CA1258965A - Composition useful as corrosion inhibitor, anti- scalant and continuous biodice for water cooling towers and method of use - Google Patents
Composition useful as corrosion inhibitor, anti- scalant and continuous biodice for water cooling towers and method of useInfo
- Publication number
- CA1258965A CA1258965A CA000489316A CA489316A CA1258965A CA 1258965 A CA1258965 A CA 1258965A CA 000489316 A CA000489316 A CA 000489316A CA 489316 A CA489316 A CA 489316A CA 1258965 A CA1258965 A CA 1258965A
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- Canada
- Prior art keywords
- ppm
- concentration
- water
- organophosphorous
- composition
- Prior art date
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Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000001816 cooling Methods 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 238000005260 corrosion Methods 0.000 title claims abstract description 45
- 230000007797 corrosion Effects 0.000 title claims abstract description 45
- 239000003112 inhibitor Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 19
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 86
- 125000003118 aryl group Chemical group 0.000 claims abstract description 38
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 34
- 239000003139 biocide Substances 0.000 claims abstract description 22
- 230000003115 biocidal effect Effects 0.000 claims abstract description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 19
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 12
- 150000003868 ammonium compounds Chemical group 0.000 claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims description 12
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 11
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 9
- -1 anionic halogen Chemical class 0.000 claims description 9
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 125000006353 oxyethylene group Chemical group 0.000 claims description 8
- 239000003619 algicide Substances 0.000 claims description 7
- 230000005764 inhibitory process Effects 0.000 claims description 7
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001412 amines Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 4
- 230000000694 effects Effects 0.000 claims 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims 2
- 150000002148 esters Chemical group 0.000 claims 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 239000012964 benzotriazole Substances 0.000 abstract description 5
- 150000002903 organophosphorus compounds Chemical class 0.000 description 13
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 241000195493 Cryptophyta Species 0.000 description 4
- 230000009182 swimming Effects 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- WWYNJERNGUHSAO-XUDSTZEESA-N (+)-Norgestrel Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](CC)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 WWYNJERNGUHSAO-XUDSTZEESA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 101100288310 Arabidopsis thaliana KTI2 gene Proteins 0.000 description 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
COMPOSITION USEFUL AS CORROSION INHIBITOR, ANTI-SCALANT AND CONTINUOUS BIOCIDE FOR WATER COOLING
TOWERS AND METHOD OF USE
Abstract of the Disclosure An all-in-one treatment composition for a water cooling tower includes a water soluble aromatic azole corrosion inhibitor such as benzotriazole, an organophosphorous antiscalant and a polymeric quater-nary ammonium compound. The polymeric quaternary ammonium compound has the following general formula:
The composition is suitable for use at low level continuous applications rates. The polymeric quaternary ammonium compound is also suitable for use at low concentration as a continuous biocide/biostat.
This compound does not suffer from the acclimatization typically encountered when one biocide is used on a continuous low level basis.
TOWERS AND METHOD OF USE
Abstract of the Disclosure An all-in-one treatment composition for a water cooling tower includes a water soluble aromatic azole corrosion inhibitor such as benzotriazole, an organophosphorous antiscalant and a polymeric quater-nary ammonium compound. The polymeric quaternary ammonium compound has the following general formula:
The composition is suitable for use at low level continuous applications rates. The polymeric quaternary ammonium compound is also suitable for use at low concentration as a continuous biocide/biostat.
This compound does not suffer from the acclimatization typically encountered when one biocide is used on a continuous low level basis.
Description
~25~3~365 ~OMPOSITION USEFUL AS CORROSION INHIBITOR~
ANTI-SCALANT AND CONTINUOUS BIOCIDE ~OR WATER COOLING
TOWERS AND METHOD OF USE
Back~ound Water cooling systems, particularly water cooling towers, require continuous maintenance in order to avoid fouling caused by sludge, scale and microoxganisims, and corrosion. These problems are treated by adding various chemicals to the water cooling towers.
one class of compounds useful as disper-sants, antiscaling agents and corrosion inhibitors are organophosphorous compounds, particularly organophos-phorous carboxylic acids and the phosphonates. These organic phosphorus compounds have the ability to complex metal ions by sequestration or threshold treatmant. They also form inhibitive films along metal surfaces. This prevents formation of the crystalline structure in ~cale. Phosphonates are a well defined class of threshold inhibitors used to prevent scale formation. Typically used phosphonates ~ ~8965 include aminomethylenephosphonic acid and l-hydroxyl ethylidene-l,l-diphosphonic acid. A commonly employed organophosphorous carboxylic acid (phosphenite) is
ANTI-SCALANT AND CONTINUOUS BIOCIDE ~OR WATER COOLING
TOWERS AND METHOD OF USE
Back~ound Water cooling systems, particularly water cooling towers, require continuous maintenance in order to avoid fouling caused by sludge, scale and microoxganisims, and corrosion. These problems are treated by adding various chemicals to the water cooling towers.
one class of compounds useful as disper-sants, antiscaling agents and corrosion inhibitors are organophosphorous compounds, particularly organophos-phorous carboxylic acids and the phosphonates. These organic phosphorus compounds have the ability to complex metal ions by sequestration or threshold treatmant. They also form inhibitive films along metal surfaces. This prevents formation of the crystalline structure in ~cale. Phosphonates are a well defined class of threshold inhibitors used to prevent scale formation. Typically used phosphonates ~ ~8965 include aminomethylenephosphonic acid and l-hydroxyl ethylidene-l,l-diphosphonic acid. A commonly employed organophosphorous carboxylic acid (phosphenite) is
2-phosphonobutane- 1,2,4-tricarboxylic acid which can be purchased from Bayer AG.
