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WO2010008951A1 - Compositions de propylèneglycol/glycérol empêchant la corrosion - Google Patents

Compositions de propylèneglycol/glycérol empêchant la corrosion Download PDF

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Publication number
WO2010008951A1
WO2010008951A1 PCT/US2009/049666 US2009049666W WO2010008951A1 WO 2010008951 A1 WO2010008951 A1 WO 2010008951A1 US 2009049666 W US2009049666 W US 2009049666W WO 2010008951 A1 WO2010008951 A1 WO 2010008951A1
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WIPO (PCT)
Prior art keywords
glycerin
propylene glycol
weight
water
composition
Prior art date
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Ceased
Application number
PCT/US2009/049666
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English (en)
Inventor
Kevin Connor
John Cuthbert
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication of WO2010008951A1 publication Critical patent/WO2010008951A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C23F11/10—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 using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • 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
    • C23F11/10—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 using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • 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
    • C23F11/18—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 using inorganic inhibitors
    • C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds

Definitions

  • This invention relates generally to compositions of matter suitable for use as an antifreeze fluid or as a heat transfer fluid.
  • this invention more particularly relates to a composition of matter, especially an anti-freeze concentrate composition that includes propylene glycol, an amount of glycerin and at least one corrosion inhibitor as well as an anti-freeze composition that includes propylene glycol, an amount of glycerin, at least one corrosion inhibitor, and water.
  • the propylene glycol and glycerin are present in certain amounts relative to each other and water is present in an amount of at least 50 percent by weight (wt%), based upon total composition weight.
  • a variety of end use applications (e.g. plumbing systems, fire water sprinkler systems, and heat transfer systems such as those used for internal combustion engine cooling, hydronic heating and cooling of buildings, and heating of various natural gas streams) employ an anti-freeze composition.
  • a typical end use application involves use of an anti-freeze composition to protect water conveying or water containing equipment from damage caused by the formation of ice during exposure to freezing temperatures.
  • yield strength burst pressure
  • materials e.g. carbon steel, copper, polyethylene (PE) or polyvinyl chloride (PVC) used to form the piping or other confined space.
  • anti-freeze compositions often include a freezing point depressant, more preferably a water-soluble freezing point depressant.
  • a freezing point depressant more preferably a water-soluble freezing point depressant.
  • Illustrative water-soluble freezing point depressants include low molecular weight (e.g. less than 100 grams per mole (g/mol) for freezing point depressants other than salts and less than about 110 g/mol for salts used as freezing point depressants) salts, alcohols, or glycols. More specific examples include aqueous solutions of a salt such as sodium chloride, calcium chloride or potassium formate, as well as one or more of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol and glycerin.
  • a salt such as sodium chloride, calcium chloride or potassium formate
  • An anti-freeze composition desirably has a number of attributes including, without limitation, relatively low cost (e.g. less than one (1) dollar per pound (US$/lb), minimal, preferably no toxicity, little and preferably no flammability, as little as possible and preferably no corrosivity, low and preferably no adverse environmental impact, and easy pumpability or at least flow-ability at low fluid temperatures (e.g. within a range of from -40 degrees centigrade ( 0 C) to 0 0 C). Based upon information and belief, no current, commercial anti-freeze composition has all of the aforementioned attributes.
  • relatively low cost e.g. less than one (1) dollar per pound (US$/lb)
  • minimal, preferably no toxicity, little and preferably no flammability, as little as possible and preferably no corrosivity, low and preferably no adverse environmental impact e.g. within a range of from -40 degrees centigrade ( 0 C) to 0 0 C.
  • SaIt- containing or salt-based freezing point depressants such as chloride or formate brines readily corrode common metals such as steels, cast iron and copper alloys. Such corrosivity limits widespread use of such salt-containing freezing point depressants and anti-freeze compositions including the same.
  • anti-freeze composition formulators consider alcohol-based freezing point depressants such as methanol, ethanol and isopropanol to be flammable and subject to catching fire even when mixed with water.
