WO2002006420A1 - Non-aqueous heat transfer fluid and use thereof - Google Patents
Non-aqueous heat transfer fluid and use thereof Download PDFInfo
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- WO2002006420A1 WO2002006420A1 PCT/US2001/022859 US0122859W WO0206420A1 WO 2002006420 A1 WO2002006420 A1 WO 2002006420A1 US 0122859 W US0122859 W US 0122859W WO 0206420 A1 WO0206420 A1 WO 0206420A1
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- coolant
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- 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
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- 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
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- 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
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- 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 generally to a substantially non-aqueous, reduced toxicity heat transfer fluid for use in a heat exchange system and, particularly, for use as a coolant for internal combustion engines.
- Heat transfer fluids are used in a variety of applications.
- One common use of heat transfer fluids is as a coolant in internal combustion engines.
- Most heat transfer fluids that are currently used contain water mixed with ethylene glycol (EG), a hazardous substance that can cause environmental contamination as a result of improper disposal. These fluids can cause dangerous health effects upon humans and other mammals if they are ingested.
- adverse health effects can occur due to exposure to used heat transfer fluids as a result of contamination by elemental heavy metal precipitates and toxic inhibitors that are added to prevent water related reactions.
- EG ethylene glycol
- EG is a diol, a polyhydric alcohol having two hydroxyl (OH) groups.
- diols such as, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, diapropylene glycol and hexylene glycol
- EG most commonly used diol in engine coolant formulations
- an additive package containing several different chemicals is included. These additives are designed to prevent corrosion, cavitation, deposit formation and foaming, and are each present usually in concentrations of from 0.1% to 3% by weight of the coolant concentrate.
- the additives are typically mixed with the freeze point depressant to form an antifreeze concentrate, which can be blended with water to form the engine coolant. In some warm weather areas, freezing temperatures are not encountered and a freeze point depressant is not required. In these climates, the engine coolant is typically composed of water with only a corrosion inhibitor package.
- PG diol propylene glycol
- additives has been used as a freeze point depressant, primarily due to PG's lower toxicity rating as compared to EG.
- a further complication in developing a single engine coolant formulation results from the different requirements of different types of engines.
- heavy-duty engines require a high concentration of sodium nitrite as an additive to control iron erosion of cylinder liners due to cavitation.
- Cylinder liner cavitation can occur when a substantial portion of the engine coolant is made up of water.
- a mixture of 50% water and 50% EG is used (50/50 EG/W) in a heavy duty engine
- the vapor pressure of the coolant is very high, about 900 mm Hg at 240° F (132° C)
- large amounts of water vapor are produced on the coolant side of the cylinder wall.
- supplemental coolant additives are not used or required in passenger cars that have a coolant life of 20,000 miles (32,186 km) to 30,000 miles (48,279 km). Heavy duty service usually demands 200,000 miles (321,860 km) to 300,000 miles (482,790 km) before coolant replacement. The longer coolant service requirement results in the need to periodically replenish the inhibitors in heavy duty engine coolants.
- Examples of commonly used supplemental coolant additives include sodium nitrite, dipotassium phosphate, sodium molybdate dihydrate, and phosphoric acid.
- Supplemental coolant additives must be chemically balanced with the coolant volume, which can be difficult and costly to control properly. Improper balancing of additives can result in severe damage to cooling system components and the engine. If the concentration of the supplemental coolant additives in the coolant is too low, corrosion and cavitation damage to the engine and cooling system components can occur. If, on the other hand, the concentration of supplemental additives is too high, additives can precipitate from the coolant solution and clog radiator and heater cores. A further concern with supplemental coolant additives is that they may, under certain conditions, be difficult to properly dissolve in the engine coolant. If the supplemental additives do not completely dissolve, they may be a source of additional clogging problems in the engine.
- Glycols make up 95% by weight of conventional antifreeze/coolant concentrates, and after blending with water, about 30% to 70% by volume of the coolant used in the vehicle. Because of its relative abundance and lower cost as compared with alternative glycols, conventional antifreezes are almost always formulated with EG.
- a major disadvantage of using EG as a freezing point depressant for engine coolants is its high toxicity to humans and other mammals if ingested. Toxicity is generally measured in accordance with a rating system known as the LD 50 rating system, which is the amount of a substance expressed in milligrams per kilogram of body mass that, when fed to laboratory rats in a single dose, will cause the death of 50 percent of the laboratory rats.
- a lower LD 50 value indicates a higher toxicity (i.e., smaller amounts of the substance can be lethal).
