US20050104031A1 - Phosphonamide and phosphonamide blend compositions and method to treat water - Google Patents
Phosphonamide and phosphonamide blend compositions and method to treat water Download PDFInfo
- Publication number
- US20050104031A1 US20050104031A1 US11/015,781 US1578104A US2005104031A1 US 20050104031 A1 US20050104031 A1 US 20050104031A1 US 1578104 A US1578104 A US 1578104A US 2005104031 A1 US2005104031 A1 US 2005104031A1
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- US
- United States
- Prior art keywords
- composition
- water
- phosphonic acid
- phosphonamide
- acid
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 148
- 125000005541 phosphonamide group Chemical group 0.000 title claims abstract description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 73
- 238000011282 treatment Methods 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 15
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 49
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 28
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 16
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 13
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 11
- 230000001186 cumulative effect Effects 0.000 claims description 10
- 150000003009 phosphonic acids Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 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 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 6
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 claims description 5
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 5
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 2
- 229920003169 water-soluble polymer Polymers 0.000 claims 2
- 235000019645 odor Nutrition 0.000 abstract description 5
- 230000009965 odorless effect Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 10
- 239000000356 contaminant Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- -1 cyclic amine Chemical class 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 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
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical class NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010976 amide bond formation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 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 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/6533—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/542—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/685—Devices for dosing the additives
- C02F1/687—Devices for dosing solid compounds
-
- 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
- C02F5/12—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 nitrogen
-
- 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)]
- C07F9/44—Amides thereof
- C07F9/4403—Amides thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4407—Amides of acyclic saturated acids which can have further substituents on alkyl
-
- 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)]
- C07F9/44—Amides thereof
- C07F9/4403—Amides thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4423—Amides of poly (thio)phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
Definitions
- the present invention relates to a composition and method to treat water. More particularly, the invention provides a composition comprising at least one phosphonamide or phosphonamide blends to treat water.
- Water for heating and cooling apparatus must be purified or treated to avoid a plurality of problems. More specifically, boilers and cooling towers require pure water for optimal performance. However, the water coming into these systems is generally impure and contains contaminants which can foul the boilerand cooling tower.
- Feed water is generally contaminated with gases, such as oxygen and carbon dioxide.
- gases such as oxygen and carbon dioxide.
- water can leach impurities from the air. These impurities lead to scale formation, corrosion, and pitting.
- a major contaminant in many water systems is iron, often leached from water lines.
- Corrosion inhibiting chemicals as disclosed in U.S. Pat. No. 4,066,398 have been used to treat contaminated water.
- U.S. Pat. No. 3,510,436 discloses the use of organic phosphates or phosphonates in combination with zinc and/or mercaptobenzothiazole for corrosion inhibition in water systems including cooling towers.
- Compositions utilizing chromates and inorganic polyphosphates have been used to inhibit corrosion of metal surfaces in contact with cooling tower water.
- such treatments are undesirable, both from the viewpoint of handling personnel health and also problems associated with waste disposal.
- Phosphates are generally non-toxic.
- the invention is directed to a composition comprising at least one phosphonamide or blends thereof which may be added in amounts effective to treat water in water flow systems.
- Forming a phosphonamide from an amine generally eliminates odors and vapors emitted by the corresponding amine. Accordingly, phosphonamides reduce exposure related health and safety risks to the user or handling personnel associated with the preparation, manufacture, packaging, and general application of amines that have been used to treat water.
- the generally solid nature of a phosphonamide, or blend of phosphonamides typically allows the treatment composition to be formulated into a convenient dry solid or powder.
- the phosphonamide is an amine derivativized to an amide by reacting the amine with a phosphonic acid.
- the phosphonamide may be fully or partially formed depending on the mole ratios and/or weight ratios of the particular amine and phosphonic acid. Typically, amine to phosphonic acid weight ratios of about 1:1 to about 10:1 are suitable.
- Suitable amines used to form the phosphonamide include, for example, cyclohexylamine, morpholine, octadecylamine, N,N-dimethyl-1,3-propandiamine, and ammonium hydroxide.
- Suitable phosphonic acids include, for example, aminotri(methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid.
- the treatment composition may comprise a blend of phosphonamides formed by blending together individual phosphonamides or by reacting a blend of two or more amines simultaneously with a phosphonic acid.
- non-solid phosphonamides may be blended with solid phosphonamides to form a solid composition.
- blending phosphonamides provide the advantage of improving water solubility of the final composition thereby providing effective and economical water treatment.
- the treatment composition may also include other components necessary to treat contaminants in the water by mixing these components with the phosphonamide.
- an amino-phosphate ester generally formed from a hydroxy amine and a phosphonic acid may be blended with a phosphonamide.
- Additives such as a hardness control agent may also be included in the final composition.
- the precise quantities of the phosphonamide and phosphonamide blends in the final treatment composition added to the water may vary as desired by the user. Concentrations will generally depend upon the desired formulation of composition, concentration of components in the water, and the type and degree of impurities and contaminants in the water.
- the invention is directed to a composition and method of treating contaminants and impurities in water. More specifically, the composition comprises at least one phosphonamide formed from an amine and a phosphonic acid. Added benefits come from blending different phosphonamides, as well as other components, into the final treatment composition. Generally, phosphonamides are odorless and solid in nature, thereby allowing the inventive composition to be a safe and convenient treatment product. The odorless nature of the phosphonamide eliminates health and safety risks associated with amine odors which are often detected during handling, processing, and manufacture of the product.
- the phosphonamide is generally formed by reacting an amine with a phosphonic acid to affect a corresponding covalent amide bond.
- the amine used to form the corresponding phosphonamide may be any primary or secondary amine.
- the amine may have a general formula HN—R 1 R 2 , where R 1 and R 2 are independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, and heteroaryl organic structures having up to 10 atoms selected from the group consisting of C, N, and O.
- alkyl as used herein, generally refers to a straight or branched hydrocarbon chain of varying length or number of atoms, such as from 1-10 atoms.
- cycloalkyl refers to an unsaturated cyclic ring comprising carbon, nitrogen, or oxygen atoms in the ring.
