US20100326126A1 - Absorption Refrigeration Machine - Google Patents
Absorption Refrigeration Machine Download PDFInfo
- Publication number
- US20100326126A1 US20100326126A1 US12/865,758 US86575809A US2010326126A1 US 20100326126 A1 US20100326126 A1 US 20100326126A1 US 86575809 A US86575809 A US 86575809A US 2010326126 A1 US2010326126 A1 US 2010326126A1
- Authority
- US
- United States
- Prior art keywords
- refrigeration machine
- absorption refrigeration
- refrigerant
- membrane
- ionic liquids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000005057 refrigeration Methods 0.000 title claims abstract description 53
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 claims abstract description 63
- 239000003507 refrigerant Substances 0.000 claims abstract description 56
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 239000006096 absorbing agent Substances 0.000 claims abstract description 24
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000012808 vapor phase Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 239000002608 ionic liquid Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000012982 microporous membrane Substances 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 150000002892 organic cations Chemical class 0.000 claims description 6
- 150000001449 anionic compounds Chemical class 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 5
- 150000002891 organic anions Chemical class 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- -1 Heteroaromatic cations Chemical class 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 11
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000006200 vaporizer Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 230000007257 malfunction Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical group N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical group C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 1
- JYARJXBHOOZQQD-UHFFFAOYSA-N 1-butyl-3-ethylimidazol-1-ium Chemical compound CCCC[N+]=1C=CN(CC)C=1 JYARJXBHOOZQQD-UHFFFAOYSA-N 0.000 description 1
- FBYLUDUZJBTVKE-UHFFFAOYSA-N 1-butyl-3-hexylimidazol-3-ium Chemical compound CCCCCC[N+]=1C=CN(CCCC)C=1 FBYLUDUZJBTVKE-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- KRJBDLCQPFFVAX-UHFFFAOYSA-N 1-ethyl-3-hexylimidazol-3-ium Chemical compound CCCCCC[N+]=1C=CN(CC)C=1 KRJBDLCQPFFVAX-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical group C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical group C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical group N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
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- 238000000502 dialysis Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Chemical group CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Chemical group C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical group C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical group C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006294 polydialkylsiloxane Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- F25B15/14—Sorption machines, plants or systems, operating continuously, e.g. absorption type using osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
- Y02B30/62—Absorption based systems
Definitions
- the invention is related to an absorption refrigeration machine having a reduced mechanical energy requirement.
- Classical refrigeration machines are based on a circuit in which a refrigerant is vaporized and cooling is achieved as a result of the heat of vaporization taken up by the refrigerant.
- the vaporized refrigerant is then brought to a higher pressure by means of a compressor and condensed at a higher temperature than in the vaporization, resulting in the heat of vaporization being liberated again.
- the liquefied refrigerant is subsequently depressurized again to the pressure of the vaporizer.
- the classical refrigeration machines have the disadvantage that they consume a large amount of mechanical energy for compression of the gaseous refrigerant.
- Absorption refrigeration machines have a reduced mechanical energy requirement.
- Absorption refrigeration machines have, in addition to the refrigerant, the vaporizer and the condenser of a classical refrigeration machine, a sorption medium, an absorber and a desorber.
- the absorber the vaporized refrigerant is absorbed at the pressure of the vaporization in the sorption medium and is subsequently desorbed again from the sorption medium in the desorber at the higher pressure of the condensation by introduction of heat.
- the compression of the liquid working medium composed of refrigerant and sorption medium requires less mechanical energy than the compression of the refrigerant vapor in a classical refrigeration machine; the consumption of mechanical energy is replaced by the thermal energy used for desorption of the refrigerant.
- U.S. Pat. No. 1,882,258 discloses an absorption refrigeration machine in which a liquid phase composed of the absorption medium water and the refrigerant ammonia is separated in the absorber by a porous permeable wall from a gas phase containing gaseous ammonia and an inert gas.
- the machine described in this document is intended to be operated without supply of mechanical energy.
- absorber, desorber, condenser and vaporizer are all operated at the same pressure, which results in a low efficiency.
- not only ammonia but also water vapor can get from the liquid phase through the porous wall into the vaporizer and lead to malfunctions there, e.g. as a result of ice formation.
- DE 195 11 709 discloses an absorption refrigeration machine having a working medium containing LiBr or LiBr/ZnBr 2 as nonvolatile sorption medium and water or methanol as volatile refrigerant. Condensation and vaporization of the refrigerant do not occur in this machine. Instead, cooling is effected by pervaporation of refrigerant from a refrigerant-rich working medium, coming from the absorber, through a hydrophobic membrane into a refrigerant-deficient working medium, coming from the desorber. In this machine, the membrane is not located in the absorber.
