CA2092492A1 - 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 controlInfo
- Publication number
- CA2092492A1 CA2092492A1 CA 2092492 CA2092492A CA2092492A1 CA 2092492 A1 CA2092492 A1 CA 2092492A1 CA 2092492 CA2092492 CA 2092492 CA 2092492 A CA2092492 A CA 2092492A CA 2092492 A1 CA2092492 A1 CA 2092492A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- scale
- ampsa
- bis
- calcium
- 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.)
- Abandoned
Links
- 239000002253 acid Substances 0.000 title claims abstract description 52
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 111
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 55
- 150000001204 N-oxides Chemical class 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 62
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 21
- 229910021532 Calcite Inorganic materials 0.000 claims description 20
- 230000002401 inhibitory effect Effects 0.000 claims description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 17
- 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 17
- 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 15
- 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 15
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001506 calcium phosphate Substances 0.000 claims description 9
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 9
- 235000011010 calcium phosphates Nutrition 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920000570 polyether Chemical class 0.000 claims description 9
- 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 9
- OMAAXMJMHFXYFY-UHFFFAOYSA-L calcium trioxidophosphanium Chemical compound [Ca+2].[O-]P([O-])=O OMAAXMJMHFXYFY-UHFFFAOYSA-L 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 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 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 159000000003 magnesium salts Chemical class 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 5
- 125000006353 oxyethylene group Chemical group 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 22
- 239000011575 calcium Substances 0.000 abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052791 calcium Inorganic materials 0.000 abstract description 14
- 239000007787 solid Substances 0.000 abstract description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 229910001868 water Inorganic materials 0.000 description 30
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 11
- -1 anion carbonate Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000001342 alkaline earth metals Chemical class 0.000 description 7
- 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
- 239000011541 reaction mixture Substances 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000002455 scale inhibitor Substances 0.000 description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- 229910001424 calcium ion Inorganic materials 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 239000002738 chelating agent Substances 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
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium 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
- 239000003352 sequestering agent 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 238000003556 assay Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000007858 starting material Substances 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 101100289255 Mycolicibacterium smegmatis (strain ATCC 700084 / mc(2)155) lnt gene Proteins 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
- 101100208473 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) lcm-2 gene Proteins 0.000 description 1
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical class O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 101150087495 PPM2 gene Proteins 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000008859 change Effects 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
- 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
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 229960004585 etidronic acid Drugs 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
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 230000007775 late Effects 0.000 description 1
- 229920005610 lignin Polymers 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
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 101150061500 mgtL gene Proteins 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
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 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
- 230000000630 rising effect Effects 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
- JJMIAJGBZGZNHA-UHFFFAOYSA-N sodium;styrene Chemical compound [Na].C=CC1=CC=CC=C1 JJMIAJGBZGZNHA-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 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
- QGVNJRROSLYGKF-UHFFFAOYSA-N thiobarbital Chemical compound CCC1(CC)C(=O)NC(=S)NC1=O QGVNJRROSLYGKF-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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)
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Abstract
TITLE OF THE INVENTION
N-(2-hYDROXYETHYL)-N-BIS(METHYLENEPHOSPHONIC ACID) AND CORRESPONDING N-OXIDE THEREOF FOR HIGH pH SCALE
CONTROL
ABSTRACT OF THE DISCLOSURE
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 severe conditions which include elevated pH, high dissolved solids content, and high saturation levels of calcium carbonate.
N-(2-hYDROXYETHYL)-N-BIS(METHYLENEPHOSPHONIC ACID) AND CORRESPONDING N-OXIDE THEREOF FOR HIGH pH SCALE
CONTROL
ABSTRACT OF THE DISCLOSURE
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 severe conditions which include elevated pH, high dissolved solids content, and high saturation levels of calcium carbonate.
Description
TITL~ OF THE INVENTIQ~
N-(2-HYDROXYET~YL)-N-BIS(METH~LENEPEOSPHONIC ACID) AND CORRESPONDING N-OXIDE T~EREOE FOR HIGH p~ SCALE
CONTROL
~Ç~_O~ND OF T~E INV~NTI~N
1. Field of the Invenkion 2~ The present in~ention relates to compositions and methods for inhibiting the formation, deposition and adherence o~ alkaline earth metal scale deposits,.
especially calcium carbonate (CaC03) scale deposit~, on metallic surfaces of aqueous systems, esp~cially under conditions of high p~ and high calcite concentration, e.g., those found in cycled up cooling tower systems, where those compositions are ?~9~
N-(2-hydro~yethyl~--N-bis~methylenephosphonic acid) and correspondin~ N oxide thexeof.
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, ~or 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 ear~h metal cation calcium is usually prevalent7 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 deposit~ when the concentration of the anion and cation comprising the reaction product, i. e., calcium carbonate, exceeds the solubility of the reaction product itsel~. Thus, when the concentrations of calcium ion and carbonate ion exceed the solubility of the calcium carbonate ~5 reaction product, a solid phase o~ calcium carbonate will form as a precipitate. Precipltation of the reaction product will continue until the solubility product concentrations o~ the constituent ions are no longer exceeded.
Numerous factors may be responsible for producing a condition of supersaturation for the reaction 2 ~ 9 ~
~811H - 3 - G-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 supersa~urated in the region adjacen~ the heating surface of the system, The thin viæcous film of water in this region tends to become more o concentrated than the remainder of the solution outside this region. Precipitation is also favored on the heat transfer surface because o~ the inverse solubility relationship of calcium carbonate. As a result, the solubility of the scale-forming calcium carbonate salt reaction product is first e~ceeded in this thin film, and crystallization of calcium carbonate scale results directly on the heating or hea~ exchange surface.
ln addition to this, a common source of scale in boiler systems is the breakdown of calcium bicarbonate tc ~orm calcium carbonate, water and carbon dioxide under the influence of heat. For open recirculating cooling water ~ystems, in which a cooling tower, spray pond, evaporative condenser, and 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 ~orming when concentrated ~, J~
two, four, or six times. Moreover, alkalinity o:E the makeup water, with evaporative cycles over time results in an increasing alkalinity of the water in the overall system, often reaching pE~s of 8.5 - 9.5 and even higher. Conventionai scale inhibiting composition~ 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 lo 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 ~acilitates underdeposit corrosive processeæ, and a substantial calcium carbonate scale deposit will interfere materially with fluid flow. Consequent~y, 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 inhibit:ing the deposition of calcium carbonate scale, the most prevalent type of scale deposit, it is also applicable to inhibiting 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, æuch as calcium a~d magnesium, ~nd several anions such as bicarbonate, carbonate, and 2 ~
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 o~ heat exchangers and on other heat e~change surfaces, such as those in cooling towers~ Particular systemæ or applications areas where severe conditions lead to exceptional ~uildup 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-hydro~yethyl)-N-bis~methylenephosphonic acid) and corresponding N-oxide of the present invention are used in the same range of amounts as threshold inhibitors i~ the scale inhibition method of the present invention, rather than as sequestering 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 solubility of their reaction products is not exceeded. Generally, this requires many times as much chelating or ~equestering agent as cation, since chelation is a ætoichiometric reaction, and these .
~ ~,9,~
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, ~or example, Hatch and Rice, Indust. En~. Chem , 31, 51-53 (1939);
Reitemeier and Buehrer, J. Phys. Chem., 44 (5), 535-536 (1940); Fink and Richardson U.S. Pat. No.