Alkali and alkaline earth metal molybdate salts are superior corrosion inhibitors to chromate and nitrite salts used at higher concentrations.
Sodium molybdate is an anodic inhibitor and is the most commonly used molybdate inhibitor.
Also used for corrosion inhibition are the aromatic azoles. These are specific corrosion inhibi-tors for copper and its alloys. They are chemisorbed on the metal surfaces and are capable of excellent protection at a minimal dosage of 1 to 2 parts per million. Generally included within the aromatic azoles are benzotriazole, tolyltriazole, and mercapto-benzothiazole.
Organophosphorous carboxylic acids, phospho-nates and azoles are used in combination to provide acorrosion and scale inhibition program. Functionally these are all anionic in solution and therefore generally quite compatible.
In addition to corrosion and scale inhibi-tors and dispersants, water cooling towers ar~generally treated with certain biocides or biostats to prevent or inhibit algae r fungi and bacteria. Two general types of these are oxidizing and nonoxidizing.
,f . .
` ' ~;' ~2~39~5 Typical oxidizing biocides are ClO2, chlorine and chlorine release compounds such as chlorinated isocyanurates, hypochlorites and chlorinated hydan-toins. Quaternary ammonium compounds are the primary nonoxidizing biocides and biostats. The quaternary ammonium salts are cationic surface active chemicals which are most effective against algae and bacteria in alkaline pH xanges.
One particular class of quaternary ammonium complexes are polymeric quaternary ammonium salts.
These complexes are generally nontoxic and accordingly safer to use. They are formed by reacting a bis tertiary amine with a dihalo compound or a hydroxy halocompound. Several of these compounds are current-ly used to treat water cooling towers. One suchproduct is WSCP from Buckman Laboratories which i9 poly[oxyethylene(dimethylimminio)ethylene(dimethyl-imminio)ethylenedichloride]. This product is used as a swimming pool algicide at two parts per million(ppm) as a maintenance dose and 5 ~o 8ppm to rid pools of heavy objectionable algae growth. Swimming pools are more easily treated than water cooling towers. The chlorination o~ swimming pools and other ~iocidal treatmen~ pre~ents acclima~ization. Further, swimming 25 pools are not actively aerated. Water cooling towers inherently aerate the water which promotes growth of aerobic microorganisms. The manufacturers of WCSP
1~5~3965 recommend use of WCSP at 20 to 40 parts per million of active product as a biocide for water cooling towers.
Another polymeric quaternary ammonium compound is Mirapol A-15. This product is poly[N-[3(di-methylammonio)propyl]-N'-[3-(ethyleneoxyethylene-dimethylammonio)propyl~ urea dichloride]. This is inhibitory against certain bacteria at 100 parts per million. A third polymeric quaternary ammonium com~ound i5 ETC-PQ from Onyx Chemical Company which is ~-4-[1 tris~2-hydroxy ethyl)ammonium chloride 2-bu-tenyl]poly[1 dimethylammonium chloride-2-butenyl]-~
-tris(2 hydroxyethyl)ammonium chloride. This also acts as a bacterio~tat.
Quaternary ammonium salts are excellent biocides for use in water cooliny towers. However because quaternary ammonium compounds are cationic in nature and when combined with corrosion inhibitors, dispersants and antiscalants which are anionic in nature, the compounds tend to salt out via chemical reaction thereby destroying functionality. The corrosion inhibitors and antiscalants are used continuously and remain effective even though used continuously. Biocides and biostats on the other hand are not used continuously. Bacteria and other micro-organisms can acclimatize to a particular biocide rendering ths biocide totally ineffective. This is particularly a problem when low levels of a biocide * trade mark 1~5~965 are used as is required for continuous application.
Of course at extremely high concentration, certain biocides would be effective on a continuous basis.
But this would be environmental1y objectionable and economically unfeasible. Other biocides and biostats are totally ineffective at low levels used in contin-uous treatment. For these reasuns biocides and biostats are generally applied periodically in high concentration, slug doses which kill a high proportion of bacteria or algae. A typical treatment for a water cooling tower will use multiple slug doses of different biocides to preven~ acclimatization to any particular hiocide.
ummary of the_Invention The present invention is premised upon the discovery that a particular quaternary ammonium complex, a poly[oxyalkylene(dialkylimminio)alkylene(di-alkylimminio)] salt, is effective as a continuous biocide/biostat at low levels.
~ The invention is further premised on the discovery that this quaternary ammonium compound is ~S~39~5 compatible at high concentrations with organophos-phorous carboxylic acid dispersants and scale inhibi-tors, as well as with molybdate corrosion inhibitors and azole type corrosion inhibitors.
S Thus the present invention provides a means to continuously treat a water cooling system, particu-larly a water cooling tower, with one composition which prevents corrosion; scaling and acts as a bacteriostat and an algicide~ These and other advan-tages of the present invention will be appreciated in light of the detailed description.
Detailed Description According to the present invention an all-in-one treatment ayent for a water cooling system includes a polymeric quaternary ammonium compound as a biocide/biostat, an organophosphorous carboxylic acid compound which acts as a scale control agent, dispersant and corrosion inhibitor and an azole type corrosion inhibitor. These are provided in high concentrations for storage and shipment and are applied at low l~vel concentration on a continuous basis in a water coo]ing tower.