- An LD 5 0 value of less than or equal to 5,000 milligrams per kilogram of body mass (mg/kg) can classify an antifreeze concentrate as hazardous. Because EG has an LD 50 value of 4,700 mg kg, EG is considered hazardous by this rating system.
- EG is a known toxin to humans at relatively low levels. When ingested, EG is metabolized to glycolic and oxalic acids, causing an acid-base disturbance which may result in kidney damage. As reported in Toxic Release Inventory- Reporting; Notice of Receipt of Petition, Federal Register, Vol. 63, No.
- PG Due to the toxicity of EG, in recent years a base fluid concentrate with about 95% PG and additives has been used as a substitute for EG with additives in many antifreeze formulations.
- PG has an LD 50 value of 20,000 mg kg as compared to EG's 4,700 mg/kg. PG is considered essentially non-toxic, and it has been approved by the U.S. Food and Drug Administration as a food additive.
- One impediment to more widespread usage of PG as a base fluid for antifreeze concentrates is its relatively high cost as compared to EG.
- All conventional antifreeze concentrates whether EG or PG based, contain water in their formulations.
- EG antifreeze concentrates require a small percentage of water in their formulation because EG, by itself and without any water, freezes at +7.7°F (-13.5°C). A small amount of water must be added to depress the freezing point. Addition of four percent water by volume to ethylene glycol lowers the freezing point of the mixture to -3° F (-19.4° C). The freezing point of PG (by itself and without water) is relatively low, -76° F (-60° C).
- water is added to all conventional concentrate mixtures. Three to five percent by weight water is typically included in coolant concentrates to dissolve certain additives that will not dissolve in glycols. Added water is essential in conventional concentrates to keep the additives dissolved, particularly as the concentrates may be stored for extended periods.
- the water added to concentrates to form an engine coolant can also cause formation of potentially hazardous products.
- Water at elevated temperatures can be highly reactive with the metal surfaces in a cooling system.
- the water can react with lead and copper materials from radiators, including brass and lead solder.
- precipitates of heavy metals, such as lead and copper can become suspended in the water portion of the circulating coolant in the engine.
- Water is also highly reactive with light alloys, such as aluminum, and the water fraction of the coolant can generate large amounts of aluminum precipitates, particularly at higher coolant temperatures. Even with the addition of additives to control these reactions, aluminum is constantly lost to the conventional engine coolants containing approximately 50/50 mixtures of EG and water.
- Corrosion of metal surfaces in engine cooling systems using conventional glycol/water coolants is also caused by the formation of organic acids in the coolant, such as pyruvic acid, lactic acid, formic acid, and acetic acid.
- the organic diols such as EG and PG, can produce acidic oxidation products when in the presence of hot metal surfaces, oxygen from either entrapped air or water, vigorous aeration, and metal ions which catalyze the oxidation process.
- formation of lactic acid and acetic acid is accelerated in coolant solutions at 200°F (93.3°C) or above while in the presence of copper.
- Formation of acetic acid is further accelerated in the presence of aluminum in coolant solutions at 200°F (93.3°C) or above.
- These acids can lower the pH of the coolant.
- iron and steel are the most reactive to solutions containing organic acids, whereas light metals and alloys, such as aluminum, are considerably less reactive.
- buffers in their formulations
- the buffers act to maintain the pH of the engine coolant in the range of approximately 10 to 11 as organic acids are formed.
- typically utilized buffers include sodium tetraborate, sodium tetraborate decahydrate, sodium benzoate, phosphoric acid and sodium mercaptobenzothiazole. These buffers also require water in order to enter into and remain in solution. As the buffers in the coolant solution become depleted over time, the water fraction of the coolant reacts with the heat, air and metals of the engine, and, as a result, the pH decreases because of the acids that form.
- the additive package that is included in known coolant concentrate formulations can consist of from 5 to 15, and typically from 8 to 15, different chemicals. These additives are broken down into major and minor categories, depending upon the amount used in an engine coolant formulation:
- the present invention relates to a heat transfer fluid that uses diols, preferably propylene glycol (PG) or a mixture of propylene glycol and ethylene glycol (PG and EG), as its base fluid without the addition of water, and is therefore termed non-aqueous.
- diols preferably propylene glycol (PG) or a mixture of propylene glycol and ethylene glycol (PG and EG)
- PG and EG propylene glycol
- the use of water in the non-aqueous heat transfer fluid is not required as a means to dissolve additives, because the only additives used are corrosion inhibitors that are soluble in neat PG and EG.