- aryl refers to an aromatic ring consisting of carbon atoms
- heteroaryl refers to an aromatic ring having heteroatoms including nitrogen and oxygen.
- R 1 and R 2 taken together with a nitrogen to which they are attached, may form a 5- or 6-membered ring containing 0-2 additional heteroatoms selected from nitrogen or oxygen.
- morpholine a cyclic amine wherein R 1 and R 2 taken together forms a 6-member ring containing an oxygen atom at the 4-position
- R 1 and R 2 substitutions may bear other functional groups, such as ethers or amines, which do not participate in the amide bond formation.
- Suitable amines include, but are not limited to, cyclohexylamine, octadecylamine, and N,N-dimethyl-1,3-propanediamine, and even ammonium hydroxide.
- the amines may be purchased commercially from vendors such as Aldrich Chemical Co., or synthesized as desired, to optimize physical and chemical properties of the resulting phosphonamide.
- phosphonic acid generally refers to phosphonic acids having different general formulae which may react with an amine to produce a phosphonamide.
- a phosphonic acid having the general formula (OR) 2 —P(O)OH wherein the R groups may be identical or different is suitable for the invention.
- a phosphonic acid having a general formula (OH) 2 —P(O)OR is also suitable.
- a phosphonamide formed from an amine and a phosphonic acid of the former formula will have a general structure: (OR) 2 —P(O)N—R 1 R 2
- a phosphonamide formed from an amine and a phosphonic acid of the latter formula may have a general structure: RO—P(O)—(N—R 1 R 2 ) 2
- Suitable phosphonic acids for use in the invention may be commercially purchased or synthesized depending upon desired properties of the final treatment composition. Examples of suitable phosphonic acids include, but are not limited to, amino tri(methylene phosphonic acid), 1-hydroxyethylidene-1-1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid.
- the phosphonamide may be purchased commercially, if available, or synthesized using conventional synthetic methods and reagents necessary to form the amide bond.
- the phosphonamide may be formed by mixing the amine and phosphonic acid together using conventional mixing apparatus and methods.
- the amine in desired molar or weight quantities, may be first added to a powder blender.
- the blender may then be activated while a phosphonic acid, in desired molar or weight quantities, is added to the amine.
- reaction of the amine with the phosphonic acid may be sufficiently exothermic to form the amide bond.
- phosphonamides may be utilized to optimize the reaction and provide maximum conversion of the amine and phosphonic acid to the corresponding phosphonamide.
- the reaction mixture precipitates to generate a solid phosphonamide product.
- the resulting phosphonamide is then cooled and processed by conventional techniques to eliminate by-products and catalysts, if any, and to purify the phosphonamide.
- Particularly useful phosphonamides include, without limitation, phosphonamides formed from amines reacted with 1-hydroxyethylidene-1-1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid respectively.
- a composition comprising a blend of more than one phosphonamide.
- blend as used herein, is intended to mean a mixture or combination of more than one component, such as a phosphonamide.
- Phosphonamide blends facilitate formation for a solid treatment composition while optimizing the level and specificity of treatment by utilizing different amines.
- phosphonamide blends have the advantage of minimizing or eliminating hygroscopicity or deliquescence of a treatment composition where one phosphonamide is mildly hygroscopic in nature, i.e., tending to absorb moisture over time, thereby posing a risk to the stability of the phosphonamide and the overall treatment composition.
- blending a non-hygroscopic phosphonamide with a mildly hydroscopic phosphonamide may provide a phosphonamide blend composition which is stable, resistant to absorption of moisture, and has a long shelf life.
- the treatment composition comprises a blend of at least two phosphonamides formed from different amines reacted with a phosphonic acid.
- blending phosphonamides may provide the advantage of improving the water solubility of a final treatment composition which may include a non-water soluble phosphonamide.
- a final treatment composition which may include a non-water soluble phosphonamide.
- One factor influencing the water solubility of a phosphonamide is the hygroscopicity or deliquescent nature of the phosphonamide discussed above.
- Water solubility may be improved by blending desirable hygroscopic or deliquescent components, such as desired phosphonamides, in quantities resulting in a composition having greater solubility characteristics.
- blending a non-hygroscopic phosphonamide with a liquid or semi-solid component, such as an amino-phosphate ester, discussed in more detail further below may improve water solubility of the final composition.
- Blends of phosphonamides may be prepared by combining more than one phosphonamide, each prepared individually, and blending them together.
- blends of phosphonamides may be prepared by mixing different amines, i.e., amines having different R groups, together in a blender, adding a single phosphonic acid to the mixture of amines, and causing the mixture to react to form a mixture or blend of different phosphonamides.
- a mixture of two or more amines in desired molar quantities or weight percent may be blended with a desired phosphonic acid.
- the molar or weight ratios of the amines to phosphonic acid should be in the range of about 1:1 to about 10:1.
- An amine to phosphonic acid mole ratio of equal to or greater than 1:1 will generally allow complete conversion of every amine to a corresponding phosphonamide.
- the blend has an amine to phosphonic acid mole ratio ranging from about 3:2 to about 4:1 to provide adequate water treatment.
- phosphonic acids depending upon the general formula discussed above, may utilize two molecules of amine per molecule of phosphonic acid to form a phosphonamide.
- a phosphonic acids having the general formula (OH) 2 —P(O)OR may react with two molecules of an amine to form a phosphonamide having two moles of the amine per mole of phosphonic acid.
- the corresponding phosphonamide may be completely formed where the amine to phosphonic acid mole ratio is at least 2:1.
- the amount of the phosphonamide, or blends thereof, used to effectively treat water will depend upon the user and other factors such as the level of the impurities and contaminants in the water, the desired water concentration of the phosphonamides, and the desired formulation of the final composition. Effective concentrations of the phosphonamide in the water may generally vary. For example, in a steam boiler, the concentration of the phosphonamide should be in the range of 1-200 ppm for effective treatment of water, and 1-200 ppm for effective treatment of condensate in the boiler feed lines.
- the phosphonamide composition must be added to the water.
- the precise amount will depend upon the particular phosphonamide concentration in the composition.
- the phosphonamide may generally be present in the composition in at least about 10% by weight of the final treatment composition. Water may be more effectively treated where the phosphonamide concentration is higher. Where the composition includes a blend of two or more phosphonamides, it is beneficial to have each individual phosphonamide present in at least about 10% by weight of the final composition.