Further tha unique polymeric quaternary ammonium compound used in the invention can be used alone as a low level continuous bac~eriostat and algicide.
For use in the present invention the poly-meric quaternary ammonium compound is a _7_ 1~5~965 poly[oxy-alkylene(dialkylimminio~alkylene(dialkylimminio)alkyl-ene] compound having the following general formula:
- - O - R i N - R4 N - R7 l I
R3 R6 - n wherein: -Rl, R4 and R7 are Cl-C10 alkylene and preferably Cl-C3 alkylene;
R2, R3, R5 and R6 represent Cl-C5 alkyl and preferably methyl; and n is 5-12 and preferably 7-10.
The +2 charge is preferably offset by anionic halogen atoms preferably Cl .
The preferred polyquaternary ammonium com-pound for use in the present invention is poly[oxy-ethylene(dimethylimminio)ethylene(dimethylimminio)eth-ylenedichloride]. The terminal groups of the polymer may vary but generally should be hydrogen or a halogen such as chlorine. This compound is produced by reacting dichloroethyl ether with the following .. .
, ., , l~SB9~iS
compound in an aqueous medium via a rate/temperature controlled reaction:
CH3 c~3 The amount of polymeric quaternary ammonium compound(active) used in the present invention will generally be about 5%-60% and preferably 10~ based on the total amount of organophosphorous compound, azole corrosion inhibitor and polymeric quaternary ammonium compound.
The antiscalant di.spersant of the present invention is one or more organic phosphorous com-pounds. Organophosphorous antiscalants are a known class of compounds. The two preferred compounds are phosphonates and organophosphorous carboxylic acids and their salts. Suitable phosphonates are water . .
~5~5 _9_ soluble phosphonates which have the followiny general formula:
Ho O
\11 P r~8 wherein R8 represents Cl-C5 alkyl or substituted alkyl such as amine substituted alkyl and phosphonic acid substituted alkyl. Preferred phosphonates are poly-lS phosphonates where R8 is substituted with one or more phosphonate groups. The most commonly used is l-hydroxyethylidene-l, l-diphosphonic acid~HEDP).
The organophosphorous carboxylic acid compounds suitable for use in the present invention are the water soluble organic phosphorous carboxylic acids typically used as antiscalants in the water treatment industry. These have the following general -10~ S
formula.
\ p R C - R
C--O
wherein Rg and Rlo represent hydrogen, Cl-C5 alkyl or C1-C5 alkyl substituted by an amine, carboxylic acid group or ester group. In use, since the final composition is alkaline, the compound will be present as alkali or alkaline earth metal salts or Cl~C5 alkyl esters~
The relative percentage of organophosphorous antiscalant based on the total amount o~ poly ~uater-nary ammonium compound, azole corrosion inhibitor and organophosphorous compound in the present formulation should generally range from 20~ to 85%(actives) preferably 60%. At higher concentrations it tends to salt out.
The organophosphorous antiscalan~s can be added as a combination of phosphonates and organophos-phorous carboxylic acid for applications encountering hard water. In such applications the two ~L~5~5 organophosphorous antiscalants preferred are l-hydroxyethylidene 1, l-diphosphonic acid~HEDP) and 2-phosphonobutane-1, 2,4 tricarboxylic acid(PBS-AM).
Further the all in one treatment composition of the present invention includes a water soluble aromatic azole type corrosion inhibitor. These include benzotriazole, Cl-C10 alkylbenzotriazoles such as tolyltriazole and thiozoles such as mercaptob~nzo-~hiozole. Preferred azoles are benzotriazole and tolyltriazole.
The aromatic azole corrosion inhibitors should be present in a percentage of 2 to 20 based on combined amounts of polyquaternary ammonium compound, organophosphorous compound, and azole.
In the composition of the present invention the relative percentages of organophosphorous com-pound, aromatic azole and polyquaternary ammonium compound are provided so that in use in a water cooling tower when the polyquaternary ammonium com-pound is present at a concentration of less than or equal to about 15ppm, the concentration of organophos-phorous compound and aromatic azole will be high enough to provide effective corrosion and scale inhibition. The use levels are usually at least about .5ppm for the aromatic azole and at least about 5ppm for the organophosphorous compound.
A preferred compo~i~ion for use in the present invention would include 32%
, , ~ , ~58~3~:iS
-12~
poly[oxyethyleneIdiethylimminio) ethylene(dimethylim-minio)ethylenedichloride] as the quaternary, 24% HEDP
and 38~ PBS~AM as the organophosphorous and 6%
benzotriazole, based on the total actives content.
Further the above compositions may also include a base in an amount effective to establish the pH at about 7 to 8.5. Suitable bases include the alkali metal hydroxides particularly sodium and potas-sium hydroxide.
In use in a water cooling tower, it is desirable to have the following approximate concentra-tions of components:
Ran~e~referred aromatic azole .5 - 5ppmlppm Organophosphorous anti-scalant(Total) 5 - l5ppm9.7ppm HEDP O - 15ppm3.7ppm PBS-AM O - 15ppm6ppm Poly Quaternary 2 - lSppmSppm For water cooling towers which employ low hardness or low alkalinity water, a modified all-in-one treatment composition can be used. Specifically, a molybdate corrosion inhibitor can be added. The molybdates are compatible with the polyquaternary compound used in the present invention. Because this formulation is adapted for use in soft water, it can be used with a single organophosphorous component.
, i -13- 1 ~ 5 ~ 965 Accordingly PBS-AM may be employed alone as the organophosphorous antiscalant.