- the formulation of the present invention is easier to blend and requires much less time to blend, thereby lowering blending costs.
- the instant invention of a substantially water-free diol based heat transfer fluid (preferably PG or PG with EG), utilizes a unique formulating process which results in a fully-formulated and stabilized, non-toxic, non-aqueous heat transfer fluid suitable for use as an engine coolant in virtually any climate in the world.
- EG based non-aqueous heat transfer fluids are provided that are non-toxic.
- the inventors have discovered that when PG is mixed with EG, PG acts as an antidote for EG poisoning, thereby rendering mixtures of PG and EG essentially non-toxic even up to EG proportions of 70 percent by weight.
- the invention creates coolants formulated with stable inhibitors that remain in solution, giving the coolants long-term shelf lives.
- the non-aqueous heat transfer fluid can be used as an engine coolant in environmental conditions ranging from ambient temperatures of -35° F to +130° F or hotter, including several arctic and all tropical and desert regions.
- Another advantage of the present invention is that, when the non-aqueous heat transfer fluid is used in a cooling system such as those disclosed in U.S. Patent Nos.
- the coolant system can operate at a significantly lower pressure, thereby reducing stress on engine system components.
- the lubricous nature of the non-aqueous coolant of the present invention is benign to rubber, and allows the pump seals, hoses and system components to normally last
- a further advantage of the present invention is that the corrosion inhibitor additives will remain dissolved, without agitation, for many years of storage.
- Another advantage is that non-aqueous PG or PG with EG will not cause cylinder liner cavitation. As a result, there is no need for the addition of sodium nitrite to the fluid when used in heavy duty engines.
- Yet another advantage of the present invention is that the lack of water in the fully- formulated PG or PG and EG-based non-aqueous heat transfer fluids substantially reduces, and in most instances eliminates, the problem of contamination from precipitates of heavy metals, such as lead and copper. Also, because pH (acidity) is not a concern with the non- aqueous formulated coolant of the present invention there is no need for additives such as borates and phosphates.
- Another advantage of the present invention is that the essentially water-free nature of the coolant formulation eliminates other water, air, heat and metal-based reactions and eliminates the need for additives to control these reactions.
- the reactions and additives that are eliminated include :
- the non-aqueous heat transfer fluid of the present invention may be prepared by two different methods.
- the additives are mixed with and dissolved in a quantity of the diol base fluid, such as PG or PG and EG, to form an additive/base fluid concentrate.
- the concentrated solution is blended into the bulk tank which is filled with industrial grade PG or PG and EG.
- the additives are introduced in powder form directly into the bulk blending tank, which is filled with industrial grade PG or PG and EG. Either of these methods is easier and less costly than the methods presently used to mix heat transfer concentrates for use in engines with water.
- Fig. 1 is a graph showing Predicted LD 50 Values for Mixtures of Ethylene Glycol and Propylene Glycol with Corrosion Inhibitors That Total a Constant Concentration of 1.5 Percent (by Weight).
- Fig. 2 is a graph showing Viscosity vs. Temperature for 100% PG and a 30% PG/70%
- Fig. 3 is a graph showing Thermal Conductivity vs. Temperature for 100% PG and a 30% PG/70% EG blend by weight.
- Fig.4 is a graph showing Specific Heat vs. Temperature for 100% PG and a 30% PG/70% EG blend by weight.
- Fig. 5 is a graph showing Density vs. Temperature for 100%) PG and a 30% PG/70% EG blend by weight.
- the present invention relates to a diol based non-aqueous heat transfer fluid containing additives that are essentially completely soluble in the diols and that do not require water to dissolve.
- the diol fraction of the non-aqueous heat transfer fluid contains at least one diol that acts as an antidote for EG poisoning when it is mixed with EG.
- antidote means a substance that prevents or counteracts the toxic effects of ethylene glycol.
- PG acts as an antidote for EG poisoning when it is mixed with EG.
- the diol fraction is comprised of either PG or a mixture of PG and EG.
- a mixture of PG and EG is used as the base liquid for the non-aqueous heat transfer fluid.
- the non-aqueous heat transfer fluid may contain EG in any amount ranging between 0 percent by weight to about 70 percent by weight of the total weight of EG and PG in the fluid.
- EG comprises about 70 percent by weight
- PG comprises about 30 percent by weight of the total weight of EG and PG in the fluid.
- PG and EG are very close in chemical structure, and the two fluids will combine to form a homogeneous mixture in virtually any ratio. After they are combined, the fluids remain chemically stable, and neither fluid will separate from the other. The result is a fluid which will remain stable as blended, which is important for long term storage.