- U.S. Pat. No. 4,152,9001 and U.S. Pat. No. 5,873,260 disclose absorption refrigeration machines in which the desorber is provided with a membrane through which desorption of refrigerant from the working medium occurs.
- sorption medium passes through the membrane and gets into the vaporizer.
- U.S. Pat. No. 5,873,260 too, it is stated that the sorption medium water passes as vapor through the membrane.
- the invention provides an absorption refrigeration machine having a working medium, containing a nonvolatile sorption medium and a volatile refrigerant, and an absorber, in which a vapor phase containing refrigerant and a liquid phase containing sorption medium are separated from one another by a membrane, wherein the membrane is a semipermeable membrane which is permeable to the refrigerant and impermeable to the sorption medium.
- Arrangement of a semipermeable membrane, which separates the gaseous refrigerant from the liquid working medium, in the absorber in combination with a nonvolatile sorption medium allows absorption even against a pressure difference between the gaseous refrigerant and the liquid working medium, without sorption medium being able to get into the vapor space of the absorber and into the vaporizer.
- the refrigerant can be absorbed even at a pressure of the liquid working medium which is significantly higher than the pressure of the vaporization without any compression of the gaseous refrigerant being necessary and without malfunctions occurring as a result of sorption medium getting into the vaporizer.
- the mechanical energy requirement for compression of the liquid working medium can be reduced compared to the absorption refrigeration machines known from the prior art by an increase in the pressure of the liquid working medium in the absorber.
- the absorption refrigeration machine of the invention comprises a working medium, containing a nonvolatile sorption medium and a volatile refrigerant, and a semipermeable membrane which is permeable to the refrigerant and impermeable to the sorption medium.
- a working medium containing a nonvolatile sorption medium and a volatile refrigerant
- a semipermeable membrane which is permeable to the refrigerant and impermeable to the sorption medium.
- the working medium preferably contains water, ammonia or carbon dioxide as volatile refrigerant. Water is particularly preferably used as refrigerant.
- the working medium additionally contains a nonvolatile sorption medium.
- nonvolatile sorption medium refers to a sorption medium whose vapor pressure is a factor of more than 10 000 lower than the vapor pressure of the refrigerant. Preference is given to sorption media which at 20° C. have a vapor pressure of less than 10 ⁇ 3 mbar, particularly preferably less than 10 ⁇ 6 mbar. Preference is given to using polymeric or salt-like sorption media as nonvolatile sorption media.
- a working medium which is known from the prior art and is suitable for the absorption refrigeration machine of the invention is an aqueous solution of lithium bromide with water as refrigerant and lithium bromide as nonvolatile sorption medium.
- a sorption medium comprising one or more ionic liquids is preferably used in the absorption refrigeration machine of the invention.
- the term ionic liquid refers to a salt or a mixture of salts composed of anions and cations, where the salt or the mixture of salts has a melting point of less than 100° C.
- ionic liquids Compared to conventional sorption media such as lithium bromide, ionic liquids have the advantage that a larger proportion of the refrigerant can be driven off in the desorber without solidification of the sorption medium.
- the absorption refrigeration machine can therefore be operated without malfunctions at a higher capacity of the working medium for the refrigerant, which allows more compact construction of the absorption refrigeration machine.
- the ionic liquid preferably consists of one or more salts of organic cations with organic or inorganic anions. Mixtures of a plurality of salts having different organic cations and the same anion are particularly preferred.
- Suitable organic cations are, in particular, cations of the general formulae (I) to (V):
- Heteroaromatic cations having in the ring at least one quaternary nitrogen atom bearing a radical R 1 as defined above, preferably derivatives of pyrrole, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyrazine, indole, quinoline, isoquinoline, cinnoline, quinoxaline or phthalazine substituted on the nitrogen atom, are likewise suitable.
- Suitable inorganic anions are, in particular, tetrafluoroborate, hexafluorophosphate, nitrate, sulfate, hydrogensulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, hydroxide, carbonate, hydrogencarbonate and the halides, preferably chloride.
- Suitable organic anions are, in particular, R a OSO 3 ⁇ , R a SO 3 ⁇ , R a OPO 3 2 ⁇ , (R a O) 2 PO 2 ⁇ , R a PO 3 2 ⁇ , R a COO ⁇ , R a O ⁇ , (R a CO) 2 N ⁇ , (R a SO 2 ) 2 N ⁇ and NCN ⁇
- R a is a linear or branched aliphatic hydrocarbon radical having from 1 to 30 carbon atoms, a cycloaliphatic hydrocarbon radical having from 5 to 40 carbon atoms, an aromatic hydrocarbon radical having from 6 to 40 carbon atoms, an alkylaryl radical having from 7 to 40 carbon atoms or a linear or branched perfluoroalkyl radical having from 1 to 30 carbon atoms.