  • Ethylene glycol is relatively toxic, at least in comparison to salt-containing freezing point depressants and propylene glycol-based freezing point depressants.
  • Propylene glycol and glycerin are viscous and difficult to pump at low fluid temperatures (i.e. within a range of from -40 0 C to -15 0 C).
  • glycerin degrades quite readily compared to ethylene glycol or propylene glycol and glycerin degradation compounds contribute to excessive corrosion of common metals.
  • USP United States Patent
  • 71, 948 (Baker) teaches use of salted water, glycerin, or their equivalents to prevent freezing in transmitting and diffusing heat through ordinary pipes, tubes or radiators.
  • USP 1,687,094 discloses a composition of matter for depressing the freezing point of water or an aqueous solution.
  • the composition comprises a soluble amide (e.g. formamide) and glycerin, or a soluble amide, glycerin and diacetone alcohol.
  • USP 1,711,324 (Osterlund) describes anti-freeze compositions that comprise sodium glycerol-phosphate and glycerin.
  • USP 1,742,349 (Haag et al.) provides teachings relative to anti-freeze mixtures that consist of water, glycerin and glucose.
  • USP 1,752,145 discloses a non-corrosive mixture comprising an aqueous solution of a polyhydric alcohol and a higher fatty acid (e.g. stearic acid, oleic acid and palmitic acid) that is substantially soluble in water.
  • a polyhydric alcohol e.g. stearic acid, oleic acid and palmitic acid
  • USP 1,754,457 (Calcott et al.) teaches a non-corrosive aqueous solution of a polyhydric alcohol, or a mixture of polyhydric alcohols and monohydric alcohols, containing a primary aromatic diamine.
  • the solution optionally includes a higher fatty acid and/or a secondary diaromatic amine.
  • European Patent Application (EP) 1 010 740 Al discusses concentrated cooling liquids that comprise 80 wt% to 95 wt% of glycerin, 1 to 12 wt% of water and 2.0 wt% to 5.0 wt% of an additive such as a corrosion inhibitor, a stabilizing additive or a pH adjustment additive.
  • EP' 740 also discusses diluted cooling liquids that comprise water in volume proportions of one part of the concentrated liquid to 0.01 parts to 10 parts of water.
  • USP 4,131,250 (Binckley) provides teachings relative to a means for preventing accumulation of ice on a helicopter main rotor blade using a freezing point depressant fluid.
  • the freezing point depressant fluid comprises, for example, a glycerin- alcohol mixture.
  • British Patent Publication (UK) 2 050 398 (Sewell) relates to polyethylene glycol (EG) based de-icing and anti-icing compositions.
  • the compositions comprise EG and a low molecular weight alcohol, possibly in paste form.
  • the compositions may also include one or more of shellac, polyvinyl acetate, a liquid detergent or a water-insoluble plasticizer.
  • USP 7,387,748 (Pellet et al.) describes an improved antifreeze coolant composition that has a pH of from about 7.8 to 11.1 and consisting of water and a glycol in a weight ratio of about 95:5 to 5:95 respectively, and about 0.01 wt% to about 5 wt% of at least one additive selected from a group of hydroxy benzoic acids and their alkali metal salts.
  • Pellet et al. notes that most glycol coolant formulations will contain a ratio of water to glycol which varies from about 60:40 to about 40:60 respectively.
  • the glycol is, per the claims, at least one of eight glycols, two of which are propylene glycol and glycerin. Sapienza et al., in a series of patents and patent publications, one of which is United
  • the fluids may contain, for example, glycerin, an organic acid salt and water.
  • An alternate fluid includes a hydroxyl-containing organic compound such as a hydrocarbyl aldoside or a glycol, a carbonate salt and water.
  • Suitable glycols include glycerin, ethylene glycol and propylene glycol.
  • compositions consist essentially of one or more polyhydric alcohols and one or more non-potassium, low carbon percentage organic compounds and, optionally, one or more non-potassium, non-halide inorganic compounds and/or monohydric alcohols.
  • this invention is an antifreeze composition, the composition comprising propylene glycol, glycerin, water and at least one corrosion inhibitor, the water being present in an amount within a range of from 50 percent by weight (wt%) to 90 wt%, the propylene glycol and the glycerin being present in a combined amount within a range of from 10 wt% to 50 wt%, the amounts of water, propylene glycol and glycerin combining to equal 100 percent by weight, with all percentages by weight being based upon combined weight of water, propylene glycol and glycerin, the propylene glycol and the glycerin being present in a weight ratio of glycerin to propylene glycol that falls within a range of from 0.05:1 to 1:1, and the corrosion inhibitor being present in an amount within a range of from 0.5 part by weight per 100 parts by weight of combined weights of water, propylene glycol and glycerin (phr) to 5 p
  • this invention is a concentrate composition suitable for use in preparing the anti-freeze compositions of this invention.
