US20130061612A1 - Refrigerant storage in secondary loop refrigeration systems - Google Patents

Refrigerant storage in secondary loop refrigeration systems Download PDF

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US20130061612A1
US20130061612A1 US13/509,044 US201013509044A US2013061612A1 US 20130061612 A1 US20130061612 A1 US 20130061612A1 US 201013509044 A US201013509044 A US 201013509044A US 2013061612 A1 US2013061612 A1 US 2013061612A1
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ionic liquid
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alkene
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Mark Brandon Shiflett
Akimichi Yokozeki
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • F25B45/00—Arrangements for charging or discharging refrigerant
    • 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
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • 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
    • F25B25/00—Machines, plants or systems, using a combination of modes of operation covered by two or more of the groups F25B1/00 - F25B23/00
    • F25B25/005—Machines, plants or systems, using a combination of modes of operation covered by two or more of the groups F25B1/00 - F25B23/00 using primary and secondary 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
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D17/00—Arrangements for circulating cooling fluids; Arrangements for circulating gas, e.g. air, within refrigerated spaces
    • F25D17/02—Arrangements for circulating cooling fluids; Arrangements for circulating gas, e.g. air, within refrigerated spaces for circulating liquids, e.g. brine
    • 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
    • F25B2309/00—Gas cycle refrigeration machines
    • F25B2309/06—Compression machines, plants or systems characterised by the refrigerant being carbon dioxide
    • 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
    • F25B2500/00—Problems to be solved
    • F25B2500/27—Problems to be solved characterised by the stop of the refrigeration cycle

Definitions

  • This invention relates to the field of refrigeration systems. More specifically, the invention relates to a process and system for storing a secondary refrigerant such as carbon dioxide in a secondary loop refrigeration system using ionic liquids.
  • Secondary loop refrigeration systems have found widespread use in supermarkets and storage warehouses. This type of refrigeration system incorporates a primary refrigeration system and a secondary loop.
  • the primary refrigeration system is often a traditional direct expansion design that uses a phase change refrigerant and a compressor to circulate a primary refrigerant.
  • the secondary loop contains a nontoxic and nonflammable refrigerant such as carbon dioxide or propylene glycol.
  • a heat exchanger is used to transfer energy between the primary refrigerant and the refrigerant in the secondary loop.
  • the primary refrigeration system is typically restricted to an isolated location, e.g. a machine room or roof top, and the secondary loop runs through the storage compartments for storing refrigerated goods, e.g. supermarket display cases.
  • Secondary loop refrigeration systems offer many advantages over conventional refrigeration systems, one of the most important being a significant improvement in energy efficiency. Additionally, secondary loop refrigeration systems are more compact, operate with a small charge of refrigerant, and minimize the effects of refrigerant leakage.
  • Carbon dioxide is widely used as the secondary refrigerant in the secondary loop of these refrigeration systems.
  • a problem arises when there is a shutdown of the primary refrigeration system, e.g. due to a loss of electrical power.
  • the secondary refrigerant in the secondary loop increases in pressure, which can lead to very high pressures, such that the secondary refrigerant may need to be vented to prevent rupture of the secondary loop.
  • a safety relief device is used in these systems so that when the pressure reaches the set point of the relief device, the device opens to the atmosphere, releasing the secondary refrigerant.
  • the loss of the secondary refrigerant requires the system to be recharged when operation is restarted in order for the secondary loop to function properly.
  • Ionic liquids are known to absorb refrigerants such as carbon dioxide, and have been used to remove carbon dioxide from gas mixtures.
  • Moriya US 2007/00843414
  • Tonkovich US 2009/0071335
  • ionic liquids have not been used as storage media for a secondary refrigerant such as carbon dioxide in secondary loop refrigeration systems.
  • This invention solves the stated problem by providing a method and apparatus for storing and recovering a secondary refrigerant, such as carbon dioxide, in a secondary loop refrigeration system using ionic liquids.
