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
  • C09K5/02—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
• • 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
  • C09K5/047—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for absorption-type refrigeration systems
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
  • F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type

Definitions

• the invention relates to a working medium for
• Absorption heat pumps which are a refrigerant, an ionic liquid as sorbent and an additive for
• Improvement of the material and heat transfer includes.
• Classic heat pumps are based on a cycle of a refrigerant via an evaporator and a condenser.
• a refrigerant is evaporated, wherein heat is removed from a first medium by the heat of vaporization absorbed by the refrigerant. The evaporated
• Refrigerant is then pressurized to a higher pressure and condensed at a higher temperature than the vaporization in the condenser, releasing the heat of vaporization and releasing heat to a second medium at a higher temperature level. Subsequently, the liquefied refrigerant is relieved to the pressure of the evaporator.
• Refrigerant, the evaporator and the condenser of a conventional heat pump nor a sorbent, an absorber and a desorber In the absorber, the vaporized refrigerant is absorbed at the pressure of evaporation in the sorbent and then desorbed in the desorber at the higher pressure of the condensation by supplying heat back from the sorbent.
• Sorbent requires less mechanical energy than the compression of the refrigerant vapor in a traditional heat pump, rather than the consumption of mechanical Energy occurs for the desorption of the refrigerant
• Absorption heat pump is calculated as the ratio of the used for cooling or heating heat flow to the
• Absorption heat pump is supplied, and is called
• Absorption heat pumps use a working medium that uses water as the refrigerant and lithium bromide as
• Working media containing water as refrigerant and lithium bromide as sorbent have the disadvantage that a water concentration of 35 to 40 wt .-% in Working medium may not fall below, otherwise it would lead to the crystallization of lithium bromide and thereby
• EP 2 093 278 A1 discloses fatty alcohols, such as isostearyl alcohol and oleyl alcohol, as wetting-requiring additives for ionic liquids.
• Contain liquid with organic cations as a sorbent, which can improve the mass or heat transfer in the absorption of an absorption heat pump.
• Refrigerant water completely different behavior than the sorbent lithium bromide, as they unlike LiBr not increase the surface tension compared to water, but significantly reduce, as for example, from W. Liu et al, J. Mol. Liquids 140 (2008) 68- 72 is known.
• the ionic liquid shows a similar surfactant behavior as 2-ethyl-l-hexanol and enriches in a mixture with water at the
• aliphatic alcohol having 6 to 10 carbon atoms such as 2-ethyl-1-hexanol, containing water as a refrigerant and ionic liquid as a sorbent
• the invention accordingly is a
• the at least one refrigerant at least one monohydric aliphatic alcohol having 6 to 10 carbon atoms and at least one ionic liquid of at least one organic
• the invention is also a
• Absorption heat pump which includes an absorber, a desorber, a condenser, an evaporator and a
• inventive working medium comprises.
• absorption heat pump according to the invention includes all devices that absorb heat at a low temperature level and at a higher
• Absorptive heat pumps according to the invention thus include both absorption chillers and absorption heat pumps in the narrower sense, in which absorber and evaporator are operated at a lower working pressure than desorber and condenser, as well as absorption heat transformers in which absorber and evaporator at a higher
• Working pressure can be operated as a desorber and a condenser.
• absorption chillers the intake of
• Evaporative heat in the evaporator used to cool a medium.
• absorption heat pumps in the narrower sense, the heat released in the condenser and / or absorber is used to heat a medium.
• Absorption heat transformers the absorption heat released in the absorber is used for heating a medium, wherein the heat of absorption at a higher
• the working medium according to the invention comprises at least one refrigerant, at least one monohydric aliphatic alcohol having 6 to 10 carbon atoms and at least one ionic liquid of at least one organic
• the working medium preferably comprises from 4 to 67% by weight of refrigerant, from 0.0001 to 10% by weight of alcohol having from 6 to 10 carbon atoms and from 30 to 95% by weight of ionic liquid.