2,358,222; and Hatch, U.S. Pat. No. 2,539,305.
Similarly, anionic 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 that it is possible to achie~e essentially non-adherent scale using only threshold inhibitor dosage levels of the compositions of the present invention.
Recently, attention has been focused on controlling scaling under severe conditions, ~here conventional treatments such as those described above do not provide complete scale control. Current technology in scale control can be used to inhibit CaC03 scale up to 100 to 120 times calcite 3Q saturation, i.e. t a water containing Ca2~ and C023 present at 100 times (100 X) their ~ .J 1 ~
solubility limit. ~owever, what is desired are inhibitors effective in greater than 150X water, especially in greater than 250X water, an~ more especially in greater than 300 X water, i.e., where the calcite ions can be prevented rom 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 der:lved in accordance with the following equation:
SI = CCa 2~][C03 2-]
K spCaCO3 where SI is the saturation index ~or calcium carbonate, [Ca2+] is the concentration of free calcium ions, [C03 2 ] is the concentration of free carhonate ions, and KspCaC03 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.
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, Cri~ical Stabilitv Constants, Vol. 4:
I'Inorganic Complexes", Smith & Mantell (1976), Plenum Press; and Aguatic Chemistry, Chap. 5, 2nd ed., Stumm 2~2~
& Morgan ~1981), Wiley ~ Sons.
Another characteristic ~eature of the severe conditions uncler which the scale controlling compositions of the present invention are especially useful is hîgh pH, i.e. a p~ 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.
One o~ the particular advantages o$ the scale inhibiting compositions of the present invention is the exceptional calcium tolerances which they exhibit. Calcium tolerance is a measure of a lo chemical compound's ability to remain soluble in the presence of calcium ions (Ca2+). One of the parameters of scale control under severe conditions is p~. As pH increases, calcium tolerance decreases rapidly for traditional CaC03 threshold inhibitors, e.g., l-hydro~y ethylidene l,l-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 an acid feed to the water of, e.g., a cooling tower system in order to lower pH and thus avoid the calcium tolerance problem for conventional inhibitors, the danger to handlers ~hich such acid feeding poses makes it all the more important to find ~5 scale inhibitors which operate at high p~'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 2811~ - 9 - C-1573 particular importance.in cooling syætems such as those using cycled up cooling towers. Such systems maintain a large body of water for a considerable length of time exposed to the atmo~phere under condi.tions which do not include sufficient aeration and e~posure 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 operati~g the cooling system.
lo 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-oxicle of the present invention offers significant resi.stance to such degradation; and it will continue to provlde scale inhibition when dosed in accordance with the ranges set out herein.
It is also a surpri~ing attribute o~ the 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 æystems characterized by the severe conditions of high p~, high calcite 2 ~
2811~ - 10 - C-1573 concentration, etc., and having severe scaling tendencies, as described in detail further herein.
It was wholly unexpected that compounds having that attribute, would also provide resistance ~o degradation by oxidizing biocides as well, under the se~ere conditions and scaling tendencies just described.
2. Brief Description of the Prior Art Early effort~ to reduce scale formation in water-carrying systems employed compounds such as tannins, modified lignins, algins, and other similar materials. Chelating or sequestering agents ha~e also been employed to prevent precipitation or crystallizzltion of scale-~orming calcium carbonate.
Another type of agent which has been acti~ely explored heretofore as a calcium carbonate scale inhibiting material is the threshold active inhibitor. Such materials are ef~ective as scale inhibitors in amounts considerabl~y less than that ætoichiometrical~y required, and this amount, as already mentioned, is termed the threshold amount.
Inorganic polyphosphates have lon,g been used as ~uch threshold active inhibitors. For examples of such materials, see Fink - US 2,358,222; Hatch - US
2,539,305; and Ralston US 3,434,9S9. Certain water soluble polymers, including groups derived from acrylamide and acrylic acid ha~e been used to condition water containing scale forming calcium carbonate. For example, see ~S 2,783,200; 3,514,476;
2,~80,610; 3,285,886; 3,463,730; 3,518,204;
N-(2-HYDROXYET~YL)-N-BIS(METH~LENEPEOSPHONIC ACID) AND CORRESPONDING N-OXIDE T~EREOE FOR HIGH p~ SCALE
CONTROL
~Ç~_O~ND OF T~E INV~NTI~N
1. Field of the Invenkion 2~ The present in~ention relates to compositions and methods for inhibiting the formation, deposition and adherence o~ alkaline earth metal scale deposits,.
especially calcium carbonate (CaC03) scale deposit~, on metallic surfaces of aqueous systems, esp~cially under conditions of high p~ and high calcite concentration, e.g., those found in cycled up cooling tower systems, where those compositions are ?~9~
N-(2-hydro~yethyl~--N-bis~methylenephosphonic acid) and correspondin~ N oxide thexeof.
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, ~or 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 ear~h metal cation calcium is usually prevalent7 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 deposit~ when the concentration of the anion and cation comprising the reaction product, i. e., calcium carbonate, exceeds the solubility of the reaction product itsel~. Thus, when the concentrations of calcium ion and carbonate ion exceed the solubility of the calcium carbonate ~5 reaction product, a solid phase o~ calcium carbonate will form as a precipitate. Precipltation of the reaction product will continue until the solubility product concentrations o~ the constituent ions are no longer exceeded.
Numerous factors may be responsible for producing a condition of supersaturation for the reaction 2 ~ 9 ~
~811H - 3 - G-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 supersa~urated in the region adjacen~ the heating surface of the system, The thin viæcous film of water in this region tends to become more o concentrated than the remainder of the solution outside this region. Precipitation is also favored on the heat transfer surface because o~ the inverse solubility relationship of calcium carbonate. As a result, the solubility of the scale-forming calcium carbonate salt reaction product is first e~ceeded in this thin film, and crystallization of calcium carbonate scale results directly on the heating or hea~ exchange surface.
ln addition to this, a common source of scale in boiler systems is the breakdown of calcium bicarbonate tc ~orm calcium carbonate, water and carbon dioxide under the influence of heat. For open recirculating cooling water ~ystems, in which a cooling tower, spray pond, evaporative condenser, and 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 ~orming when concentrated ~, J~
two, four, or six times. Moreover, alkalinity o:E the makeup water, with evaporative cycles over time results in an increasing alkalinity of the water in the overall system, often reaching pE~s of 8.5 - 9.5 and even higher. Conventionai scale inhibiting composition~ 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 lo 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 ~acilitates underdeposit corrosive processeæ, and a substantial calcium carbonate scale deposit will interfere materially with fluid flow. Consequent~y, 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 inhibit:ing the deposition of calcium carbonate scale, the most prevalent type of scale deposit, it is also applicable to inhibiting 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, æuch as calcium a~d magnesium, ~nd several anions such as bicarbonate, carbonate, and 2 ~
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 o~ heat exchangers and on other heat e~change surfaces, such as those in cooling towers~ Particular systemæ or applications areas where severe conditions lead to exceptional ~uildup 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-hydro~yethyl)-N-bis~methylenephosphonic acid) and corresponding N-oxide of the present invention are used in the same range of amounts as threshold inhibitors i~ the scale inhibition method of the present invention, rather than as sequestering 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 solubility of their reaction products is not exceeded. Generally, this requires many times as much chelating or ~equestering agent as cation, since chelation is a ætoichiometric reaction, and these .