  • the concentrate composition comprises propylene glycol, glycerin and at least one corrosion inhibitor and, preferably very little (e.g. less than 10 wt%, based upon total concentrate weight), and more preferably from greater than 0 wt% to less than 3 wt%.
  • Skilled artisans understand that a water content of 0 wt%, while possible, is impractical when one wants to include any corrosion inhibitor that is both substantially insoluble in a glycol such as PG but soluble, often highly soluble in water.
  • the concentrate composition includes water in an amount sufficient to facilitate addition of glycol-insoluble corrosion inhibitors.
  • references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 2003. Also, any references to a Group or Groups shall be to the Group or Groups reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
  • compositions claimed herein through use of the term “comprising” may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary.
  • the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability.
  • the term “consisting of” excludes any component, step or procedure not specifically delineated or listed.
  • Anti-freeze compositions used in at least some embodiments of this invention comprise a mixture of propylene glycol (PG) and glycerin that is diluted with water in an amount of at least 50 wt%, based upon total composition weight. Such compositions have a lower viscosity than that of an anti-freeze composition containing the same amount of water and an amount of PG that equals weight percentage of the mixture of propylene glycol and glycerin.
  • anti-freeze compositions of this invention that include a controlled amount of glycerin (e.g.
  • glycerin to PG in a weight ratio of glycerin to PG of less than 1: 1, preferably within a range of from 0.1: 1 to 0.5:1, and more preferably within a range of from 0.2: 1 to 0.4:1) and a water content of at least 50 wt%, based upon total composition weight, have a lower viscosity but comparable or near equivalent antifreeze properties and corrosion-resistance properties relative to an anti-freeze composition containing the same amount of water and an amount of PG that equals the volume percentage of the mixture of PG and glycerin.
  • Anti-freeze compositions of the present invention have utility in all conventional anti-freeze and heat transfer fluid applications. They have particular utility in anti-freeze applications such as plumbing anti-freeze used for winterization of recreational vehicles (RVs), food industry applications as secondary coolants used for refrigeration or freezing purposes, and various other Low Temperature Thermal Fluid (LTTF) applications.
  • RVs recreational vehicles
  • LTTF Low Temperature Thermal Fluid
  • glycerin has a higher viscosity than pure PG. Skilled artisans also understand that, when diluted with water, glycerin decreases in viscosity more substantially and more rapidly than propylene glycol. See Table 1 below for viscosity data (in centipoises (cps)) relative to pure glycerin and pure propylene glycol as well as mixtures of either glycerin or PG with various amounts of water. In particular, Table 1 shows that glycerin-water solutions with a water content of at least 50 wt%, based on total solution weight, have a lower viscosity than solutions of PG-water with the same water content.
  • cps centipoises
  • Table 2 below illustrates a discovery that, up to a ratio of glycerin to propylene glycol that is less than or equal to 1:1, mixtures of glycerin and propylene glycol with a water content of at least 50 wt%, based upon total mixture weight, have a lower viscosity than a composition that contains propylene glycol rather than a mixture of propylene glycol and glycerin at the same water content. While mixtures of glycerin and propylene glycol with a ratio in excess of 1 : 1 may be used in at least some of the end use applications noted above (e.g. RV antifreeze), reductions in viscosity that follow substitution of some glycerin for an equal volume (or weight) of propylene glycol, tend to shrink in magnitude with increasing glycerin content.
  • Glycerin has a higher molecular weight than PG. This tends to make glycerin less efficient than PG in depressing the freezing point of water.
  • Glycerin also has a higher density than PG, a factor that offsets at least some of lowered freezing point depression efficiency as long as one compares volumetric mixtures of glycerin.
  • replacing some propylene glycol with an equal volume of glycerin means that a given volume of a mixture of propylene glycol and glycerin has a greater mass than an equal volume of propylene glycol when each is used as a freezing point depressant.
  • Table 3 shows that a glycerin to propylene glycol ratio of from greater than 0.0:1 to 1.0:1 or less in glycerin/propylene glycol water solutions causes a reduction in anti-freezing properties, relative to PG water solutions, of less than 1%.
  • Glycerin has a number of characteristics that favor its use as a substitute for a portion of propylene glycol in a propylene glycol/water solution used in an anti-freeze end use application.
  • glycerin exhibits toxicity, flammability and environmental impact comparable to that of propylene glycol.