• the working medium according to the invention comprises at least one refrigerant which is volatile, so that when using the working medium in an absorption heat pump, a portion of the refrigerant in the desorber can be evaporated by supplying heat from the working medium.
• the invention Working medium contains as refrigerant preferably water, methanol, ethanol or mixtures of these refrigerants.
• the refrigerant is methanol, ethanol, a mixture of methanol and ethanol, a mixture of ethanol with water or a mixture of methanol with water.
• the refrigerant is ethanol.
• Methanol, ethanol or mixtures of methanol or ethano with water can be used in absorption chillers to cool to temperatures less than 0 ° C
• Working media according to the invention which contain water as refrigerant, do not form any ignitable vapors when using the working medium in an absorption heat pump.
• the working medium according to the invention also comprises at least one monohydric aliphatic alcohol having 6 to 10 carbon atoms, which in the use of the
• the alcohol is preferably a primary alcohol and preferably has a branched alkyl radical.
• Suitable alcohols are in principle all hexanols, heptanols, octanols, nonanols, decanols and mixtures thereof, the alcohols being 2-methyl-1-hexanol, 2-ethyl-1-hexanol and 3,5,5-trimethyl-1-hexanol are preferred and 2-ethyl-l-hexanol is particularly preferred.
• the working medium according to the invention preferably comprises at least 0.0001 wt .-%, particularly preferably at least 0.001 wt .-% and in particular at least 0.0015 wt .-% of the alcohol having 6 to 10 carbon atoms.
• the working medium according to the invention preferably comprises at most 10% by weight, more preferably at most
• the proportion of alcohol in the working medium depending on the refrigerant used and the used ionic liquid preferably chosen so that with the least possible amount of alcohol a
• the working medium according to the invention further comprises at least one ionic liquid of at least one organic cation and at least one anion, which in the use of the working medium in a
• ionic liquid refers to salts or mixtures of salts free of nonionic substances or additives.
• the ionic liquid is one or more salts of organic cations with organic or inorganic anions.
• the ionic liquid preferably has a melting point of less than 20 ° C in order to use the
• the anion (s) of the ionic liquid may be mono-, di- or poly-negatively charged and are preferably simply negatively charged and more preferably anions of monovalent acids.
• the one or more anions of the ionic liquid may be mono-, di- or poly-negatively charged and are preferably simply negatively charged and more preferably anions of monovalent acids.
• the one or more anions of the ionic liquid may be mono-, di- or poly-negatively charged and are preferably simply negatively charged and more preferably anions of monovalent acids.
• the one or more anions of the ionic liquid may be mono-, di- or poly-negatively charged and are preferably simply negatively charged and more preferably anions of monovalent acids.
• the one or more anions of the ionic liquid may be mono-, di- or poly-negatively charged and are preferably simply negatively charged and more preferably anions of monovalent acids.
• the one or more anions of the ionic liquid may be mono-, di- or poly-negatively charged and are preferably
• Suitable anions are anions of monovalent ones
• inorganic acids preferably halides, nitrate, nitrite and cyanate, as well as anions of monovalent
• organic acids preferably carboxylic acids such as
• inorganic acids preferably sulfate, hydrogen sulfate, carbonate and bicarbonate, as well as mono- and dianions of divalent organic acids, preferably oxalate, succinate and malonate.
• mono-, di- and trianions of trivalent inorganic acids preferably sulfate, hydrogen sulfate, carbonate and bicarbonate, as well as mono- and dianions of divalent organic acids, preferably oxalate, succinate and malonate.
• phosphate preferably phosphate, hydrogen phosphate and
• Dihydrogen phosphate Dihydrogen phosphate.
• suitable inorganic anions are tetrafluoroborate, hexafluorophosphate, hydroxide,
• Perfluoroalkyl radical having 1 to 30 carbon atoms, as well as saccharinate and anions of the formulas R a OS0 3 ⁇ and R a S0 3 ⁇ , in which R a is a polyether radical.