  • a secondary refrigerant such as carbon dioxide
  • this invention provides, in a secondary loop refrigeration system that comprises a primary refrigeration loop containing a primary refrigerant, a secondary refrigeration loop containing a secondary refrigerant, and a heat exchanger contacted by both the primary and secondary refrigeration loops, a method of storing secondary refrigerant, comprising (a) flowing at least a portion of the secondary refrigerant from the secondary loop to an auxiliary container; and (b) absorbing at least a portion of the flowed secondary refrigerant with an ionic liquid in the auxiliary container to form a mixture thereof.
  • this invention provides an apparatus for adjusting the temperature of an object, medium or space, comprising (a) a primary refrigeration module that comprises a primary refrigeration loop containing a primary refrigerant, a condenser and an expansion valve; (b) a secondary refrigeration module that comprises a secondary refrigeration loop containing a secondary refrigerant, and an evaporator; (c) and a heat exchanger contacted by both the primary and secondary refrigeration loops; and (d) an auxiliary container in fluid communication with the secondary refrigeration loop through a flow interrupter, said auxiliary container containing at least one ionic liquid; wherein the condenser is located in proximity to an object, medium or space to be heated, or the evaporator is located in proximity to an object, medium or space to be cooled.
  • this invention provides a process for storing carbon dioxide in a secondary loop refrigeration system comprising the steps of (a) providing a secondary loop refrigeration system comprising a secondary loop containing carbon dioxide; (b) releasing the carbon dioxide from the secondary loop; and (c) contacting the carbon dioxide released from the secondary loop with at least one ionic liquid, whereby at least a portion of the carbon dioxide is absorbed by the ionic liquid.
  • this invention provides a refrigeration system comprising (a) an object, space or medium to be cooled; (b) a primary refrigeration system containing a primary refrigerant, said primary refrigeration system comprising a compressor, a condenser, and an expansion valve; (c) a second refrigeration loop containing carbon dioxide; (d) an evaporator in open communication with the second refrigeration loop for transferring heat from said object, space or medium to the carbon dioxide; (e) a heat exchanger for transferring heat from the carbon dioxide in the second refrigeration loop to said primary refrigerant in the primary refrigeration system; and (f) an expansion tank in fluid communication with the second refrigeration loop through a flow interrupter, said expansion tank containing at least one ionic liquid.
  • FIG. 1 is a schematic drawing of an exemplary secondary loop refrigeration system for use with the process disclosed herein.
  • FIG. 2 is a layout of the components of a vapor compression cycle.
  • FIG. 3 is a layout of the components of an absorption cycle.
  • secondary loop refrigeration system refers to a refrigeration system in which a thermal energy transfer medium contained in a secondary loop is used to transport thermal energy from a heat source to a primary refrigeration system.
  • secondary loop refers to the path over which the thermal energy transfer medium travels while it is being cycled between the heat source and the primary refrigeration system.
  • second refrigerant refers to the thermal energy transfer medium in the secondary loop.
  • primary refrigeration system refers to the part of a secondary loop refrigeration system where heat is transferred to an object, medium or space, such as the external environment, by way of a compressor or an absorber/generator system.
  • primary refrigerant refers to the thermal energy transfer medium in the primary refrigeration system.
  • ionic liquid refers to an organic salt that is fluid at or below about 100° C.
  • refrigerant refers to a fluidic substance such as a fluorocarbon (FC), hydrofluorocarbon (HFC), chlorofluorocarbon (CFC), hydrochlorofluorocarbon (HCFC), or ammonia, alkanes, alkenes, aromatics, carbon dioxide, or other gas such as hydrogen, oxygen, nitrogen, and argon that may be used as a thermal energy transfer medium.
  • FC fluorocarbon
  • HFC hydrofluorocarbon
  • CFC chlorofluorocarbon
  • HCFC hydrochlorofluorocarbon
  • ammonia alkanes, alkenes, aromatics, carbon dioxide, or other gas such as hydrogen, oxygen, nitrogen, and argon that may be used as a thermal energy transfer medium.