  • mixtures of glycerin and propylene glycol should merit a rating of "non-toxic, non-flammable and environmentally benign" just as propylene glycol does.
  • both glycerin and propylene glycol merit a classification of
  • glycerin and propylene glycol could also be used as direct food additives.
  • glycerin nor propylene glycol has a measurable flash point when mixed with at least 15 wt% water.
  • the anti-freeze compositions of various embodiments of this invention should pose no risk of ignition into flames or supporting a fire.
  • Propylene glycol and glycerin are both considered to be readily bio-degradable and can be produced from bio-renewable sources.
  • aqueous solutions of glycols e.g. PG
  • glycols e.g. PG
  • glycerin oxidize and form acidic degradation compounds like formic, glycolic or lactic acids as well as various aldehydes. They also know that such solutions undergo a decrease in pH over time.
  • skilled practioners typically add at least one of a corrosion inhibitor and a buffering compound to the aqueous solutions.
  • Dipotassium phosphate represents a commonly-added, acid-neutralizing compound that at least partially protects common metals like carbon steel, cast iron, solders and even copper alloys from corrosion.
  • Skilled artisans further know that degradation reactions for glycerin tend to be far more facile than degradation reactions for propylene glycol such that corrosion inhibitors and pH buffering components like dipotassium phosphate are less effective in solutions based upon glycerin as sole freezing point depressant relative to solutions based on PG as sole freezing point depressant.
  • the anti-freeze compositions of various embodiments of this invention have a lower thermal oxidative degradation rate, as shown by a lower reduction in pH and a lower weight loss, than 100 % glycerin.
  • Table 4 below for data related to pH and weight loss for carbon steel and cast iron, with weight loss being determined in accord with American Society for Testing and Materials (ASTM) D 1384-05 (Corrosion Test for Engine Coolants in Glassware Corrosion, current edition approved June 1, 2005). All Table 4 solutions contain 0.5wt% dipotassium phosphate as a corrosion inhibitor.
  • the % values shown in Table 4 represent wt%, based upon combined weight of PG and glycerol in a concentrate prior to dilution of the concentrate in accord with ASTM D 1384-05.
  • Table 4 The effect of propylene glycol addition on glycerin degradation and corrosivity
  • 100 wt% glycerin (in this instance USP Grade glycerin) has a corrosion rate for cast iron and carbon steel that is more than 100 times as severe as that for 100wt% PG.
  • the severity is consistent with the drop in pH of 100% glycerin relative to the drop in pH for 100% PG.
  • impurities such as chlorides and acid salts should increase severity of the degradation.
  • the data in Table 4 show that a 50/50 wt/wt mixture of glycerin and PG has an unexpectedly low corrosion weight loss relative to pure glycerin.
  • Degradation compounds of glycerin and propylene glycol tend to be acidic in nature. Accordingly, the pH of anti-freezing compositions based upon either of glycerin and propylene glycol or, in embodiments of this invention, a mixture of glycerin and propylene glycol normally decreases with time particularly when subjected to the conditions of ASTM D 1384-05. As a general rule, glycerin degradation reactions tend to be more facile than propylene glycol degradation reactions. On that basis, many of the corrosion inhibitors and pH buffering compounds that function acceptably well in solutions of propylene glycol either have limited effectiveness or are totally ineffective in solutions of glycerin.
  • the anti-freeze compositions of various embodiments of this invention have a surprisingly acceptable corrosivity performance notwithstanding the presence of glycerin in mixtures of glycerin and propylene glycol with a glycerin to propylene glycol ratio of greater than 0:1 but less than 0.5:1.
  • ASTM D1384-05 specifies dilution of a concentrate with water to form a solution that contains 33-1/3 volume percent (vol%) concentrate components and 67-2/3 vol% water, each vol% being based on total volume of water and concentrate.
  • Each concentrate contains 2.0 wt% of dipotassium phosphate as a corrosion inhibitor. This provides the solution with a dipotassium phosphate content of about 0.67 wt%, based upon solution weight
  • the weight ratio of glycerin to propylene glycol preferably falls within a range of from 0.1:1 to 0.5:1.
  • the weight ratio of glycerin to propylene glycol more preferably within a range of from 0.2:1 to 0.4:1.
  • the corrosion inhibitor is at least one inhibitor selected from a group consisting of a water-soluble, alkali metal phosphate, an alkali metal or ammonium hydroxide-neutralized aliphatic monocarboxylic acid having from eight to 14 carbon atoms and a pH within a range of from 7 to 10, an alkali metal or ammonium hydroxide-neutralized aliphatic dicarboxylic acid having from eight to 14 carbon atoms and a pH within a range of from 7 to 10, an aromatic or substituted aromatic monocarboxylic acid that has from seven to 14 carbon atoms or its alkali metal salt or ammonium salt, an alkali metal borate, an alkali metal silicate, an alkali metal molybdate, an alkali metal nitrate, and an alkali metal nitrite.
