WO2001096493A1 - Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid - Google Patents
Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid Download PDFInfo
- Publication number
- WO2001096493A1 WO2001096493A1 PCT/US2001/040902 US0140902W WO0196493A1 WO 2001096493 A1 WO2001096493 A1 WO 2001096493A1 US 0140902 W US0140902 W US 0140902W WO 0196493 A1 WO0196493 A1 WO 0196493A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethylene glycol
- antifreeze
- heat transfer
- transfer fluid
- composition
- Prior art date
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 395
- 230000002528 anti-freeze Effects 0.000 title claims abstract description 59
- 239000012141 concentrate Substances 0.000 title claims abstract description 53
- 239000013529 heat transfer fluid Substances 0.000 title claims abstract description 52
- 231100000252 nontoxic Toxicity 0.000 title description 10
- 230000003000 nontoxic effect Effects 0.000 title description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 257
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 31
- 239000000729 antidote Substances 0.000 claims abstract description 22
- 208000021241 Ethylene glycol poisoning Diseases 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 59
- 239000012530 fluid Substances 0.000 claims description 43
- 238000009835 boiling Methods 0.000 claims description 16
- 238000005260 corrosion Methods 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 9
- 239000000872 buffer Substances 0.000 claims description 8
- 239000002455 scale inhibitor Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000013530 defoamer Substances 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims 5
- 239000002826 coolant Substances 0.000 abstract description 27
- 231100000419 toxicity Toxicity 0.000 abstract description 21
- 230000001988 toxicity Effects 0.000 abstract description 21
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 25
- 238000009472 formulation Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 12
- 241000700159 Rattus Species 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 231100001261 hazardous Toxicity 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 231100000331 toxic Toxicity 0.000 description 7
- 230000002588 toxic effect Effects 0.000 description 7
- 208000005374 Poisoning Diseases 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 231100000572 poisoning Toxicity 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- -1 Alkylene glycols Chemical class 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 210000003734 kidney Anatomy 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 206010058667 Oral toxicity Diseases 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 231100000460 acute oral toxicity Toxicity 0.000 description 3
- 239000012223 aqueous fraction Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 231100000418 oral toxicity Toxicity 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 231100000171 higher toxicity Toxicity 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 150000002913 oxalic acids Chemical class 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100001228 moderately toxic Toxicity 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 231100000916 relative toxicity Toxicity 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical class [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
Definitions
- the present invention relates to a non-hazardous, reduced toxicity ethylene glycol- based antifreeze/heat transfer fluid concentrate comprised of (1) ethylene glycol, (2) an antidote for ethylene glycol poisoning that has a boiling point above about 150 degrees Celsius, preferably propylene glycol, and optionally (3) selected additives to impart desirable characteristics or properties to the concentrate.
- the concentrate may be combined with water to form an antifreeze/heat transfer fluid, such as a coolant for internal combustion engines.
- antifreeze/heat transfer fluid concentrates have been used to form aqueous solutions used to cool internal combustion engines. These concentrates have also been used for deicing solutions used, for example, to deice airplanes or power lines.
- Alkylene glycols are often used as the base material for these antifreeze/heat transfer fluid concentrates. Alkylene glycols typically make up 95% by weight of the antifreeze/heat transfer fluid concentrate and, after blending with water, about 40% to 60% by volume of the solution used for cooling the engine in a vehicle.
- Conventional antifreeze/heat transfer fluid concentrates have for years been formulated using ethylene glycol (EG) as the base material.
- EG ethylene glycol
- EG has proved to be an efficient and cost effective means of providing freezing and boiling protection for engine coolants.
- EG is used in a variety of other applications, including production of polyethylene terephthalate for use in polyester films, fibers, and resins.
- Water - the primary heat removal fluid is typically 40% to 70% by volume depending upon the severity of the winter climate. In some warm weather areas, freezing temperatures are not encountered, and water with a corrosion prevention additive is used, or EG is added solely to raise the boiling point of the coolant solution.