- the ionic liquid comprises one or more 1,3-dialkylimidazolium salts, where the alkyl groups are particularly preferably selected independently from among methyl, ethyl, n-propyl, n-butyl and n-hexyl.
- Particularly preferred ionic liquids are salts of one or more of the cations 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-(n-butyl)-3-methylimidazolium, 1-(n-butyl)-3-ethylimidazolium, 1-(n-hexyl)-3-methylimidazolium, 1-(n-hexyl)-3-ethylimidazolium and 1-(n-hexyl)-3-butylimidazolium with one of the anions chloride, acetate, methylsulfate, ethylsulfate, dimethylphosphate or methylsulfonate.
- the ionic liquid comprises one or more quaternary ammonium salts having a monovalent anion and cations of the general formula (I) in which
- Ionic liquids stable to hydrolysis display less than 5% degradation by hydrolysis in a mixture with 50% by weight of water on storage at 80° C. for 8000 h.
- Ionic liquids forming a nonideal mixture with the refrigerant with lowering of the vapor pressure of the refrigerant are preferably used as sorption media.
- the working medium can contain further additives in addition to the sorption medium and the refrigerant.
- the working medium preferably further contains one or more corrosion inhibitors.
- corrosion inhibitors it is possible to use all nonvolatile corrosion inhibitors which are known from the prior art to be suitable for the materials used in the absorption refrigeration machine.
- the semipermeable membrane in the absorber is a solution diffusion membrane.
- a solution diffusion membrane has virtually no pores.
- the selective permeability of the membrane for the refrigerant is based on the refrigerant dissolving in the material of the membrane and diffusing through the membrane, while the sorption medium is insoluble in the material of the membrane.
- the suitability of a dissolution diffusion membrane for the absorption refrigeration machine of the invention can therefore be determined by a person skilled in the art by simple experiments on the solubility of refrigerant and sorption medium in the material of the membrane.
- the material used for the solution diffusion membrane is preferably a hydrophilic or hydrophilically functionalized polymer containing polyvinyl alcohol, polyimide, polybenzimidazole, polybenzimidazolone, polyamide hydrazide, cellulose ester, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose butyrate, cellulose nitrate, polyurea, polyfuran, polyethylene glycol, poly(octylmethyl-siloxane), polysiloxane, polyalkylsiloxane, polydialkylsiloxane, polyester-polyether block copolymer, polysulfone, sulfonated polysulfone, polyamide, in particular aromatic polyamide, polyether, polyether ether ketone, polyester, polyether-urea composite, polyamide-urea composite, polyether sulfone, polycarbonate, polymethyl methacrylate, polyacrylic acid or polyacrylonitrile.
- the semipermeable membrane in the absorber is a microporous membrane.
- microporous membranes are membranes which have pores extending through the membrane having a minimum diameter in the range from 0.3 nm to 100 ⁇ m.
- the membrane preferably has pores in the range from 0.3 nm to 0.1 ⁇ m.
- the term wetting means a contact angle between working medium and microporous membrane of less than 90°, which leads to intrusion of working medium into pores of the membrane as a result of capillary forces.
- the contact angle between working medium and microporous membrane is preferably more than 120 degrees, particularly preferably more than 140 degrees.
- hydrophobic microporous membrane As refrigerant, preference is given to using a hydrophobic microporous membrane as semipermeable membrane.
- Suitable hydrophobic microporous membranes are known to those skilled in the art as waterproof membranes which are permeable to water vapor in the technical field of functional clothing.
- hydrophobic microporous membranes composed of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride or fluoroalkyl-modified polymers. It is likewise possible to use mixtures or copolymers of two or more of these polymers.
- Inorganic hydrophobic microporous membranes or composite membranes comprising an inorganic hydrophobic microporous material for example membranes whose pores are formed by silicalite or hydrophobicized silica, are likewise suitable.
- the semipermeable membrane is preferably arranged on a porous support layer. Arrangement on a porous support layer enables a mechanically stable membrane unit to be achieved even when a thin semipermeable membrane is used. This allows more rapid mass transfer through the membrane and thus a smaller and more compact design of the absorber.
- the support layer is preferably arranged on the side of the semipermeable membrane which is in contact with the vapor phase. Such an arrangement of the support layer leads to a reduced mass transfer resistance than an arrangement of the support layer on the side of the membrane facing the liquid working medium.
- the porous support layer can comprise either inorganic or organic materials.
- the membrane is preferably arranged on a porous support layer composed of a hydrophobic polymer, in particular a polyolefin, a polyester or polyvinylidene fluoride.
- the support layer can additionally contain reinforcement, e.g. by layers of fabric.
- the semipermeable membrane is arranged in the absorber in the form of hollow fibers.
- the configuration of the membrane in the form of hollow fibers allows a particularly compact construction of the absorber and operation of the absorber at a higher pressure difference between the vapor phase and the liquid phase in the absorber.
