the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or N-oxide compositions of the present invention which will be added to any particular aqueous system in order to achieve the maximum amount 25 of inhibition of alkaline earth metal, especially calcium carbonate scale formation, deposition and adherence in that aqueous system. The calculation of S. those amounts is well within the skill of the artisan in this field.
2811H 22 C-1573 When the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) or N-oxide compositions of thepresent invention are used in combination with one or more of the polymers recited further above, the amounts of that combination which must be added in order to inhibit the formation, deposition and adherence of scale-forming salts in an aqueous system, will as a general matter be within the ranges of amounts sufficient to establish the ranges of concentrations of the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) and corresponding N-oxide used alone, as recited in detail above. Again, however, calculation of the actual amount is well within the skill of the art.
The phrases "inhibiting the precipitation" and "inhibiting the formation and deposition" are meant to include threshold inhibition, dispersion, solubilization, or particle size reduction. The phrases "inhibiting the adherence" and "increasing the non-adherence", are meant to define the formation of a scale deposit which is easily removed, by simple rinsing, a scale deposit which is not so 20 firmly bonded to the surface to which it is attached that it cannot be removed by simple physical means as opposed to harsh mechanical or chemical treatment.
SThe phrase "scale-forming salts" is meant to include any of the scale-forming salts selected from 25 the group consisting essentially of calcium carbonate, calcium phosphate, calcium'phosphonate (including calcium hydroxyethylidene diphosphonic S. acid), and the corresponding magnesium salts.
The phrase "aqueous system" means commercial or industrial systems utilizing water and involving heat 2811H 23 C-1573 exchange surfaces, usually of metal, including cooling water systems including cooling towers, boiler water systems, desalination systems, gas scrubbers, and thermal conditioning equipment. Of particular importance are those systems which operate under severe conditions as detailed herein, including at least high pH and high calcite concentrations.
Typical of such systems are cycled up cooling towers, reverse osmosis systems, sugar refining evaporators, and certain types of gas scrubbers.
The manner of addition of any particular N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or N-oxide composition of the present invention, to an aqueous system will also be straightforward to a person of ordinary skill in this art. It may be added in liquid form by mechanical dispensers of known design. It may also be added in diluted liquid form The N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) or N-oxide composition may also be combined with other chemical treatment agents for dispensing to the aqueous system; and these in combination may be dispensed in liquid form.
S 20 In the embodiments of the present invention described herein, it has been contemplated that, as a practical matter, only a single N-(2-hydroxyethyl)-Nbis(methylenephosphonic acid) or N-oxide composition of those described above would be used for the 25 purpose of inhibiting scale. Of course, it would be possible to employ more than one such compound, and that forms a part of the present invention. However, it is also contemplated that one of these compositions not only could be combined, but preferably will be combined with one or more 2811H 24 C-1573 polyelectrolytes so as to provide an even more effective product for the inhibition of scale under the severe conditions described herein. Indeed, it has been found that several such polyelectrolytes, when combined with the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) and corresponding N-oxide, provide a surprising increase in the scale inhibiting efficiency of the phosphonate compound alone. Such combinations are, consequently, particularly preferred embodiments of the present invention.
For example, there could be used in such a combination one or more members selected from the group consisting of homopolymers, copolymers and terpolymers comprising one or more monomers of acrylamide acrylic acid (AA), 2-acrylamide-methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid polyether esters of acrylic and methacrylic acids and polyethefs based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol (MH) monomethacrylate (PGM), maleic anhydride f maleic acid t-butyl acrylamide (TBAM), sodium styrene sulfonate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulfonic acid (AHPS), and vinyl phosphonic acid. Weight average molecular 25 weights for such polymer additives should range from about 500 to 250,000.