- Addition of EG also raises the boiling point of the solution, and the same range of ethylene glycol is typically used during the summer in temperate regions and year round in warmer climates.
- Additive Package - containing several different chemicals that are initially added to the glycol to form an antifreeze or concentrate and eventually blended with water to form the coolant. These additives are designed to prevent corrosion, deposit formation, and foaming, and are typically each present, in concentrations of 0.1% to 3% by weight of the final coolant.
- LD50 values acute oral toxicity ratings are useful in comparing the relative toxicities of substances.
- the LD 5 o value for a substance is the dose level (in mg/kg of body weight) administered at the beginning of a two week period, required to kill 50 percent of a group of laboratory rats.
- a coolant material that has an LD 5 o value of 5,000 mg/kg or lower may be classified as hazardous, with lower LD 5 o ratings indicative of increased toxicity.
- EG has an acute oral toxicity (LD 50 ) of 4,700 mg/kg. Although marginally hazardous by this rating system, EG is a known toxin to humans at relatively low levels (reported as low as 1,570 mg/kg) and consequently is classified by many regulatory authorities as a hazardous material. When ingested, EG is metabolized to glycolic and oxalic acids, which leads to an acid-base disturbance and results in kidney damage. In addition, EG has a sweet smell and taste, making it attractive to children and animals.
- An accepted means for estimating the toxicity of a formulation containing several components is by a calculation method using the acute oral toxicity rating of each component.
- the LD 5 o value of each formulation component is divided into the component's weight fraction in the formulation, and this "reciprocal" value is added to that of all the other components.
- the sum of this calculation is then divided into 1 and this is an estimate of the LD 5 o of the formulation.
- the calculation method described above is used in Table 1 to estimate the LD 5 o value of the standard ASTM antifreeze/coolant formulation, GM-6038.
- ethylene glycol is the largest single component in the formulation, and its LD 5 o value largely determines the estimated formulation LD 5 o Because they are present in very low concentrations, the small contribution of the Pluronic L-61 and the dye were not considered. Also, the water present to solubilize the additives will tend to dilute the toxic effects of the other components and raise the LD 5 o level of the formulation. The water is assumed to add no toxicity.
- Additive packages may be added to an antifreeze/heat transfer fluid concentrate to replenish inhibitors.
- Supplemental coolant additives (SCAs) used to replenish inhibitors will often consist of from 5 to 15 different chemicals. These additives, as shown below, are broken down into major and minor categories depending on the amount used in an engine antifreeze/heat transfer fluid formulation:
- the toxicity of some antifreeze/heat transfer fluid additives is affected by their alkalinity.
- the more alkaline forms of silicate, phosphate, and borate have lower LD 5 o values, and accordingly have a higher toxicity rating.
- the more alkaline metaborate Na B 2 0 .4H 2 O
- sodium silicate with an SiO /Na 2 O ratio of 1 has an LD 50 value of 600 mg/kg as compared to 1,600 mg/kg for the less alkaline silicate with an SiO 2 /Na 2 O ratio of 2.
- the toxicity, or more appropriately the skin corrosiveness, of metasilicate (pH 13 @ 5%) is greatly neutralized when blended into an antifreeze/heat transfer fluid with a pH in the range of 10.
- the best example of this is the blending of phosphoric acid with potassium hydroxide in an antifreeze coolant or liquid SCA.
- the end product is a mildly alkaline salt which exhibits much less toxicity and corrosiveness than the starting materials.
- the chemicals that may be included in an antifreeze/heat transfer fluid additive package have many common uses. Some of these chemicals, such as adipate, benzoate, carbonate, nitrite, phosphate, and silicate, are used in foods. Even nitrite, which has the lowest LD 50 (i.e., the highest oral toxicity) of any of the common additives, is used as a food preservative and in medicines. Borate, benzo triazole, carbonate, phosphate, silicate, and triethanolamine are used in soaps and detergents. As with all chemical products, additive chemicals should be handled with care, but in a formulated engine antifreeze/heat transfer fluid, these chemicals present no extraordinary health risk.