- the absorption refrigeration machine of the invention can additionally contain a membrane in the desorber, through which desorption of refrigerant from the working medium occurs.
- a membrane in the desorber it is in principle possible to use all membranes which are suitable as semipermeable membrane for the absorber of the absorption refrigeration machine of the invention.
- the use of a membrane in the desorber also makes it possible to use working media which tend to foam during desorption.
- the absorption refrigeration machine of the invention can also be configured in the form of a multistage refrigeration machine, as described in F. Ziegler, R. Kahn, F. Summerer, G. Alefeld “Multi-Effect absorption chillers”, Rev. Int. Froid 16 (1993) 301-311.
- the absorption refrigeration machine of the invention is particularly suitable for mobile use, in particular in motor vehicles and ships. Furthermore, the absorption refrigeration machine of the invention is also particularly suitable for the air-conditioning of buildings since it can be operated with particularly low noise and allows for efficient air-conditioning using solar energy.
Abstract
An absorption refrigeration machine with a working medium, containing a nonvolatile sorption medium and a volatile refrigerant, and an absorber in which a vapor phase containing refrigerant and a liquid phase containing sorption medium are separated from one another by a semipermeable membrane which is permeable to the refrigerant and impermeable to the sorption medium.
Description
- The invention is related to an absorption refrigeration machine having a reduced mechanical energy requirement.
- Classical refrigeration machines are based on a circuit in which a refrigerant is vaporized and cooling is achieved as a result of the heat of vaporization taken up by the refrigerant. The vaporized refrigerant is then brought to a higher pressure by means of a compressor and condensed at a higher temperature than in the vaporization, resulting in the heat of vaporization being liberated again. The liquefied refrigerant is subsequently depressurized again to the pressure of the vaporizer.
- The classical refrigeration machines have the disadvantage that they consume a large amount of mechanical energy for compression of the gaseous refrigerant.
- In comparison, absorption refrigeration machines have a reduced mechanical energy requirement. Absorption refrigeration machines have, in addition to the refrigerant, the vaporizer and the condenser of a classical refrigeration machine, a sorption medium, an absorber and a desorber. In the absorber, the vaporized refrigerant is absorbed at the pressure of the vaporization in the sorption medium and is subsequently desorbed again from the sorption medium in the desorber at the higher pressure of the condensation by introduction of heat. The compression of the liquid working medium composed of refrigerant and sorption medium requires less mechanical energy than the compression of the refrigerant vapor in a classical refrigeration machine; the consumption of mechanical energy is replaced by the thermal energy used for desorption of the refrigerant.
- U.S. Pat. No. 1,882,258 discloses an absorption refrigeration machine in which a liquid phase composed of the absorption medium water and the refrigerant ammonia is separated in the absorber by a porous permeable wall from a gas phase containing gaseous ammonia and an inert gas. The machine described in this document is intended to be operated without supply of mechanical energy. In the machine described in this document, absorber, desorber, condenser and vaporizer are all operated at the same pressure, which results in a low efficiency. In addition, not only ammonia but also water vapor can get from the liquid phase through the porous wall into the vaporizer and lead to malfunctions there, e.g. as a result of ice formation.
- The same problem occurs in the process proposed in DE 633 146, in which the absorber is provided with a diaphragm through which the absorption medium water can likewise get in vapor form into the absorber, and also the process proposed in WO 2004/104496 which likewise uses water as sorption medium.
- DE 195 11 709 discloses an absorption refrigeration machine having a working medium containing LiBr or LiBr/ZnBr2 as nonvolatile sorption medium and water or methanol as volatile refrigerant. Condensation and vaporization of the refrigerant do not occur in this machine. Instead, cooling is effected by pervaporation of refrigerant from a refrigerant-rich working medium, coming from the absorber, through a hydrophobic membrane into a refrigerant-deficient working medium, coming from the desorber. In this machine, the membrane is not located in the absorber.
- U.S. Pat. No. 4,152,9001 and U.S. Pat. No. 5,873,260 disclose absorption refrigeration machines in which the desorber is provided with a membrane through which desorption of refrigerant from the working medium occurs. In the process of U.S. Pat. No. 4,152,9001, sorption medium passes through the membrane and gets into the vaporizer. In U.S. Pat. No. 5,873,260, too, it is stated that the sorption medium water passes as vapor through the membrane.
- Accordingly, there continues to be a need to further reduce the mechanical energy requirement compared to prior art absorption refrigeration machines, without malfunctions occurring as a result of absorption medium getting into the vaporizer of the refrigeration machine.
