PT1716216E - Composições contendo olefinas substituídas por flúor - Google Patents
Composições contendo olefinas substituídas por flúor Download PDFInfo
- Publication number
- PT1716216E PT1716216E PT05744161T PT05744161T PT1716216E PT 1716216 E PT1716216 E PT 1716216E PT 05744161 T PT05744161 T PT 05744161T PT 05744161 T PT05744161 T PT 05744161T PT 1716216 E PT1716216 E PT 1716216E
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- Prior art keywords
- compositions
- hfo
- present
- refrigerant
- quot
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- 239000000203 mixture Substances 0.000 title claims description 80
- 150000001336 alkenes Chemical class 0.000 title description 5
- 229910052731 fluorine Inorganic materials 0.000 title 1
- 239000011737 fluorine Substances 0.000 title 1
- 125000001153 fluoro group Chemical group F* 0.000 title 1
- 239000003507 refrigerant Substances 0.000 claims description 48
- 239000000314 lubricant Substances 0.000 claims description 21
- 238000004378 air conditioning Methods 0.000 claims description 13
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 4
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 claims description 3
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 24
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 23
- 238000005057 refrigeration Methods 0.000 description 20
- 239000003921 oil Substances 0.000 description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 description 6
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920004449 Halon® Polymers 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MEXUFEQDCXZEON-UHFFFAOYSA-N bromochlorodifluoromethane Chemical compound FC(F)(Cl)Br MEXUFEQDCXZEON-UHFFFAOYSA-N 0.000 description 2
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- -1 fluorine-substituted carbon atoms Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 description 1
- CDOOAUSHHFGWSA-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropene Chemical compound FC=CC(F)(F)F CDOOAUSHHFGWSA-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical class CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YNKZSBSRKWVMEZ-UHFFFAOYSA-N bromo-chloro-fluoromethane Chemical compound FC(Cl)Br YNKZSBSRKWVMEZ-UHFFFAOYSA-N 0.000 description 1
- LHMHCLYDBQOYTO-UHFFFAOYSA-N bromofluoromethane Chemical class FCBr LHMHCLYDBQOYTO-UHFFFAOYSA-N 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000005068 cooling lubricant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000005828 hydrofluoroalkanes Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000005647 hydrohalogenation reaction Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010726 refrigerant oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- 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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N29/00—Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
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- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/202—Aliphatic compounds
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K9/0073—Sprays or powders for inhalation; Aerolised or nebulised preparations generated by other means than thermal energy
- A61K9/008—Sprays or powders for inhalation; Aerolised or nebulised preparations generated by other means than thermal energy comprising drug dissolved or suspended in liquid propellant for inhalation via a pressurized metered dose inhaler [MDI]
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/0057—Polyhaloalkanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D11/00—Solvent extraction
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- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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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
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/08—Organic materials containing halogen
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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
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- C09K3/00—Materials not provided for elsewhere
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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
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- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
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- C—CHEMISTRY; METALLURGY
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Description
1
DESCRIÇÃO "COMPOSIÇÕES CONTENDO OLEFINAS SUBSTITUÍDAS POR FLÚOR"
CAMPO DA INVENÇÃO A invenção refere-se a composições refrigerantes, utilizáveis nos sistemas de condicionamento de ar dos automóveis.
ANTECEDENTES DA INVENÇÃO
Os líquidos à base de fluorcarbono encontraram uma vasta utilização em muitas aplicações comerciais e industriais. Por exemplo, os líquidos à base de fluorcarbono são frequentemente utilizados como liquidos de trabalho em sistemas, como sejam os de aplicações de condicionamento de ar, bombas de calor e refrigeração. O ciclo de compressão do vapor é um dos tipos de método mais vulgarmente usados para se conseguir o arrefecimento ou o aquecimento num sistema de refrigeração. 0 ciclo de compressão do vapor envolve, geralmente, a mudança de fase do refrigerante, da liquida para a fase de vapor por intermédio da absorção do calor a uma pressão relativamente baixa e depois, de vapor para a fase liquida, através da remoção do calor a uma pressão e a uma temperatura relativamente baixas, comprimindo-se o vapor para uma pressão relativamente elevada, condensando-se o vapor para a fase liquida através da remoção do calor a essa pressão e temperatura relativamente elevadas e reduzindo-se depois a pressão para se reiniciar o ciclo.