- overflows account for far more antifreeze/heat transfer fluid loss than low level leaks at the water pump, hose clamps or radiator core. Overflows occur due to overheating or when a cooling system is overfilled. When a cooling system is overfilled, operation of the engine heats the antifreeze/heat transfer fluid, causing expansion of the fluid that cannot be contained in the system. Pressure relief valve lines typically allow excess fluid to escape to the ground. Small EG spills and leaks (less than a gallon) of antifreeze/heat transfer fluid eventually will biodegrade with little impact to the environment. However, before biodegradation occurs, these spills and leaks can present a toxic danger to pets and wildlife.
- EG Ethylene Glycol
- the use of EG mixed with water in an engine coolant solution can also result in release of concentrated EG into the environment.
- the vapor pressure of water is 600 mm Hg, while the vapor pressure of EG at that temperature is just 10 mm Hg.
- Antifreeze/heat transfer fluid solutions used in internal combustion engines will typically start as 50% antifreeze (95% of the antifreeze being EG) and 50% water. Due to the difference in vapor pressure between water and EG, the solution will tend to become more concentrated in EG as water evaporates through "breathing" of the cooling system. Also as a result of the vapor pressure difference, heated antifreeze/heat transfer fluid solution that has been expelled from a cooling system will readily concentrate toward straight EG in the environment, increasing its oral toxicity. The hotter the solution expelled from the cooling system, the more rapidly the water content will pass into the atmosphere, leaving the more concentrated EG behind.
- PG propylene glycol
- PG has an LD 50 value of 20,000 mg/kg as compared to EG's 4,700 mg/kg.
- PG is so non-toxic that it is approved by the U.S. Food and Drug Administration as a food additive.
- the greatest impediment to more widespread usage of PG as a base fluid for antifreeze/heat transfer fluid concentrates is its relatively high cost as compared to EG.
- PG has been used in some applications, EG remains the antifreeze base fluid of choice among the world's major antifreeze/heat transfer fluid concentrate manufacturers.
- the present invention relates to the homogeneous blending of an antidote into an ethylene glycol based antifreeze/heat transfer fluid concentrate, whereby the blended fluid is rendered essentially non-toxic in its concentrated form, and remains non-toxic when admixed with water for use as a heat transfer fluid or an engine antifreeze/coolant.
- the invention relates to blending of propylene glycol into an ethylene glycol based antifreeze/heat transfer fluid concentrate, thereby reducing the toxicity of the antifreeze/heat transfer fluid concentrate and rendering the resulting product essentially non- toxic.
- Buffers, corrosion inhibitors, dyes, scale inhibitors and other additives may be added to the antifreeze/heat transfer fluid concentrate to impart desired characteristics to the final product.
- One advantage of the present invention is the formulation of an antifreeze/heat transfer fluid concentrate that is safe and non-toxic in all forms of storage: single gallon containers, 55 gallon drums, or any size of open container.
- the present invention results in a concentrate which is safe in the home, in chain stores and markets, and when drained from a heat exchange system (for example engines, and heating systems) and is subsequently left uncovered in the environment.
- Another advantage of the present invention is formulation of a concentrate that remains safe when lost to the environment through a heat exchange system's vent, or by system leaks.
- the formulation of the invention assures that when the water fraction of the system's heat transfer fluid evaporates due to its high vapor pressure, the reduced EG rich fluid left behind remains essentially non-toxic.
- Yet another advantage of the invention is to insure that the formulated antidote ingredient does not substantially reduce the anti-corrosive, or the freeze and boil point protection of the fluid to which it is added.
- the present invention relates to an ethylene glycol (EG) based antifreeze/heat transfer fluid concentrate that is rendered essentially and permanently non-toxic by the addition of an antidote in a range from a minor fraction to a major fraction (by weight) of the concentrate.
- the antidote combines completely and forms a homogeneous mixture with the EG.