  • a water-soluble, alkali metal phosphate an alkali metal or ammonium hydroxide-neutralized aliphatic monocarboxylic acid having from eight to 14
  • the corrosion inhibitor is dipotassium phosphate.
  • the dipotassium phosphate is preferably present in an amount within a range of from 1.5 parts by weight per 100 parts by weight of combined weights of water, propylene glycol and glycerin to 4 parts by weight per 100 parts by weight of combined weights of water, propylene glycol and glycerin.
  • the corrosion inhibitor is a combination of dipotassium phosphate and sebacic acid, each of the dipotassium phosphate and the sebacic acid being present in an amount of at least 0.5 parts by weight per 100 parts by weight of combined weights of water, propylene glycol and glycerin, and the composition further comprises an amount of alkali metal hydroxide sufficient to neutralize at least a portion of acid moieties of the sebacic acid and provide the composition with a pH within a range of from 7.8 to 8.4.
  • the corrosion inhibitor is sebacic acid, the sebacic acid being present in an amount within a range of from 1.5 parts by weight per 100 parts by weight of combined weights of water, propylene glycol and glycerin to 4 parts by weight per 100 parts by weight of combined weights of water, propylene glycol and glycerin, and the composition further comprises an amount of alkali metal hydroxide sufficient to neutralize at least a portion of acid moieties of the sebacic acid and provide the composition with a pH within a range of from 7.8 to 8.4.
  • Glycerin suitable for use in compositions of various embodiments of this invention may be obtained from any source and is preferably either synthetic or vegetable oil-based (also known as "bio-renewable"). All other factors being equal, bio-renewability makes vegetable oil-based glycerin a particularly preferred material for use in compositions of this invention. While Unites States Pharmaceutical (USP) grade glycerin yields particularly satisfactory results in any of a variety of end use applications, one may also use lesser grades of glycerin, such as industrial grade glycerin, in some less demanding applications such as those where there is essentially no likelihood of contact between the compositions and food or potable water. In addition, sources of glycerin with an assay of less than 99.5% may be used provided the source consists only of glycerin and water.
  • USP Unites States Pharmaceutical
  • Propylene glycol like glycerin, need not be obtained from any particular source or process.
  • the propylene glycol may be derived via catalytic hydrogenation of vegetable based glycerin (also known as "bio-renewable propylene glycol").
  • the propylene glycol may also be sourced from recycled or reclaimed post-consumer or industrially-use propylene glycol streams.
  • propylene glycol grades that do not meet USP requirements provided that the anti-freezing composition has no more than a possibility of incidental contact with food or potable water.
  • a source of propylene glycol with an assay substantially less than 99.5% as long as the source consists only of propylene glycol and water.
  • a preferred technique involves initial preparation of a concentrate that consists of propylene glycol, glycerin and no more than a minor fraction (e.g. less than 5 wt%) of water desired for compositions of this invention.
  • the concentrate also preferably consists of one or more corrosion inhibitors and/or pH buffering components. Dilution of the concentrate with a suitable volume of water readily facilitates preparation of anti-freezing compositions of various embodiments of this invention. If desired, one may modify an existing anti-freezing composition that consists of propylene glycol, water and a corrosion inhibitor by adding thereto an amount of glycerin sufficient to provide a weight ratio of glycerin to propylene glycol that falls within a range of from 0.05:1 to 1: 1.
  • the existing anti-freezing composition contains less than 50 percent by weight of water, based upon total composition weight, one may also modify the existing anti-freezing composition by adding water sufficient water to increase the water content to at least 50 percent by weight, preferably in conjunction with addition of the aforementioned amount of glycerin. Skilled artisans recognize that one may add water in an amount sufficient to increase the water content to at least 50 weight percent in a single aliquot or multiple aliquots and in one or more of before, at the same time as, or after addition of the glycerin.
  • test solutions with instrument grade air through a one quarter inch (0.64 centimeter (cm)) gas dispersion tube at a flow rate of 100 cubic centimeters per minute (cc/min).
  • cc/min cubic centimeters per minute
  • Example 1 Anti-freezing concentrate composition having a glycerin to PG ratio of 0.26: 1