Enquanto que a finalidade da refrigeração é remover o calor de um objecto ou de outro liquido a uma temperatura relativamente baixa, o principal propósito de uma bomba de 2 calor é acrescentar calor a uma temperatura mais elevada relativamente à do ambiente.
Determinados fluorcarbonos têm sido um componente preferido, desde há muitos anos, em muitos líquidos de permuta de calor, como sejam os refrigerantes, em muitas aplicações. Por exemplo, fluoralcanos, como sejam os derivados de clorofluormetano e de clorofluoretano, ganharam uma aplicação generalizada como refrigerantes em aplicações, que incluem o condicionamento de ar e as aplicações de bomba de calor, devido à sua combinação única de propriedades químicas e físicas. Muitos dos refrigerantes vulgarmente utilizados nos sistemas de compressão de vapor são, ou líquidos de componente único ou misturas azeotrópicas. Têm aumentado em anos recentes as preocupações acerca dos danos infligidos à atmosfera e ao clima terrestres e determinados compostos à base de cloro foram identificados como sendo especialmente problemáticos sob esse aspecto. 0 uso de composições que contêm cloro (como sejam os clorofluorcarbonos (CFCs), os hidroclorofluorcarbonos (HCFCs) e semelhantes) como refrigerantes, em sistemas de condicionamento de ar e de refrigeração, começou a ser desfavorecido devido às propriedades de destruição do ozono associadas a muitos desses compostos. Surgiu assim uma crescente necessidade de novos compostos e composições de fluorcarbonos e hidrofluorcarbonos, que ofereçam alternativas para aplicações de refrigeração e bomba de calor. Tornou-se desejável, por exemplo, recuperar sistemas de refrigeração, que continham cloro, por meio da substituição dos refrigerantes que continham cloro, por compostos refrigerantes que não continham cloro, os quais 3 não irão destruir a camada de ozono, como sejam os hidrofluorcarbonos (HFCs).
No entanto, é geralmente considerado importante que qualquer refrigerante potencialmente substituto tenha também de possuir as propriedades presentes em muitos dos líquidos mais largamente usados, como sejam excelentes propriedades de transferência de calor, estabilidade química, baixa ou nenhuma toxicidade, não inflamabilidade e compatibilidade com lubrificantes lubrificante, entre outras.
Os requerentes verificaram que a compatibilidade com lubrificantes é de particular importância em muitas aplicações. Mais particularmente, é altamente desejável que os líquidos de refrigeração sejam compatíveis com o lubrificante utilizado na unidade compressora, usado na maioria dos sistemas de refrigeração. Infelizmente, muitos dos líquidos refrigerantes, que não contêm cloro, incluindo os HFCs, são relativamente insolúveis e/ou imiscíveis nos tipos de lubrificantes usados tradicionalmente com CFCs e HFCs, incluindo, por exemplo, óleos minerais, alquilbenzenos ou poli (alfa-olefinas). Para que uma combinação de líquido de refrigeração e líquido de lubrificação funcione a um nível desejável de eficácia, dentro de um sistema de refrigeração por compressão, condicionamento de ar e/ou bomba de calor, o lubrificante deverá ser suficientemente solúvel no líquido de refrigeração ao longo de uma vasta gama de temperaturas de funcionamento. Tal solubilidade diminui a viscosidade do lubrificante e permite-lhe que flua mais facilmente através do sistema. Na ausência de tal solubilidade os lubrificantes tendem a ficar alojados nas serpentinas do 4 evaporador de refrigeração, do sistema de condicionamento do ar ou da bomba de calor, bem como em outras partes do sistema e assim a reduzir a eficácia do sistema.
No que se refere à eficácia em utilização, é importante notar que uma perda do desempenho termodinâmico ou da eficácia energética do refrigerante pode ter impactos ambientais secundários devido à utilização acrescida de combustível fóssil, por causa de um aumento da exigência de energia eléctrica.