- the treatment composition includes morpholine-1-hydroxy-ethylidene-1-phosphoryl-phosphonamide, present in a range of about 10% to about 50% by weight, and cyclohexylamine-1-hydroxy-ethylidene-1-phosphoryl-phosphonamide, present in a range of about 10% to about 66% by total weight of the amine component in the final composition.
- Further aspects of the invention include phosphonamides blended with other components to beneficially treat water.
- One such component is an amino-phosphate ester.
- Amino-phosphate esters are particularly useful in treating water at elevated temperatures, such as boiler water and condensate, as the amino-phosphate ester generally degrades at the elevated temperature, at atmospheric or slightly higher pressure to release the hydroxy amine and the phosphonic acid into the water.
- Amino-phosphate esters, depending on the amine, are generally liquids.
- Amino-phosphate esters may generally be formed from a hydroxy amine and a phosphonic acid.
- the hydroxy amine may be any hydroxy amine commercially available from vendors, such as Aldrich Chemical Co.,or synthesized. Hydroxy amines can be synthesized by modifying an amine core molecule to attach the requisite terminal hydroxy group. Conventional methods to incorporate the hydroxy terminus including conversion of a terminal functional group to a hydroxyl group may be used. Such methods are disclosed in Advanced Organic Chemistry, 4 th Ed., authored by Jerry March, published in 1992.
- Suitable hydroxy amines for the amino phosphate ester include N,N-diethylethanolamine, 2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol, and 2-dimethylamino-2-methyl-1-propanol.
- Suitable phosphonic acids used to form the amino-phosphate esters include, without limitation, those suitable for forming the phosphonamides discussed above.
- Preparation of the hydroxyl amine-phosphonic acid ester may be accomplished by synthetic methods as known to persons skilled in the art. For example, the preparation of amino phosphate esters is described in U.S. Pat. No. 3,477,956 and U.S. Pat. No. 3,528,502.
- Blends of phosphonamides and amino-phosphate esters may be prepared by mixing a plurality of amines, including one or more hydroxy amines, with a phosphonic acid in desired molar ratios or weight percent to effectively form the corresponding phosphonamides and amino-phosphate esters.
- the composition includes a blend of morpholine-1-hydroxy-ethylidene-1-phosphoryl-phosphonamide, cyclohexylamine-1-hydroxy-ethylidene-2-phosphoryl-phosphonamide, and diethylaminoethanol-1-hydroxy-ethylidene-1-phosphoryl-phosphate ester wherein each phosphonamide is present in the composition in at least about 10% by weight, and the amino-phosphate ester is present in at least about 10% by weight of the amine.
- the cumulative amine to 1-hydroxy-ethylidene-1,1-diphosphonic acid mole ratio is generally in the range of about 1:1 to about 10:1.
- Such phosphonamide-amino phosphate ester blends provide advantageous compositional properties and water treatment qualities.
- blending one or more phosphonamides with one or more amino-phosphate ester may provide the advantage of optimizing the possibility of a solid composition where one component is hygroscopic or essentially a liquid in nature.
- the blended composition may be formulated into a convenient solid.
- a blend of a mildly hygroscopic morpholine-HEDP amide and a liquid diethylaminoethanol-HEDP ester, with a non-hygroscopic cyclohexylamine-HEDP amide provides a composition which may be a solid where the weight ratio of cyclohexylamine-HEDP amide is about or greater than 25%.
- blend compositions advantageously improve water solubility of the final treatment composition, thereby improving the effectiveness of the water treatment.
- a blend of morpholine-HEDP amide, cyclohexylamine-HEDP amide, and diethylaminoethanol-HEDP ester in the right proportions may have a water solubility of 50 weight percent per volume of water or greater.
- a blend formed from a mixture of morpholine in about 13-14% by weight, cyclohexylamine in about 32-33% by weight, and diethylaminoethanol in about 54% by weight was reacted with 1-hydroxy-ethylidene-1,1-diphosphonic acid at different cumulative amine to 1-hydroxy-ethylidene-1,1-diphosphonic acid mole ratios ranging from about 3:2 to about 4:1 produced blend compositions having advantageous water solubilities in the range of from about 45% to about 80% soluble. In a case where a desirable blend composition has marginal water solubility, then a larger amount of the composition would have to be added to effectively treat the water.
- Additional components which may be added to the inventive composition include, without limitation, additional oxygen scavenging agents, alkalinity control agents, hardness reducing agents, corrosion inhibiting agents, carbonic acid neutralizing agents, and iron controlling agents. These components may be formulated with the phosphonamides, along with amino-phosphate esters, to form an all-in-one treatment composition by the addition of concentrated forms of each component at relative concentrations to allow the formulated treatment composition to be dispensed into the water to attain the desired use concentrations.
- the actual amount of each component added to the concentrated formulation generally depends on, among other factors, the precise intended use concentrations and the concentration of each component as purchased.
- a sulfonated water soluble polymeric hardness control agent such as Versiflex 1, commercially available from Alco, Inc. may be added in about 10% to about 50% by weight of the final composition to reduce hardness in the water.
- a cooling tower treatment composition includes a phosphonamide formed from mixing a cyclohexylamine with 1-hydroxyethylidene-1,1-diphosphonic acid, and having an amine to phosphonic acid mole ratio of from about 2:1 to about 10:1.
- This phosphonamide has the advantage of being a solid.
- cooling tower water may be effectively treated if the phosphonamide is added in an amount to obtain a water concentration in the range of 1-20 ppm.
- composition particularly suited for cooling tower water is the reaction product of cyclohexylamine and HEDP.
- the ratio of amine to HEDP should be in the range of from about 1 to 1 to about 10 to 1.
- cyclohexylamine in about 33% by weight and 1-dihydroxyethylidene-1,1-diphosphonic acid in about 37% by weight can be combined with a copolymer, which may be a liquid, in about 30% by weight, to form a solid.
- a copolymer which may be a liquid, in about 30% by weight
- Such a blend has minimal or no hydroscopicity and has a prolonged shelf life while maintaining the solid form.