In the composition of the present invention the relative percentages of organophosphorous com-pound, molybdate aromatic azole and polyquaternary ammonium compound are provided so that in use in a water cooling tower when the polyquaternary ammonium compound i5 present at a concentration of less than or equal to about 15ppm the concentration or organophos-phorous compound, molybdate and aromatic azole will be high enough to provide efPective corrosion and scale inhibition. The use levels are usually at least about .5ppm for the aromatic azole and at least about 5ppm for the organophosphorous compound.
In th.is formulation the aromatic azole is present at 1 to 15% of total active and preferably 7~, the organophosphorous compound is presPnt at 5% to 60%
or higher of total actives and preerably 11%; the polyquaternary compound is present at 5% to 40% of total active preferably 16% and the Na molybdate is present in 33% to 80% of total active and preferably 70%.
In use in a water cooling tower it is desirable to have the following concentration of ~s~ s individual components:
Range Preferred aromatic azole .5 - 5 lppm Organophosphorous 5 - 15ppm 6ppm (preferably P~S-AM) Polyquaternary ~mmonium Compound 2 - 15ppm 5ppm Na Molybdate 10 - 50ppm 40ppm The poly[oxyalkylene(dialkylimminio~alkylene(dialkyl-imminio~] compound previously described is useful alone as a continuous biocide/biostat at low levels of use. For use in the present invention this polyquaternary ammonium compound should be added to a water cooling tower at 2-15ppm and preferably 3-5ppm.
The water cooling system should be maintained with this concentration o~ the poly~uaternary ammonium compound on a continuous basis. Under these conditions acclimatization by algae and bacteria does not occur. The preferred polyquaternary ammonium compound is poly[oxyethylene-(dimethylimminio)ethylene(dimethylimminio)ethylene dichloride].
According to the present invention a poly~oxyalkylene-(dialkylimminio)alkylene(dialkylimminio)3 can be used at low levels to provide a continuous biostat/biocide treatment of cooling system water or it can be incorporated into an all in one water cooling system -15- l~S~9~5 treatment s~stem to control corrosion, sludge buildup, scale formation and microorganisms.
`~
Alkali and alkaline earth metal molybdate salts are superior corrosion inhibitors to chromate and nitrite salts used at higher concentrations.
Sodium molybdate is an anodic inhibitor and is the most commonly used molybdate inhibitor.
Also used for corrosion inhibition are the aromatic azoles. These are specific corrosion inhibi-tors for copper and its alloys. They are chemisorbed on the metal surfaces and are capable of excellent protection at a minimal dosage of 1 to 2 parts per million. Generally included within the aromatic azoles are benzotriazole, tolyltriazole, and mercapto-benzothiazole.
Organophosphorous carboxylic acids, phospho-nates and azoles are used in combination to provide acorrosion and scale inhibition program. Functionally these are all anionic in solution and therefore generally quite compatible.
In addition to corrosion and scale inhibi-tors and dispersants, water cooling towers ar~generally treated with certain biocides or biostats to prevent or inhibit algae r fungi and bacteria. Two general types of these are oxidizing and nonoxidizing.
,f . .
` ' ~;' ~2~39~5 Typical oxidizing biocides are ClO2, chlorine and chlorine release compounds such as chlorinated isocyanurates, hypochlorites and chlorinated hydan-toins. Quaternary ammonium compounds are the primary nonoxidizing biocides and biostats. The quaternary ammonium salts are cationic surface active chemicals which are most effective against algae and bacteria in alkaline pH xanges.
One particular class of quaternary ammonium complexes are polymeric quaternary ammonium salts.
These complexes are generally nontoxic and accordingly safer to use. They are formed by reacting a bis tertiary amine with a dihalo compound or a hydroxy halocompound. Several of these compounds are current-ly used to treat water cooling towers. One suchproduct is WSCP from Buckman Laboratories which i9 poly[oxyethylene(dimethylimminio)ethylene(dimethyl-imminio)ethylenedichloride]. This product is used as a swimming pool algicide at two parts per million(ppm) as a maintenance dose and 5 ~o 8ppm to rid pools of heavy objectionable algae growth. Swimming pools are more easily treated than water cooling towers. The chlorination o~ swimming pools and other ~iocidal treatmen~ pre~ents acclima~ization. Further, swimming 25 pools are not actively aerated. Water cooling towers inherently aerate the water which promotes growth of aerobic microorganisms. The manufacturers of WCSP
1~5~3965 recommend use of WCSP at 20 to 40 parts per million of active product as a biocide for water cooling towers.
Another polymeric quaternary ammonium compound is Mirapol A-15. This product is poly[N-[3(di-methylammonio)propyl]-N'-[3-(ethyleneoxyethylene-dimethylammonio)propyl~ urea dichloride]. This is inhibitory against certain bacteria at 100 parts per million. A third polymeric quaternary ammonium com~ound i5 ETC-PQ from Onyx Chemical Company which is ~-4-[1 tris~2-hydroxy ethyl)ammonium chloride 2-bu-tenyl]poly[1 dimethylammonium chloride-2-butenyl]-~
-tris(2 hydroxyethyl)ammonium chloride. This also acts as a bacterio~tat.
Quaternary ammonium salts are excellent biocides for use in water cooliny towers. However because quaternary ammonium compounds are cationic in nature and when combined with corrosion inhibitors, dispersants and antiscalants which are anionic in nature, the compounds tend to salt out via chemical reaction thereby destroying functionality. The corrosion inhibitors and antiscalants are used continuously and remain effective even though used continuously. Biocides and biostats on the other hand are not used continuously. Bacteria and other micro-organisms can acclimatize to a particular biocide rendering ths biocide totally ineffective. This is particularly a problem when low levels of a biocide * trade mark 1~5~965 are used as is required for continuous application.