- Preferred embodiments of the invention are described below. The preferred embodiments disclosed herein are to be considered exemplary of the principles of the present invention and are not intended to limit the invention to the embodiments described. Various modifications will be apparent to those skilled in the art based on the teachings herein without departing from the scope or spirit of the invention disclosed herein.
- antidote means a substance that prevents or counteracts the toxic effects of ethylene glycol. While not relying upon or limited to any particular theory or means by which the antidote may function, it is believed that in the preferred embodiment described below, the antidote effectively blocks the metabolism of EG and eliminates, or minimizes, the formation of glycolic and oxalic acids in the body. The acid-base disturbance within the kidneys well known to EG poisoning is thereby eliminated or minimized and the toxic effects of EG are eliminated.
- PG is added to EG as an antidote for EG toxicity and poisoning.
- EG (1,2-ethandiol) and PG (1,2-propandiol) are similarly structured chemicals. When their liquid forms are mixed, EG and PG will completely combine to form a homogeneous mixture at virtually any ratio of the two fluids.
- additives can be included in the propylene glycol/ethylene glycol mixture to impart desirable properties for particular applications.
- corrosion inhibitors, buffers, dyes, defoamers, scale inhibitors, surfactants and chelants may be added in appropriate amounts as desired.
- Sodium borates, sodium silicates, sodium phosphates, sodium nitrate, sodium nitrite, sodium molybdate, tolytriozolene or any other appropriate additive known to those skilled in the art can be included in the ethylene glycol/propylene glycol mixture.
- a heat transfer fluid concentrate is made by blending ethylene glycol with propylene glycol together with nine additives, including a small amount of water.
- EG portion of the concentrate that is comprised of glycols
- PG percent by weight
- Toxicity testing of EG/PG blends was conducted for comparison to the theoretical values, and the results of that testing provided surprising and unexpected.
- Testing of the 50/50 EG/PG mixture was conducted to determine whether the calculated LD 50 level of 7289 mg/kg had actually been achieved. The tests were conducted at a laboratory approved by the United States Environmental Protection Agency (EPA) using standard "GPL" test procedures as described in the United States Food and Drug Administration Regulations, 21 C.F.R. Part 58 and EPA Good Laboratory Practice Standards 40 C.F.R. Part 792. Limit tests and range tests were conducted in preparation for determining the LD 50 value.
- a range test is a series of limit tests that establishes a range within which an LD 50 values lies.
- Range tests showed no ill effects on the laboratory rats at doses of 7,000 mg/kg or at doses of 11,000 mg/kg. Accordingly, the LD 50 value for this EG/PG blend is necessarily substantially above 11,000 mg/kg, a very safe level.
- the mixtures have been proven to: (1) have substantially higher LD 50 values (greater than 11,000 mg/kg) than previously known or anticipated, (2) to have LD 50 levels which were extremely safe and non-hazardous, and (3) possess an unforeseen LD 50 reserve level which would allow for substantial inadvertent dilutions of EG concentrate. Additionally, the EG/PG blended fluid remains "safe" in all stored or in use conditions due to the similar saturation temperatures, and vapor pressure of the EG and PG base fluids.
- a heat transfer fluid concentrate contains about 30% PG by weight and about 70%) EG by weight. At this concentration, the PG functions as an antidote for ethylene glycol poisoning.
- the concentrate may also include additives as desired for buffering, corrosion inhibiting, defoaming, dying, scale inhibiting, surfacting, or chelating, and at least enough water to keep any of the additives used, that require water to be in solution, dissolved.
- the EG and PG portion of the entire formulation would typically be about 95 weight percent of the concentrate, the additive portion would be about 1.5 weight percent of the concentrate, and water would be about 3.5 weight percent of the concentrate.
- the concentrate can also be formulated to contain more water if a more diluted heat transfer fluid is desired.
- the concentrate may also be combined with water to form a coolant solution for use in an internal combustion engine. In either case, the EG plus PG portion and the additive portion of the formulation is decreased on a weight percent basis of the solution.