  • a refrigerant when it changes phase from liquid to vapor (evaporates), removes heat from the surroundings; and when it changes phase from vapor to liquid (condenses), it adds heat to the surroundings.
  • refrigerant may carry the connotation of
  • a secondary refrigerant such as carbon dioxide
  • the inventions hereof may be used in situations where, for example, there is a shutdown of the primary refrigeration system.
  • the methods and apparatus hereof eliminate the release of a secondary refrigerant into the environment and the need to recharge the secondary loop after a shutdown of the primary refrigeration system.
  • Secondary loop refrigeration systems find utility in refrigeration applications such as supermarket display cases and warehouse storage containers.
  • a secondary loop refrigeration system comprises a primary refrigeration system and a secondary loop.
  • the primary refrigeration system is a traditional direct expansion design that uses a phase change refrigerant and a compressor, or an absorber/generator system, to circulate the refrigerant.
  • phase change refrigerant may be used as the primary refrigerant.
  • suitable primary refrigerants include without limitation ammonia, fluorocarbons such as tetrafluoromethane (Freon 14), fluoroform (Freon 23), and hexafluoroethane (Freon 116); hydrofluorocarbons such as difluoromethane (HFC-32), 1,1-difluoroethane, 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,1,1,3,3-pentafluorobut
  • the primary refrigeration system is typically contained in an isolated location, e.g. a machine room or roof top, when the system is used for cooling and it is desired to reject heat to the atmosphere. In other embodiments, however, the system may be used for heating, and the condenser is located in proximity to an object, medium or space to be heated.
  • the secondary loop contains a secondary refrigerant, which is frequently carbon dioxide. Other suitable secondary refrigerants, however, include nitrogen, argon, helium, ammonia, perfluoroalkanes, ethylene glycols, and hydrofluoroethers.
  • the evaporator is located in proximity to an object, medium or space to be cooled.
  • heat energy from a food storage compartment is transferred to the secondary refrigerant in the secondary loop by way of an evaporator containing refrigeration coils.
  • the heat transfer to the secondary refrigerant may be facilitated by the use of fans, which circulate the air in the storage compartment.
  • the secondary refrigerant is circulated in the secondary loop to a heat exchanger by a circulating pump. In the heat exchanger, the thermal energy from the secondary refrigerant is transferred to the primary refrigerant contained in the primary refrigeration system.
  • the cooled secondary refrigerant is returned to the storage compartment by way of the secondary loop.
  • the warmed primary refrigerant is circulated through a compressor, or an absorber/generator system, to a condenser where the primary refrigerant is liquefied and cooled. By this process, the thermal energy is extracted from the primary refrigerant and rejected into the environment.
  • the primary refrigerant is then expanded through an expansion valve and returned to the heat exchanger.
  • the primary refrigerant may be routed to the condenser by either a vapor compression cycle or an absorption cycle.
  • Vapor compression and absorption cycles, and systems in which they are run, are described in Application Guide for Absorption Cooling/Refrigeration Using Recovered Heat [Dorgan et al (American Society of Heating, Refrigeration and Air Conditioning Engineers, Inc., 1995, Atlanta, Ga., Chapter 5)].
  • FIG. 2 A schematic diagram for a system in which a simple vapor compression cycle is run is shown in FIG. 2 .
  • the system is composed of condenser and evaporator units with an expansion valve, and a vapor compressor that is capable of mechanically increasing the pressure of a refrigerant vapor.
  • a schematic diagram for a simple absorption cycle is shown in FIG.
  • the system is composed of condenser and evaporator units with an expansion valve similar to an ordinary vapor compression cycle shown in FIG. 2 , but an absorber-generator solution circuit replaces the compressor.
  • the circuit may be composed of an absorber, a generator, a heat exchanger, a pressure control device (A) and a pump for circulating the solution.
  • the heat released by the absorber upon the absorption of the refrigerant by the absorbent may be used to heat a mixture of refrigerant and absorbent in the generator to separate the refrigerant in vapor form from the absorbent.
  • the absorbent can be any ionic liquid.