Além disso, é geralmente considerado desejável que os substitutos do refrigerante CFC sejam eficazes sem grandes modificações de engenharia da tecnologia convencional de compressão de vapor actualmente usada com os refrigerantes de CFC. A inflamabilidade é outra propriedade importante de muitas aplicações. Ou seja, considera-se importante ou essencial em muitas aplicações, incluindo particularmente aplicações de transferência de calor, utilizarem-se composições, que não sejam inflamáveis. É, portanto, frequentemente benéfico utilizar em tais composições, compostos que não sejam inflamáveis. Conforme aqui utilizado o termo "não inflamável" refere-se a compostos ou composições, que são determinados para ser não inflamáveis, conforme estabelecido de acordo com a norma astm e-681, datada de 2002, a qual é aqui incorporada como referência. Infelizmente, muitos HFCs, que de outro modo seriam desejáveis para utilização em composições refrigerantes, são inflamáveis. Por exemplo, o fluoralcano difluoretano (HFC-152a) e o fluoralceno 1,1,1-trifluorpropeno (HFO- 5 1243zf) são ambos inflamáveis e por isso não viáveis para uso em muitas aplicações.
Fluoralcenos mais elevados, ou seja alcenos com pelo menos cinco átomos de carbono substituídos por flúor, têm sido sugeridos para utilização como refrigerantes. A Patente U.S N° 4,788,352 - Smutny, dirige-se à produção de compostos fluoretados C5 a Cg com pelo menos um certo grau insaturação. A patente de Smutny identifica tais olefinas superiores como sendo conhecidas pela sua utilidade como refrigerantes, pesticidas, líquidos dieléctricos, líquidos de transferência de calor, solventes e intermediários em diversas reacções químicas. (Ver coluna 1, linhas 11-22).
Muito embora as olefinas fluoretadas descritas em Smutny possam ter um certo grau de eficácia em aplicações de transferência de calor, crê-se que tais compostos podem também apresentar determinadas desvantagens. Por exemplo, alguns desses compostos podem tender a atacar os substratos, particularmente plásticos de aplicação geral, como sejam as resinas acrílicas e as resinas ABS. Além disso, os compostos olefínicos superiores descritos em Smutny podem também ser indesejáveis em determinadas aplicações, devido ao nível potencial de toxicidade de tais compostos, que pode resultar da actividade pesticida observada em Smutny. Tais compostos podem também ter um ponto de ebulição, que é demasiado elevado para os tornar úteis como refrigerantes em determinadas aplicações.
Os derivados de bromofluormetano e bromoclorofluormetano, especialmente o bromotrifluormetano (Halon 1301) e o bromoclorodifluormetano (Halon 1211) ganharam uma utilização generalizada como agentes extintores de fogo em 6 áreas fechadas, como sejam cabinas de aeronaves e salas de computadores. No entanto, o uso de diversos halons tem sido afastado devido ao seu elevado potencial de destruição do ozono. Além disso, como os halons são frequentemente usados em áreas onde se encontram presentes seres humanos, os substitutos adequados têm também de ser seguros para o homem nas concentrações necessárias para suprimir ou extinguir o fogo. A JP 04 110 388 A dirige-se à obtenção de líquidos novos destinados a finalidades de transferência de calor, os quais são adequados para bombas de calor e motores térmicos. A invenção descrita é um meio de transferência de calor, que compreende um composto orgânico, o qual pode ser representado pela fórmula molecular C3HmFn (em que m representa entre 1 e 5, n representa entre le5em+n= 6) e que possui um vínculo duplo na estrutura molecular. A US 6,111,150 descreve um método para a produção de um alcano fluoretado, nomeadamente 1,1,1,3,3-pentafluorpropano, que se diz ser útil como agente produtor de espuma, como refrigerante e semelhantes. O método inclui um passo de adição de fluoreto de hidrogénio ao 1,1,1,3,3-pentafluorpropeno numa fase líquida, em presença de um catalisador de hidro-halogenação. É também descrito Um método para a formação de 1,3,3,3-tetrafluorpropeno, que se diz ser útil como intermediário de medicamentos, de químicos agrícolas, como material funcional e como refrigerante e semelhantes. A US 6,089,032 descreve um conjunto de adaptação técnica e um método para a reconversão de um condicionador de ar R-12 num condicionador de ar R134A. 7
RESUMO
Os requerentes verificaram que composições compreendendo um tetrafluorpropeno (HFO-1234) são utilizáveis nos sistemas de condicionamento de ar de automóveis.