For example, such compositions include copolymers of 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA. Other preferred polymer additives for use with the N-(2-hydroxyethyl)-N-bis- 2811H 25 C-1573 (methylenephosphonic acid) and corresponding N-oxide of the present invention include 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA; 100 AA; 50/50 and 75/25 SSS/MA; 75/25 AA/AHPS; 33/33/34 AA/MAA/IA; 50/50 AA/AM; 70/20/10 AA/AMPSA/PGM-5, and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively); and AA/AMPSA/TBAM. The most preferred polymer additives are 75/25 or 60/40 AA/AMPSA; 100 AA; 50/50 or 75/25 SSS/MA; or 70/20/10 Combinations using these polymers together with the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or N-oxide compositions of the present invention can increase to a surprising extent the amount of scale control and deposit control which is achieved under the severe conditions described herein.
EXAMPLES OF PREFERRED EMBODIMENTS The following examples are presented for the purpose of illustrating the present invention, but are not intended to be in any way a limitation thereof.
*o 2811H 26 C-1573 EXAMPLE 1 CaCO3 Scale Inhibition at pH 9 and 300X Calcite Saturation N-(2-Hydroxyethyl)-N-bis(Methylenephosphonic Acid) and Corresponding N-Oxide In order to demonstrate the improved scale inhibition performance of the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide used in the method of the present invention, and to compare that performance with that of other compounds under severe conditions, the following procedure was used: PROCEDURE: Scaling water containing 250 mg/L of -2 CO3 and 600 mg/L of alkalinity at a pH of and 55°C was used to evaluate scale inhibition performance of test solutions over a 24 hr period.
Test solutions were analyzed by withdrawing 10 g of test solution and adding it to the appropriate container through a 0.2 p filter, titrating for calcium, and calculating inhibition by the S 20 Schwarzenbach method.
The results obtained are shown in the table of values below.
*25 S• 0* 0* 2811H 27 C-1573 TABLE 1 CaCO 3 SCALE INHIBITION
SAMPLE
NO. DESCRIPTION 20 ppm 30 ppm 50 ppm 1 HOCH 2
CH
2
NZ
2 74 85 91 2 HOCH 2
CH
2 N(-40)Z 2 56 67 3 NZ 3 (AMP) 21 22 52 4 N(->0)Z 3 42 42 69 where Z -CH 2 P0 3
H.
The above results clearly show the surprising improvement in calcium carbonate scale inhibition under severe conditions which can be achieved using the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide of the present invention, compared to such commercial products as
AMP.
i.
EXAMPLE 2 CaC03 Scale Inhibition at pH 9 25 Swhich also sets forth the scale inhibition activites 30X CalteSaturation obtaiN-(2-ydroxyethyl)-N-bisethylenephosphonic acid) 25 Under Varying Conditions The procedures of Example 1 above were followed, but with some variation in the conditions of the *assay as noted in the table of values which follows, which also sets forth the scale inhibition activites obtained.
2811H 28 C-1573 TABLE 2 VARIATION IN TEST CONDITIONS pH 9; 300X CaCO3; 60 0 C; 10% Excess Ca/Alk; 24hrs 4days 5Q0pm 25pm Sample No. 1 90.8 87.5 82.6 67.8 85.6 EXAMPLE 3 CaCO 3 Scale Inhibition at pH 9 and 300X Calcite Saturation N-(2-Hydroxyethyl)-N-bis(Methylenephosphonic acid) In Combination with Polyelectrolytes Following the test procedures described in Example 1 above, the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid), Sample No. 1, was evaluated in combination with a number of different 2* 0 polyelectrolytes, and at different ratios. The inhibition was calculated at 24 hours. The results of those evaluations revealed the unusually, and on occasion, surpr 4 singly high degree of scale inhibition which can be achieved with such combinations under the severe conditions of the assay 25 employed.