- Another advantage of mixing PG and EG for non-aqueous heat transfer fluid is that, when mixed, EG and PG will evaporate at about the same rate. This is a result of another similar physical characteristic of the two fluids, their vapor pressures.
- EG has a vapor pressure at 200° F (93.3° C) of 10 mm Hg
- PG at the same temperature has the relatively similar vapor pressure of 16 mm Hg. Accordingly, the two fluids will evaporate at about the same rate.
- water has a vapor pressure of 600 mm Hg at 200°F, and therefore water will evaporate more rapidly than either EG or PG when exposed to the ambient atmosphere.
- PG is substantially more viscous than EG at lower temperatures.
- viscosity at any given temperature decreased as the percentage of EG increased.
- the freezing point is -35° F (-37.2° C), which is satisfactory for all but the most severe arctic environments.
- unexpected improvements in the viscosity of the heat transfer fluid occur when EG is mixed with PG.
- the viscosity of the 30/70 PG/EG mixture at -35°F(-37.2°C) is approximately 1500 centipoise (cp), as compared to a viscosity of approximately 10,000 cp for neat PG at this temperature.
- PG has a boiling point of 369°F (187.2°C), which is satisfactory for use as an engine coolant.
- the boiling point of EG at atmospheric pressure is 387°F (197.3°C), which is also satisfactory.
- the acceptable upper limit for the atmospheric boiling point of a non- aqueous heat transfer fluid used as an engine coolant is about 410°F (about 210°C). If the atmospheric boiling point is significantly higher than 410°F, the coolant and critical engine metal temperatures can become too hot.
- the boiling points of diethylene glycol, triethylene glycol and tripropylene glycol are 472.6°F (244.8°C), 545.9°F (285.5°C) and 514.4°F (268°C) respectively.
- these diols by themselves, are unacceptable as non-aqueous coolants, any of them may, in low concentrations (for example about 10 percent by weight), be combined with EG and/or PG to produce a non- aqueous heat transfer fluid with an acceptable boiling point.
- the non-aqueous heat transfer fluid of the present invention contains only PG and EG.
- PG and EG mixtures have boiling points that fall between the boiling points for neat PG and neat EG, all of which are satisfactory for a non-aqueous engine coolant.
- the preferred 30/70 PG/EG mixture has a boiling point of 375°F (190.5°C).
- a non-aqueous heat transfer fluid composed of 30/70 PG EG is also improved over the thermal conductivity of pure PG.
- Fig. 3 presents the results of tests which compare the thermal conductivity of 100% non-aqueous PG to the thermal conductivity of a 30/70 PG/EG mixture.
- the 30/70 PG/EG mixture has a thermal conductivity that is approximately 25% better than the thermal conductivity of 100% PG in the operating temperature range of 0°F (-17.8°C) to 250°F (121.1°C).
- Fig. 4 shows that the specific heat of a 30/70 PG/EG mixture is slightly less than the specific heat of 100% PG. This loss is offset as a result of the increased density of the 30/70 PG/EG mixture over 100% PG. As shown in Fig. 5, the density of 30/70 PG/EG mixtures is about 5% greater than the density of 100% PG, and the resultant increase in mass of the 30/70 PG EG blend for a given volume of heat transfer fluid more than offsets the slight decrease in specific heat.
- Limit tests and range tests were conducted in order to estimate the final LD 50 value of PG EG mixtures.
- a limit test establishes whether or not an LD 50 value lies above or below a specific dose.
- a range test is a series of limit tests that establishes a range within which an LD 50 value lies. Before any testing is performed on rats using a mixture of substances that have established LD 50 values, a mathematical estimate of the LD 50 value is performed.
- Ingesting less of a toxic substance decreases its toxic impact. Accordingly, when a mixture of a toxic substance and a non-toxic substance is ingested, in which the concentration of the toxic substance is reduced, more of the mixture must be ingested to produce the same toxic effect as the pure substance.
- EG by itself has an acute oral (rat) LD 50 value of 4,700 mg/kg. If the EG is mixed with a substance that is completely non-toxic such that the mixture is Vz EG, the acute oral (rat) LD 50 value of the mixture would be estimated to be 9,400 mg/kg, or twice that of EG by itself. This is a reasonable estimate since the same quantity of the mixture would contain only Vz the amount of EG.
- PG has an acute oral (rat) LD 50 value of 20,000 mg/kg.
- LD 50 of a mixture containing substances having known LD 50 values can be estimated by the following formula:
- Acute oral toxicity tests were performed to determine the toxicity of the mixtures of PG and EG of the present invention.