- polymers which may be combined with a phosphonamide to treat water in cooling towers include, without limitation, polyacrylate.
- the invention is a composition and method of treating water by adding an amount of a phosphonamide or blends thereof to treat the water.
- the phosphonamide may be applied as a concentrated liquid, a dry powder, or as one of many components in a treatment composition formulated as a concentrated liquid or, more preferably, as a dry powdery solid.
- Phosphonamides do not produce pungent odors typically associated with amines. Furthermore, they provide a solid which can be added to boilers and cooling towers to provide an amine and a phosphate.
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Abstract
The invention is a water treatment composition comprising at least one phosphonamide and blends thereof and a method to treat water. As phosphonamides are generally odorless, and typically solids, phosphonamide and phosphonamide blend compositions are generally odorless, conveniently processed and manufactured, and safely used without risks of exposure to odors and vapors associated with the corresponding amines. Advantageously, phosphonamides blended with amino-phosphate esters provide useful treatment compositions. The inventive compositions are generally used to treat water contained in water flow systems such as boilers and cooling towers.
Description
- This application is related to application Ser. No. 10/231,531, entitled Phosphonamide and Phosphonamide Blend Compositions and Method to Treat Water, filed Aug. 30, 2002 (abandoned), and application Ser. No. 10/348,161, also entitled Phosphonamide and Phosphonamide Blend Compositions and Method to Treat Water, filed Jan. 21, 2003 (allowed Oct. 8, 2004).
- The present invention relates to a composition and method to treat water. More particularly, the invention provides a composition comprising at least one phosphonamide or phosphonamide blends to treat water.
- Water for heating and cooling apparatus must be purified or treated to avoid a plurality of problems. More specifically, boilers and cooling towers require pure water for optimal performance. However, the water coming into these systems is generally impure and contains contaminants which can foul the boilerand cooling tower.
- Feed water is generally contaminated with gases, such as oxygen and carbon dioxide. In addition, water can leach impurities from the air. These impurities lead to scale formation, corrosion, and pitting. A major contaminant in many water systems is iron, often leached from water lines.
- In cooling towers, such problems may escalate due to evaporation of the water, thereby increasing concentration of the contaminants and resulting in a higher rate of subsequent corrosion and deposition tendencies. Higher temperatures also tends to increase corrosion potential. A longer retention time of contaminants in the water coupled with warmer water tends to reduce the effectiveness of heat transfer surfaces and increases the potential for microbiological growth.
- Currently there are a variety of different physical and chemical treatments for contaminated water. Conventional treatments for water systems, such as a boiler, have included the use of amines, particularly to scavenge oxygen and neutralize carbon dioxide. These amines are generally volatile having boiling points comparable to the elevated temperatures achieved in the boiler and generally vaporize into the steam to treat the resulting condensate. However, amines, commonly used to treat water, are typically commercially available only as liquids. Conventional water treatment compositions containing such amines are generally prepared and stored as liquids. These liquid compositions typically emit repugnant and potentially toxic odors which may be detected during manufacture, packaging, or shipping processes, and particularly during the use in treating boiler water.
- Corrosion inhibiting chemicals as disclosed in U.S. Pat. No. 4,066,398 have been used to treat contaminated water. U.S. Pat. No. 3,510,436 discloses the use of organic phosphates or phosphonates in combination with zinc and/or mercaptobenzothiazole for corrosion inhibition in water systems including cooling towers. Compositions utilizing chromates and inorganic polyphosphates have been used to inhibit corrosion of metal surfaces in contact with cooling tower water. However, such treatments are undesirable, both from the viewpoint of handling personnel health and also problems associated with waste disposal. Phosphates are generally non-toxic. However, due to hydrolysis of polyphosphates to orthophosphates and the limited solubility of calcium orthophosphate, which is likely to form, it has been impossible in many instances to maintain adequate concentrations of phosphates. Furthermore, from a water pollution standpoint, effluent containing a sufficiently high phosphate residual, may serve as a nutrient to aquatic life. For these reasons, the use of chromates, inorganic phosphates and other phosphates have been entirely unsatisfactory.
- Thus, there remains a need to provide a composition to treat water in water flow systems effectively and safely, from a health and handling perspective, with minimal waste disposal problems.
- Accordingly, the invention is directed to a composition comprising at least one phosphonamide or blends thereof which may be added in amounts effective to treat water in water flow systems. Forming a phosphonamide from an amine generally eliminates odors and vapors emitted by the corresponding amine. Accordingly, phosphonamides reduce exposure related health and safety risks to the user or handling personnel associated with the preparation, manufacture, packaging, and general application of amines that have been used to treat water. In addition, the generally solid nature of a phosphonamide, or blend of phosphonamides, typically allows the treatment composition to be formulated into a convenient dry solid or powder.
- The phosphonamide is an amine derivativized to an amide by reacting the amine with a phosphonic acid. The phosphonamide may be fully or partially formed depending on the mole ratios and/or weight ratios of the particular amine and phosphonic acid. Typically, amine to phosphonic acid weight ratios of about 1:1 to about 10:1 are suitable.
- Suitable amines used to form the phosphonamide include, for example, cyclohexylamine, morpholine, octadecylamine, N,N-dimethyl-1,3-propandiamine, and ammonium hydroxide. Suitable phosphonic acids include, for example, aminotri(methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid.
- Alternatively, the treatment composition may comprise a blend of phosphonamides formed by blending together individual phosphonamides or by reacting a blend of two or more amines simultaneously with a phosphonic acid. Advantageously, non-solid phosphonamides may be blended with solid phosphonamides to form a solid composition. In addition, blending phosphonamides provide the advantage of improving water solubility of the final composition thereby providing effective and economical water treatment.
- The treatment composition may also include other components necessary to treat contaminants in the water by mixing these components with the phosphonamide. For example, an amino-phosphate ester generally formed from a hydroxy amine and a phosphonic acid may be blended with a phosphonamide. Additives such as a hardness control agent may also be included in the final composition.
- The precise quantities of the phosphonamide and phosphonamide blends in the final treatment composition added to the water may vary as desired by the user. Concentrations will generally depend upon the desired formulation of composition, concentration of components in the water, and the type and degree of impurities and contaminants in the water.