2811HR 29 C-1573 TABLE 3 Po YLECTROLYTE 60/40 AA/AMPSA (24-Hour Data) of
DOSAGE
RATIOS OF POLYELEC- TROLYTE :PHOSPHONATE 1:1 1:1i5 1:2 i:3 1:4 62.0 99.9 56.0 66.0 88.0 90 .6 60.6 94.4 58.0 75.0 84.6 90.0 53.5 t S *5 S S S 56S .5 S S S. S 55 S S 5*6 S S S I) S @5 S S
S
55*5 60/40 AA/AMPSA (24-Hour Data) it 70/25 AA/ANPSA (24-Hour Data) (4-Day Data) 50/50 555/MA VERSA TL-7'* (24-Hour Data) 15 (4-Day Data) 75/25 AA/AHPS AQUATREAT CPA-Ill (24-Hour Data) (4-Day Data) 20 75/25
SSS/M~A
VERSA TL-4* (24-Hour Data) 100 AA (24-Hour Data) (4-Day Data) 25 33/33/34
AA/MAA/IA
POLACRYL WT_315A** (24-Hour Data) (4-Day Data) Poly(AA/A:N) (24-Hour Data) (4-Day Data) 70/20/10 (24-Hour Data) 62.0 71.8 84.14 69.6 92.6 86.8 58.8 70.6 62.0 54.9 92.8 58.0 89.7 57.4 82.3 70.6 84.1 89.9 69.6 82.3 85.3 55.9 72.1 84.1 84.1 81.2 87.0 79.7 79.7 58.0 61.0 66.0 .0 81.0 60.0 74.0 83 .0 79.0 2811H 30 C-1573 VERSA TL-4 and TL-7 and AQUATREAT CPA-III are registered trademarks of National Starch Chemical Corp., Bridgewater, NJ.
POLACRYL WT-315A is a registered trademark of Polacryl Co., Division of Coatex Caluire, France.
EXAMPLE 4 CaCO3 Scale Inhibition at pH 9 and 300X Calcite Saturation N-(2-Hydroxyethyl)-N-bis(Methylenephosphonic acid) N-Oxide In Combination with Polyelectrolytes Following the test procedures described in Example 3 above, but using the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) N-oxide combinations with different 15 polyelectrolytes were evaluated. The inhibition was calculated at 24 hours.
TABLE 4 20 20 RATIOS OF POLYELEC- DOSAGE TROLYTE:PHOSPHONATE POLYELECTROLYTE (ppm) 1:1 1:4 60/40 AA/AMPSA 50 74 79 70/20/10 25 AA/AMPSA/PGM-5 50 78 74 *e 2811H 31 C-1573 EXAMPLE Preparation of N-(2-Hydroxyethyl)-N-Bis- (Methylenephosphonic Acid)
HOCH
2
CH
2
N(CH
2
PO
3
H
2 2 To a 500 mL 3-neck flask fitted with magnetic stirring, thermometer, condenser and addition funnel is added 30.0g (0.49 mole) of ethanolamine, 65g of water, 82.0g (1.0 mole) of 70% phosphorus acid and mL of concentrated hydrochloric acid. This mix is heated to reflux and 150.Og (1.85 moles) of 37% formaldehyde is added over a 30 minute period. The resulting solution is heated at reflux for 3 hours to complete the reaction. The volume of the reaction mixture is then reduced by about 25% by the use of a .Barret tube and the entire reaction mixture is concentrated cn a rotary evaporator at full vacuum at 92-95"C to yield an aqueous solution of 62.4%.
Analysis of the 31 P NMR spectra of this solution indicated the desired product.
2* 2811H 32 C-1573 EXAMPLE 6 Preparation of N-(2-Hydroxyethyl)-N-Bis- (Methylenephosphonic Acid) N-Oxide
HOCH
2
CH
2
(CH
2
PO
3
H
2 2 The starting material from Example 4 (24.91g, O.lOmole) was added to a reaction vessel and the pH was adjusted to 10.00 with a 50% aqueous solution of sodium hydroxide (24.99g). The reaction mixture was then transferred to an Erlenmeyer flask, after which a 35% hydrogen peroxide solution was added dropwise to the reaction mixture (total: 10.69g.0.11mole).