- the tests were conducted by a laboratory approved by the United States Environmental Protection Agency (EPA) using standard "GLP" test procedures as described in 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.
- EPA United States Environmental Protection Agency
- GLP GLP
- the fraction of PG in the mixture as compared to the total of the diols was 30 percent and the fraction of EG was 70 percent.
- the predicted LD 50 value for this formulation is 5,762 mg/kg, which is about 23 percent greater than ethylene glycol' s LD 50 value of 4,700 mg/kg.
- a range test was conducted in which the rats were given up to maximum possible doses of approximately 21,000 mg/kg (an amount that completely filled the rats' stomachs). No rat deaths were reported, and all of the rats actually gained a significant amount of weight during the test period.
- the inventor does not wish to rely on or be limited to any particular theory as to why the addition of PG to EG results in an unexpectedly low oral toxicity for the mixture, it appears that the PG has antidotal qualities for the EG fraction within the coolant, preventing or minimizing the formation of glycolic and oxalic acids in the animal or human body. The damage caused by glycolic and oxalic acids to the kidneys and other organs, well known in EG poisonings, is thereby prevented.
- the resulting mixture would be reduced in toxicity, from the EG added, far beyond the reduction predicted by dilution alone and would most likely be essentially non-hazardous to the environment.
- other diols may be present, in low concentrations, in mixtures of PG and EG without altering the essentially non-hazardous characteristics of the non-aqueous heat transfer fluid.
- the non-aqueous heat transfer fluid of the present invention utilizes only additives that are soluble in PG and in EG, and thus does not require water for the additives to enter into or remain in solution.
- each chosen additive is a corrosion inhibitor for one or more specific metals that may be present in an engine.
- a nitrate compound such as sodium nitrate, is utilized as an additive to inhibit corrosion for iron or alloys containing iron, such as cast iron. Although the primary function of sodium nitrate is to prevent corrosion of iron, it also slightly inhibits solder and aluminum corrosion.
- An azole compound, such as tolyltriazole functions as a corrosion-inhibiting additive for both copper and brass.
- a molybdate compound such as sodium molybdate, primarily functions as a corrosion inhibitor for lead (from solder), but is also beneficial in decreasing corrosion for many other metals. Notably, there is no need for nitrites in any formulation of the non-aqueous heat transfer fluid.
- the choice of PG and EG-soluble additives thus depends on which metals are of concern with regard to corrosion of metal surfaces.
- sodium nitrate, tolyltriazole and sodium molybdate would be added to formulate a universally usable heat transfer fluid because iron, solder, aluminum, copper and/or brass are often used in engine cooling system components.
- an additive could be reduced or eliminated if the particular metal it acts on is eliminated. For example, if lead-based solder is eliminated, then the content of sodium molybdate could be reduced, or it might not be required at all.
- the corrosion inhibitor additives may be present in a range from a concentration of about 0.05% by weight to about 5.0% by weight of the formulated heat transfer fluid, and are preferably present at a concentration of less than 3.0% by weight. Solutions below about 0.1% by weight are not as effective for long life inhibition, while solutions over about 5.0% may result in precipitation of the additive. In a preferred embodiment, each corrosion inhibitor additive is present in a concentration of about 0.3% to about 0.5% by weight depending upon the service life of the coolant. Another advantage of the present invention is that light alloys will have little or no corrosion in PG or PG and EG non-aqueous fluids.
- metals such as magnesium and aluminum will exhibit little or no corrosion, and additives to limit corrosion of these metals can be eliminated.
- sodium nitrate, tolyltriazole and sodium molybdate as corrosion inhibitor additives has many advantages.
- these additives are not rapidly depleted in service, and therefore the engine coolant may be formulated to last for heretofore unobtainable service periods, without change or additive replenishment, of up to about 10,000 hours or 400,000 miles (643,720 km) in many forms of engines and vehicles.
- Another advantage of these PG or PG and EG soluble additives is that the additives go into solution or suspension readily and remain in solution or suspension, even in extreme concentrations. These additives will not precipitate from the solutions even when each additive is present in concentrations of up to 5.0 percent by weight.
- these additives will not degrade significantly as a result of interactions with each other, the additives are not abrasive, and the additives and coolant protect all metals, including magnesium, for the same operating period.