~ ~,9,~
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, ~or example, Hatch and Rice, Indust. En~. Chem , 31, 51-53 (1939);
Reitemeier and Buehrer, J. Phys. Chem., 44 (5), 535-536 (1940); Fink and Richardson U.S. Pat. No.
2,358,222; and Hatch, U.S. Pat. No. 2,539,305.
Similarly, anionic 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 that it is possible to achie~e essentially non-adherent scale using only threshold inhibitor dosage levels of the compositions of the present invention.
Recently, attention has been focused on controlling scaling under severe conditions, ~here conventional treatments such as those described above do not provide complete scale control. Current technology in scale control can be used to inhibit CaC03 scale up to 100 to 120 times calcite 3Q saturation, i.e. t a water containing Ca2~ and C023 present at 100 times (100 X) their ~ .J 1 ~
solubility limit. ~owever, what is desired are inhibitors effective in greater than 150X water, especially in greater than 250X water, an~ more especially in greater than 300 X water, i.e., where the calcite ions can be prevented rom 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 der:lved in accordance with the following equation:
SI = CCa 2~][C03 2-]
K spCaCO3 where SI is the saturation index ~or calcium carbonate, [Ca2+] is the concentration of free calcium ions, [C03 2 ] is the concentration of free carhonate ions, and KspCaC03 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.
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, Cri~ical Stabilitv Constants, Vol. 4:
I'Inorganic Complexes", Smith & Mantell (1976), Plenum Press; and Aguatic Chemistry, Chap. 5, 2nd ed., Stumm 2~2~
& Morgan ~1981), Wiley ~ Sons.
Another characteristic ~eature of the severe conditions uncler which the scale controlling compositions of the present invention are especially useful is hîgh pH, i.e. a p~ 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.
One o~ the particular advantages o$ the scale inhibiting compositions of the present invention is the exceptional calcium tolerances which they exhibit. Calcium tolerance is a measure of a lo chemical compound's ability to remain soluble in the presence of calcium ions (Ca2+). One of the parameters of scale control under severe conditions is p~. As pH increases, calcium tolerance decreases rapidly for traditional CaC03 threshold inhibitors, e.g., l-hydro~y ethylidene l,l-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 an acid feed to the water of, e.g., a cooling tower system in order to lower pH and thus avoid the calcium tolerance problem for conventional inhibitors, the danger to handlers ~hich such acid feeding poses makes it all the more important to find ~5 scale inhibitors which operate at high p~'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 2811~ - 9 - C-1573 particular importance.in cooling syætems such as those using cycled up cooling towers. Such systems maintain a large body of water for a considerable length of time exposed to the atmo~phere under condi.tions which do not include sufficient aeration and e~posure 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 operati~g the cooling system.
lo 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-oxicle of the present invention offers significant resi.stance to such degradation; and it will continue to provlde scale inhibition when dosed in accordance with the ranges set out herein.
It is also a surpri~ing attribute o~ the 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 æystems characterized by the severe conditions of high p~, high calcite 2 ~
2811~ - 10 - C-1573 concentration, etc., and having severe scaling tendencies, as described in detail further herein.
It was wholly unexpected that compounds having that attribute, would also provide resistance ~o degradation by oxidizing biocides as well, under the se~ere conditions and scaling tendencies just described.
2. Brief Description of the Prior Art Early effort~ to reduce scale formation in water-carrying systems employed compounds such as tannins, modified lignins, algins, and other similar materials. Chelating or sequestering agents ha~e also been employed to prevent precipitation or crystallizzltion of scale-~orming calcium carbonate.
Another type of agent which has been acti~ely explored heretofore as a calcium carbonate scale inhibiting material is the threshold active inhibitor. Such materials are ef~ective as scale inhibitors in amounts considerabl~y less than that ætoichiometrical~y required, and this amount, as already mentioned, is termed the threshold amount.
Inorganic polyphosphates have lon,g been used as ~uch threshold active inhibitors. For examples of such materials, see Fink - US 2,358,222; Hatch - US
2,539,305; and Ralston US 3,434,9S9. Certain water soluble polymers, including groups derived from acrylamide and acrylic acid ha~e been used to condition water containing scale forming calcium carbonate. For example, see ~S 2,783,200; 3,514,476;
2,~80,610; 3,285,886; 3,463,730; 3,518,204;
3,928,196; 3,965,027i and 4,936,987. In part;cular, there has been employed anionic polyelectrolytes such 2~2'~ ~
2811~ - 11 - C-1573 as polyacrylates, polymaleic anhydrides, copolymers of acrylates and sulfonates, and polymers of sulfonated styrenes. See, for example, US 4,640,793;
2811~ - 11 - C-1573 as polyacrylates, polymaleic anhydrides, copolymers of acrylates and sulfonates, and polymers of sulfonated styrenes. See, for example, US 4,640,793;
4,~50,591; 4,457,847 ; and 4,671,888. ~owever, 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, havc been used as scale inhibiting agents, as described above, no similar use has been made of polycationic agent , apparently because of the difference in electronic charge and the lo 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 levf!ls, with enhanced resistance to degradation by oxidizing biocides, has not heretofore been suggested.
For e~ample, US 4,080,375 discloses me~hylene phosphonates of amino-terminated o~yalkylates ~or use as scale inhibitors, but these compositions are not the same as those of the present in~ention, nor is there any ~ug~estion that such compositions would be useful under severe condi~io~s 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 ~ormation involving a high brine environment susceptible to 2 ~
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 de~ined herein, 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 72Z, all disclose methylene phosphonates which are N-o~ides, including N-(2~hydro}~ethyl)-N-(methylenephosphonic acid) N-oxide, useful for preventing Rcale and/or corrosion. There is no teaching or suggestion in any of these references, however, of their particular usefulness for controlling 3cale under severe conditions.
~MARY OF THE INVENTIQN
The present invention relates to a composition useful a~ 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 hydro~yethylidene 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 N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid) of the following formula:
CHzP03M2 xo~c~[2-CH2-N
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:
C~I2P03M2 HO-CH2 -CH2-N~O
where M is as defined above; preferably, M ;s hydrogen, The present invention also relates to a composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds selected from the group consi~ting essentially of calcium carbonate; calcium phosphate; calcium pho~phonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium æalts, in an aqueous system having a p~ of at least about 9 and a calcite concentration greater than about 250X, COMPRISING, IN COMBINATION, N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or 2811H - 14 - C-1~73 corresponding N~oxide of the formulas above, together with one or more members selected from the group consisting of homo- and copolymers including ~erpolymers comprising one or more of acrylamide (AM), acrylic acid (AA), 2-acrylamide--methyl propane SUlfGniC acid (AMPSA), methacrylic acid (~AA), itaconie acid (IA~, polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), t-butyl acrylamide (TBAM), sodium styrene sulfonate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2 hydroxy propane sulfonic acid (A~PS) 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 combination where the polymer additive is a member selected from the group consisting e3sentially of 90/10 to 10/90 M/AMPSA, pre~erably 75/25 and ~0/40 AA/AMRSA; 100 AA; 50/50 and 75/25 SSS/MA; 75/25 AA/AHPS; 33/33/34 M /MAA/IA; 50/50 AA/AM; 70/20/10 AA/AMPSA/PGM-5, 10 and 20 ~having 5, 10 and 20 repeating oxyethylene units, respectively); and AA/AMPSA/TBAM. More particularly, the present invention relates to ~uch a combination where the polymer additive is 75/25 or 60/40 AA/AMPSA; lOQ M ;
50/50 or 75/25 SSS/MA; or 70/20/10 AA/AMPSA/PGM-5.