After several drops were added, the reaction mixture was heated up and then cooled below 15 0 C. The maximum temperature was 25 0 C. The reaction mixture was then stirred at room temperature for 17 hours.
15 The desired product was recovered as a 38.54% solution, based on the sodium salt. NMR results Sindicated 100% conversion of the starting material to N-oxide groups.
It has been found that the scale control 20 performance of the N-(2-hydroxyethyl)-N-bis- (methylenephosphonic acid) and corresponding N-oxide of the present invention depends to some extent, although not a very significant extent, on the variations in the process parameters described 25 above. Best results are obtained, consequently, by employing the optimum conditions as outlined above.
Claims (6)
1. A composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds selected from the group consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, COMPRISING, IN COMBINATION, N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) of the following formula: 1o CH 2 P03M2 HO-CH 2 -CH 2 -N CH 2 PO3M2 where M is hydrogen or a suitable cation; or OPTIONALLY, the compound of the above formula which is an N-oxide, in which event it has the following formula: CH 2 P03M2 HO-CH 2 -CH2-N->O CH 2 P0 3 M 2 where M is as defined above; 20 TOGETHER WITH one or more members selected. from the group consisting of homo- and copolymers including terpolymers comprising one or more of itaconic acid polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MAH), maleic acid 25 t-butyl acrylamide (TBAM), sodium styrene sulfonate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulfonic acid (AHPS) sodium salt, and vinyl phosphonic acid, wherein the weight average molecular weight for such polymer additives is in the range of from about 500 to 250,000. 30 2. A composition according to Claim 1 wherein M is hydrogen and the compound is N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid).
3. A composition according to Claim 1 wherein the polymer additive is selected from the group consisting of 50/50 and 75/25 SSS/MA; 75/25 AA/AHPS; 33/33/34 AA/MAA/IA; 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and repeating oxyethylene units, respectively); and AA/AMPSA/TBAM; where AA is acrylic acid, AMPSA is 2-acrylamide-methyl propane sulfonic acid, AM is acrylamide, and MAA is methacrylic acid. S [n:\libdd]00158:AHT -34-
4. A composition according to Claim 3 wherein the polymer additive is 50/50 or 75/25 SSS/MA; or 70/20/10 A method of inhibiting the formation, deposition and adherence of scale-forming salts selected from the group consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, COMPRISING THE STEP of adding to said system an amount sufficient to establish a concentration of from 1 to 100 mg/L of N-(2-hydroxyethyl)-N- bis(methylenephosphonic acid) of the following formula: CH 2 P03M2 I HO-CH 2 -CH2-N q* CH 2 P03M2 15 where M is hydrogen or a suitable cation; or S* OPTIONALLY, the compound of the above formula which is an N-oxide, in which event it has the following formula: CH 2 P0 3 M2 I HO-CH2-CH2-N->0 CH2PO3M2 where M is as defined above. a 6. A method according to Claim 5 wherein calcium carbonate is the *0 P scale-forming salt, the aqueous system comprises a cooling tower, said compound is N- S 25 (2-hydroxyethyl)-N-bis(methylenephosphonic acid), and said compound is added to the aqueous system being treated in an amount sufficient to establish a concentration of from 10 to 50 mg/L.