- The invention provides an absorption refrigeration machine having a working medium, containing a nonvolatile sorption medium and a volatile refrigerant, and an absorber, in which a vapor phase containing refrigerant and a liquid phase containing sorption medium are separated from one another by a membrane, wherein the membrane is a semipermeable membrane which is permeable to the refrigerant and impermeable to the sorption medium.
- Arrangement of a semipermeable membrane, which separates the gaseous refrigerant from the liquid working medium, in the absorber in combination with a nonvolatile sorption medium allows absorption even against a pressure difference between the gaseous refrigerant and the liquid working medium, without sorption medium being able to get into the vapor space of the absorber and into the vaporizer. As a result, the refrigerant can be absorbed even at a pressure of the liquid working medium which is significantly higher than the pressure of the vaporization without any compression of the gaseous refrigerant being necessary and without malfunctions occurring as a result of sorption medium getting into the vaporizer. The mechanical energy requirement for compression of the liquid working medium can be reduced compared to the absorption refrigeration machines known from the prior art by an increase in the pressure of the liquid working medium in the absorber.
- The absorption refrigeration machine of the invention comprises a working medium, containing a nonvolatile sorption medium and a volatile refrigerant, and a semipermeable membrane which is permeable to the refrigerant and impermeable to the sorption medium. In principle, it is possible to use all working media, having a nonvolatile sorption medium and a volatile refrigerant, which are known from the prior art for absorption refrigeration machines, in combination with a suitable semipermeable membrane.
- The working medium preferably contains water, ammonia or carbon dioxide as volatile refrigerant. Water is particularly preferably used as refrigerant.
- The working medium additionally contains a nonvolatile sorption medium. In this context, the term nonvolatile sorption medium refers to a sorption medium whose vapor pressure is a factor of more than 10 000 lower than the vapor pressure of the refrigerant. Preference is given to sorption media which at 20° C. have a vapor pressure of less than 10−3 mbar, particularly preferably less than 10−6 mbar. Preference is given to using polymeric or salt-like sorption media as nonvolatile sorption media.
- A working medium which is known from the prior art and is suitable for the absorption refrigeration machine of the invention is an aqueous solution of lithium bromide with water as refrigerant and lithium bromide as nonvolatile sorption medium.
- A sorption medium comprising one or more ionic liquids is preferably used in the absorption refrigeration machine of the invention. In this context, the term ionic liquid refers to a salt or a mixture of salts composed of anions and cations, where the salt or the mixture of salts has a melting point of less than 100° C. Compared to conventional sorption media such as lithium bromide, ionic liquids have the advantage that a larger proportion of the refrigerant can be driven off in the desorber without solidification of the sorption medium. Using an ionic liquid as sorption medium, the absorption refrigeration machine can therefore be operated without malfunctions at a higher capacity of the working medium for the refrigerant, which allows more compact construction of the absorption refrigeration machine.
- The ionic liquid preferably consists of one or more salts of organic cations with organic or inorganic anions. Mixtures of a plurality of salts having different organic cations and the same anion are particularly preferred.
- Suitable organic cations are, in particular, cations of the general formulae (I) to (V):
-
R1R2R3R4N+ (I) -
R1R2N+═CR3R4 (II) -
R1R2R3R4P+ (III) -
R1R2P+═CR3R4 (IV) -
R1R2R3S+ (V) - where
-
- R1, R2, R3, R4 are identical or different and are each hydrogen, a linear or branched aliphatic or olefinic hydrocarbon radical having from 1 to 30 carbon atoms, a cycloaliphatic or cycloolefinic hydrocarbon radical having from 5 to 40 carbon atoms, an aromatic hydrocarbon radical having from 6 to 40 carbon atoms, an alkylaryl radical having from 7 to 40 carbon atoms, a linear or branched aliphatic or olefinic hydrocarbon radical which has from 2 to 30 carbon atoms and is interrupted by one or more —O—, —NH—, —NR′—, —O—C(O)—, —(O)C—O—, —NH—C(O)—, —(O)C—NH—, —(CH3)N—C(O)—, —(O)C—N(CH3)—, —S(O2)—O—, —O—S (O2)—, —S (O2) —NH—, —NH—S (O2)—, —S (O2)—N (CH3)— or —N (CH3)—S (O2)— groups, a linear or branched aliphatic or olefinic hydrocarbon radical which has from 1 to 30 carbon atoms and is terminally functionalized by OH, OR′, NH2, N(H)R′ or N(R′)2 or a polyether radical of the formula —(R5—O)n—R6 having a block or random structure,
- R′ is an aliphatic or olefinic hydrocarbon radical having from 1 to 30 carbon atoms,
- R5 is a linear or branched hydrocarbon radical containing from 2 to 4 carbon atoms,
- n is from 1 to 200, preferably from 2 to 60,
- R6 is hydrogen, a linear or branched aliphatic or olefinic hydrocarbon radical having from 1 to 30 carbon atoms, a cycloaliphatic or cycloolefinic hydrocarbon radical having from 5 to 40 carbon atoms, an aromatic hydrocarbon radical having from 6 to 40 carbon atoms, an alkylaryl radical having from 7 to 40 carbon atoms or a —C(O)—R7 radical,
- R7 is a linear or branched aliphatic or olefinic hydrocarbon radical having from 1 to 30 carbon atoms, a cycloaliphatic or cycloolefinic hydrocarbon radical having from 5 to 40 carbon atoms, an aromatic hydrocarbon radical having from 6 to 40 carbon atoms or an alkylaryl radical having from 7 to 40 carbon atoms,
- where at least one and preferably all of the radicals R1, R2, R3 and R4 is different from hydrogen.