The present in~ention further relates to a method of inhibiting the formation, deposition and adherence 2 i~ ,9 ~
of scale-forming salts selected from the group consisting essentially of calcium caxbonate; calcium phosphate; calcium phosphonate, including calcium hyd r oxyethylidene diphosphonic acid; and the corresponding ma~nesium salts, in an aqueous æystem having a pH of at least abouJ.; 9 and a calcite concentration greater than about 250X, CO~RISING THE STEP of adding to said system an amount ~ufficient 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 lo invention r~lates to such a method in which calcium carbonate ;æ 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 15 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 20 phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium 3alt8, 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 mgtL of a composition comprising N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or corresponding N-oxide of the formulas above, together with one or more members selected from the group consisting o~:
homo- and copolymers including terpolymers comprising one or more of acrylamide (AM), acrylic acid (AA), 2-acrylamide--methyl propane sulfonic aeid (AMPSA~, methacrylic acid ~MAA), etho~ylated methacrylate, itaconic acid (IA), polyether ester~ of acrylic and methacrylic acids and polyetheræ based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), t-butyl acrylamide (TBAM), sodium styrene sulfonate, ~odium vinyl sulfonate, hydroxy propyl acrylate, hydro~y propyl methacrylate, 3-allylo~y-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 c:omposition is added to the aqueous system being treat:ed in an amount suf~icient to establish a concentration o~ ~rom 10 to 50 mg/L, and said polymer ad.ditive is a member selected from the group eon~istirlg essentially of 90/10 to 10/90 AA/AMPSA, preferably 75l25 and 60/4Q
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 M /AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively); and AA/AMPSA/TBAM. More particularly, the present invention relates to such a method where the polymer 2~ 2~
2~ 17 ~ C-1573 additive is 75/25 or 60J40 AA/AMPSA; 100 AA; 50/50 or 75/25 SSS/MA; or 70/20/10 AA/AMPSA/PGM-5.
DETAILED DESCRIPTION OF THE INVENTION
The composition of the present invention usefu~
as a deposit control agent to control the formation, deposition and adherency of scale imparting compounds selected from the group consisting ~ssentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; a~d the corresponding magnesium salts, in an agueous system having a p~ of at least about 9 and a calcite concentration greater than about 250~, comprises N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid) of the formula:
~IO-CH2 -CH2-N
C~2PO3M2 where M is hydrogen or a suitable cation.
OPTIONALLY, the compound of the above formula may b-e N-oxide, in which event it ha~ the following ormula:
CiEI2P03M2 ~IO C~2~C~I2-N~O
where M is as defined above; preferably, M is hydrogen. This key feature of the compounds o~ the present invention con~ers significant resistance to degradation by oxidizing biocides, presuma~ly by preventing oxidative attack on the nitrogen atom of the group.
In order to obtain high levels of control of ~cale deposits, especially under the severe conditions defined herein, it has been found that there are certain essential components o~ the structure of the N-(?-hydroxyethyl)-N-bis-(methylenephosphonic acid) and corresponding N-o~ide of the present invention which are necessary to provide that per~ormance, and thus clearly distinguish the compositions of the present invention from those o~ the prior art. Tor example, the N,N-bis(phosphonomethyl)amino portion of the struc~ure 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 be, ln their ionized form. Thus, it i~ not critical whether "M~' is hydrogen or a suitable cation, and the selection of an appropriate ealt form is well within the skill of the art. Alkali metal salts are the most simple, and are preferred ~or that reason.
25 Overall, however, it is preferr~d that M is hydrogen.
Another ~tructural element of the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide to be considered is the terminal hydro~yl moiety: OH, which together with the ethylene group: -CH2-CH2-, bridging the terminal 2 ~
hydroxyl and the N-bis(methylenephosphonic acid) group, allows the overall molecule to provide a surprising degree of e~fectiveness in inhibiting scale in aqueous systems characterized by the severe conditions of high p~ 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-oxlde of the present invention must be considered, i.e., the N-~O
moiety. As has already been described, this feature of the overall structure confers resistance ~o degradation by oxidizing biocides which is sufficient to ensure adequate scale inhibition at dosing leve1s within the ranges herein described.
The N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid) and corresponding N-oxide of the compositions and methods vf the present invention are prepared by phosphonomethylation of the primary amine, i.e., ethanolamine. The ethanolamine starting materiat and its method of preparation are well known. The phosphonomethylation of the primary amine is then carrled out by a Mcmnich reaction such as that described in K. Moedritzer and R. Irani, J.
0rg~_ic ~hem. 31(5) 1603-7, "The Direct Synthesis of alpha~Aminomethyl Phosphonic Acids; Mannich-Type Reactions with Orthophosphorous Acid~, May 1965. In 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 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 10 matter, preparation of the N-~2-hydroxyethyl)-N-bis-(methylenephosphonic acid) of the present invention, as described in detail ~urther below, usually results in only about 80 to 90% phosphonomethylation. Other side products give N substitution with H, CH3, CH20~, etc. It is not practical, as a matter o~
simple production economics, however, to isolate and purify the completely phosphonomethylated compounds herein claimed, since the side products just described do not inter~ere with scale inhibition.
Such side products, are consequently, usually allowed to remain.
The optional N-oxide of the compoæitions and methods of the px~sent invention is prepared first by phosphonomethylatio~ of the ethanolamine, as described above, followed by an oxidation step which provides the N-oxide moietie. Once the desired phosphonomethylated ethano~amine 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, e.g., simply by adding 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. Qf course, it is also possible to use other well known techniques for carrying out such a step o~ oxidation, and any number o~ these may be success~ully employed.
When the N~(2-hydroxyethyl)-N-bis-(methylenepho~phonic acid) or N-oxide compositions of the present invention are used to inhibit the precipitation, deposition, and adherence of scale-forming salts in an agueous 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 lS most pre~erably, the amount added will be sufficient to establish a concentration of rom 10 to 50 mg/L o~
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 present invention, will determine the actual amount o$ the N-(2-~ydroxyethyl~ 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 vf inhibition of alkaline earth metal, especially calcium carbonate scale formation, deposition and adherence in that agueous system. The calculation of those amounts is well within the skill of the artisan in this field.
2~2~
2811H - 2~ - C-1573 When the N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid) or N-o~ide compositions of the preæent invention are used in combination with one or more of the polymers recited further abo~e, 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 5 system, will as a general matter be within the ranges of amounts suf~icient 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 ~ormation and deposition" are meant to include threshold inhibition, dispersion, solubiliæation, or particle size reduction. The phrases "inhibiting the adhere~ce" and "increasing the non-adherence", are meant to define the formation of a scale deposit which is easily removed, e.g., by simple rinsing, i.e., a scale deposit which is not so 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.
The phrase "scale-forming salts" is meant to include any of the scale-forming salts selected from 2s the group consisting essentially of calcium carbonate, calcium phosphate, calcium phosphonate (including calcium hydroxyethylidene diphosphonic acid), and the corresponding magnesium salts.
The phrase "aqueous system" means commercial or industrial systems utilizing water and involving heat 2'~ J1~
exchange surfaces, usually of metal, including cooling water systems inc1uding cooling towers, boiler water systems, desalination systems, gas scrubbels, and thermal conditionin~ equipment. Of particular importance are those systems which operate under severe conditions as detailed herein, including at least high pH and high calcite concentrations.