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  • Engineering & Computer Science (AREA)
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  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

L'invention porte sur des concentrés antigel comprenant du propylèneglycol, une quantité spécifiée de glycérol et un inhibiteur de corrosion. Les solutions antigel résultent d'une dilution d'un concentré avec au moins 50 pour cent en poids d'eau, par rapport au poids total de la solution. Les solutions antigel ont une viscosité inférieure à celle d'une solution antigel préparée avec le même pourcentage en poids d'eau mais exempte de tout glycérol. Les solutions antigel ont des propriétés de point de congélation (par exemple une baisse du point de congélation) et des propriétés de résistance à la corrosion (par exemple de corrosion de fonte) comparables à celles de la solution antigel préparée avec le même pourcentage en poids d'eau mais exempte de tout glycérol.
PCT/US2009/049666 2008-07-16 2009-07-06 Compositions de propylèneglycol/glycérol empêchant la corrosion Ceased WO2010008951A1 (fr)

Applications Claiming Priority (2)

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US8106408P 2008-07-16 2008-07-16
US61/081,064 2008-07-16

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012154768A3 (fr) * 2011-05-09 2013-04-04 Lubrizol Advanced Materials, Inc. Fluide d'extinction d'incendie contenant un sel de type carboxylate
ITMI20112290A1 (it) * 2011-12-16 2013-06-17 Dks Aromatic Srl Composizione per sigarette elettroniche
WO2014160349A3 (fr) * 2013-03-13 2014-11-27 Globaltech Fluids, Llc Systèmes de liquide de refroidissement de glycérol
CN104531087A (zh) * 2014-12-01 2015-04-22 张山 一种高聚物复合的防冻液
CN107987802A (zh) * 2016-10-26 2018-05-04 中国石油化工股份有限公司 一种耐高温的发动机冷却液
WO2020077175A1 (fr) * 2018-10-12 2020-04-16 Lubrizol Advanced Materials, Inc. Fluide d'extinction d'incendie contenant un sel de type carboxylate
EP4153695A4 (fr) * 2020-05-19 2024-06-26 Tyco Fire Products LP Antigel amélioré pour systèmes gicleurs d'incendie

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US4455248A (en) * 1982-06-01 1984-06-19 Shell Oil Company Antifreeze compositions
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WO2012154768A3 (fr) * 2011-05-09 2013-04-04 Lubrizol Advanced Materials, Inc. Fluide d'extinction d'incendie contenant un sel de type carboxylate
ITMI20112290A1 (it) * 2011-12-16 2013-06-17 Dks Aromatic Srl Composizione per sigarette elettroniche
WO2013088230A1 (fr) * 2011-12-16 2013-06-20 Dks Aromatic S.R.L. Composition pour cigarettes électroniques
US9596881B2 (en) 2011-12-16 2017-03-21 Dks Aromatic S.R.L. Composition for electronic cigarettes
WO2014160349A3 (fr) * 2013-03-13 2014-11-27 Globaltech Fluids, Llc Systèmes de liquide de refroidissement de glycérol
CN104531087A (zh) * 2014-12-01 2015-04-22 张山 一种高聚物复合的防冻液
CN107987802A (zh) * 2016-10-26 2018-05-04 中国石油化工股份有限公司 一种耐高温的发动机冷却液
CN107987802B (zh) * 2016-10-26 2020-06-09 中国石油化工股份有限公司 一种耐高温的发动机冷却液
WO2020077175A1 (fr) * 2018-10-12 2020-04-16 Lubrizol Advanced Materials, Inc. Fluide d'extinction d'incendie contenant un sel de type carboxylate
CN112839719A (zh) * 2018-10-12 2021-05-25 路博润先进材料公司 含有羧酸盐的灭火流体
KR20210072011A (ko) * 2018-10-12 2021-06-16 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 카복실레이트 염을 함유하는 화재 진압 유체
US12151132B2 (en) 2018-10-12 2024-11-26 Lubrizol Advanced Materials, Inc. Fire suppression fluid containing a carboxylate salt
AU2019358080B2 (en) * 2018-10-12 2025-04-10 Lubrizol Advanced Materials, Inc. Fire suppression fluid containing a carboxylate salt
KR102806835B1 (ko) 2018-10-12 2025-05-12 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 카복실레이트 염을 함유하는 화재 진압 유체
EP4153695A4 (fr) * 2020-05-19 2024-06-26 Tyco Fire Products LP Antigel amélioré pour systèmes gicleurs d'incendie

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