- Cations of the formulae (I) to (V) in which the radicals R1 and R3 together form a 4- to 10-membered, preferably 5- to 6-membered, ring are likewise suitable.
- Heteroaromatic cations having in the ring at least one quaternary nitrogen atom bearing a radical R1 as defined above, preferably derivatives of pyrrole, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyrazine, indole, quinoline, isoquinoline, cinnoline, quinoxaline or phthalazine substituted on the nitrogen atom, are likewise suitable.
- Suitable inorganic anions are, in particular, tetrafluoroborate, hexafluorophosphate, nitrate, sulfate, hydrogensulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, hydroxide, carbonate, hydrogencarbonate and the halides, preferably chloride.
- Suitable organic anions are, in particular, RaOSO3 −, RaSO3 −, RaOPO3 2−, (RaO)2PO2 −, RaPO3 2−, RaCOO−, RaO−, (RaCO)2N−, (RaSO2)2N− and NCN− where Ra is a linear or branched aliphatic hydrocarbon radical having from 1 to 30 carbon atoms, a cycloaliphatic hydrocarbon radical having from 5 to 40 carbon atoms, an aromatic hydrocarbon radical having from 6 to 40 carbon atoms, an alkylaryl radical having from 7 to 40 carbon atoms or a linear or branched perfluoroalkyl radical having from 1 to 30 carbon atoms.
- In a preferred embodiment, the ionic liquid comprises one or more 1,3-dialkylimidazolium salts, where the alkyl groups are particularly preferably selected independently from among methyl, ethyl, n-propyl, n-butyl and n-hexyl. Particularly preferred ionic liquids are salts of one or more of the cations 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-(n-butyl)-3-methylimidazolium, 1-(n-butyl)-3-ethylimidazolium, 1-(n-hexyl)-3-methylimidazolium, 1-(n-hexyl)-3-ethylimidazolium and 1-(n-hexyl)-3-butylimidazolium with one of the anions chloride, acetate, methylsulfate, ethylsulfate, dimethylphosphate or methylsulfonate.
- In a further preferred embodiment, the ionic liquid comprises one or more quaternary ammonium salts having a monovalent anion and cations of the general formula (I) in which
-
- R1 is an alkyl radical having from 1 to 20 carbon atoms,
- R2 is an alkyl radical having from 1 to 4 carbon atoms,
- R3 is a (CH2CHRO)n—H radical where n is from 1 to 200 and R═H or CH3 and
- R4 is an alkyl radical having from 1 to 4 carbon atoms or a (CH2CHRO)n—H radical where n is from 1 to 200 and R═H or CH3.
- Particular preference is given to chloride, acetate, methylsulfate, ethylsulfate, dimethylphosphate or methylsulfonate as anion.
- Processes for preparing the ionic liquids are known to those skilled in the art from the prior art.
- Preference is given to using ionic liquids which are stable at a temperature of 150° C. as sorption media. When water is used as refrigerant, preference is given to using an ionic liquid which is stable to hydrolysis.
- Ionic liquids stable to hydrolysis display less than 5% degradation by hydrolysis in a mixture with 50% by weight of water on storage at 80° C. for 8000 h.
- Ionic liquids forming a nonideal mixture with the refrigerant with lowering of the vapor pressure of the refrigerant are preferably used as sorption media.
- The working medium can contain further additives in addition to the sorption medium and the refrigerant. The working medium preferably further contains one or more corrosion inhibitors. Here, it is possible to use all nonvolatile corrosion inhibitors which are known from the prior art to be suitable for the materials used in the absorption refrigeration machine.
- In a preferred embodiment of the absorption refrigeration machine of the invention, the semipermeable membrane in the absorber is a solution diffusion membrane. A solution diffusion membrane has virtually no pores. With a solution diffusion membrane, the selective permeability of the membrane for the refrigerant is based on the refrigerant dissolving in the material of the membrane and diffusing through the membrane, while the sorption medium is insoluble in the material of the membrane. The suitability of a dissolution diffusion membrane for the absorption refrigeration machine of the invention can therefore be determined by a person skilled in the art by simple experiments on the solubility of refrigerant and sorption medium in the material of the membrane.