- the relative ratio of PG to EG in these diluted formulations will remain the same, that is, the PG will remain at about 30 weight percent of the sum of the weights of the EG and the PG in the solutions.
- PG as an antidote for EG toxicity is especially useful in fluids that are used as antifreezes or coolants in engines. After they are mixed together, EG and PG remain chemically stable and remain permanently mixed in a homogeneous fluid blend where neither fluid will separate from the other. The result is a fluid which will remain "as blended" at any ratio of one to the other. This stability of the blended fluids is important for long term storage of heat transfer fluid concentrates formed by combinations of these materials.
- the combined EG/PG solution fraction When heat is applied to the blended EG/PG concentrate, or to a coolant solution containing an EG/PG blend admixed with water, the combined EG/PG solution fraction will remain stable and will not separate. Also, the proportions of EG and PG present in the heated mixture will remain relatively constant. The tendency of the two fluids to remain combined and act as one when heated is due to their very close boiling points. EG has a boiling point of 390°F (198.8°C) at atmospheric pressure, while PG a has a boiling point of 369°F (187.2°C) at atmospheric pressure. As a result, when combined and heated, the two fluids will boil off at about the same rate, and their proportions relative to each other in the remaining fluid will not change significantly.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Fuel Cell (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA02012231A MXPA02012231A (en) | 2000-06-10 | 2001-06-08 | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid. |
AU2001287159A AU2001287159A1 (en) | 2000-06-10 | 2001-06-08 | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
EP01966666A EP1303573A4 (en) | 2000-06-10 | 2001-06-08 | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
CA2421813A CA2421813C (en) | 2000-06-10 | 2001-06-08 | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
JP2002510616A JP4812227B2 (en) | 2000-06-10 | 2001-06-08 | Non-toxic ethylene glycol antifreeze / heat transfer fluid concentrate and antifreeze / heat transfer fluid |
KR10-2002-7016816A KR100506550B1 (en) | 2000-06-10 | 2001-06-08 | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21068000P | 2000-06-10 | 2000-06-10 | |
US60/210,680 | 2000-06-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001096493A1 true WO2001096493A1 (en) | 2001-12-20 |
Family
ID=22783835
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/040902 WO2001096493A1 (en) | 2000-06-10 | 2001-06-08 | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
Country Status (9)
Country | Link |
---|---|
US (2) | US20020020828A1 (en) |
EP (1) | EP1303573A4 (en) |
JP (2) | JP4812227B2 (en) |
KR (1) | KR100506550B1 (en) |
CN (1) | CN100482762C (en) |
AU (1) | AU2001287159A1 (en) |
CA (1) | CA2421813C (en) |
MX (1) | MXPA02012231A (en) |
WO (1) | WO2001096493A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1320575A4 (en) * | 2000-07-19 | 2009-08-26 | Evans Cooling Systems Inc | Non-aqueous heat transfer fluid and use thereof |
WO2009103380A1 (en) * | 2008-02-21 | 2009-08-27 | Takata-Petri Ag | Airbag module for a motor vehicle |
WO2014068367A1 (en) | 2012-10-30 | 2014-05-08 | Istanbul Kurumsal Pazarlama Danismanlik Kimya Sanayi Ve Ticaret Anonim Sirketi | An energy saving fluid |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020020828A1 (en) * | 2000-06-10 | 2002-02-21 | Evans John W. | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