• the anion (s) are of the ionic type
• Liquid selected from hydroxide, halides, nitrate, nitrite, carboxylates, phosphate, alkyl phosphates,
• Hexafluorophosphate and more preferably selected from the group consisting of hydroxide, chloride, bromide, nitrate, nitrite, formate, acetate, propionate, glycolate, Dimethyl phosphate, diethyl phosphate, methyl sulfate and
• this comprises
• Working fluid an ionic liquid with phosphate or phosphonate ions, in particular dimethyl phosphate or
• Diethyl phosphate in combination with methanol or ethanol as a refrigerant. This combination can be when using the working medium in one
• Absorption heat pump at the same time achieve a high mass and heat transfer in the absorber and low corrosion and avoid solidification of the ionic liquid in the sorbent circuit.
• the organic cation (s) of the ionic liquid may be singly, doubly or multiply positively charged and are preferably simply positively charged.
• the organic cation (s) of the ionic liquid preferably have a molecular weight of at most 260 g / mol, more preferably of at most 220 g / mol,
• R 1 RN + C (NR 3 R 4 ) (NR 5 R 6 ) (IV)
• R 1 RN + C (NR 3 R 4 ) (XR 5 ) (V) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are the same or different and
• Hydrogen a linear or branched aliphatic or olefinic hydrocarbon radical, a
• Hydrocarbon radical an alkylaryl radical, a
• R ' is an aliphatic or olefinic
• Hydrocarbon radical is,
• R 7 is a linear or branched alkylene radical containing 2 or 3 carbon atoms, n is from 1 to 3,
• R 8 is hydrogen or a linear or branched one
• X is an oxygen atom or a sulfur atom, and wherein at least one and preferably each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is other than hydrogen.
• heteroaromatic cations having at least one quaternary nitrogen atom in the ring, which carries a radical R 1 as defined above, preferably nitrogen atom-substituted derivatives of pyrrole, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, Pyrimidine, pyrazine, indole, quinoline, isoquinoline, cinnoline, quinoxaline or phthalazine.
• the organic cation contains a quaternary nitrogen atom.
• the organic cation is preferably a 1-alkylimidazolium ion, 1, 3-dialkylimidazolium ion,
• each other are hydrogen, alkyl or hydroxyethyl and R 4 is an alkyl radical.
• the organic cation is a 1, 3-dialkylimidazolium ion, wherein the
• Alkyl groups are independently selected from methyl, ethyl, n-propyl and n-butyl.
• the organic cations are N-alkylated alkylpyridinium ions, hereinafter referred to as N-alkyl-alkylpyridinium ions, which are obtainable by alkylating a mixture of alkylpyridines unsubstituted on the nitrogen atom,
• N-methylalkylpyridinium ions and N-butylalkylpyridinium ions Particular preference is given to N-alkylalkylpyridinium ions which are obtained by alkylating a mixture of picolines, dimethylpyridines and ethylpyridines
• Preferred organic cations are 1-methylimidazolium, 1, 3-dimethylimidazolium, 1-ethyl-3-methylimidazolium,
• the refrigerant is water and the ionic liquid is 2-hydroxyethyltrimethylammonium acetate,
• N-methylpyridinium chloride N-methylpyridinium acetate
• Tetramethylammonium formate tetramethylammonium acetate, 1-butyltrimethylammonium acetate,
• Working medium according to the invention is the refrigerant
• the ionic liquids can be prepared by methods known in the art,
• the ionic liquids are preferably liquid at 20 ° C and has at this temperature a viscosity according to DIN 53 019 from 1 to 15,000 mPas, more preferably from 2 to 10,000 mPa's, especially 5 to 5,000 mPa's and most preferably from 10 to 3,000 mPa's , At a temperature of 50 ° C, the ionic liquid
• ionic liquids are used which are immiscible with water indefinitely, stable to hydrolysis and thermally stable up to a temperature of 100 ° C.
• Hydrolysis-stable ionic liquids in a mixture with 50% by weight of water when stored at 80 ° C. within 8000 h show less than 5% degradation by hydrolysis.