- The present invention will be further appreciated in light of the following detailed description.
- The invention is directed to a composition and method of treating contaminants and impurities in water. More specifically, the composition comprises at least one phosphonamide formed from an amine and a phosphonic acid. Added benefits come from blending different phosphonamides, as well as other components, into the final treatment composition. Generally, phosphonamides are odorless and solid in nature, thereby allowing the inventive composition to be a safe and convenient treatment product. The odorless nature of the phosphonamide eliminates health and safety risks associated with amine odors which are often detected during handling, processing, and manufacture of the product.
- The phosphonamide is generally formed by reacting an amine with a phosphonic acid to affect a corresponding covalent amide bond. The amine used to form the corresponding phosphonamide may be any primary or secondary amine. For example, without limitation, the amine may have a general formula HN—R1R2, where R1 and R2 are independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, and heteroaryl organic structures having up to 10 atoms selected from the group consisting of C, N, and O. The term “alkyl” as used herein, generally refers to a straight or branched hydrocarbon chain of varying length or number of atoms, such as from 1-10 atoms. The term “cycloalkyl”, as used herein, refers to an unsaturated cyclic ring comprising carbon, nitrogen, or oxygen atoms in the ring. The term “aryl”, as used herein, refers to an aromatic ring consisting of carbon atoms, and the term “heteroaryl”, as used herein, refers to an aromatic ring having heteroatoms including nitrogen and oxygen. Alternatively, R1 and R2 taken together with a nitrogen to which they are attached, may form a 5- or 6-membered ring containing 0-2 additional heteroatoms selected from nitrogen or oxygen. For example, morpholine, a cyclic amine wherein R1 and R2 taken together forms a 6-member ring containing an oxygen atom at the 4-position, may be used to form a phosphonamide for the treatment composition. In addition, the R1 and R2 substitutions may bear other functional groups, such as ethers or amines, which do not participate in the amide bond formation.
- Examples of suitable amines include, but are not limited to, cyclohexylamine, octadecylamine, and N,N-dimethyl-1,3-propanediamine, and even ammonium hydroxide. The amines may be purchased commercially from vendors such as Aldrich Chemical Co., or synthesized as desired, to optimize physical and chemical properties of the resulting phosphonamide.
- A variety of phosphonic acids and derivatives thereof may be used to react with the amine. Persons of ordinary skill in the art readily understand that the term “phosphonic acid”, as used herein, generally refers to phosphonic acids having different general formulae which may react with an amine to produce a phosphonamide. For example, a phosphonic acid having the general formula (OR)2—P(O)OH wherein the R groups may be identical or different, is suitable for the invention. Alternatively, a phosphonic acid having a general formula (OH)2—P(O)OR is also suitable. Thus, a phosphonamide formed from an amine and a phosphonic acid of the former formula will have a general structure: (OR)2—P(O)N—R1R2, whereas, a phosphonamide formed from an amine and a phosphonic acid of the latter formula may have a general structure: RO—P(O)—(N—R1R2)2. Suitable phosphonic acids for use in the invention may be commercially purchased or synthesized depending upon desired properties of the final treatment composition. Examples of suitable phosphonic acids include, but are not limited to, amino tri(methylene phosphonic acid), 1-hydroxyethylidene-1-1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid.
- The phosphonamide may be purchased commercially, if available, or synthesized using conventional synthetic methods and reagents necessary to form the amide bond. For instance, the phosphonamide may be formed by mixing the amine and phosphonic acid together using conventional mixing apparatus and methods. For example, the amine, in desired molar or weight quantities, may be first added to a powder blender. The blender may then be activated while a phosphonic acid, in desired molar or weight quantities, is added to the amine. Depending on the class and structure of the amine and particular phosphonic acid, reaction of the amine with the phosphonic acid may be sufficiently exothermic to form the amide bond. Alternatively, heat or catalysts may be utilized to optimize the reaction and provide maximum conversion of the amine and phosphonic acid to the corresponding phosphonamide. With most phosphonamides, as the amide bond forms, the reaction mixture precipitates to generate a solid phosphonamide product. The resulting phosphonamide is then cooled and processed by conventional techniques to eliminate by-products and catalysts, if any, and to purify the phosphonamide. Particularly useful phosphonamides include, without limitation, phosphonamides formed from amines reacted with 1-hydroxyethylidene-1-1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid respectively.
- It is desirable and economical, for optimal water treatment and solid formulation, to use a composition comprising a blend of more than one phosphonamide. The term ‘blend’ as used herein, is intended to mean a mixture or combination of more than one component, such as a phosphonamide. Phosphonamide blends facilitate formation for a solid treatment composition while optimizing the level and specificity of treatment by utilizing different amines. In addition, phosphonamide blends have the advantage of minimizing or eliminating hygroscopicity or deliquescence of a treatment composition where one phosphonamide is mildly hygroscopic in nature, i.e., tending to absorb moisture over time, thereby posing a risk to the stability of the phosphonamide and the overall treatment composition. For example, blending a non-hygroscopic phosphonamide with a mildly hydroscopic phosphonamide may provide a phosphonamide blend composition which is stable, resistant to absorption of moisture, and has a long shelf life. In one embodiment of the invention, the treatment composition comprises a blend of at least two phosphonamides formed from different amines reacted with a phosphonic acid.
- In addition, blending phosphonamides may provide the advantage of improving the water solubility of a final treatment composition which may include a non-water soluble phosphonamide. One factor influencing the water solubility of a phosphonamide is the hygroscopicity or deliquescent nature of the phosphonamide discussed above. Water solubility may be improved by blending desirable hygroscopic or deliquescent components, such as desired phosphonamides, in quantities resulting in a composition having greater solubility characteristics. For example, blending a non-hygroscopic phosphonamide with a liquid or semi-solid component, such as an amino-phosphate ester, discussed in more detail further below, may improve water solubility of the final composition.
- Blends of phosphonamides may be prepared by combining more than one phosphonamide, each prepared individually, and blending them together. Alternatively, blends of phosphonamides may be prepared by mixing different amines, i.e., amines having different R groups, together in a blender, adding a single phosphonic acid to the mixture of amines, and causing the mixture to react to form a mixture or blend of different phosphonamides. For example, a mixture of two or more amines in desired molar quantities or weight percent may be blended with a desired phosphonic acid.