  • This invention thus involves an apparatus for adjusting the temperature of an object, medium or space wherein the refrigerant is routed to the condenser by either a vapor compression cycle or an absorption cycle, as described herein, to cool or heat an object (for example a conduit or a container), a medium (for example a fluid such as air or water) or a space.
  • an object for example a conduit or a container
  • a medium for example a fluid such as air or water
  • the apparatus may thus be composed of a mechanical compressor, a condenser and evaporator units with an expansion valve; or it may include components such as an absorber-generator solution circuit (which by the outflow and inflow of heat increases the pressure of refrigerant vapor as a compressor does mechanically) where the circuit may be composed of an absorber, a generator, a heat exchanger, a pressure control device and a pump for circulating the solution.
  • an absorber-generator solution circuit which by the outflow and inflow of heat increases the pressure of refrigerant vapor as a compressor does mechanically
  • the circuit may be composed of an absorber, a generator, a heat exchanger, a pressure control device and a pump for circulating the solution.
  • Vapor compression and absorption systems are further described in US 2006/0197053 and US2007/0019708, each of which is by this reference incorporated in its entirety as a part hereof for all purposes.
  • An apparatus of this invention may be deployed for use in, or fabricated or operated as, a refrigerator, a freezer, an ice machine, an air conditioner, an industrial cooling system, a heater or heat pump.
  • Each of these instruments may be situated in a residential, commercial or industrial setting, or may be incorporated into a mobilized device such as a car, truck, bus, train, airplane, or other device for transportation, or may be incorporated into a piece of equipment such as a medical instrument.
  • Ionic liquids suitable for use as disclosed herein can, in principle, be any ionic liquid that absorbs a secondary refrigerant such as carbon dioxide; however, ionic liquids that have minimal absorption of the refrigerant will be less effective. Ideally, ionic liquids having high absorption of the selected refrigerant are desired for efficient use as described herein. Additionally, mixtures of two or more ionic liquids may be used.
  • ionic liquids are formed by reacting a nitrogen-containing heterocyclic ring, preferably a heteroaromatic ring, with an alkylating agent (for example, an alkyl halide) to form a quaternary ammonium salt, and performing ion exchange or other suitable reactions with various Lewis acids or their conjugate bases to form the ionic liquid.
  • alkylating agent for example, an alkyl halide
  • suitable heteroaromatic rings include substituted pyridines, imidazole, substituted imidazole, pyrrole and substituted pyrroles. These rings can be alkylated with virtually any straight, branched or cyclic C 1-20 alkyl group, but preferably, the alkyl groups are C 1-16 groups.
  • Ionic liquids suitable for use herein may also be synthesized by salt metathesis, by an acid-base neutralization reaction or by quaternizing a selected nitrogen-containing compound; or they may be obtained commercially from several companies such as Merck (Darmstadt, Germany), BASF (Mount Olive, N.J.), Fluka Chemical Corp. (Milwaukee, Wis.), and Sigma-Aldrich (St. Louis, Mo.).
  • ionic liquids suitable for use herein are included among those that are described in sources such as J. Chem. Tech. Biotechnol., 68:351-356 (1997); Chem. Ind., 68:249-263 (1996); J. Phys. Condensed Matter, 5: (supp 34B):B99-B106 (1993); Chemical and Engineering News, Mar. 30, 1998, 32-37; J. Mater. Chem., 8:2627-2636 (1998); Chem. Rev., 99:2071-2084 (1999); and US 2008/0028777 (which is by this reference incorporated in its entirety as a part hereof for all purposes), and references cited therein.
  • a library i.e.
  • a combinatorial library of ionic liquids may be prepared, for example, by preparing various alkyl derivatives of a quaternary ammonium cation, and varying the associated anions.
  • the acidity of the ionic liquids can be adjusted by varying the molar equivalents and type and combinations of Lewis acids.
  • Ionic liquids suitable for use herein comprise an anion and a cation.