Of course at extremely high concentration, certain biocides would be effective on a continuous basis.
But this would be environmental1y objectionable and economically unfeasible. Other biocides and biostats are totally ineffective at low levels used in contin-uous treatment. For these reasuns biocides and biostats are generally applied periodically in high concentration, slug doses which kill a high proportion of bacteria or algae. A typical treatment for a water cooling tower will use multiple slug doses of different biocides to preven~ acclimatization to any particular hiocide.
ummary of the_Invention The present invention is premised upon the discovery that a particular quaternary ammonium complex, a poly[oxyalkylene(dialkylimminio)alkylene(di-alkylimminio)] salt, is effective as a continuous biocide/biostat at low levels.
~ The invention is further premised on the discovery that this quaternary ammonium compound is ~S~39~5 compatible at high concentrations with organophos-phorous carboxylic acid dispersants and scale inhibi-tors, as well as with molybdate corrosion inhibitors and azole type corrosion inhibitors.
S Thus the present invention provides a means to continuously treat a water cooling system, particu-larly a water cooling tower, with one composition which prevents corrosion; scaling and acts as a bacteriostat and an algicide~ These and other advan-tages of the present invention will be appreciated in light of the detailed description.
Detailed Description According to the present invention an all-in-one treatment ayent for a water cooling system includes a polymeric quaternary ammonium compound as a biocide/biostat, an organophosphorous carboxylic acid compound which acts as a scale control agent, dispersant and corrosion inhibitor and an azole type corrosion inhibitor. These are provided in high concentrations for storage and shipment and are applied at low l~vel concentration on a continuous basis in a water coo]ing tower.
Further tha unique polymeric quaternary ammonium compound used in the invention can be used alone as a low level continuous bac~eriostat and algicide.
For use in the present invention the poly-meric quaternary ammonium compound is a _7_ 1~5~965 poly[oxy-alkylene(dialkylimminio~alkylene(dialkylimminio)alkyl-ene] compound having the following general formula:
- - O - R i N - R4 N - R7 l I
R3 R6 - n wherein: -Rl, R4 and R7 are Cl-C10 alkylene and preferably Cl-C3 alkylene;
R2, R3, R5 and R6 represent Cl-C5 alkyl and preferably methyl; and n is 5-12 and preferably 7-10.
The +2 charge is preferably offset by anionic halogen atoms preferably Cl .
The preferred polyquaternary ammonium com-pound for use in the present invention is poly[oxy-ethylene(dimethylimminio)ethylene(dimethylimminio)eth-ylenedichloride]. The terminal groups of the polymer may vary but generally should be hydrogen or a halogen such as chlorine. This compound is produced by reacting dichloroethyl ether with the following .. .
, ., , l~SB9~iS
compound in an aqueous medium via a rate/temperature controlled reaction:
CH3 c~3 The amount of polymeric quaternary ammonium compound(active) used in the present invention will generally be about 5%-60% and preferably 10~ based on the total amount of organophosphorous compound, azole corrosion inhibitor and polymeric quaternary ammonium compound.
The antiscalant di.spersant of the present invention is one or more organic phosphorous com-pounds. Organophosphorous antiscalants are a known class of compounds. The two preferred compounds are phosphonates and organophosphorous carboxylic acids and their salts. Suitable phosphonates are water . .
~5~5 _9_ soluble phosphonates which have the followiny general formula:
Ho O
\11 P r~8 wherein R8 represents Cl-C5 alkyl or substituted alkyl such as amine substituted alkyl and phosphonic acid substituted alkyl. Preferred phosphonates are poly-lS phosphonates where R8 is substituted with one or more phosphonate groups. The most commonly used is l-hydroxyethylidene-l, l-diphosphonic acid~HEDP).
The organophosphorous carboxylic acid compounds suitable for use in the present invention are the water soluble organic phosphorous carboxylic acids typically used as antiscalants in the water treatment industry. These have the following general -10~ S
formula.
\ p R C - R
C--O
wherein Rg and Rlo represent hydrogen, Cl-C5 alkyl or C1-C5 alkyl substituted by an amine, carboxylic acid group or ester group. In use, since the final composition is alkaline, the compound will be present as alkali or alkaline earth metal salts or Cl~C5 alkyl esters~
The relative percentage of organophosphorous antiscalant based on the total amount o~ poly ~uater-nary ammonium compound, azole corrosion inhibitor and organophosphorous compound in the present formulation should generally range from 20~ to 85%(actives) preferably 60%. At higher concentrations it tends to salt out.
The organophosphorous antiscalan~s can be added as a combination of phosphonates and organophos-phorous carboxylic acid for applications encountering hard water. In such applications the two ~L~5~5 organophosphorous antiscalants preferred are l-hydroxyethylidene 1, l-diphosphonic acid~HEDP) and 2-phosphonobutane-1, 2,4 tricarboxylic acid(PBS-AM).
Further the all in one treatment composition of the present invention includes a water soluble aromatic azole type corrosion inhibitor. These include benzotriazole, Cl-C10 alkylbenzotriazoles such as tolyltriazole and thiozoles such as mercaptob~nzo-~hiozole. Preferred azoles are benzotriazole and tolyltriazole.
The aromatic azole corrosion inhibitors should be present in a percentage of 2 to 20 based on combined amounts of polyquaternary ammonium compound, organophosphorous compound, and azole.