- The molar or weight ratios of the amines to phosphonic acid should be in the range of about 1:1 to about 10:1. An amine to phosphonic acid mole ratio of equal to or greater than 1:1 will generally allow complete conversion of every amine to a corresponding phosphonamide. In one embodiment of the invention, the blend has an amine to phosphonic acid mole ratio ranging from about 3:2 to about 4:1 to provide adequate water treatment. Persons of ordinary skill in the art readily understand that some phosphonic acids, depending upon the general formula discussed above, may utilize two molecules of amine per molecule of phosphonic acid to form a phosphonamide. For instance, a phosphonic acids having the general formula (OH)2—P(O)OR may react with two molecules of an amine to form a phosphonamide having two moles of the amine per mole of phosphonic acid. In this case, the corresponding phosphonamide may be completely formed where the amine to phosphonic acid mole ratio is at least 2:1.
- The amount of the phosphonamide, or blends thereof, used to effectively treat water will depend upon the user and other factors such as the level of the impurities and contaminants in the water, the desired water concentration of the phosphonamides, and the desired formulation of the final composition. Effective concentrations of the phosphonamide in the water may generally vary. For example, in a steam boiler, the concentration of the phosphonamide should be in the range of 1-200 ppm for effective treatment of water, and 1-200 ppm for effective treatment of condensate in the boiler feed lines.
- To obtain such water concentrations, sufficient amounts of the phosphonamide composition must be added to the water. The precise amount will depend upon the particular phosphonamide concentration in the composition. The phosphonamide may generally be present in the composition in at least about 10% by weight of the final treatment composition. Water may be more effectively treated where the phosphonamide concentration is higher. Where the composition includes a blend of two or more phosphonamides, it is beneficial to have each individual phosphonamide present in at least about 10% by weight of the final composition. In one embodiment, the treatment composition includes morpholine-1-hydroxy-ethylidene-1-phosphoryl-phosphonamide, present in a range of about 10% to about 50% by weight, and cyclohexylamine-1-hydroxy-ethylidene-1-phosphoryl-phosphonamide, present in a range of about 10% to about 66% by total weight of the amine component in the final composition.
- Further aspects of the invention include phosphonamides blended with other components to beneficially treat water. One such component is an amino-phosphate ester. Amino-phosphate esters are particularly useful in treating water at elevated temperatures, such as boiler water and condensate, as the amino-phosphate ester generally degrades at the elevated temperature, at atmospheric or slightly higher pressure to release the hydroxy amine and the phosphonic acid into the water. Amino-phosphate esters, depending on the amine, are generally liquids.
- Amino-phosphate esters may generally be formed from a hydroxy amine and a phosphonic acid. The hydroxy amine may be any hydroxy amine commercially available from vendors, such as Aldrich Chemical Co.,or synthesized. Hydroxy amines can be synthesized by modifying an amine core molecule to attach the requisite terminal hydroxy group. Conventional methods to incorporate the hydroxy terminus including conversion of a terminal functional group to a hydroxyl group may be used. Such methods are disclosed in Advanced Organic Chemistry, 4th Ed., authored by Jerry March, published in 1992. Examples of suitable hydroxy amines for the amino phosphate ester include N,N-diethylethanolamine, 2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol, and 2-dimethylamino-2-methyl-1-propanol.
- Suitable phosphonic acids used to form the amino-phosphate esters include, without limitation, those suitable for forming the phosphonamides discussed above. Preparation of the hydroxyl amine-phosphonic acid ester may be accomplished by synthetic methods as known to persons skilled in the art. For example, the preparation of amino phosphate esters is described in U.S. Pat. No. 3,477,956 and U.S. Pat. No. 3,528,502.
- Blends of phosphonamides and amino-phosphate esters may be prepared by mixing a plurality of amines, including one or more hydroxy amines, with a phosphonic acid in desired molar ratios or weight percent to effectively form the corresponding phosphonamides and amino-phosphate esters. For example, in one embodiment of the invention, the composition includes a blend of morpholine-1-hydroxy-ethylidene-1-phosphoryl-phosphonamide, cyclohexylamine-1-hydroxy-ethylidene-2-phosphoryl-phosphonamide, and diethylaminoethanol-1-hydroxy-ethylidene-1-phosphoryl-phosphate ester wherein each phosphonamide is present in the composition in at least about 10% by weight, and the amino-phosphate ester is present in at least about 10% by weight of the amine. In preparing this blend, the cumulative amine to 1-hydroxy-ethylidene-1,1-diphosphonic acid mole ratio is generally in the range of about 1:1 to about 10:1.
- Such phosphonamide-amino phosphate ester blends provide advantageous compositional properties and water treatment qualities. As discussed earlier, blending one or more phosphonamides with one or more amino-phosphate ester may provide the advantage of optimizing the possibility of a solid composition where one component is hygroscopic or essentially a liquid in nature. Depending upon the precise weight ratios of non-deliquescent components relative to the deliquescent components, the blended composition may be formulated into a convenient solid. For example, a blend of a mildly hygroscopic morpholine-HEDP amide and a liquid diethylaminoethanol-HEDP ester, with a non-hygroscopic cyclohexylamine-HEDP amide provides a composition which may be a solid where the weight ratio of cyclohexylamine-HEDP amide is about or greater than 25%.
- Furthermore, such blend compositions advantageously improve water solubility of the final treatment composition, thereby improving the effectiveness of the water treatment. For instance, a blend of morpholine-HEDP amide, cyclohexylamine-HEDP amide, and diethylaminoethanol-HEDP ester in the right proportions may have a water solubility of 50 weight percent per volume of water or greater. For example, a blend formed from a mixture of morpholine in about 13-14% by weight, cyclohexylamine in about 32-33% by weight, and diethylaminoethanol in about 54% by weight, was reacted with 1-hydroxy-ethylidene-1,1-diphosphonic acid at different cumulative amine to 1-hydroxy-ethylidene-1,1-diphosphonic acid mole ratios ranging from about 3:2 to about 4:1 produced blend compositions having advantageous water solubilities in the range of from about 45% to about 80% soluble. In a case where a desirable blend composition has marginal water solubility, then a larger amount of the composition would have to be added to effectively treat the water.