5 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 liguid 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.
In the embodiments of the present invention described herein, it has been contemplated that, as a practical matter, only a single N-(2-hydro~yethyl)-N-bis(methylenephosphonic acid) or N-oxide composition of those described above would be used for the 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 2 ~ 9 ~
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, pro~ide 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 $rom the group consisting of homopolymers, copolymers and terpolymers comprising one or more monomers of acrylamide (AM), acrylic acid (AA), 2-acrylamide-methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid (IA), polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), t-butyl acrylamide (TBAM), sodium styrene sul~onate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulionic acid (A~PS~, and vinyl phosphonic acid. Weight average molecular weights ~or such polymer additives should range from about 500 to ~50,000.
For example 9 such compositions include copolymers of 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA. Other preferred polymer additi~es for use with the N (2-hydroxyethyl)-N-bis-2~2~2 (methylenephosphonic acid) and corresponding N-oxide of the present invention include ~0/~0 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA; 100 AA; 50/50 and 75/25 SSS/MA; 75f~5 M /AHPS; 33/33/34 ~A/MAA/IA; 50/50 AA/AM; 70/20/10 AA/AMPSA/PGM-5, 10 and ~0 (having 5, 10 and 20 repeating oxyethylene units, respectively); and ~A/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 AA/AMPSA/PGM-5.
Combinations using these polymers together with the N-~2-hydro~yethyl)-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.
20~2~2 CaC03 Scale Inhibition at pE 9 and 300X Calcite Saturation -N-(2-~ydroxyethyl)-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 per~ormance lo with that of other compounds under severe conditions, the following pxocedure was used:
PROCEDURE: Scaling water containing 250 mg/L of C032 and 600 mg/L of alkalinity at a pH of 9.G
and 55C 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 thle appropriate container through a 0.2 ~ filter, titrating for calcium, and calculating % inhibition by the Schwarzenbach method.
The results obta1ned are shown in the table of values below.
2 ~ t~2 2811H - 27 ~ C-1573 % CaC03 SCALE IN~IBITION
SAMPLE
NO. _ DESCRIPTION _2~ ppm 30 ppm 50 ppm 1 ~ocH2cH2Nz2 74 85 91 2 HOC~2CE2N(~O)z~ 56 67 75 3 NZ3 (AMP) 21 22 52 4 N(~O)Z3 4~. 42 69 * where Z = -CH2Po3H2 The above results clearly show the surprising improvement in calcium carbonate æcale 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 .
CaCO3 Scale Inhibition at pH 9 and 300X Calcite Saturation -N-(2-~ydroxyethyl)-~-bis(Methylenephosphonic acid) 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 fo~lows, which also sets forth the scale inhibition activites 3 obtained.
2~92~
VARIATION IN TEST CONDITIONS
pH 9; 300X CaC03; 60C; 10% Excess Ca/Alk;
5Qppm: 24hrs 4days 5Q~-2~ppm 50ppm Sample No. 1 90.8 87.5 82.6 67.8 85.6 CaC03 Scale Inhibition at pH 9 and 300X Calcite Saturation -N-(2-~ydro~yethyl)-~-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 o~ different polyelectrolytes, and at di~ferent ratios. The %
inhibition was calculated at 24 hours. The results o~ those evaluations revealed the unusually, and on occasion, surprisingly high degree of scale inhibitlon which can be achie~ed with such 2s combinations under the severe conditions of the assay employed.
2 ~ 2 TABLE ~
RATIOS OF POLYELEC-DOSASE TROLYTE:P~OSPHONATE
POLYEL~ÇTROL~rT~ (ppm) ~ 1.5 1:2 1:3 1:4 60/40 M tAMPSA
(24-Eour Data) 20 -- 56.0 -- 58.0 53.5 " 30 -- 66.0 60.6 75.0 --" 4062.0 88.0 ~.4 84.6 --" 5099.9 90.6 -- 90.0 --(24-Hour Data) 40 -- -- 62.0 54,9 __ " 5062.0 71.8 -- -- --(24-~our Da~a) 50 -- 84.14 -- -- 92.8 (4-Day Data) 50 -- 69.6 -- -- 58.0 VERSA TL-7*
(24-Hour Data) 5092.6 86.8 89.7 -- __ (4-Day Data~ 5058.8 70.6 57.4 --- -75/25 AA/A~PS
AQUATREAT CPA-III*
(24-Hour Data) 5082.3 B5.3 -- -- 82.3 (4-Day Data) 5055.9 72.1 -- -- 70.6 VERSA TL-4*
(24-Hour Data) 50 - 84.1 -- -- 84.1 ~24-Hour Data) 50 -- -- -- -- 89.9 (4-Day Data? 50 - -- -- -- 69.6 . 25 33/33/34 MlMAA/IA
POLACRYL WT-315A**
~24-~our Data) 50 -- -- -- -- 84.1 (4-Day Data~ 50. ~ - 81.2 Poly( M /AM) 30 (24-Hour Data) S0 -- -- 87.0 79.7 (4-Day Data) 50 __ __ 79.7 58.0 (24-Eour Data) 20 -- 61.0 -- 60.0 --" 30 -- 66.0 -- 74.0 " 40 -- 80.0 -- g3.0 " 50 -- ~1.0 ~- 79.0 2~2~2 * VERSA TL-4 and TL-7 and AQUATREAT CPA-III are registered trademarkæ of National Starch & Chemical Corp., Bridgewater, NJ.
** POLACRYL WT-315A is a registered trademark of Polacryl Co., Division of Coatex S.A., Caluire, France.
E~AMPLE 4 CaC03 Scale Inhibition at pH 9 and 300X Calcite Saturation -N-(2-~ydroxyethyl)-N-bis(Methylene-phosphonic acid) N-O~ide In Combination with Polyelectrolytes Following the test procedures described in Example 3 above, but using the N-(2-hydro~yethyl)-N-bis(methylene-phosphonic acid) N~oxide combinations with different polyelectrolytes were evaluated. The % inhibition was calculated at 24 hours.
T~BLE 4 RATIOS OF POLYELEC-DOSAGE TROLYTE:PHOSPEONATE
POLYELECTROLYTE (ppm2 1~ 4 ~ ~ c~
~MPLE 5 Preparation of N-(2-Hydroxyethyl~-N-Bis-(Methylenephosphonic Acid) ~IOCH2C~2N ( CE2PO3H2 ) Z
To a 500 mL 3-neck flask fitted with magnetic stirring, thermometer, condenser and addition funnel is added 3Q.Og (0.49 mole) of ethanolamine, 65g of water, 82.0g (1.0 mole~ of 70% phosphorus acid and 50 mL of concentrated hydrochloric acid. This mix is heated to re:~lux and 150.0g (1.85 moles) of 37%
lo formaldehyde is added over a 30 minute period. The resul~ing 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 cf a Barret tube and the entire reaction mixture is concentrated on a rotary evaporator at full vacuum at 92-95OC to yield an aqueous solution of 62.4%.
Analysis of the 31p NMR spectra oi this ~olution indicated the desired product.
2 ~
~XAMPLE 6 Preparation of N-(2-~ydro~ethyl)-N~Bis-(Methylenephosphonic Acid) N-Oxide HocH2cH2N(-~o)(c~2po3~2)2 The starting material ~rom Example 4 (24.91g, O.lOmole) was added to a reaction vessel and the pH
was adjusted to 10.00 with a 50% aqueou3 solution of sodium hydroxide (24.99g). The reaction mixture was then transferred to an Erlenmeyer flask, a~ter which a 35% hydrogen peroxide solution was added dropwise lo to the reaction mixture (total: 10.69gØ11mole).