In the composition of the present invention the relative percentages of organophosphorous com-pound, aromatic azole and polyquaternary ammonium compound are provided so that in use in a water cooling tower when the polyquaternary ammonium com-pound is present at a concentration of less than or equal to about 15ppm, the concentration of organophos-phorous compound and aromatic azole will be high enough to provide effective corrosion and scale inhibition. The use levels are usually at least about .5ppm for the aromatic azole and at least about 5ppm for the organophosphorous compound.
A preferred compo~i~ion for use in the present invention would include 32%
, , ~ , ~58~3~:iS
-12~
poly[oxyethyleneIdiethylimminio) ethylene(dimethylim-minio)ethylenedichloride] as the quaternary, 24% HEDP
and 38~ PBS~AM as the organophosphorous and 6%
benzotriazole, based on the total actives content.
Further the above compositions may also include a base in an amount effective to establish the pH at about 7 to 8.5. Suitable bases include the alkali metal hydroxides particularly sodium and potas-sium hydroxide.
In use in a water cooling tower, it is desirable to have the following approximate concentra-tions of components:
Ran~e~referred aromatic azole .5 - 5ppmlppm Organophosphorous anti-scalant(Total) 5 - l5ppm9.7ppm HEDP O - 15ppm3.7ppm PBS-AM O - 15ppm6ppm Poly Quaternary 2 - lSppmSppm For water cooling towers which employ low hardness or low alkalinity water, a modified all-in-one treatment composition can be used. Specifically, a molybdate corrosion inhibitor can be added. The molybdates are compatible with the polyquaternary compound used in the present invention. Because this formulation is adapted for use in soft water, it can be used with a single organophosphorous component.
, i -13- 1 ~ 5 ~ 965 Accordingly PBS-AM may be employed alone as the organophosphorous antiscalant.
In the composition of the present invention the relative percentages of organophosphorous com-pound, molybdate aromatic azole and polyquaternary ammonium compound are provided so that in use in a water cooling tower when the polyquaternary ammonium compound i5 present at a concentration of less than or equal to about 15ppm the concentration or organophos-phorous compound, molybdate and aromatic azole will be high enough to provide efPective corrosion and scale inhibition. The use levels are usually at least about .5ppm for the aromatic azole and at least about 5ppm for the organophosphorous compound.
In th.is formulation the aromatic azole is present at 1 to 15% of total active and preferably 7~, the organophosphorous compound is presPnt at 5% to 60%
or higher of total actives and preerably 11%; the polyquaternary compound is present at 5% to 40% of total active preferably 16% and the Na molybdate is present in 33% to 80% of total active and preferably 70%.
In use in a water cooling tower it is desirable to have the following concentration of ~s~ s individual components:
Range Preferred aromatic azole .5 - 5 lppm Organophosphorous 5 - 15ppm 6ppm (preferably P~S-AM) Polyquaternary ~mmonium Compound 2 - 15ppm 5ppm Na Molybdate 10 - 50ppm 40ppm The poly[oxyalkylene(dialkylimminio~alkylene(dialkyl-imminio~] compound previously described is useful alone as a continuous biocide/biostat at low levels of use. For use in the present invention this polyquaternary ammonium compound should be added to a water cooling tower at 2-15ppm and preferably 3-5ppm.
The water cooling system should be maintained with this concentration o~ the poly~uaternary ammonium compound on a continuous basis. Under these conditions acclimatization by algae and bacteria does not occur. The preferred polyquaternary ammonium compound is poly[oxyethylene-(dimethylimminio)ethylene(dimethylimminio)ethylene dichloride].
According to the present invention a poly~oxyalkylene-(dialkylimminio)alkylene(dialkylimminio)3 can be used at low levels to provide a continuous biostat/biocide treatment of cooling system water or it can be incorporated into an all in one water cooling system -15- l~S~9~5 treatment s~stem to control corrosion, sludge buildup, scale formation and microorganisms.
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Claims (33)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition adapted to prevent scale and corrosion and to act as a continuous bacteriostat and algicide, comprising:
2% to 20% by weight of an aromatic azole corrosion inhibitor;
20% to 85% by weight of an organophosphorous anti-scalant; and 5% to 60% of a polymeric quaternary ammonium compound having the following general formula:
wherein R1, R4, and R7 represent C1-C10 alkylene; and R2, R3, R5 and R6 represent C1-C5 alkyl; and n represents 5-12;
wherein the +2 charge is offset by anionic halogen;
said aromatic azole and said organophosphorous antiscalant provided in amounts relative to said polymeric quaternary ammonium compound which are effective to provide corrosion inhibition and antiscaling activity in a water cooling system when said polymeric quaternary ammonium compound is present at a use concentration from at least about 2 ppm to about 15 ppm.
2% to 20% by weight of an aromatic azole corrosion inhibitor;
20% to 85% by weight of an organophosphorous anti-scalant; and 5% to 60% of a polymeric quaternary ammonium compound having the following general formula:
wherein R1, R4, and R7 represent C1-C10 alkylene; and R2, R3, R5 and R6 represent C1-C5 alkyl; and n represents 5-12;
wherein the +2 charge is offset by anionic halogen;
said aromatic azole and said organophosphorous antiscalant provided in amounts relative to said polymeric quaternary ammonium compound which are effective to provide corrosion inhibition and antiscaling activity in a water cooling system when said polymeric quaternary ammonium compound is present at a use concentration from at least about 2 ppm to about 15 ppm.