- non-aqueous PG or PG and EG soluble additives of the present invention do not become depleted over extended hourly usage or mileage and thus the need for supplemental coolant additives is ordinarily eliminated. Nevertheless, if it should become desirable to add supplemental coolant additives, the non-aqueous formulation exhibits advantages because the supplemental coolant additives will more readily enter stable solution or suspension with the present invention than in aqueous coolants. Moreover, the proper balance of supplemental coolant additives is easier to maintain, with a broad possible range of concentrations from about 0.05% by weight to about 5.0% by weight.
- the supplements may be added in either dry powder form, or as a dissolved concentrate directly to the cooling system.
- the supplements may be added to a cool engine (50°F or above) and will dissolve into solution merely by idling the engine, without clogging the radiator or heater cores.
- the preferred target base solution for each additive is about 0.5% by weight and the saturated limit is about 5.0%, there is little chance of inadvertent addition of an unacceptable amount of supplemental additive.
- current water-based additives must be added to a hot coolant, then run hard (to enter solution) and are easily oversaturated, which can cause radiator and heater damage.
- non-aqueous means that water is present only as an impurity in the non-aqueous heat transfer fluid preferably, in no greater than a starting concentration of about 0.5% by weight. Most preferably, the non-aqueous heat transfer fluid contains virtually no water. Although an increase in water is not desired during use, the present invention can accommodate the presence of some water. Because PG is a hygroscopic substance, water can enter the coolant from the atmosphere, or water can escape from the combustion chamber into the coolant from a combustion gasket leak into the cooling chamber.
- the essence of the invention is to avoid water, the invention will permit some water as an impurity; however, the water fraction of the coolant in use is preferably restricted to below about 5.0% by weight, and more preferably, to below about 3.0% by weight. Further, the invention and related cooling systems can tolerate water, from absorption during use, up to a maximum concentration of about 10% by weight and retain reasonably acceptable operating characteristics.
- the heat transfer fluid of the present invention does not contain substantial amounts of water, several of the problems associated with aqueous heat transfer fluids are eliminated.
- aqueous coolants can form violent vapor bubbles (cavitation) in the cooling system leading to lead and copper erosion from the effects of the vapor/gases and the reaction of water with the metals.
- the present invention is non-aqueous in nature, coolant vapor bubbles are substantially minimized and water vapor bubbles are essentially eliminated, thereby reducing the quantity of heavy metal precipitates in the coolant.
- conventional water-based coolants acidity of the coolant is a concern. If the coolant is acidic, corrosion of metal surfaces may be increased. To avoid acidic conditions, conventional water-based coolants require buffering agents to make the coolant more basic (an increase in the pH to 10 to 14). At least about 5% of the content of conventional antifreeze concentrates must be water in order to dissolve these buffers (e.g. phosphates, borates, carbonates, and the like).
- the non-aqueous heat transfer fluid of the present invention does not require buffering because acid anhydrides that are present would require the presence of water to form acids. Without the water, the non-aqueous coolant does not become corrosive and no buffers are needed.
- the percentage of diols in the final mixture would be > 98.4%.
- the percentage of the fully formulated coolant, by weight, that is PG would be about 29.5%.
- the figure for the EG would be about 68.9%.
- the remainder of the formulation is corrosion inhibitors and possibly a trace amount of water present only as an impurity.
- Coolant "A” was a non-aqueous heat transfer fluid of the present invention in which the diol portion was 100 percent PG.
- Coolant "B” was a conventional engine coolant formulation comprised of an EG based antifreeze concentrate mixed with water.
- the coolant is aerated by bubbling air up through the glassware, and maintained at a test temperature of 190°F (88°C) for 336 hours. This procedure was modified to more accurately reflect the conditions that would be experienced by the metals in an engine coolant system in use. The tests were conducted at a control temperature of 215°F (101.6°C) to simulate severe duty use. Coolant "A" was tested without aeration being applied in order to more closely approximate its operation in a non-aqueous engine cooling system, such as, for example, the engine cooling system described in U.S. Patents Nos.
- Coolant "A” was a non-aqueous coolant of the present invention with 100 percent PG. To simulate the operating conditions of a coolant system using a non-aqueous coolant, the test using Coolant “A” was conducted at a temperature of 275°F (135°C) and a pressure of 2 psig (14 kPa), which is slightly above ambient pressure.
- Test Coolant "B” contained an ASTM prescribed corrosive water used to make up the water fraction of a 50/50 EG/water coolant.
- the test conditions for Coolant B which simulate the conditions in an aqueous coolant engine cooling system, were a temperature of 275°F (135°C) and a pressure of 28 psig (193 kPa).
- a 3.8L V-6 engine was operated over the road for a test period of 55,000 miles (88,511.5 km).