US20020033470A1 (en) * | 2000-07-19 | 2002-03-21 | Evans John W. | Non-aqueous heat transfer fluid and use thereof |
CN1507485A (en) | 2001-03-10 | 2004-06-23 | ���ܿ���ϵͳ����˾ | Reduced toxicity ethylene glycol-based antifreeze-heat transfer fluid concentrates and antifreeze/heat transfer flulds |
US20070090324A1 (en) * | 2005-10-21 | 2007-04-26 | Virgil Flanigan | Antifreeze/liquid coolant composition and method of use |
CN101671549A (en) * | 2008-09-10 | 2010-03-17 | 郝克强 | Non-aqueous system internal-combustion engine cooling liquid |
CN104497993B (en) * | 2014-12-09 | 2017-10-24 | 广东三和化工科技有限公司 | A kind of anti-icing fluid and preparation method thereof |
CN104845594B (en) * | 2015-05-04 | 2018-03-06 | 宁波保税区韬鸿化工科技有限公司 | Life-cycle water-free cooling solution |
BR112017023945B8 (en) * | 2015-05-07 | 2022-01-25 | Evans Cooling Systems Inc | Method for cooling an internal combustion engine having a circulating liquid engine cooling system using an ethylene glycol based heat transfer fluid |
CN105484322A (en) * | 2015-12-23 | 2016-04-13 | 武汉广益交通科技股份有限公司 | Anti-freezing preservative for cold region tunnel fire protection and use method thereof |
WO2020196509A1 (en) * | 2019-03-26 | 2020-10-01 | 株式会社デンソー | Heat transportation medium and heat transportation system using same |
JP7291512B2 (en) * | 2019-03-26 | 2023-06-15 | 株式会社デンソー | heat transfer system |
JP7291511B2 (en) * | 2019-03-26 | 2023-06-15 | 株式会社デンソー | heat transfer system |
JP2020159612A (en) * | 2019-03-26 | 2020-10-01 | 株式会社デンソー | Heat transport system |
JP2020159610A (en) * | 2019-03-26 | 2020-10-01 | 株式会社デンソー | Heat transport system |
CN112724942A (en) * | 2021-02-28 | 2021-04-30 | 资源县枫木衡温汽车冷却液制造厂 | All-weather nano anhydrous cooling liquid and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55125181A (en) * | 1979-03-22 | 1980-09-26 | Wako Pure Chem Ind Ltd | Antifreezing agent |
JPH0331388A (en) * | 1989-06-27 | 1991-02-12 | Nippon Oil Co Ltd | Freezing-preventive composition |
WO1996037570A1 (en) * | 1995-05-24 | 1996-11-28 | Evans Cooling Systems, Inc. | Non-aqueous heat transfer fluid and use thereof |
US5817252A (en) * | 1997-04-16 | 1998-10-06 | Octagon Process Inc. | Deicing and anti-icing composition for aircraft |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1031556A (en) * | 1973-07-19 | 1978-05-23 | The Dow Chemical Company | Method for reducing the strength of ice |
US4382870A (en) * | 1981-07-06 | 1983-05-10 | Northern Petrochemical Company | Antifreeze corrosion inhibitor composition for aluminum engines |
US4455248A (en) * | 1982-06-01 | 1984-06-19 | Shell Oil Company | Antifreeze compositions |
US4452715A (en) * | 1982-10-25 | 1984-06-05 | Basf Wyandotte Corporation | High pH coolant containing carbonate ion |
DE3390316C2 (en) * | 1982-11-18 | 1994-06-01 | Evans Cooling Ass | Method and cooling system for evaporative cooling of internal combustion engines |
US4545925A (en) * | 1984-05-07 | 1985-10-08 | Norchem, Inc. | Corrosion inhibited freeze protected heat transfer fluid |
US4550694A (en) * | 1984-05-11 | 1985-11-05 | Evans Cooling Associates | Process and apparatus for cooling internal combustion engines |
US4561990A (en) * | 1984-10-04 | 1985-12-31 | Texaco Inc. | High lead solder corrosion inhibitors |
US4717495A (en) * | 1984-11-30 | 1988-01-05 | Fleetguard, Inc. | Diesel engine cooling system compositions |
FR2579613B1 (en) * | 1985-03-26 | 1987-05-15 | Bp Chimie Sa | APPLICATION OF A NON-AQUEOUS FLUID BASED ON ALCOYLENEGLYCOL MONOETHER AS A HEAT TRANSFER |