After several drops were added, the reaction mixture was heated up and then cooled below 15C. The maximum temperature was 25C. The reactior. mixture was then stirred at room temperature for 17 houræ.
The desired product was recovered as a 38.54U/o solution, based on the sodium salt. NMR results indicated 100% conversion of the starting material to N-oxide groups.
It has been found that the ~cale control performance of the N-~2-hydroxyethyl)-N-bis-(methylenephosphonic acid) and correspondi~g N-oxide of the present invention depends to some extent, although not a very signi.~icant extent, on ~he variations in the process parameters described 2s above. Best results are obtained, consequently, by employing the optimum conditions as outlined above.
-
While various polycarboxylates, including polyacrylic acid, havc been used as scale inhibiting agents, as described above, no similar use has been made of polycationic agent , apparently because of the difference in electronic charge and the lo 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 levf!ls, with enhanced resistance to degradation by oxidizing biocides, has not heretofore been suggested.
For e~ample, US 4,080,375 discloses me~hylene phosphonates of amino-terminated o~yalkylates ~or use as scale inhibitors, but these compositions are not the same as those of the present in~ention, nor is there any ~ug~estion that such compositions would be useful under severe condi~io~s 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 ~ormation involving a high brine environment susceptible to 2 ~
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 de~ined herein, 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 72Z, all disclose methylene phosphonates which are N-o~ides, including N-(2~hydro}~ethyl)-N-(methylenephosphonic acid) N-oxide, useful for preventing Rcale and/or corrosion. There is no teaching or suggestion in any of these references, however, of their particular usefulness for controlling 3cale under severe conditions.
~MARY OF THE INVENTIQN
The present invention relates to a composition useful a~ 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 hydro~yethylidene 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 N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid) of the following formula:
CHzP03M2 xo~c~[2-CH2-N
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:
C~I2P03M2 HO-CH2 -CH2-N~O
where M is as defined above; preferably, M ;s hydrogen, The present invention also relates to a composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds selected from the group consi~ting essentially of calcium carbonate; calcium phosphate; calcium pho~phonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium æalts, in an aqueous system having a p~ of at least about 9 and a calcite concentration greater than about 250X, COMPRISING, IN COMBINATION, N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or 2811H - 14 - C-1~73 corresponding N~oxide of the formulas above, together with one or more members selected from the group consisting of homo- and copolymers including ~erpolymers comprising one or more of acrylamide (AM), acrylic acid (AA), 2-acrylamide--methyl propane SUlfGniC acid (AMPSA), methacrylic acid (~AA), itaconie acid (IA~, polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), t-butyl acrylamide (TBAM), sodium styrene sulfonate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2 hydroxy propane sulfonic acid (A~PS) 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 combination where the polymer additive is a member selected from the group consisting e3sentially of 90/10 to 10/90 M/AMPSA, pre~erably 75/25 and ~0/40 AA/AMRSA; 100 AA; 50/50 and 75/25 SSS/MA; 75/25 AA/AHPS; 33/33/34 M /MAA/IA; 50/50 AA/AM; 70/20/10 AA/AMPSA/PGM-5, 10 and 20 ~having 5, 10 and 20 repeating oxyethylene units, respectively); and AA/AMPSA/TBAM. More particularly, the present invention relates to ~uch a combination where the polymer additive is 75/25 or 60/40 AA/AMPSA; lOQ M ;
50/50 or 75/25 SSS/MA; or 70/20/10 AA/AMPSA/PGM-5.
The present in~ention further relates to a method of inhibiting the formation, deposition and adherence 2 i~ ,9 ~
of scale-forming salts selected from the group consisting essentially of calcium caxbonate; calcium phosphate; calcium phosphonate, including calcium hyd r oxyethylidene diphosphonic acid; and the corresponding ma~nesium salts, in an aqueous æystem having a pH of at least abouJ.; 9 and a calcite concentration greater than about 250X, CO~RISING THE STEP of adding to said system an amount ~ufficient 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 lo invention r~lates to such a method in which calcium carbonate ;æ 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 15 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 20 phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; and the corresponding magnesium 3alt8, 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 mgtL of a composition comprising N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) or corresponding N-oxide of the formulas above, together with one or more members selected from the group consisting o~:
homo- and copolymers including terpolymers comprising one or more of acrylamide (AM), acrylic acid (AA), 2-acrylamide--methyl propane sulfonic aeid (AMPSA~, methacrylic acid ~MAA), etho~ylated methacrylate, itaconic acid (IA), polyether ester~ of acrylic and methacrylic acids and polyetheræ based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), t-butyl acrylamide (TBAM), sodium styrene sulfonate, ~odium vinyl sulfonate, hydroxy propyl acrylate, hydro~y propyl methacrylate, 3-allylo~y-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 c:omposition is added to the aqueous system being treat:ed in an amount suf~icient to establish a concentration o~ ~rom 10 to 50 mg/L, and said polymer ad.ditive is a member selected from the group eon~istirlg essentially of 90/10 to 10/90 AA/AMPSA, preferably 75l25 and 60/4Q
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 M /AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively); and AA/AMPSA/TBAM. More particularly, the present invention relates to such a method where the polymer 2~ 2~
2~ 17 ~ C-1573 additive is 75/25 or 60J40 AA/AMPSA; 100 AA; 50/50 or 75/25 SSS/MA; or 70/20/10 AA/AMPSA/PGM-5.
DETAILED DESCRIPTION OF THE INVENTION
The composition of the present invention usefu~
as a deposit control agent to control the formation, deposition and adherency of scale imparting compounds selected from the group consisting ~ssentially of calcium carbonate; calcium phosphate; calcium phosphonate, including calcium hydroxyethylidene diphosphonic acid; a~d the corresponding magnesium salts, in an agueous system having a p~ of at least about 9 and a calcite concentration greater than about 250~, comprises N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid) of the formula:
~IO-CH2 -CH2-N
C~2PO3M2 where M is hydrogen or a suitable cation.
OPTIONALLY, the compound of the above formula may b-e N-oxide, in which event it ha~ the following ormula:
CiEI2P03M2 ~IO C~2~C~I2-N~O
where M is as defined above; preferably, M is hydrogen. This key feature of the compounds o~ the present invention con~ers significant resistance to degradation by oxidizing biocides, presuma~ly by preventing oxidative attack on the nitrogen atom of the group.
In order to obtain high levels of control of ~cale deposits, especially under the severe conditions defined herein, it has been found that there are certain essential components o~ the structure of the N-(?-hydroxyethyl)-N-bis-(methylenephosphonic acid) and corresponding N-o~ide of the present invention which are necessary to provide that per~ormance, and thus clearly distinguish the compositions of the present invention from those o~ the prior art. Tor example, the N,N-bis(phosphonomethyl)amino portion of the struc~ure 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 be, ln their ionized form. Thus, it i~ not critical whether "M~' is hydrogen or a suitable cation, and the selection of an appropriate ealt form is well within the skill of the art. Alkali metal salts are the most simple, and are preferred ~or that reason.