DESCRIÇÃO PORMENORIZADA DE FORMAS DE REALIZAÇAO PREFERIDAS
DAS COMPOSIÇÕES A presente invenção dirige-se à utilização de composições, que compreendem pelo menos um tetrafluorpropeno, em sistemas de condicionamento de ar de automóveis.
Inesperada e surpreendentemente, os requerentes verificaram que determinados compostos, utilizáveis na invenção, apresentam um nível muito desejável de baixa toxicidade quando comparados com outros desses compostos. Conforme pode ser facilmente entendido, esta verificação é potencialmente de uma enorme vantagem e beneficio para a formulação, não apenas de composições refrigerantes, como também de qualquer ou de todas as composições, que satisfaçam as fórmulas acima descritas, as quais de outro modo conteriam compostos relativamente tóxicos.
As composições da presente invenção compreendem um ou mais tetrafluorpropenos. 0 termo "HFO-1234" é aqui usado para referir todos os tetrafluorpropenos. Entre os tetrafluorpropenos, tanto o cis- como o trans-1,3,3,3-tetrafluorpropeno (HFO-1234ze) são especialmente preferidos. 0 termo HFO-1234ze é aqui genericamente usado para referir o 1,3,3,3-tetrafluorpropeno, independentemente de se encontrar na forma cis- ou na forma trans-. Os termos "cisHFO-1234ze" e "transHFO-1234ze" são aqui utilizadas 8 para descrever respectivamente as formas cis- e trans- do 1,3,3,3-tetrafluorpropeno. 0 termo "HFO-1234ze" inclui por isso, no seu âmbito, cisHFO-1234ze, transHFO-1234ze e todas as combinações e misturas desses.
Embora as propriedades do cisHFO-1234ze e do transHFO-1234ze difiram, pelo menos nalguns aspectos, está contemplado que cada um desses compostos pode ser adaptado para utilização, seja isoladamente seja em conjunto com outros compostos que incluam o seu estereoisómero. Consequentemente, deve entender-se que os termos "HFO-1234ze" e 1,3,3,3-tetrafluorpropeno se referem a ambos os estereoisómeros e o uso deste termo pretende indicar que cada uma das formas cis- e trans- se aplica e/ou é útil para a finalidade declarada, a menos que esteja indicado de outro modo.
Os compostos de HFO-1234 são materiais conhecidos e encontram-se listados na base de dados de Chemical Abstracts. A produção de fluorpropenos, como seja o CF3CH=CH2 por meio de fluoretação catalítica da fase de vapor de diversos compostos halogéneos, saturados e insaturados, contendo C3, encontra-se descrita nas patentes U.S. N°s 2, 889,379; 4, 798, 818 e 4,465, 786, cada uma das quais é aqui incorporada como referência. A EP 974,571, também aqui incorporada como referência, descreve a preparação de 1,1,1,3-tetrafluorpropeno por meio da colocação em contacto de 1,1,1,3,3-pentafluorpropano (HFC-245fa), na fase de vapor, com um catalisador à base de crómio a uma temperatura elevada, ou, na fase líquida, com uma solução alcoólica de KOH, NaOH, Ca(OH)2 ou Mg(OH)2. Além disso são descritos genericamente métodos para a produção de compostos de acordo com a presente invenção, em 9 ligação com a patente pendente norte-americana intitulada “Process for Producing Fluoropropenes"[Processo para a Produção de Fluorpropenos], portadora do número de agente (H0003789 (26267)), que é também aqui incorporada como referência.