US4758367A (en) * | 1986-05-22 | 1988-07-19 | Union Carbide Corporation | Triethylene glycol-based heat transfer fluids |
US4743393A (en) * | 1986-06-06 | 1988-05-10 | Basf Corporation | Antifreeze concentrates and coolants containing heteropolymolybdate compounds |
US4698172A (en) * | 1986-08-04 | 1987-10-06 | Fmc Corporation | Aircraft anti-icing fluid containing carrageenan |
US4978469A (en) * | 1987-05-15 | 1990-12-18 | Ecolab Inc. | Cleaning composition suitable for the cleaning of sub-freezing surfaces |
US4759864A (en) * | 1987-09-04 | 1988-07-26 | Texaco Inc. & S.A. Texaco Petro, N.V. | Corrosion-inhibited antifreeze formulation |
US4946616A (en) * | 1988-11-14 | 1990-08-07 | The Dow Chemical Company | Heat transfer fluids containing dicarboxylic acid mixtures as corrosion inhibitors |
US5085791A (en) * | 1990-10-01 | 1992-02-04 | Texaco Chemical Company | Corrosion-inhibited antifreeze/coolant composition containing cyclohexane acid(s) |
US5085793A (en) * | 1990-11-19 | 1992-02-04 | Texaco Chemical Company | Corrosion-inhibited antifreeze/coolant composition |
US5422026A (en) * | 1990-12-14 | 1995-06-06 | Arco Chemical Technology, L.P. | Phosphate-free antifreeze formulation |
US5240631A (en) * | 1991-11-13 | 1993-08-31 | Arco Chemical Technology, L.P. | Antifreeze formulation containing phosphorous acid |
EP0564721B1 (en) * | 1992-04-06 | 1997-06-04 | Texaco Services (Europe) Ltd. | Corrosion-inhibiting antifreeze formulations |
CA2106804A1 (en) * | 1992-09-24 | 1994-03-25 | James A. Lott | Antifreeze compositions and uses |
US5385688A (en) * | 1993-01-08 | 1995-01-31 | American Polywater Corporation | Antifreeze gel composition for use in a cable conduit |
BR9407438A (en) * | 1993-09-10 | 1996-04-09 | Evans Cooling Systems Inc | Fluid heat transfer composition for use in a heat exchanger system |
US8137579B2 (en) * | 1993-09-10 | 2012-03-20 | Evans John W | Non-aqueous heat transfer fluid and use thereof |
JP3028182B2 (en) * | 1994-10-13 | 2000-04-04 | シーシーアイ株式会社 | Coolant composition |
US5651916A (en) * | 1995-08-23 | 1997-07-29 | Prestone Products Corporation | Process for the preparation of a propylene glycol antifreeze containing an alkali metal silicate |
JPH1161117A (en) * | 1997-08-27 | 1999-03-05 | Tokyo Fine Chem Kk | Rust preventive solution |
US6143243A (en) * | 1997-12-29 | 2000-11-07 | Prestone Products Corporation | Method of inhibiting cavitation-erosion corrosion of aluminum surfaces using carboxylic acid based compositions comprising polymerizable-acid graft polymers |
US5997763A (en) * | 1998-04-27 | 1999-12-07 | Shell Oil Company | Corrosion inhibiting antifreeze compositions containing various carboxylic acids |
US6228283B1 (en) * | 1998-05-22 | 2001-05-08 | Ashland Inc. | Aqueous corrosion inhibitor |
US20020020828A1 (en) * | 2000-06-10 | 2002-02-21 | Evans John W. | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
JP2004513982A (en) * | 2000-07-19 | 2004-05-13 | エバンズ・クーリング・システムズ・インコーポレイテッド | Anhydrous heat transfer fluid and method of using same |
-
2001
- 2001-06-08 US US09/877,306 patent/US20020020828A1/en not_active Abandoned
- 2001-06-08 EP EP01966666A patent/EP1303573A4/en not_active Ceased
- 2001-06-08 WO PCT/US2001/040902 patent/WO2001096493A1/en active IP Right Grant
- 2001-06-08 MX MXPA02012231A patent/MXPA02012231A/en active IP Right Grant
- 2001-06-08 AU AU2001287159A patent/AU2001287159A1/en not_active Abandoned
- 2001-06-08 CN CNB018128823A patent/CN100482762C/en not_active Expired - Fee Related