7. A method of inhibiting the formation, deposition and adherence of scale-forming salts selected from the group consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, COMPRISING THE STEP of adding to said system an amount sufficient to establish a concentration of from 1 to 100 mg/L of a composition comprising N-(2- hydroxyethyl)-N-bis(methylenephosphonic acid) of the following formula: CH 2 P03M2 HO-CH 2 -CH 2 -N ZCH 2 P0 3 M 2 [n:\libdd]00158:AHT where M is hydrogen or a suitable cation; or OPTIONALLY, the compound of the above formula which is an N-oxide, in which event it has the following formula: CH 2 P0 3 M 2 HO-CH2-CH 2 -N->0 CH 2 P03M2 where M is as defined above; TOGETHER WITH one or more members selected from the group consisting of: homo- and copolymers including terpolymers comprising one or more of acrylamide acrylic acid 2-acrylamide--methyl propane sulfonic acid (AMPSA), a methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MAH), maleic acid t-butyl acrylamide (TBAM), sodium styrene sulfonate, sodium vinyl sulfonate, hydroxy propyl S acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulfonic acid (AHPS), sodium salt, and vinyl phosphonic acid, wherein the weight average molecular weight for such polymer additives is in the range of from about 500 to 250,000.
8. A method according to Claim 7 wherein calcium carbonate is the scale-forming salt, the aqueous system comprises a cooling tower, said compound is N- -10:*4 (2-hydroxyethyl)-N-bis(methylenephosphonic acid), said composition is added to the aqueous system being treated in an amount sufficient to establish a concentration of 25 from 10 to 50 mg/L, and said polymer additive is a member selected from the group consisting essentially of 75/25 and 60/40 AA/AMPSA; 100 AA; 50/50 and 75/25 SSS/MA; 75/25 AA/AHPS; 33/33/34 AA/MAA/IA; 50/50 AA/AM; 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, S respectively); and AA/AMPSA/TBAM.
9. A method according to Claim 8 wherein the polymer additive is 75/25 or 60/40 AA/AMPSA; 100 AA; 50/50 or 75/25 SSS/MA; or 70/20/10 A method of inhibiting the formation, deposition and adherence of scale-forming salts selected from the group consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X [n:\libdd]00158:AHT 36 substantially as hereinbefore described with reference to any one of the Examples but excluding the comparative examples. Dated 11 August, 1995 Calgon Corporation Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON a, S 6* 'S o S 340 S S S. I OS ~'e -J S ;J a, a, a 0 *OSq *a 00 S [nA\Ibddj00 158: AHT N-(2-Hydroxyethyl)-N-Bis(Methylenephosphonic Acid) And Corresponding N-Oxide Thereof For High pH Scale Control Abstract N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide thereof possess high calcium tolerance and have been found to give excellent inhibition of the formation, deposition and adherence of scale-forming salts, especially calcium carbonate, under se'v rc conditions which include elevated pH, high dissolved solids content, and high sat'w--t7on levels of calcium carboi.ate. The invention provides a composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds selected from the group consisting essentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium salts, in an aqueous system having a pH of at least about 9 and a calcite concentration greater than about 250X, comprising, in combination, N-(2-hydroxyethyl)-N-bis (methylenephosphonic 15 acid) of the following formula: CH 2 -P0 3 M 2 HO-CH 2 -CH 2 -N CH 2 -P0 3 M 2 where M is hydrogen or a suitable cation; or optionally, the compound of the above formula which is an N-oxide, in which event it has the following formula: CH 2 -PO 3 M 2 HO-CH 2 -CH 2 -N--O CH 2 -P03M 2 where M is as defined above; together .vith one or more members selected from the group consisting of homo- and copolymers including terpolymers comprising one or more of acrylamide, acrylic acid, 2-acrylamide--methyl propane sulfonic acid, methacrylic acid, itaconic acid, polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide end polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate maleic anhydride, maleic acid, t-butyl acrylamide, sodium styrene sulfonate, sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulfonic acid sodium salt, and vinyl phosphonic acid, wherein the weight average molecular weight for such polymer additives is in the range of from about 500 to 250 000. ILIbM00209:JOC