- In the case of the preferred embodiment using water as refrigerant and a salt-like sorption medium, it is possible to use as the solution diffusion membrane any pore-free membrane which is known to those skilled in the art as suitable for desalination of aqueous salt solutions from the technical fields of dialysis, reverse osmosis and pervaporation.
- The material used for the solution diffusion membrane is preferably a hydrophilic or hydrophilically functionalized polymer containing polyvinyl alcohol, polyimide, polybenzimidazole, polybenzimidazolone, polyamide hydrazide, cellulose ester, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose butyrate, cellulose nitrate, polyurea, polyfuran, polyethylene glycol, poly(octylmethyl-siloxane), polysiloxane, polyalkylsiloxane, polydialkylsiloxane, polyester-polyether block copolymer, polysulfone, sulfonated polysulfone, polyamide, in particular aromatic polyamide, polyether, polyether ether ketone, polyester, polyether-urea composite, polyamide-urea composite, polyether sulfone, polycarbonate, polymethyl methacrylate, polyacrylic acid or polyacrylonitrile. It is likewise possible to use mixtures or copolymers of two or more of these polymers. Particular preference is given to solution diffusion membranes composed of cellulose acetate, crosslinked polyethylene glycol, crosslinked polydimethylsiloxane or a polyester-polyether block copolymer.
- In a preferred embodiment of the absorption refrigeration machine of the invention, the semipermeable membrane in the absorber is a microporous membrane. For the purposes of the invention, microporous membranes are membranes which have pores extending through the membrane having a minimum diameter in the range from 0.3 nm to 100 μm. The membrane preferably has pores in the range from 0.3 nm to 0.1 μm.
- Preference is given to using a microporous membrane which is not wetted by the working medium composed of sorption medium and refrigerant in the absorber. For the present purposes, the term wetting means a contact angle between working medium and microporous membrane of less than 90°, which leads to intrusion of working medium into pores of the membrane as a result of capillary forces. The contact angle between working medium and microporous membrane is preferably more than 120 degrees, particularly preferably more than 140 degrees. By use of a nonwetting microporous membrane, a flow of the liquid working medium through the pores of the membrane to the vapor side of the membrane can be prevented even for a pressure on the side of the liquid working medium which is higher than that on the vapor side. A person skilled in the art can therefore determine the suitability of a microporous membrane for the absorption refrigeration machine of the invention by determining the contact angle between the working medium and the membrane.
- In the preferred embodiment using water as refrigerant, preference is given to using a hydrophobic microporous membrane as semipermeable membrane. Suitable hydrophobic microporous membranes are known to those skilled in the art as waterproof membranes which are permeable to water vapor in the technical field of functional clothing.
- Preference is given to using hydrophobic microporous membranes composed of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride or fluoroalkyl-modified polymers. It is likewise possible to use mixtures or copolymers of two or more of these polymers. Inorganic hydrophobic microporous membranes or composite membranes comprising an inorganic hydrophobic microporous material, for example membranes whose pores are formed by silicalite or hydrophobicized silica, are likewise suitable.
- The semipermeable membrane is preferably arranged on a porous support layer. Arrangement on a porous support layer enables a mechanically stable membrane unit to be achieved even when a thin semipermeable membrane is used. This allows more rapid mass transfer through the membrane and thus a smaller and more compact design of the absorber. The support layer is preferably arranged on the side of the semipermeable membrane which is in contact with the vapor phase. Such an arrangement of the support layer leads to a reduced mass transfer resistance than an arrangement of the support layer on the side of the membrane facing the liquid working medium.
- The porous support layer can comprise either inorganic or organic materials. The membrane is preferably arranged on a porous support layer composed of a hydrophobic polymer, in particular a polyolefin, a polyester or polyvinylidene fluoride. The support layer can additionally contain reinforcement, e.g. by layers of fabric.
- In a preferred embodiment, the semipermeable membrane is arranged in the absorber in the form of hollow fibers. The configuration of the membrane in the form of hollow fibers allows a particularly compact construction of the absorber and operation of the absorber at a higher pressure difference between the vapor phase and the liquid phase in the absorber.
- The absorption refrigeration machine of the invention can additionally contain a membrane in the desorber, through which desorption of refrigerant from the working medium occurs. In the desorber, it is in principle possible to use all membranes which are suitable as semipermeable membrane for the absorber of the absorption refrigeration machine of the invention. The use of a membrane in the desorber also makes it possible to use working media which tend to foam during desorption.
- The absorption refrigeration machine of the invention can also be configured in the form of a multistage refrigeration machine, as described in F. Ziegler, R. Kahn, F. Summerer, G. Alefeld “Multi-Effect absorption chillers”, Rev. Int. Froid 16 (1993) 301-311.