- the engine cooling system in the vehicle was configured as described in U.S. Patent No. 5,031,579.
- Coolant "A" was identical to the non-aqueous coolant described in Example 1 above. There was no draining or replacing of the coolant during the test period.
- a metal specimen bundle was placed within the full flow of the engine coolant stream (lower hose) and was kept submerged in the coolant at all times. Performance of the test coolant's ability to inhibit metal corrosion was evaluated by comparing the results in milligrams lost of the specimen at the end of the test period to ASTM test standards. The results were as follows:
- the non-aqueous heat transfer fluid of the present invention may be manufactured by the methods described below.
- the non-aqueous heat transfer fluid may be made in a batch process. Initially, calculations must be performed to determine the required quantity for the ingredients. For example, the following calculations would be performed to determine the quantity of each ingredient to mix 6,500 gallons of non-aqueous heat transfer fluid: 1. Determine the approximate weight of 6,500 gallons of the final product. a. From the desired percentage (by weight) of PG (% P G) in the diols portion of the formulated coolant (a figure in the range of 30% to 100%), compute the density (lbs. per gallon) of the mixed diols according to the following formula:
- the tolyltriazole will weigh 0.005 x EstWt 650 o.
- the sodium nitrate will weigh 0.005 x EstWt 650 o. 3.
- the sodium molybdate will weigh 0.005 x EstWt 650 o.
- the weight of the total diols (Wt To tDfois) will be (1 - .015) X EstWt 6500 .
- the PG will weigh % PG x Wt TotD i o i s /l 00 lbs.
- the EG will weigh (100 - % PG ) x Wtxofl l 00 lbs.
- the non-aqueous heat transfer fluid may be mixed together using a variety of methods.
- the additives may be pre-mixed with a portion of the diol(s) that will be used in the main body of the non- aqueous heat transfer fluid.
- this method would be performed using at least the following steps:
- the method of manufacturing the heat transfer fluid by pre-mixing additives with a diol may be as follows:
- the additives may be mixed directly into the diol(s), and the pre-mixing steps may be eliminated.
- this method is performed using at least the following steps:
- This method may also be used to produce heat transfer fluids comprised of mixtures of PG and EG. For example, for a heat transfer fluid comprised of 30 percent PG by weight and 70 percent EG by weight, at least the following steps would be performed:
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU8064501A AU8064501A (en) | 2000-07-19 | 2001-07-19 | Non-aqueous heat transfer fluid and use thereof |
KR10-2003-7000742A KR100506549B1 (en) | 2000-07-19 | 2001-07-19 | Non-aqueous heat transfer fluid and use thereof |
JP2002512315A JP2004513982A (en) | 2000-07-19 | 2001-07-19 | Anhydrous heat transfer fluid and method of using same |
AU2001280645A AU2001280645B2 (en) | 2000-07-19 | 2001-07-19 | Non-aqueous heat transfer fluid and use thereof |
EP01959053.8A EP1320575B1 (en) | 2000-07-19 | 2001-07-19 | Non-aqueous heat transfer fluid and use thereof |
BRPI0112642A BRPI0112642B1 (en) | 2000-07-19 | 2001-07-19 | reduced toxicity non-aqueous heat transfer fluid; method for reducing the toxicity of a non-aqueous heat transfer fluid |
MXPA03000538 MX246518B (en) | 2000-07-19 | 2001-07-19 | NON-WATER HEAT TRANSFER FLUID AND USE OF IT. |
CA2422012A CA2422012C (en) | 2000-07-19 | 2001-07-19 | Non-aqueous heat transfer fluid and use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21918900P | 2000-07-19 | 2000-07-19 | |
US60/219,189 | 2000-07-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002006420A1 true WO2002006420A1 (en) | 2002-01-24 |
Family
ID=22818245
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/022859 WO2002006420A1 (en) | 2000-07-19 | 2001-07-19 | Non-aqueous heat transfer fluid and use thereof |
Country Status (10)
Country | Link |
---|---|
US (3) | US20030136809A1 (en) |
EP (1) | EP1320575B1 (en) |
JP (1) | JP2004513982A (en) |
KR (1) | KR100506549B1 (en) |
CN (2) | CN1511187A (en) |