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86046592A | 1992-03-30 | 1992-03-30 | |
| US860465 | 1992-03-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU3558293A AU3558293A (en) | 1993-10-07 |
| AU664426B2 true AU664426B2 (en) | 1995-11-16 |
Family
ID=25333282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU35582/93A Ceased AU664426B2 (en) | 1992-03-30 | 1993-03-29 | N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide thereof for high pH scale control |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0564248A1 (en) |
| JP (1) | JPH07108299A (en) |
| AU (1) | AU664426B2 (en) |
| CA (1) | CA2092492A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5322636A (en) * | 1992-03-30 | 1994-06-21 | Calgon Corporation | Polyether polyamino methylene phosphonate n-oxides for high pH scale control |
| US5259974A (en) * | 1992-03-30 | 1993-11-09 | Calgon Corporation | N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers and N-oxides thereof for high PH scale control |
| US5262061A (en) * | 1992-07-01 | 1993-11-16 | Calgon Corporation | Zinc, iron and manganese stabilization using polyether polyamino methylene phosphonates |
| CN1082058C (en) * | 1997-03-25 | 2002-04-03 | 北京天龙水处理技术公司 | Co-polymer of sulfonate, the prepn. method and use thereof |
| US5888405A (en) * | 1997-07-29 | 1999-03-30 | Buckman Laboratories International Inc. | Methods for controlling biofouling using amino methyl phosphonic acids |
| WO2000018695A2 (en) * | 1998-09-30 | 2000-04-06 | Albright & Wilson Uk Limited | Water treatment |
| FR2803304B1 (en) * | 1999-12-29 | 2006-03-24 | Ceca Sa | INORGANIC DEPOSIT INHIBITORS, ESPECIALLY IN OIL WELLS |
| GB2455776A (en) * | 2007-12-21 | 2009-06-24 | Rhodia Operations | Scale inhibition |
| JP5558357B2 (en) * | 2008-09-12 | 2014-07-23 | 株式会社日本触媒 | Method for producing sulfonic acid group-containing ether compound |
| JP5439942B2 (en) * | 2009-05-14 | 2014-03-12 | 栗田工業株式会社 | Water treatment agent addition method in a simple boiler |
| WO2013019627A1 (en) * | 2011-07-29 | 2013-02-07 | Kemira Oyj | Scale-inhibiting polymers and methods for preventing scale formation |
| CN102786160A (en) * | 2012-08-29 | 2012-11-21 | 明增安 | Salt manufacturing antisludging agent and application for salt manufacturing antisludging agent |
| CN103570145B (en) * | 2013-11-19 | 2015-06-03 | 常州大学 | Preparation method of olefin ether and unsaturated carboxylic acid copolymer anti-sludging agent |
| AR104517A1 (en) | 2015-12-07 | 2017-07-26 | Dow Global Technologies Llc | METHOD FOR THE TREATMENT OF INHIBITION OF FRESH WATER INCRUSTATIONS USED IN A WELL OF OIL, GAS, OR GEOTHERMAL PRODUCTION OR UNDERGROUND TRAINING |
| EP3585856A1 (en) | 2017-02-27 | 2020-01-01 | General Electric Company | Sulfate scale inhibition in high pressure and high temperature applications |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973744A (en) * | 1989-12-15 | 1990-11-27 | W. R. Grace & Co.-Conn. | Ethoxylated N,N-bis-phosphonomethyl 2-(hydroxy)ethylamine N-oxides and water-soluble salts thereof |
| US5087376A (en) * | 1990-10-15 | 1992-02-11 | Calgon Corporation | Multifunctional scale inhibitors |
| US5096595A (en) * | 1989-12-15 | 1992-03-17 | W. R. Grace & Co.-Conn. | Control of scale in aqueous systems using certain phosphonomethyl amine oxides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2964549A (en) * | 1958-06-16 | 1960-12-13 | Victor Chemical Works | Alkanolaminealkanephosphonic acids and derivatives thereof |