- Owing to the compact construction and the low mechanical energy requirement, the absorption refrigeration machine of the invention is particularly suitable for mobile use, in particular in motor vehicles and ships. Furthermore, the absorption refrigeration machine of the invention is also particularly suitable for the air-conditioning of buildings since it can be operated with particularly low noise and allows for efficient air-conditioning using solar energy.
Claims (21)
1-12. (canceled)
13. An absorption refrigeration machine, comprising:
a) a working medium containing a nonvolatile sorption medium and a volatile refrigerant; and
b) an absorber comprising a semipermeable membrane which is permeable to said refrigerant and impermeable to said sorption medium and which is capable of separating a vapor phase containing said refrigerant from a liquid phase containing said sorption medium.
14. The absorption refrigeration machine of claim 13 , wherein said refrigerant is water.
15. The absorption refrigeration machine of claim 13 , wherein said refrigerant is ammonia or carbon dioxide.
16. The absorption refrigeration machine of claim 13 , wherein said sorption medium comprises one or more ionic liquids.
17. The absorption refrigeration machine of claim 16 , wherein said ionic liquids consist of salts of organic cations with organic or inorganic anions.
18. The absorption refrigeration machine of claim 17 , wherein that the ionic liquids comprise one or more 1,3-dialkylimidazolium salts.
19. The absorption refrigeration machine of claim 16 , wherein the ionic liquids comprise one or more quaternary ammonium salts of the general formula R1R2R3R4N+A−, where
R1 is an alkyl radical having from 1 to 20 carbon atoms,
R2 is an alkyl radical having from 1 to 4 carbon atoms,
R3 is a (CH2CHRO)n—H radical where n is from 1 to 200 and R═H or CH3,
R4 is an alkyl radical having from 1 to 4 carbon atoms or a (CH2CHRO)n—H radical where n is from 1 to 200 and R═H or CH3 and
A− is a monovalent anion.
20. The absorption refrigeration machine of claim 19 , wherein said refrigerant is water.
21. The absorption refrigeration machine of claim 19 , wherein said refrigerant is ammonia or carbon dioxide.
22. The absorption refrigeration machine of claim 13 , wherein the semipermeable membrane is a solution diffusion membrane.
23. The absorption refrigeration machine of claim 13 , wherein the semipermeable membrane is a microporous membrane which is not wetted by the working medium.
24. The absorption refrigeration machine of claim 23 , wherein the refrigerant is water and the semipermeable membrane is a hydrophobic microporous membrane.
25. The absorption refrigeration machine of claim 24 , wherein said sorption medium comprises one or more ionic liquids.
26. The absorption refrigeration machine of claim 25 , wherein the ionic liquids consist of salts of organic cations with organic or inorganic anions.
27. The absorption refrigeration machine of claim 13 , wherein the semipermeable membrane is arranged on a porous support layer.
28. The absorption refrigeration machine of claim 27 , wherein the support layer is arranged on the side of the semipermeable membrane which is in contact with the vapor phase.
29. The absorption refrigeration machine of claim 13 , wherein the semipermeable membrane is arranged in the absorber in the form of hollow fibers.
30. The absorption refrigeration machine of claim 29 , wherein said sorption medium comprises one or more ionic liquids.
31. The absorption refrigeration machine of claim 30 , wherein the ionic liquids consist of salts of organic cations with organic or inorganic anions.
32. The absorption refrigeration machine of claim 30 , wherein the refrigerant is water.
Applications Claiming Priority (3)
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EP08101297.3A EP2088389B1 (en) | 2008-02-05 | 2008-02-05 | Absorption cooling machine |
EP08101297.3 | 2008-02-05 | ||
PCT/EP2009/050958 WO2009098155A1 (en) | 2008-02-05 | 2009-01-28 | Absorption type refrigerating machine |
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EP (1) | EP2088389B1 (en) |
JP (1) | JP2011511258A (en) |
KR (1) | KR20100121635A (en) |
CN (1) | CN101939602A (en) |
CA (1) | CA2714425A1 (en) |
IL (1) | IL207324A0 (en) |
RU (1) | RU2010136663A (en) |
WO (1) | WO2009098155A1 (en) |
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Also Published As
Publication number | Publication date |
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JP2011511258A (en) | 2011-04-07 |
EP2088389B1 (en) | 2017-05-10 |
RU2010136663A (en) | 2012-03-20 |
WO2009098155A1 (en) | 2009-08-13 |
IL207324A0 (en) | 2010-12-30 |
EP2088389A1 (en) | 2009-08-12 |
CN101939602A (en) | 2011-01-05 |
CA2714425A1 (en) | 2009-08-13 |
KR20100121635A (en) | 2010-11-18 |
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