  • the cation is selected from the group consisting of cations represented by the structures of the following formulae:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 and R 13 are independently selected from the group consisting of:
  • R 7 , R 8 , R 9 , and R 10 are independently selected from the group consisting of:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 can together form a cyclic or bicyclic alkanyl or alkenyl group
  • the ionic liquid comprises an anion selected from one or more members of the group consisting of: [CH 3 CO 2 ] ⁇ , [HSO 4 ] ⁇ , [CH 3 OSO 3 ] ⁇ , [C 2 H 5 OSO 3 ] ⁇ , [AlCl 4 ] ⁇ , [CO 3 ] 2 ⁇ , [HCO 3 ] ⁇ , [NO 2 ] ⁇ , [NO 3 ] ⁇ , [SO 4 ] 2 ⁇ , [PO 3 ] 3 ⁇ , [HPO 3 ] 2 ⁇ , [H 2 PO 3 ] 1 ⁇ , [PO 4 ] 3 ⁇ , [HPO 4 ] 2 ⁇ , [H 2 PO 4 ] ⁇ , [HSO 3 ] ⁇ , [CuCl 2 ] ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , SCN ⁇ , carborates optionally substituted with alkyl or substituted alkyl; carboranes
  • the ionic liquid comprises a cation selected from one or more members of the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, phosphonium, ammonium, benzyltrimethylammonium, choline, dim ethylimidazolium, guanidinium, phosphonium choline, tetramethylammonium, and tetramethylphosphonium.
  • a cation selected from one or more members of the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, phosphonium, ammonium, benzyltrimethylammonium, choline, dim ethylimida
  • the ionic liquid comprises an anion selected from one or more members of the group consisting of aminoacetate, ascorbate, benzoate, catecholate, citrate, dimethylphosphate, formate, fumarate, gallate, glycolate, glyoxylate, iminodiacetate, isobutyrate, kojate, lactate, levulinate, oxalate, pivalate, propionate, pyruvate, salicylate, succinamate, succinate, tiglate, tetrafluoroborate, tetrafluoroethanesulfonate, tropolonate, [CH 3 CO 2 ] ⁇ , [HSO 4 ] ⁇ , [CH 3 OSO 3 ] ⁇ , [C 2 H 5 OSO 3 ] ] , [AlCl 4 ] ⁇ , [CO 3 ] 2 ⁇ , [HCO 3 ] ⁇ , [NO 2 ] ⁇ , [NO 3 ] ⁇ , [NO 3
  • R 11 is selected from the group consisting of:
  • the ionic liquid is selected from the group consisting of 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF 6 ], 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF 4 ], 1-hexyl-3-methylimidazolium bistrifluoromethylsulfonylimide [hmim][Tf 2 N], and 1-butyl-3-methylimidazolium acetate [bmim][acetate].
  • the method disclosed herein for storing a secondary refrigerant in a secondary loop refrigeration system comprises the following steps.
  • the first step is providing a secondary loop refrigeration system, as described above.
  • the secondary refrigerant is released from the secondary loop and contacted with at least one ionic liquid, as described above, whereby at least a portion of the secondary refrigerant is absorbed by the ionic liquid.
  • the portion of the secondary refrigerant absorbed is sufficient to relieve the pressure in the secondary loop.
  • the amount of ionic liquid needed will depend on the amount of secondary refrigerant contained in the secondary loop and the absorption capability of the ionic liquid used.
  • the absorbed secondary refrigerant may be released from the ionic liquid back into the secondary loop.
  • the secondary refrigerant can be released from the ionic liquid most conveniently by heating the ionic liquid containing the secondary refrigerant.
  • FIG. 1 shows a schematic drawing of an exemplary secondary loop refrigeration system in cooling mode that may be used to practice the method disclosed herein.
  • the secondary loop refrigeration system illustrated in FIG. 1 is suitable for use, for example, in a supermarket or grocery store. Similar systems may be useful for other applications, e.g. storage warehouses.
  • the secondary loop containing the secondary refrigerant is depicted by dashed arrows and runs through an evaporator 10 in a refrigerated display case 90 (an example of a storage compartment for storing refrigerated goods), which is located in the interior of the store 100 .