25 Overall, however, it is preferr~d that M is hydrogen.
Another ~tructural element of the N-(2-hydroxyethyl)-N-bis(methylenephosphonic acid) and corresponding N-oxide to be considered is the terminal hydro~yl moiety: OH, which together with the ethylene group: -CH2-CH2-, bridging the terminal 2 ~
hydroxyl and the N-bis(methylenephosphonic acid) group, allows the overall molecule to provide a surprising degree of e~fectiveness in inhibiting scale in aqueous systems characterized by the severe conditions of high p~ 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-oxlde of the present invention must be considered, i.e., the N-~O
moiety. As has already been described, this feature of the overall structure confers resistance ~o degradation by oxidizing biocides which is sufficient to ensure adequate scale inhibition at dosing leve1s within the ranges herein described.
The N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid) and corresponding N-oxide of the compositions and methods vf the present invention are prepared by phosphonomethylation of the primary amine, i.e., ethanolamine. The ethanolamine starting materiat and its method of preparation are well known. The phosphonomethylation of the primary amine is then carrled out by a Mcmnich reaction such as that described in K. Moedritzer and R. Irani, J.
0rg~_ic ~hem. 31(5) 1603-7, "The Direct Synthesis of alpha~Aminomethyl Phosphonic Acids; Mannich-Type Reactions with Orthophosphorous Acid~, May 1965. In 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 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 10 matter, preparation of the N-~2-hydroxyethyl)-N-bis-(methylenephosphonic acid) of the present invention, as described in detail ~urther below, usually results in only about 80 to 90% phosphonomethylation. Other side products give N substitution with H, CH3, CH20~, etc. It is not practical, as a matter o~
simple production economics, however, to isolate and purify the completely phosphonomethylated compounds herein claimed, since the side products just described do not inter~ere with scale inhibition.
Such side products, are consequently, usually allowed to remain.
The optional N-oxide of the compoæitions and methods of the px~sent invention is prepared first by phosphonomethylatio~ of the ethanolamine, as described above, followed by an oxidation step which provides the N-oxide moietie. Once the desired phosphonomethylated ethano~amine 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, e.g., simply by adding 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. Qf course, it is also possible to use other well known techniques for carrying out such a step o~ oxidation, and any number o~ these may be success~ully employed.
When the N~(2-hydroxyethyl)-N-bis-(methylenepho~phonic acid) or N-oxide compositions of the present invention are used to inhibit the precipitation, deposition, and adherence of scale-forming salts in an agueous 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 lS most pre~erably, the amount added will be sufficient to establish a concentration of rom 10 to 50 mg/L o~
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 present invention, will determine the actual amount o$ the N-(2-~ydroxyethyl~ 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 vf inhibition of alkaline earth metal, especially calcium carbonate scale formation, deposition and adherence in that agueous system. The calculation of those amounts is well within the skill of the artisan in this field.
2~2~
2811H - 2~ - C-1573 When the N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid) or N-o~ide compositions of the preæent invention are used in combination with one or more of the polymers recited further abo~e, 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 5 system, will as a general matter be within the ranges of amounts suf~icient 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 ~ormation and deposition" are meant to include threshold inhibition, dispersion, solubiliæation, or particle size reduction. The phrases "inhibiting the adhere~ce" and "increasing the non-adherence", are meant to define the formation of a scale deposit which is easily removed, e.g., by simple rinsing, i.e., a scale deposit which is not so 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.
The phrase "scale-forming salts" is meant to include any of the scale-forming salts selected from 2s the group consisting essentially of calcium carbonate, calcium phosphate, calcium phosphonate (including calcium hydroxyethylidene diphosphonic acid), and the corresponding magnesium salts.
The phrase "aqueous system" means commercial or industrial systems utilizing water and involving heat 2'~ J1~
exchange surfaces, usually of metal, including cooling water systems inc1uding cooling towers, boiler water systems, desalination systems, gas scrubbels, and thermal conditionin~ equipment. Of particular importance are those systems which operate under severe conditions as detailed herein, including at least high pH and high calcite concentrations.
5 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 liguid 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.
In the embodiments of the present invention described herein, it has been contemplated that, as a practical matter, only a single N-(2-hydro~yethyl)-N-bis(methylenephosphonic acid) or N-oxide composition of those described above would be used for the 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 2 ~ 9 ~
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, pro~ide 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 $rom the group consisting of homopolymers, copolymers and terpolymers comprising one or more monomers of acrylamide (AM), acrylic acid (AA), 2-acrylamide-methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid (IA), polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), t-butyl acrylamide (TBAM), sodium styrene sul~onate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulionic acid (A~PS~, and vinyl phosphonic acid. Weight average molecular weights ~or such polymer additives should range from about 500 to ~50,000.
For example 9 such compositions include copolymers of 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA. Other preferred polymer additi~es for use with the N (2-hydroxyethyl)-N-bis-2~2~2 (methylenephosphonic acid) and corresponding N-oxide of the present invention include ~0/~0 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA; 100 AA; 50/50 and 75/25 SSS/MA; 75f~5 M /AHPS; 33/33/34 ~A/MAA/IA; 50/50 AA/AM; 70/20/10 AA/AMPSA/PGM-5, 10 and ~0 (having 5, 10 and 20 repeating oxyethylene units, respectively); and ~A/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 AA/AMPSA/PGM-5.
Combinations using these polymers together with the N-~2-hydro~yethyl)-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.
20~2~2 CaC03 Scale Inhibition at pE 9 and 300X Calcite Saturation -N-(2-~ydroxyethyl)-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 per~ormance lo with that of other compounds under severe conditions, the following pxocedure was used:
PROCEDURE: Scaling water containing 250 mg/L of C032 and 600 mg/L of alkalinity at a pH of 9.G
and 55C 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 thle appropriate container through a 0.2 ~ filter, titrating for calcium, and calculating % inhibition by the Schwarzenbach method.
The results obta1ned are shown in the table of values below.
2 ~ t~2 2811H - 27 ~ C-1573 % CaC03 SCALE IN~IBITION
SAMPLE
NO. _ DESCRIPTION _2~ ppm 30 ppm 50 ppm 1 ~ocH2cH2Nz2 74 85 91 2 HOC~2CE2N(~O)z~ 56 67 75 3 NZ3 (AMP) 21 22 52 4 N(~O)Z3 4~. 42 69 * where Z = -CH2Po3H2 The above results clearly show the surprising improvement in calcium carbonate æcale 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 .
CaCO3 Scale Inhibition at pH 9 and 300X Calcite Saturation -N-(2-~ydroxyethyl)-~-bis(Methylenephosphonic acid) 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 fo~lows, which also sets forth the scale inhibition activites 3 obtained.
2~92~
VARIATION IN TEST CONDITIONS
pH 9; 300X CaC03; 60C; 10% Excess Ca/Alk;
5Qppm: 24hrs 4days 5Q~-2~ppm 50ppm Sample No. 1 90.8 87.5 82.6 67.8 85.6 CaC03 Scale Inhibition at pH 9 and 300X Calcite Saturation -N-(2-~ydro~yethyl)-~-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 o~ different polyelectrolytes, and at di~ferent ratios. The %
inhibition was calculated at 24 hours. The results o~ those evaluations revealed the unusually, and on occasion, surprisingly high degree of scale inhibitlon which can be achie~ed with such 2s combinations under the severe conditions of the assay employed.