| US4104131A (en) * | 1976-07-08 | 1978-08-01 | United States Steel Corporation | Process for separating ammonia and acid gases from waste waters containing fixed ammonia salts |
| US5019343A (en) * | 1989-12-15 | 1991-05-28 | W. R. Grace & Co.-Conn. | Control of corrosion in aqueous systems using certain phosphonomethyl amines |
| ZA905799B (en) * | 1989-12-15 | 1991-05-29 | Grace W R & Co | Control of scale in aqueous systems using certain phosphonomethyl amine oxides |
-
1993
- 1993-03-25 CA CA 2092492 patent/CA2092492A1/en not_active Abandoned
- 1993-03-29 AU AU35582/93A patent/AU664426B2/en not_active Ceased
- 1993-03-29 JP JP9361693A patent/JPH07108299A/en active Pending
- 1993-03-30 EP EP93302489A patent/EP0564248A1/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973744A (en) * | 1989-12-15 | 1990-11-27 | W. R. Grace & Co.-Conn. | Ethoxylated N,N-bis-phosphonomethyl 2-(hydroxy)ethylamine N-oxides and water-soluble salts thereof |
| US5096595A (en) * | 1989-12-15 | 1992-03-17 | W. R. Grace & Co.-Conn. | Control of scale in aqueous systems using certain phosphonomethyl amine oxides |
| US5087376A (en) * | 1990-10-15 | 1992-02-11 | Calgon Corporation | Multifunctional scale inhibitors |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0564248A1 (en) | 1993-10-06 |
| AU3558293A (en) | 1993-10-07 |
| JPH07108299A (en) | 1995-04-25 |
| CA2092492A1 (en) | 1993-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0516382B1 (en) | Polyether polyamino methylene phosphonates for high pH scale control | |
| US5338477A (en) | Polyether polyamino methylene phosphonates for high pH scale control | |
| AU664426B2 (en) | N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide thereof for high pH scale control | |
| US5565106A (en) | Stabilization of polyether polyamino methylene phosphonate scale inhibitors against degradation by bromine and chlorine biocides | |
| EP0481668A1 (en) | Multifunctional scale inhibitors | |
| AU621137B2 (en) | Method for controlling scale deposition in aqueous systems using allyl sulfonate maleic anhydride polymers | |
| EP0711733B1 (en) | Polyether polyamino methylene phosphonates for high pH scale control | |
| AU662398B2 (en) | Polyether polyamino methylene phosphonate N-oxides for high pH scale control | |
| AU662212B2 (en) | N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers and N-oxides thereof for high pH scale control | |
| JPS60143899A (en) | Scale inhibiting composition and method | |
| US5160630A (en) | Scale inhibition | |
| AU719896B2 (en) | A method for controlling scale in an aqueous system using a synergistic combination | |
| US5580462A (en) | Controlling calcium carbonate and calcium phosphate scale in an aqueous system using a synergistic combination | |
| US5707529A (en) | Method for controlling scale in an aqueous system using a synergistic combination | |
| US5772913A (en) | Aqueous system containing a synergistic combination for scale control | |
| US5593595A (en) | Method for controlling scale using a synergistic phosphonate combination | |
| GB2127801A (en) | Composition and method for inhibiting scale | |
| US5709814A (en) | Aqueous system containing a synergistic phosphonate scale control combination | |
| US5702634A (en) | Aqueous system containing a synergistic combination including polyether polyamino methylene phosphates for controlling calcium carbonate and calcium phosphate scale | |
| EP0767145B1 (en) | Use of a synergistic composition for scale control | |
| CA2187121A1 (en) | Aqueous system containing a synergistic phosphonate scale control combination | |
| CA2351508A1 (en) | Scale and corrosion inhibitor | |
| CA2187145A1 (en) | Aqueous system containing a synergistic combination for controlling calcium carbonate and calcium phosphate scale | |
| MXPA96004569A (en) | An aqueous system containing a synergistic combination for controlling calcium and phosphate calculation incrustations | |
| MXPA96004570A (en) | An aqueous system that contains a synergistic combination for the control of defrosf incrustations |