  • the evaporator is in open communication with the secondary loop for transferring heat from the display case to the secondary refrigerant.
  • the primary refrigeration system is depicted by solid arrows and comprises a compressor 30 , a condenser 40 , and an expansion valve 50 .
  • the heat exchanger 20 serves to transfer heat energy from the secondary refrigerant in the secondary loop to the primary refrigerant in the primary refrigeration system, as described above.
  • pressure in the secondary loop increases. This pressure increase may be sensed by a pressure sensor 70 in fluid communication with the secondary loop.
  • a flow interrupter for example a valve such as a pressure relief valve 80 depicted in FIG. 1 , is opened, thereby releasing the secondary refrigerant from the secondary loop.
  • the released secondary refrigerant enters an expansion tank 60 , which is in fluid communication with the secondary loop, where it is contacted with at least one ionic liquid contained in the tank, whereby at least a portion of the released secondary refrigerant is absorbed by the ionic liquid.
  • the absorbed secondary refrigerant may be released from the ionic liquid back into the secondary loop by heating the ionic liquid using a heat source 65 , such as an electrical heating element, a natural gas or oil fueled heat source, that is in thermal contact with the expansion tank.
  • a heat source 65 such as an electrical heating element, a natural gas or oil fueled heat source, that is in thermal contact with the expansion tank.
  • min means minute(s)
  • hr means hour(s)
  • mL means milliliter(s)
  • ⁇ L means microliter(s)
  • g means gram(s)
  • mg means milligram(s)
  • ⁇ g means microgram(s)
  • Pa means pascal(s)
  • kPa means kilopascal(s)
  • MPa means megapascal(s).
  • the 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyflimide [hmim][Tf 2 N] (Lot EQ500831 632) was purchased from EMD Chemicals, Inc. (Gibbstown, N.J.) with a purity of >99%.
  • Coleman grade CO 2 was obtained from MG Industries (Malvern, Pa.), with a minimum purity of 99.99%.
  • a molecular sieve trap was installed to remove trace amounts of water from the CO 2 .
  • This example illustrates the solubility of carbon dioxide in 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF 6 ] at temperatures of 283.15° K, 298.15° K, 323.15° K, and 348.15° K.
  • the gas solubility measurements were made using a gravimetric microbalance (IGA-003 Multicomponent Analyzer, Hiden Isochema Ltd., Warrington WAS 7TN UK).
  • the IGA design integrates precise computer-control and measurement of weight change, pressure and temperature to enable fully automatic and reproducible determination of gas absorption isotherms and isobars.
  • the microbalance consists of an electrobalance with sample and counterweight components inside a stainless steel pressure-vessel.
  • the balance has a weigh range of 0-100 mg with a resolution of 0.1 ⁇ g.
  • An enhanced pressure stainless steel (SS316LN) reactor capable of operation to 2.0 MPa and 773.15° K was installed.
  • a mixture of 30% ethylene glycol and 70% water by volume was used as the recirculating fluid with a temperature range from 278.15 to 363.15° K.
  • the sample mass slowly decreased as residual water and gases were removed. Once the mass had stabilized for at least 60 min, the sample dry mass was recorded.
  • the percent weight loss for the ionic liquid was about 1-3%. This weight loss can be attributed to the loss of residual water.
  • the IGA-003 can operate in both dynamic and static modes. All absorption measurements were performed in static mode. Static mode operation introduces gas into the top of the balance away from the sample, and both the admittance and exhaust valves control the set-point pressure.
  • the sample temperature was measured with a type K thermocouple with an accuracy of ⁇ 0.1° K.
  • the thermocouple was located inside the reactor next to the sample container. The water jacket maintained the set-point temperature automatically to within an accuracy of ⁇ 0.1° K.
  • Four isotherms at 283.15, 298.15, 323.15, and 348.15° K) were measured beginning with 283.15° K. Once the desired temperature was achieved and stabilized, the admittance and exhaust valves automatically opened and closed to adjust the pressure to the first set-point.