2. The composition claimed in claim 1 wherein said organophosphorous antiscalant is selected from the group consisting of water soluble phosphonate and water soluble organophosphorous carboxylic acids.
3. The composition claimed in claim 2 wherein said aromatic azole is selected from the group consisting of 1,2,3-benzotriazole, tolyltriazole and mercaptobenzothiozole.
4. The composition claimed in claim 1 wherein said organophosphorous antiscalant is selected from the group consisting of 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and mixtures thereof.
5. The composition claimed in claim 1 wherein said polymeric quaternary ammonium compound comprises poly[oxyethyl-ene(dimethylimminio)ethylene(dimethylimminio)ethylene dichloride].
6. The composition claimed in claim 1 wherein said aromatic azole is selected from the group consisting of 1,2,3-benzotriazole, tolyltriazole and mercaptobenzothiozole and said organophosphorous antiscalant is selected from the group consisting of 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and mixtures thereof and said polyquaternary ammonium compound comprises poly[o1yethylene(dimethylimminio)ethylene(dimethylimminio)-ethylene dichloride].
7. The composition claimed in claim 2 wherein said phosphonate antiscalant has the following general formula:
wherein R8 represents C1-C10 alkyl, amine substituted alkyl and phosphonic acid substituted alkyl and said organophos-phorous carboxylic acid has the following general formula:
wherein R9 and R10 represent hydrogen, C1-C5 alkyl, carboxylic acid substituted C1-C5 alkyl, amine substituted C1-C5 alkyl and ester substituted C1-C5 alkyl.
wherein R8 represents C1-C10 alkyl, amine substituted alkyl and phosphonic acid substituted alkyl and said organophos-phorous carboxylic acid has the following general formula:
wherein R9 and R10 represent hydrogen, C1-C5 alkyl, carboxylic acid substituted C1-C5 alkyl, amine substituted C1-C5 alkyl and ester substituted C1-C5 alkyl.
8. A method of treating water in a water cooling system comprising adding to water in said cooling system the composi-tion claimed in claim 1 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
9. A method of treating water in a water cooling system comprising adding to water in said cooling system the composi-tion claimed in claim 2 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
10. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 3 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
11. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 4 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of organophosphorous antiscalant at 5 15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of organophosphorous antiscalant at 5 15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
12. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 5 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm: and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of organophosphorous antiscalant at 5-15 ppm: and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
13. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 6 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
14. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 7 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2 15 ppm.
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2 15 ppm.
15. A composition adapted to prevent scale and corrosion and to act as a bacteriostat and algicide, compris-ing:
2% to 20% of an aromatic azole selected from the group consisting of 1,2,3-benzotriazole, tolyltriazole and mercaptobenzothiozole;
20% to 85% of an organophosphorous antiscalant selected from the group consisting of 2-phosphonobutane-1,2,4-tricarboxylic acid and 1-hydroxyethylidene-1,1-diphosphonic acid and mixtures thereof; and 5% to 60% of poly[oxyethylene(dimethylimminio)-ethylene(dimethylimminio)ethylene dichloride];
said aromatic azole and said organophosphorous antiscalant provided in amounts relative to said poly-[oxyethylene(dimethylimminio)ethylene(dimethylimminio)ethylene dichloride] which are effective to provide corrosion inhibition and antiscaling activity in a water cooling tower when said polymeric quaternary ammonium compound is present at a use concentration from about 2 ppm to about 15 ppm.
2% to 20% of an aromatic azole selected from the group consisting of 1,2,3-benzotriazole, tolyltriazole and mercaptobenzothiozole;
20% to 85% of an organophosphorous antiscalant selected from the group consisting of 2-phosphonobutane-1,2,4-tricarboxylic acid and 1-hydroxyethylidene-1,1-diphosphonic acid and mixtures thereof; and 5% to 60% of poly[oxyethylene(dimethylimminio)-ethylene(dimethylimminio)ethylene dichloride];
said aromatic azole and said organophosphorous antiscalant provided in amounts relative to said poly-[oxyethylene(dimethylimminio)ethylene(dimethylimminio)ethylene dichloride] which are effective to provide corrosion inhibition and antiscaling activity in a water cooling tower when said polymeric quaternary ammonium compound is present at a use concentration from about 2 ppm to about 15 ppm.
16. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 15 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of poly[oxyethylene(dimethylimminio)-ethylene(dimethylimminio)ethylene dichloride] at 2-15 ppm.
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of poly[oxyethylene(dimethylimminio)-ethylene(dimethylimminio)ethylene dichloride] at 2-15 ppm.
17. A composition adapted to prevent scale and corrosion and to act as a bacteriostat and algicide, comprising:
1% to 15% of an aromatic azole corrosion inhibitor:
5% to 60% of a water soluble organophosphorous antiscalant;
30% to 80% of a molybdate corrosion inhibitor; and 5% to 40% of a biocide comprising a polymeric quaternary ammonium compound having the following general formula:
wherein R1, R4 and R7 represent C1-C10 alkylene; and R2, R3, R5 and R6 represent C1-C5 alkyl; and n represents 5-12:
wherein the +2 charge is offset by anionic halogen;
said aromatic azole and said organophosphorous antiscalant and said molybdate corrosion inhibitor provided in amounts relative to said polymeric quaternary ammonium compound which are effective to provide corrosion inhibition and antiscaling activity in a water cooling tower when said polymeric quaternary ammonium compound is present at a use concentration from about 2 ppm to about 15 ppm.