Crê-se que as composições para utilização na presente invenção, especialmente aquelas que compreendem HFO-1234ze, possuem propriedades, as quais são vantajosas por um grande número de razões. Por exemplo, os requerentes crêem, com base, pelo menos parcialmente, em modelos matemáticos, que as fluorolefinas da presente invenção não terão um efeito substancialmente negativo sobre a química da atmosfera, sendo contribuintes negligenciáveis para a destruição do ozono, quando comparados com outras espécies halogenadas. As composições preferidas da presente invenção têm portanto a vantagem de não contribuir substancialmente para a destruição do ozono. As composições preferidas também não contribuem substancialmente para o aquecimento global, quando comparadas com muitos dos hidrofluoralcanos presentemente utilizados.
Em determinadas formas preferidas as composições destinadas a ser utilizadas na presente invenção, possuem um Potencial de Aquecimento Global (Global Warming Potential (GWP)) não superior a cerca de 1000, mais preferivelmente não superior a 500 e ainda mais preferivelmente não superior a cerca de 150. Em certas formas de realização, o GWP das presentes composições não é superior a 100 e ainda mais preferivelmente não é superior a cerca de 75. Conforme aqui utilizado, o "GWP" é medido em relação ao do dióxido de carbono e ao longo de um horizonte temporal de 100 anos, conforme definido em "Scientífíc Assessment of Ozone 10
Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project" [Avaliação Científica da Destruição do Ozono, 2002, um relatório do Projecto de Investigação e Monitorização Global do Ozono, da Associação Meteorológica Mundial], que é aqui incorporado como referência.
Em determinadas formas preferidas as composições para utilização na presente invenção têm também, de preferência um Potencial de Destruição do Ozono (Ozone Depletion Potential - (ODP)) não superior a 0,05, mais preferivelmente não superior a 0,02 e ainda mais preferivelmente de cerca de zero. Conforme aqui utilizado "ODP" é como está definido em "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project", o qual é aqui incorporado como referência. A quantidade de hfo-1234 contida nas presentes composições pode variar muito, dependendo da aplicação particular e composições contendo mais do que quantidades vestigiais e menos de 100% do composto situam-se dentro do âmbito alargado da presente invenção. Além disso, as composições para utilização na presente invenção podem ser azeotrópicas, tipo azeotrópico, ou não azeotrópicas. Em formas de realização preferidas, as composições compreendem HFO-1234, preferivelmente HFO-1234ze, em quantidades situadas entre cerca de 5% em peso e cerca de 99% em peso e mesmo mais, preferivelmente entre cerca de 5% e cerca de 95%. Muitos compostos adicionais podem ser incluídos nas presentes composições e a presença de todos esses compostos situa-se dentro do âmbito alargado da invenção. Em determinadas formas de realização preferidas, as 11 composições incluem, além de HFO-1234ze, um ou mais dos seguintes:
Difluorometano (HFC-32)
Pentafluoretano (HFC-125) 1.1.2.2- Tetrafluoretano (HFC-134) 1.1.1.2- Tetrafluoretano (HFC-134a)
Difluoretano (HFC-152a) 1.1.1.2.3.3.3- Heptafluoropropano (HFC-227ea) 1.1.1.3.3.3- Hexafluoropropano (HFC-236fa) 1.1.1.3.3- Pentafluoropropano (HFC-245fa) 1.1.1.3.3- Pentafluorobutano (HFC-365mfc) Água C02 A quantidade relativa de qualquer dos componentes acima referidos, bem como de quaisquer componentes adicionais, que possam ser incluídos nas composições destinadas a ser utilizadas na presente invenção, pode variar muito no âmbito alargado geral da presente invenção, de acordo com a aplicação particular da composição e todas essas quantidades relativas são consideradas como situando-se dentro do âmbito da invenção.