- 2001-06-08 KR KR10-2002-7016816A patent/KR100506550B1/en not_active Expired - Fee Related
- 2001-06-08 JP JP2002510616A patent/JP4812227B2/en not_active Expired - Fee Related
- 2001-06-08 CA CA2421813A patent/CA2421813C/en not_active Expired - Fee Related
-
2002
- 2002-10-03 US US10/264,041 patent/US20030038276A1/en not_active Abandoned
-
2008
- 2008-08-05 JP JP2008202039A patent/JP2008291276A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55125181A (en) * | 1979-03-22 | 1980-09-26 | Wako Pure Chem Ind Ltd | Antifreezing agent |
JPH0331388A (en) * | 1989-06-27 | 1991-02-12 | Nippon Oil Co Ltd | Freezing-preventive composition |
WO1996037570A1 (en) * | 1995-05-24 | 1996-11-28 | Evans Cooling Systems, Inc. | Non-aqueous heat transfer fluid and use thereof |
US5817252A (en) * | 1997-04-16 | 1998-10-06 | Octagon Process Inc. | Deicing and anti-icing composition for aircraft |
US5935488A (en) * | 1997-04-16 | 1999-08-10 | Octagon Process Inc. | Deicing and anti-icing concentrated composition for aircraft |
Non-Patent Citations (1)
Title |
---|
See also references of EP1303573A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1320575A4 (en) * | 2000-07-19 | 2009-08-26 | Evans Cooling Systems Inc | Non-aqueous heat transfer fluid and use thereof |
WO2009103380A1 (en) * | 2008-02-21 | 2009-08-27 | Takata-Petri Ag | Airbag module for a motor vehicle |
WO2014068367A1 (en) | 2012-10-30 | 2014-05-08 | Istanbul Kurumsal Pazarlama Danismanlik Kimya Sanayi Ve Ticaret Anonim Sirketi | An energy saving fluid |
Also Published As
Publication number | Publication date |
---|---|
KR100506550B1 (en) | 2005-08-05 |
EP1303573A4 (en) | 2007-11-28 |
JP2008291276A (en) | 2008-12-04 |
JP4812227B2 (en) | 2011-11-09 |
AU2001287159A1 (en) | 2001-12-24 |
US20020020828A1 (en) | 2002-02-21 |
KR20030027898A (en) | 2003-04-07 |
CN100482762C (en) | 2009-04-29 |
CA2421813C (en) | 2013-05-28 |
CA2421813A1 (en) | 2001-12-20 |
EP1303573A1 (en) | 2003-04-23 |
MXPA02012231A (en) | 2004-05-21 |
US20030038276A1 (en) | 2003-02-27 |
CN1444636A (en) | 2003-09-24 |
JP2004503657A (en) | 2004-02-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8431038B2 (en) | Reduced toxicity ethylene glycol-based antifreeze/heat transfer fluid concentrates and antifreeze/heat transfer fluids | |
CA2421813C (en) | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid | |
US7655154B2 (en) | Non-aqueous heat transfer fluid and use thereof | |
US8394287B2 (en) | Non-aqueous heat transfer fluid and use thereof | |
AU2001280645A1 (en) | Non-aqueous heat transfer fluid and use thereof | |
US10266741B2 (en) | Apparatus and method for addition of ADH enzyme inhibitors to existing engine cooling systems |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
ENP | Entry into the national phase |
Ref document number: 2002 510616 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2002/012231 Country of ref document: MX Ref document number: 1020027016816 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2001287159 Country of ref document: AU |
|
REEP | Request for entry into the european phase |
Ref document number: 2001966666 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2001966666 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 018128823 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2421813 Country of ref document: CA |
|
WWP | Wipo information: published in national office |
Ref document number: 1020027016816 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2001966666 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1020027016816 Country of ref document: KR |