- Additional components which may be added to the inventive composition include, without limitation, additional oxygen scavenging agents, alkalinity control agents, hardness reducing agents, corrosion inhibiting agents, carbonic acid neutralizing agents, and iron controlling agents. These components may be formulated with the phosphonamides, along with amino-phosphate esters, to form an all-in-one treatment composition by the addition of concentrated forms of each component at relative concentrations to allow the formulated treatment composition to be dispensed into the water to attain the desired use concentrations. The actual amount of each component added to the concentrated formulation generally depends on, among other factors, the precise intended use concentrations and the concentration of each component as purchased. For example, in one embodiment, a sulfonated water soluble polymeric hardness control agent, such as Versiflex 1, commercially available from Alco, Inc. may be added in about 10% to about 50% by weight of the final composition to reduce hardness in the water.
- The inventive water treatment compositions are also useful for treating water in cooling towers. The particular treatment composition will generally vary depending upon the quantity of water, the temperature of the water, and the level of contamination. For example, in one embodiment, a cooling tower treatment composition includes a phosphonamide formed from mixing a cyclohexylamine with 1-hydroxyethylidene-1,1-diphosphonic acid, and having an amine to phosphonic acid mole ratio of from about 2:1 to about 10:1. This phosphonamide has the advantage of being a solid. Generally, cooling tower water may be effectively treated if the phosphonamide is added in an amount to obtain a water concentration in the range of 1-20 ppm.
- In one composition particularly suited for cooling tower water is the reaction product of cyclohexylamine and HEDP. The ratio of amine to HEDP should be in the range of from about 1 to 1 to about 10 to 1. Further, cyclohexylamine in about 33% by weight and 1-dihydroxyethylidene-1,1-diphosphonic acid in about 37% by weight, can be combined with a copolymer, which may be a liquid, in about 30% by weight, to form a solid. Such a blend has minimal or no hydroscopicity and has a prolonged shelf life while maintaining the solid form. Examples of polymers which may be combined with a phosphonamide to treat water in cooling towers include, without limitation, polyacrylate.
- Accordingly, the invention is a composition and method of treating water by adding an amount of a phosphonamide or blends thereof to treat the water. The phosphonamide may be applied as a concentrated liquid, a dry powder, or as one of many components in a treatment composition formulated as a concentrated liquid or, more preferably, as a dry powdery solid. Phosphonamides do not produce pungent odors typically associated with amines. Furthermore, they provide a solid which can be added to boilers and cooling towers to provide an amine and a phosphate.
- While the present invention has been illustrated by a description of various embodiments, and while these embodiments have been described in detail, it is not the intention of the applicants to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative methods as shown and described. Accordingly, it is apparent that certain modifications or alterations can be made without departing from the spirit or scope of the invention set forth in the appended claims.
Claims (35)
1. A water treatment composition comprising at least one phosphonamide formed from an amine selected from the group consisting of cyclohexylamine, morpholine, octadecylamine, N,N-dimethyl-1,3-propandiamine, and ammonium hydroxide, and
a phosphonic acid selected from the group consisting of aminotri(methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid, and blends thereof to treat water.
2. The composition of claim 1 wherein the blend comprising at least two phosphonamides formed from at least two amines and a phosphonic acid, said blend having a cumulative amine to phosphonic acid mole ratio in the range of from about 1:1 to about 10:1.
3. The composition of claim 1 further comprising an amino-phosphate ester formed from a hydroxyamine and a phosphonic acid.
4. The composition of claim 1 further comprising a hardness control agent.
5. The composition of claim 1 wherein the phosphonamide is present in at least about 10% by weight of the composition.
6. The composition of claim 1 wherein the composition is a solid.
7. The composition of claim 2 wherein the phosphonamide is present in at least about 10% by weight of the composition.
8. The composition of claim 3 wherein the amino-phosphate ester is present in at least about 10% by weight of the composition.
9. The composition of claim 3 wherein the hydroxyamine is selected from the group consisting of N,N-diethylethanolamine, 2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol, and 2-dimethylamino-2-methyl-1-propanol.
10. The composition of claim 4 wherein the hardness control agent is a sulfonated water soluble polymeric compound.
11. A water treatment composition comprising a blend of:
at least two phosphonamides formed from at least two amines independently selected from the group consisting of cyclohexylamine, morpholine, octadecylamine, N,N-dimethyl-1,3-propanediamine, and ammonium hydroxide, and a first phosphonic acid; and
an amino-phosphate ester formed from a hydroxyamine selected from the group consisting of N,N-diethylethanolamine, 2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol, and 2-dimethylamino-2-methyl-1-propanol, and a second phosphonic acid,
said blend having a cumulative amine to cumulative phosphonic acid mole ratio in the range of from about 1:1 to about 10:1, and used to treat water.
12. The composition of claim 11 wherein the first phosphonic acid is the same as the second phosphonic acid.
13. The composition of claim 11 wherein the first and second phosphonic acids are independently selected from the group consisting of polyphosphoric acid, aminotri(methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid.
14. The composition of claim 1 comprising a blend of:
a morpholine-1-hydroxy-ethylidene-phosphoryl-phosphonamide present in at least about 10% by weight;
a cyclohexylamine-1-hydroxy-ethylidene-phosphoryl-phosphonamide present in at least about 10% by weight; and
a diethylaminoethanol-1-hydroxy-ethylidene-phosphoryl-phosphonate ester present in at least about 10% by weight of the blend,
said blend being formed from a mixture of morpholine, cyclohexylamine, and N,N-diethylethanolamine reacted with 1-hydroxy-ethylidene-1,1-di-phosphonic acid and having a cumulative amine to 1-hydroxy-ethylidene-1,1-di-phosphonic acid mole ratio in the range of from about 1:1 to about 10:1.
15. A method of treating water comprising the step of:
adding to water at least one phosphonamide formed from a reaction between an amine and a phosphonic acid, in an amount sufficient to treat the water.