Muito embora esteja contemplado que as composições para utilização na presente invenção incluem um HFO-1234, em quantidades que variam muito, é geralmente preferido que as composições compreendam um HFO-1234 e preferivelmente HFO-1234ze, numa quantidade, que seja pelo menos de cerca de 50% em peso e mesmo mais, preferivelmente de pelo menos cerca de 70% em peso, da composição. Em muitas formas de realização é preferido que as composições para utilização na presente invenção compreendam transHFO-1234ze. Em determinadas formas de realização preferidas, as 12 composições para utilização na presente invenção compreendem uma combinação de cisHFO-1234ze e transHFO-1234ze numa proporção de peso cisrtrans de entre cerca de 1:99 e cerca de 10:99, mais preferivelmente de cerca de 1:99 a cerca de 3:97.
As composições para uso na presente invenção podem incluir outros componentes com a finalidade de melhorar ou proporcionar determinada funcionalidade à composição ou, nalguns casos, reduzir o custo da composição. Por exemplo, as composições podem incluir um lubrificante, geralmente em quantidades de entre cerca de 30 e cerca de 50 por cento em peso da composição. Além disso, as composições podem também incluir um compatibilizador, como seja o propano, com o objectivo de acrescentar compatibilidade e/ou solubilidade ao lubrificante. Tais compatibilizadores, que incluem propano, butanos e pentanos, estão de preferência presentes em quantidades de entre cerca de 0,5 e cerca de 5 por cento em peso da composição. Combinações de agentes tensioactivos e de agentes solubilizadores podem também ser acrescentadas às presentes composições, para ajudar à solubilidade do óleo, conforme descrito pela patente U.S.N0 6.516.837, cuja descrição é aqui incorporada como referência. Lubrificantes vulgarmente utilizados em refrigeração, como sejam Ésteres de Poliol (POEs) ou Polialquileno Glicóis (PAGs), óleo de silicone, óleo mineral, alquilbenzenos (ABs) e poli (alfa-olefinas) (PAO), que são utilizados na maquinaria de refrigeração com refrigerantes de hidrofluorcarbono (HFC), podem ser usados com as composições destinadas a ser utilizadas na presente invenção.
Muitos sistemas de refrigeração instalados estão actualmente adaptados para utilização em ligação com os 13 refrigerantes existentes e crê-se que as composições da presente invenção são adaptáveis para utilização em muitos de tais sistemas, seja com, seja sem modificações do sistema. As composições utilizáveis na presente invenção podem fornecer uma vantagem como substitutos, em sistemas que actualmente se baseiam em refrigerantes, possuidores de uma capacidade relativamente elevada. Para mais, em formas de realização, nas quais se deseje utilizar composições refrigerantes de menor capacidade devido a, por exemplo, razões de custos, para substituir um refrigerante de maior capacidade, as formas de realização das composições utilizáveis na presente invenção proporcionam uma vantagem potencial. Assim, é preferido, em determinadas formas de realização, utilizar-se composições, particularmente composições que compreendem uma proporção substancial de e nalgumas formas de realização sejam essencialmente constituídas por transHFO-1234ze, como substituto para os refrigerantes existentes, como seja o HFC-134a. Em determinadas aplicações, os refrigerantes da presente invenção permitem, potencialmente, a utilização benéfica de compressores de grande deslocação, disso resultando uma melhor eficácia energética do que com outros refrigerantes, como seja o HFC-134a. Por isso as composições utilizáveis na presente invenção, particularmente as composições que compreendem transHFO-1234ze, proporcionam a possibilidade de se conseguir uma vantagem competitiva, numa base energética, para aplicações de substituição de refrigerantes.