  • Pressures from 10 ⁇ 10 to 10 ⁇ 2 MPa were measured using a capacitance manometer (model PKR25, Pfeiffer Vacuum Inc.), and pressures from 10 ⁇ 2 to 2.0 MPa were measured using a piezo-resistive strain gauge (model PDCR4010, Druck, New Faifield, Conn.).
  • the reactor pressure set-point was maintained to within ⁇ 0.4 to 0.8 kPa.
  • the pressure ramp rate was set at 20 kPa/min and the temperature ramp rate was set at 1° K/min.
  • the upper pressure limit of the stainless steel reactor was 2.0 MPa, and several isobars up to 2.0 MPa (0.01, 0.05, 0.1, 0.4, 0.7, 1.0, 1.3, 1.5, and 2.0 MPa) were measured. To ensure sufficient time for gas-liquid equilibrium, the ionic liquid sample was maintained at set-point for a minimum of 3 hr with a maximum time-out of 20 hr.
  • the IGA method exploits the relaxation behavior following pressure and temperature changes to simultaneously evaluate the time-dependent absorption and asymptotic uptake.
  • the real-time processor was used to determine the end-point for each isotherm.
  • the percent relaxation used as an end point for the real-time analysis was 99 percent.
  • the minimum weight change for real-time analysis was set at 1 ⁇ g, the acceptable average deviation of the model from the acquired data was set at 7 ⁇ g, and the target interval for weight acquisition was set at a typical value of 1 ⁇ g.
  • the temperature variation during an isotherm was maintained less than 0.1 ⁇ ° K/min.
  • This example illustrates the solubility of carbon dioxide in 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF 4 ] at temperatures of 283.15° K, 298.15° K, 323.15° K, and 348.15° K.
  • This example illustrates the solubility of carbon dioxide in 1-hexyl-3-methylimidazolium bistrifluoromethylsulfonylimide [hmim][Tf 2 N] at temperatures of 283.15° K, 298.15° K, 323.15° K, and 348.15° K.
  • This example illustrates the solubility of carbon dioxide in 1-butyl-3-methylimidazolium acetate [bmim][acetate] at temperatures of 283.15° K, 298.15° K, 323.15° K, and 348.15° K.
  • invention as used herein is a non-limiting term, and is not intended to refer to any single embodiment of the various inventions hereof to the exclusion of others, but encompasses all possible embodiments as described in the specification and the claims.

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US20110203301A1 (en) * 2008-11-07 2011-08-25 E.I. Du Pont De Nemours And Company Absorption cycle utilizing ionic compounds and/or non-ionic absorbents as working fluids
US20110223087A1 (en) * 2010-03-12 2011-09-15 E. I. Du Pont De Nemours And Company Amino compounds for carbon dioxide and sulfur dioxide removal
US20120324926A1 (en) * 2010-03-19 2012-12-27 Arkema France Refrigerant for high-temperature heat transfer
US11045783B2 (en) * 2016-08-12 2021-06-29 Purdue Research Foundation Systems and methods for increasing reaction yield
US11105539B2 (en) 2017-12-01 2021-08-31 Johnson Controls Technology Company Heating, ventilation, and air conditioning system with primary and secondary heat transfer loops

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US11584483B2 (en) 2010-02-11 2023-02-21 Allen Szydlowski System for a very large bag (VLB) for transporting liquids powered by solar arrays
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US20120324926A1 (en) * 2010-03-19 2012-12-27 Arkema France Refrigerant for high-temperature heat transfer
US8679363B2 (en) * 2010-03-19 2014-03-25 Arkema France Refrigerant for high-temperature heat transfer
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US11105539B2 (en) 2017-12-01 2021-08-31 Johnson Controls Technology Company Heating, ventilation, and air conditioning system with primary and secondary heat transfer loops
US11906211B2 (en) 2017-12-01 2024-02-20 Johnson Controls Tyco IP Holdings LLP Heating, ventilation, and air conditioning system with primary and secondary heat transfer loops

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