2 ~ 2 TABLE ~
RATIOS OF POLYELEC-DOSASE TROLYTE:P~OSPHONATE
POLYEL~ÇTROL~rT~ (ppm) ~ 1.5 1:2 1:3 1:4 60/40 M tAMPSA
(24-Eour Data) 20 -- 56.0 -- 58.0 53.5 " 30 -- 66.0 60.6 75.0 --" 4062.0 88.0 ~.4 84.6 --" 5099.9 90.6 -- 90.0 --(24-Hour Data) 40 -- -- 62.0 54,9 __ " 5062.0 71.8 -- -- --(24-~our Da~a) 50 -- 84.14 -- -- 92.8 (4-Day Data) 50 -- 69.6 -- -- 58.0 VERSA TL-7*
(24-Hour Data) 5092.6 86.8 89.7 -- __ (4-Day Data~ 5058.8 70.6 57.4 --- -75/25 AA/A~PS
AQUATREAT CPA-III*
(24-Hour Data) 5082.3 B5.3 -- -- 82.3 (4-Day Data) 5055.9 72.1 -- -- 70.6 VERSA TL-4*
(24-Hour Data) 50 - 84.1 -- -- 84.1 ~24-Hour Data) 50 -- -- -- -- 89.9 (4-Day Data? 50 - -- -- -- 69.6 . 25 33/33/34 MlMAA/IA
POLACRYL WT-315A**
~24-~our Data) 50 -- -- -- -- 84.1 (4-Day Data~ 50. ~ - 81.2 Poly( M /AM) 30 (24-Hour Data) S0 -- -- 87.0 79.7 (4-Day Data) 50 __ __ 79.7 58.0 (24-Eour Data) 20 -- 61.0 -- 60.0 --" 30 -- 66.0 -- 74.0 " 40 -- 80.0 -- g3.0 " 50 -- ~1.0 ~- 79.0 2~2~2 * VERSA TL-4 and TL-7 and AQUATREAT CPA-III are registered trademarkæ of National Starch & Chemical Corp., Bridgewater, NJ.
** POLACRYL WT-315A is a registered trademark of Polacryl Co., Division of Coatex S.A., Caluire, France.
E~AMPLE 4 CaC03 Scale Inhibition at pH 9 and 300X Calcite Saturation -N-(2-~ydroxyethyl)-N-bis(Methylene-phosphonic acid) N-O~ide In Combination with Polyelectrolytes Following the test procedures described in Example 3 above, but using the N-(2-hydro~yethyl)-N-bis(methylene-phosphonic acid) N~oxide combinations with different polyelectrolytes were evaluated. The % inhibition was calculated at 24 hours.
T~BLE 4 RATIOS OF POLYELEC-DOSAGE TROLYTE:PHOSPEONATE
POLYELECTROLYTE (ppm2 1~ 4 ~ ~ c~
~MPLE 5 Preparation of N-(2-Hydroxyethyl~-N-Bis-(Methylenephosphonic Acid) ~IOCH2C~2N ( CE2PO3H2 ) Z
To a 500 mL 3-neck flask fitted with magnetic stirring, thermometer, condenser and addition funnel is added 3Q.Og (0.49 mole) of ethanolamine, 65g of water, 82.0g (1.0 mole~ of 70% phosphorus acid and 50 mL of concentrated hydrochloric acid. This mix is heated to re:~lux and 150.0g (1.85 moles) of 37%
lo formaldehyde is added over a 30 minute period. The resul~ing 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 cf a Barret tube and the entire reaction mixture is concentrated on a rotary evaporator at full vacuum at 92-95OC to yield an aqueous solution of 62.4%.
Analysis of the 31p NMR spectra oi this ~olution indicated the desired product.
2 ~
~XAMPLE 6 Preparation of N-(2-~ydro~ethyl)-N~Bis-(Methylenephosphonic Acid) N-Oxide HocH2cH2N(-~o)(c~2po3~2)2 The starting material ~rom Example 4 (24.91g, O.lOmole) was added to a reaction vessel and the pH
was adjusted to 10.00 with a 50% aqueou3 solution of sodium hydroxide (24.99g). The reaction mixture was then transferred to an Erlenmeyer flask, a~ter which a 35% hydrogen peroxide solution was added dropwise lo to the reaction mixture (total: 10.69gØ11mole).
After several drops were added, the reaction mixture was heated up and then cooled below 15C. The maximum temperature was 25C. The reactior. mixture was then stirred at room temperature for 17 houræ.
The desired product was recovered as a 38.54U/o solution, based on the sodium salt. NMR results indicated 100% conversion of the starting material to N-oxide groups.
It has been found that the ~cale control performance of the N-~2-hydroxyethyl)-N-bis-(methylenephosphonic acid) and correspondi~g N-oxide of the present invention depends to some extent, although not a very signi.~icant extent, on ~he variations in the process parameters described 2s above. Best results are obtained, consequently, by employing the optimum conditions as outlined above.
-
Claims (9)
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:
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:
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 (AM), acrylic acid (AA),
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:
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:
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 (AM), acrylic acid (AA),
2-acrylamide--methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), itaconic acid (IA), polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), 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.
2. A composition according to Claim 1 wherein M is hydrogen and the compound is N-(2-hydroxyethyl)-N-bis-(methylenephosphonic acid).
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 75/25 and 60/40 AA/AMPSA; 100 M ; 50/50 and 75/25 SSS/MA; 75/25 M/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, respectively); and AA/AMPSA/TBAM.
50/50 AA/AM; 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively); and AA/AMPSA/TBAM.
4. A composition according to Claim 3 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 M/AMPSA/PGM-5.
50/50 or 75/25 SSS/MA; or 70/20/10 M/AMPSA/PGM-5.
5. 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:
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:
where M is as defined above.
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:
where M is as defined above.
6. A method according to Claim 5 wherein calcium carbonate is the scale-forming salt, the aqueous system comprises a cooling tower, said compound is N-(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:
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:
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 (AM), acrylic acid (AA), 2-acrylamide--methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid (IA), polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), 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.
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:
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 (AM), acrylic acid (AA), 2-acrylamide--methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid (IA), polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), 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.
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-(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 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 M/AM; 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively); and AA/AMPSA/TBAM.
100 AA; 50/50 and 75/25 SSS/MA; 75/25 AA/AHPS;
33/33/34 AA/MAA/IA; 50/50 M/AM; 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, 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 AA/AMPSA/PGM-5.
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2092492 Abandoned CA2092492A1 (en) | 1992-03-30 | 1993-03-25 | 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 |
WO2010030024A1 (en) * | 2008-09-12 | 2010-03-18 | 株式会社日本触媒 | Manufacturing method for 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 |
AP2014007390A0 (en) * | 2011-07-29 | 2014-01-31 | 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 |
AU2017400534B2 (en) | 2017-02-27 | 2023-05-11 | Bl Technologies, Inc. | Sulfate scale inhibition in high pressure and high temperature applications |
Family Cites Families (7)
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 |
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 |
ZA905799B (en) * | 1989-12-15 | 1991-05-29 | Grace W R & Co | Control of scale in aqueous systems using certain phosphonomethyl amine oxides |
US5087376A (en) * | 1990-10-15 | 1992-02-11 | Calgon Corporation | Multifunctional scale inhibitors |
-
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
Also Published As
Publication number | Publication date |
---|---|
AU664426B2 (en) | 1995-11-16 |
AU3558293A (en) | 1993-10-07 |
EP0564248A1 (en) | 1993-10-06 |
JPH07108299A (en) | 1995-04-25 |
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