1% to 15% of an aromatic azole corrosion inhibitor:
5% to 60% of a water soluble organophosphorous antiscalant;
30% to 80% of a molybdate corrosion inhibitor; and 5% to 40% of a biocide comprising a polymeric quaternary ammonium compound having the following general formula:
wherein R1, R4 and R7 represent C1-C10 alkylene; and R2, R3, R5 and R6 represent C1-C5 alkyl; and n represents 5-12:
wherein the +2 charge is offset by anionic halogen;
said aromatic azole and said organophosphorous antiscalant and said molybdate corrosion inhibitor provided in amounts relative to said polymeric quaternary ammonium compound which are effective to provide corrosion inhibition and antiscaling activity in a water cooling tower when said polymeric quaternary ammonium compound is present at a use concentration from about 2 ppm to about 15 ppm.
18. The composition claimed in claim 17 wherein said organophosphorous antiscalant is selected from the group consisting of phosphonate antiscalants and organophosphorous carboxylic acids.
19. The composition claimed in claim 18 wherein said phosphonate antiscalant has the following general formula:
wherein R8 represents C1-C5 alkyl, amine substituted C1-C5 alkyl, and C1-C5 phosphonic acid substituted alkyl; and said organophosphorous carboxylic acid has the following general formula:
wherein R9 and R10 represents hydrogen, C1-C5 alkyl, carboxylic acid substituted C1-C5 alkyl, amine substituted C1-C5 alkyl and ester substituted C1-C5 alkyl.
wherein R8 represents C1-C5 alkyl, amine substituted C1-C5 alkyl, and C1-C5 phosphonic acid substituted alkyl; and said organophosphorous carboxylic acid has the following general formula:
wherein R9 and R10 represents hydrogen, C1-C5 alkyl, carboxylic acid substituted C1-C5 alkyl, amine substituted C1-C5 alkyl and ester substituted C1-C5 alkyl.
20. The composition claimed in claim 19 wherein said organophosphorous antiscalant is selected from the group consisting of 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene 1,1-diphosphonic acid and mixtures thereof.
21. The composition claimed in claim 20 wherein said polyquaternary ammonium compound comprises poly[oxyethylene-(dimethylimminio)ethylene(dimethylimminio)ethylene dichloride].
22. The composition claimed in claim 17 wherein said aromatic azole is selected from the group consisting of 1,2,3-benzotriazole, tolyltriazole and mercaptobenzothiozole.
23. The composition claimed in claim 22 wherein said molybdate is selected from the group consisting of alkali and alkaline earth metal molybdates.
24. The composition claimed in claim 23 wherein said molybdate is sodium molybdate.
25. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 18 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
26. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 19 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
27. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 20 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2 15 ppm.
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2 15 ppm.
28. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 21 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
29. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 22 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
30. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 23 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
31. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 24 in an amount effective to establish a concentration of aromatic azole at 0.05-5 ppm;
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of polymeric quaternary ammonium compound at 2-15 ppm.
32. A composition adapted to prevent scale and corrosion and to act as a bacteriostat and algicide comprising:
1% to 15% of an aromatic azole corrosion inhibitor selected from the group consisting of 1,2,3-benzotriazole, tolyltriazole and mercaptobenzothiozole;
5% to 60% of an organophosphorous antiscalant selected from the group consisting of 2-phosphonobutane-1,2,4-tricarboxyli acid and 1-hydroxyethylidene-1,1-diphosphonic acid;
30% to 80% of sodium molybdate; and 5% to 40% of poly[oxyethylene(dimethylimminio)-ethylene(dimethylimminio)ethylene dichloride].
1% to 15% of an aromatic azole corrosion inhibitor selected from the group consisting of 1,2,3-benzotriazole, tolyltriazole and mercaptobenzothiozole;
5% to 60% of an organophosphorous antiscalant selected from the group consisting of 2-phosphonobutane-1,2,4-tricarboxyli acid and 1-hydroxyethylidene-1,1-diphosphonic acid;
30% to 80% of sodium molybdate; and 5% to 40% of poly[oxyethylene(dimethylimminio)-ethylene(dimethylimminio)ethylene dichloride].
33. A method of treating water in a water cooling tower comprising adding to water in said cooling tower the composition claimed in claim 32 in an amount effective to establish a concentration of aromatic azole at 0.5-5 ppm;
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of poly[oxyethylene(dimethylimminio)-ethylene(dimethylimminio)ethylene dichloride] at 2-15 ppm.
a concentration of molybdate corrosion inhibitor at 10 to 50 ppm;
a concentration of organophosphorous antiscalant at 5-15 ppm; and a concentration of poly[oxyethylene(dimethylimminio)-ethylene(dimethylimminio)ethylene dichloride] at 2-15 ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72828785A | 1985-04-29 | 1985-04-29 | |
| US728,287 | 1985-04-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258965A true CA1258965A (en) | 1989-09-05 |
Family
ID=24926217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000489316A Expired CA1258965A (en) | 1985-04-29 | 1985-08-23 | Composition useful as corrosion inhibitor, anti- scalant and continuous biodice for water cooling towers and method of use |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1258965A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774925A (en) * | 2022-04-24 | 2022-07-22 | 西安热工研究院有限公司 | Efficient corrosion inhibitor for biochemical treatment of circulating cooling water and preparation method and application thereof |
-
1985
- 1985-08-23 CA CA000489316A patent/CA1258965A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774925A (en) * | 2022-04-24 | 2022-07-22 | 西安热工研究院有限公司 | Efficient corrosion inhibitor for biochemical treatment of circulating cooling water and preparation method and application thereof |
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