EXEMPLOS
Os exemplos que se seguem são fornecidos com a finalidade de ilustrar a presente invenção, mas sem lhe limitar o respectivo âmbito. 14 EXEMPLO 1 0 coeficiente de desempenho (COP - coefficient of performance) é uma medida universalmente aceite do desempenho de refrigeração, especialmente útil na representação da eficácia termodinâmica relativa de um refrigerante num ciclo especifico de aquecimento ou arrefecimento, que envolva a evaporação ou a condensação do refrigerante. Na engenharia de refrigeração, esse termo expressa a razão entre a refrigeração útil e a energia aplicada pelo compressor, ao comprimir o vapor. A capacidade de um refrigerante representa a quantidade de arrefecimento ou de aquecimento que fornece e proporciona uma determinada medida da capacidade de um compressor para bombear quantidades de calor para uma determinada taxa de fluxo volumétrico de refrigerante. Por outras palavras, dado um compressor especifico, um refrigerante com uma capacidade mais elevada fornecerá mais energia de arrefecimento ou de aquecimento. Uma maneira de calcular o COP de um refrigerante em condições de funcionamento especificas, é a partir das propriedades termodinâmicas do refrigerante com utilização de técnicas normalizadas de análise do ciclo de refrigeração (ver, por exemplo, R.C.Downing, FLUOROCARBON REFRIGERANTS HANDBOOK [Manual de Refrigerantes de Fluorcarbono] capitulo 3, Prentice-Hall, 1988) . É fornecido um sistema de ciclo de refrigeração/ condicionamento de ar, em que a temperatura do condensador é de cerca de 150°F e a temperatura do evaporador é de cerca de -35°F, sob uma compressão nominalmente isentrópica com uma temperatura interna do compressor de cerca de 50°F. 15 0 COP é determinado para diversas composições da presente invenção, ao longo de uma gama de temperaturas do condensador e do evaporador e é apresentado no Quadro 1 abaixo, com base num HFC-134a com um valor COP de 1,00, um valor de capacidade de 1,00 e uma temperatura de descarga de 175°F. QUADRO 1 COMPOSIÇÃO REFRIGERANTE COP Relativo CAPACIDADE Relativa TEMPERATURA DE DESCARGA (°F) HFO 1225ye* 1,02 0,76 158 HFO trans-1234ze 1,04 0,70 165 HFO cis-1234ze 1,13 0,36 155 HFO 1234yf 0,98 1,10 168 * Não abramgid a pela presente invenção.
Este exemplo mostra que algumas das composições preferidas para utilização na presente invenção, têm, cada uma delas, uma melhor eficácia energética do que o HFC-134a (1,02, 1,04 e 1,13 em comparação com 1,00) e o compressor, que utiliza as presentes composições refrigerantes, irá produzir temperaturas de descarga (158, 165 e 155 em comparação com 175), o que é vantajoso, uma vez que tal resultado irá conduzir à redução dos problemas de manutenção. EXEMPLO 2 É testada a capacidade de mistura da HFO-1225ye (não coberta pela presente invenção) e da HFO-1234ze, com diversos lubrificantes de refrigeração. Os lubrificantes testados são óleo mineral (C3), alquilbenzeno (Zerol 150), 16 óleo estérico (Mobil EAL 22 cc e Solest 120), óleo de polialquileno glicol (PAG) (Goodwrench Refrigeration Oil para sistemas 134a)e um óleo de poli(alfa-olefina) (CP-6005-100). Para cada combinação refrigerante/óleo são testadas três composições, nomeadamente 5, 20 e 50 por cento em peso do lubrificante, sendo o restante de cada uma o composto da presente invenção a ser testado.
As composições lubrificantes são colocadas em tubos de vidro de paredes espessas. Os tubos são postos em vácuo, o composto refrigerante de acordo com a presente invenção é introduzido e os tubos são então selados. Os tubos são depois postos numa câmara banhada por ar ambiente, cuja temperatura é variada entre cerca de -50°C e 70°C. Mais ou menos com intervalos de 10°C, são feitas observações visuais do conteúdo do tubo para detectar a existência de uma ou mais fases líquidas. No caso de ser observada mais do que uma fase líquida, a mistura é considerada como sendo imiscível. No caso de apenas ser observada uma fase líquida, a mistura é considerada como sendo miscível. Nos casos em que forem observadas duas fases líquidas, mas com uma das fases líquidas a ocupar apenas um volume muito pequeno, a mistura é considerada como parcialmente miscível.