AU (2) | AU8064501A (en) |
BR (1) | BRPI0112642B1 (en) |
CA (1) | CA2422012C (en) |
MX (1) | MX246518B (en) |
WO (1) | WO2002006420A1 (en) |
Cited By (1)
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EP1303573A1 (en) * | 2000-06-10 | 2003-04-23 | Evans Cooling Systems, Inc. | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
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US20090266519A1 (en) * | 2004-09-08 | 2009-10-29 | Honeywell International Inc. | Heat transfer system, fluid, and method |
CN102401066A (en) * | 2011-08-30 | 2012-04-04 | 芜湖禾田汽车工业有限公司 | Damping fluid for hydraulic suspension part of automobile engine and production process thereof |
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US9966590B2 (en) | 2011-09-21 | 2018-05-08 | Tesla, Inc. | Response to high voltage electrolysis of coolant in a battery pack |
US8862414B2 (en) * | 2011-09-21 | 2014-10-14 | Tesla Motors, Inc. | Detection of high voltage electrolysis of coolant in a battery pack |
US20130073234A1 (en) * | 2011-09-21 | 2013-03-21 | Tesla Motors, Inc. | Response to Low Voltage Electrolysis in a Battery Pack |
CN102367379B (en) * | 2011-11-02 | 2014-04-30 | 深圳车仆汽车用品发展有限公司 | Life-cycle water-free cooling solution |
WO2013126895A1 (en) * | 2012-02-23 | 2013-08-29 | Hydration Systems, Llc | Forward osmosis with an organic osmolyte for cooling towers |
WO2016179485A1 (en) | 2015-05-07 | 2016-11-10 | Evans Cooling Systems, Inc. | Very low water heat transfer fluid with reduced low temperature viscosity |
CN104845595B (en) * | 2015-05-13 | 2018-01-23 | 北京中德汇诚石油技术有限公司 | A kind of automobile engine water-free cooling composition |
GB201610403D0 (en) | 2016-06-15 | 2016-07-27 | Liquitherm Tech Group Ltd | Cooling system treatment |
CN108130055A (en) * | 2017-12-27 | 2018-06-08 | 佛山市顺德区施迈普电子科技有限公司 | A kind of Pluronic polyols water-free cooling and preparation method thereof |
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2001
- 2001-07-19 JP JP2002512315A patent/JP2004513982A/en active Pending
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- 2001-07-19 BR BRPI0112642A patent/BRPI0112642B1/en not_active IP Right Cessation
- 2001-07-19 CN CNA018130321A patent/CN1511187A/en active Pending
- 2001-07-19 CA CA2422012A patent/CA2422012C/en not_active Expired - Fee Related
- 2001-07-19 AU AU8064501A patent/AU8064501A/en active Pending
- 2001-07-19 EP EP01959053.8A patent/EP1320575B1/en not_active Expired - Lifetime
- 2001-07-19 KR KR10-2003-7000742A patent/KR100506549B1/en not_active IP Right Cessation
- 2001-07-19 AU AU2001280645A patent/AU2001280645B2/en not_active Ceased
- 2001-07-19 CN CN2010105083483A patent/CN102061147A/en active Pending
- 2001-07-19 MX MXPA03000538 patent/MX246518B/en active IP Right Grant
-
2003
- 2003-01-20 US US10/347,900 patent/US20030136809A1/en not_active Abandoned
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2007
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2010
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Cited By (2)
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---|---|---|---|---|
EP1303573A1 (en) * | 2000-06-10 | 2003-04-23 | Evans Cooling Systems, Inc. | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
EP1303573A4 (en) * | 2000-06-10 | 2007-11-28 | Evans Cooling Systems Inc | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid |
Also Published As
Publication number | Publication date |
---|---|
MX246518B (en) | 2007-06-18 |
CN102061147A (en) | 2011-05-18 |
EP1320575A4 (en) | 2009-08-26 |
BRPI0112642B1 (en) | 2016-02-10 |
AU8064501A (en) | 2002-01-30 |
CA2422012C (en) | 2012-12-11 |
US20100176334A1 (en) | 2010-07-15 |
AU2001280645B2 (en) | 2005-10-20 |
KR100506549B1 (en) | 2005-08-05 |
US20030136809A1 (en) | 2003-07-24 |
CN1511187A (en) | 2004-07-07 |
EP1320575A1 (en) | 2003-06-25 |
US20080061269A1 (en) | 2008-03-13 |
US7655154B2 (en) | 2010-02-02 |
BR0112642A (en) | 2004-06-22 |
KR20030097775A (en) | 2003-12-31 |
MXPA03000538A (en) | 2004-04-21 |
CA2422012A1 (en) | 2002-01-24 |
EP1320575B1 (en) | 2013-09-04 |
JP2004513982A (en) | 2004-05-13 |
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