• ionic liquids which, on analysis, show a weight loss of less than 10% and in particular less than 5%.
• the working medium according to the invention can be used in addition to
• the proportion of corrosion inhibitors is preferably 10 to 50,000 ppm, more preferably 100 to 10,000 ppm, based on the mass of the ionic
• Preferred inorganic corrosion inhibitors are Li 2 Cr0 4 , Li 2 Mo0 4 , Li 3 VO, LiVO 3 , NiBr 2 , Li 3 PO 4 , CoBr 2 and LiOH.
• Suitable organic corrosion inhibitors are amines and alkanolamines, preferably 2-aminoethanol,
• Fatty acid alkylolamides referred to amides of fatty acids with alkanolamines and their alkoxylates. Suitable is
• Phosphoric acid esters in particular phosphoric acid esters of ethoxylated fatty alcohols, and fatty acid-alkanolamine mixtures.
• Preferred organic corrosion inhibitors are benzimidazole and especially benzotriazole.
• the working medium of the invention exhibits in a corrosion test according to ASTM D1384 for all Test materials have a removal of less than 5 g / m 2 , more preferably less than 3 g / m 2 and in particular less than 2 g / m 2 .
• ASTM D1384 for all Test materials have a removal of less than 5 g / m 2 , more preferably less than 3 g / m 2 and in particular less than 2 g / m 2 .
• precisely weighed, drilled metal flakes of copper, soft solder, brass, steel, gray cast iron and cast aluminum are placed in a rack on an insulated bar one behind the other. Copper, soft solder and brass are going through
• Spacers made of brass, steel, cast iron and cast aluminum are each conductively connected by steel spacers, but the resulting "packages" are isolated from one another
• the test specimen is immersed in the medium and heated to 88 ° C. for 14 days while introducing air
• the slides are then cleaned, weighed again and the removal determined.
• Absorption heat pump can be reduced.
• the absorption heat pump according to the invention comprises an absorber, a desorber, a condenser, a
• vapor refrigerant is absorbed in low-refrigerant working medium in the absorber to obtain a
• refrigerant-rich working medium and releasing heat of absorption. From the thus obtained refrigerant-rich working medium is in the desorber with heat Refrigerant vapor desorbs to give low-refrigerant working medium, which is returned to the absorber.
• the vapor refrigerant obtained in the desorber is condensed in the condenser with the release of heat of condensation, the resulting liquid refrigerant is in the evaporator with uptake of
• the absorption heat pump according to the invention can be designed both in one stage and in several stages with several coupled circuits of the working medium.
• Absorption heat pump, an absorption chiller and the evaporator heat is absorbed from a medium to be cooled.
• the absorption heat pump according to the invention has over those known from WO 2005/113702 and WO 2006/134015
• a model CH-MG 150 absorption chiller from YAZAKI was used with working media of 80% by weight of ionic liquid and 20% by weight of refrigerant at one

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Combustion & Propulsion (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Sorption Type Refrigeration Machines (AREA)

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• 2011
  • 2011-11-04 EP EP11778629.3A patent/EP2638123B1/de not_active Not-in-force
  • 2011-11-04 KR KR1020137014601A patent/KR101404833B1/ko not_active Expired - Fee Related
  • 2011-11-04 SG SG2013016167A patent/SG188955A1/en unknown
  • 2011-11-04 MY MYPI2013000868 patent/MY153070A/en unknown
  • 2011-11-04 PH PH1/2013/500344A patent/PH12013500344A1/en unknown
  • 2011-11-04 US US13/883,573 patent/US20130219949A1/en not_active Abandoned
  • 2011-11-04 JP JP2013538135A patent/JP6358799B2/ja not_active Expired - Fee Related
  • 2011-11-04 BR BR112013007941A patent/BR112013007941A2/pt not_active IP Right Cessation
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  • 2011-11-04 WO PCT/EP2011/069402 patent/WO2012062656A1/de not_active Ceased
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• 2016
  • 2016-11-18 JP JP2016225187A patent/JP2017036914A/ja active Pending

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