Os lubrificantes de polialquileno glicol e de ésteres de óleo foram considerados como sendo miscíveis em todas as proporções testadas ao longo de toda a gama de temperaturas, com a excepção de que, para as misturas do HFO-1225ye com o polialquileno glicol, se verificou que a mistura refrigerante era imiscível na gama de temperaturas de -50°C a -30°C e era parcialmente miscível na gama de temperaturas entre -20°C e 50°C. A 50 por cento de peso de 17 concentração do PAG no refrigerante e a 60°, a mistura refrigerante/PAG era miscível. A 70°C era miscível a partir de 5 por cento em peso de lubrificante no refrigerante e até 50 por cento em peso de lubrificante no refrigerante. EXEMPLO 3 A compatibilidade das composições refrigerantes utilizáveis na presente invenção com óleos lubrificantes PAG, quando em contacto com metais usados em sistemas de refrigeração e de ar condicionado, é testada a 350°C, o que representa condições muito mais severas do que as encontradas em muitas aplicações de refrigeração e condicionamento de ar.
Aparas de alumínio, cobre e aço são introduzidas em tubos de vidro de paredes grossas. São adicionados aos tubos dois gramas de óleo. Os tubos são então sujeitos a vácuo e adiciona-se um grama de refrigerante. Os tubos são colocados num forno a 350°F durante uma semana e são feitas observações visuais. No fim do período de exposição os tubos são removidos.
Este procedimento foi efectuado para as seguintes combinações de óleo e do composto da presente invenção: a) HFO-1234ze e óleo PAG GM Goodwrench b) HF01243 zf e óleo PAG GM Goodwrench c) HFO-1234ze e óleo PAG MOPAR-56 d) HFO-1243 zf e Óleo PAG MOPAR-56 e) HFO-1225 ye (não coberto pela presente invenção) e Óleo PAG MOPAR-56
Em todos os casos há uma modificação mínima na aparência do conteúdo do tubo. Isso indica que as composições utilizáveis na presente invenção são estáveis em contacto 18 com o alumínio, o aço e o cobre, que se encontram nos sistemas de refrigeração e de condicionamento do ar e com os tipos de óleo lubrificante, que são provavelmente incluídos em tais composições ou usados com tais composições nesse tipo de sistemas.
EXEMPLO COMPARATIVO
Aparas de alumínio, cobre e aço são introduzidas num tubo de vidro de paredes grossas com óleo mineral e CFC-12 e são aquecidas durante uma semana a 350°C, como no Exemplo 3. No fim do período de exposição, o tubo é removido e são feitas observações visuais. Observa-se que o conteúdo líquido fica preto, indicando que existe uma decomposição severa do conteúdo do tubo. CFC-12 e óleo mineral têm sido até aqui a combinação escolhida em muitos sistemas e métodos de refrigeração. As composições utilizáveis na presente invenção possuem, portanto, uma estabilidade significativamente maior com muitos dos óleos de lubrificação vulgarmente utilizados, do que a combinação de refrigerante e óleo de lubrificação largamente usada na técnica anterior.
Lisboa, 4 de Fevereiro de 2010
Claims (9)
1 REIVINDICAÇÕES 1. Utilização de uma composição como refrigerante, compreendendo um tetrafluorpropeno (HFO-1234), num sistema de condicionamento de ar de um automóvel.
2. Utilização de acordo com a Reivindicação 1, em que a composição compreende entre 5 e 99% em peso de HFO-1234.
3. Utilização de acordo com a Reivindicação 2, em que a composição compreende entre 5 e 95% em peso de HFO-1234.
4. Utilização de acordo com a Reivindicação 1, em que a composição compreende ainda um lubrificante.
5. Utilização de acordo com a Reivindicação 4, em que o lubrificante se encontra presente numa quantidade situada entre 30 e 50% em peso da composição.
6. Utilização de acordo com a Reivindicação 4, em que o lubrificante compreende um lubrificante de polialquileno glicol.
7. Utilização de acordo com a Reivindicação 1, em que a composição compreende 2,3, 3,3-tetrafluorpropeno (HFO-1234yf) .
8. Utilização de acordo com a Reivindicação 7, em que a composição tem um Potencial de Aquecimento Global (GWP - Global Warming Potential) não superior a 1000. 2
9. Utilização de acordo com a Reivindicação 8, em que a composição tem um Potencial de Aquecimento Global (GWP - Global Warming Potential) não superior a 500. Lisboa, 4 de Fevereiro de 2010
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