16. The method claimed in claim 15 wherein the amine is of the general formula HN—R1R2 wherein R1 and R2 independently are selected from the group consisting of H, alkyl, cycloalkyl, aryl, and heteroaryl organic structures having up to 10 atoms selected from the group consisting of C, N, and O,
and wherein R1 and R2 taken together with the nitrogen to which they are attached can form a 5 or 6 membered ring containing 0-2 additional heteroatoms selected from N or O, and
the phosphonic acid is of the general formula (OR)2—P(O)OH wherein each R independently is selected from the group consisting of H, alkyl, cycloalkyl, aryl, and heteroaryl organic structures having up to 10 atoms selected from the group consisting of C, N and O.
17. The method claimed in claim 15 wherein the amine is selected from the group consisting of cyclohexylamine, morpholine, octadecylamine, N,N-dimethyl-1,3-propanediamine, and ammonium hydroxide.
18. The method claimed in claim 15 wherein the phosphonic acid is selected from the group consisting of polyphosphoric acid, aminotri(methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid.
19. The method claimed in claim 15 comprising adding to the water a blend of at least two phosphonamides formed from different amines and a phosphonic acid, wherein said blend has a cumulative amine to phosphonic acid mole ratio in the range of from about 1:1 to about 10:1.
20. The method claimed in claim 15 further comprising adding to the water an amino-phosphate ester formed from a hydroxyamine and a phosphonic acid.
21. The method claimed in claim 15 further comprising adding to the water a hardness control agent.
22. The method claimed in claim 15 wherein the phosphonamide is present in at least about 10% by weight of the composition.
23. The method claimed in claim 15 wherein the composition is a solid.
24. The method claimed in claim 19 wherein each phosphonamide is present in at least about 10% by weight of the composition.
25. The method claimed in claim 20 wherein the amino-phosphate ester is present in at least about 10% by weight of the composition.
26. The method claimed in claim 20 wherein the hydroxyamine is selected from the group consisting of N,N-diethylethanolamine, 2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol, and 2-dimethylamino-2-methyl-1-propanol.
27. The method claimed in claim 15 wherein the composition is added to boiler water to treat water in a boiler and boiler feedlines.
28. The method claimed in claim 15 wherein the composition is added to water in a cooling tower.
29. The method claimed in claim 21 wherein the hardness control agent is a sulfonated water soluble polymeric compound.
30. The method claimed in claim 15 comprising adding to water an amount of a blend of:
at least two phosphonamides formed from at least two different amines selected from the group consisting of cyclohexylamine, morpholine, octadecylamine, N,N-dimethyl-1,3-propanediamine, and ammonium hydroxide, and a first phosphonic acid; and
an amino-phosphate ester formed from a hydroxyamine selected from the group consisting of N,N-diethylethanolamine, 2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol, and 2-dimethylamino-2-methyl-1-propanol, and a second phosphonic acid,
wherein the blend has a cumulative amine to cumulative amine to phosphonic acid mole ratio in the range of from about 1:1 to about 10:1.
31. The method claimed in claim 30 wherein the first acid is the same as the second acid.
32. The method claimed in claim 30 wherein the first and second phosphonic acids are independently selected from the group consisting of polyphosphoric acid, aminotri(methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphono-butane-1,2,4-tricarboxylic acid.
33. The method claimed in claim 15 comprising adding to water an amount of a blend of:
a morpholine-1-hydroxy-ethylidene-phosphoryl-phosphonamide formed from morpholine present in a range of from about 10% to about 50% by weight and 1-hydroxy-ethylidene-1,1-di-phosphonic acid;
a cyclohexylamine-1-hydroxy-ethylidene-phosphoryl-phosphonamide formed from cyclohexylamine present in a range of from about 10% to about 66% by weight and 1-hydroxy-ethylidene-1,1-di-phosphonic acid; and
a diethylaminoethanol-1-hydroxy-ethylidene-phosphoryl-phosphonate ester formed from diethylaminoethanol present in a range of from about 10% to about 70% by weight and 1-hydroxy-ethylidene-1,1-di-phosphonic acid,
wherein the cumulative amine to 1-hydroxy-ethylidene-1,1-di-phosphonic acid weight ratio is in the range of from about 1:1 to about 10:1.
34. The method claimed in claim 33 wherein the blend is added to boiler water to treat water in a boiler and boiler feedlines.
35. The method claimed in claim 15 comprising adding to water in a cooling tower:
a cyclohexylamine-1-hydroxy-ethylidene-phosphoryl-phosphonamide formed from cyclohexylamine and 1-hydroxy-ethylidene-diphosphonic acid and having a cyclohexylamine to 1-hydroxy-ethylidene-diphosphonic acid mole ratio in the range of from about 1:10 to about 2:1, and
a copolymer,
in an amount sufficient to treat the water.
Priority Applications (2)
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US11/015,781 US20050104031A1 (en) | 2003-01-21 | 2004-12-17 | Phosphonamide and phosphonamide blend compositions and method to treat water |
US11/258,301 US7077976B2 (en) | 2002-08-30 | 2005-10-25 | Phosphonamide and phosphonamide blend compositions to treat water |
Applications Claiming Priority (2)
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US10/348,161 US6846419B2 (en) | 2002-08-30 | 2003-01-21 | Phosphonamide and phosphonamide blend compositions and method to treat water |
US11/015,781 US20050104031A1 (en) | 2003-01-21 | 2004-12-17 | Phosphonamide and phosphonamide blend compositions and method to treat water |
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US10/348,161 Division US6846419B2 (en) | 2002-08-30 | 2003-01-21 | Phosphonamide and phosphonamide blend compositions and method to treat water |
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CN110015764A (en) * | 2019-03-11 | 2019-07-16 | 江苏新亿源环保科技有限公司 | A kind of preparation method of antisludging agent |
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US7880770B2 (en) * | 2006-07-28 | 2011-02-01 | Accelerated Pictures, Inc. | Camera control |
WO2008014487A2 (en) * | 2006-07-28 | 2008-01-31 | Accelerated Pictures, Inc. | Scene organization in computer-assisted filmmaking |
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US20060131241A1 (en) | 2006-06-22 |
US7077976B2 (en) | 2006-07-18 |
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