WO2012116174A1 - Dispositif d'amplification de pression activé thermiquement pour chauffage thermodynamique et génération d'énergie - Google Patents

Dispositif d'amplification de pression activé thermiquement pour chauffage thermodynamique et génération d'énergie Download PDF

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Publication number
WO2012116174A1
WO2012116174A1 PCT/US2012/026313 US2012026313W WO2012116174A1 WO 2012116174 A1 WO2012116174 A1 WO 2012116174A1 US 2012026313 W US2012026313 W US 2012026313W WO 2012116174 A1 WO2012116174 A1 WO 2012116174A1
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Prior art keywords
stream
working fluid
pressure
absorbent
thermally activated
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PCT/US2012/026313
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English (en)
Inventor
Jianguo Xu
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Jianguo Xu
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Application filed by Jianguo Xu filed Critical Jianguo Xu
Priority to CN2012800103350A priority Critical patent/CN103403476A/zh
Priority to US14/001,389 priority patent/US20140053594A1/en
Publication of WO2012116174A1 publication Critical patent/WO2012116174A1/fr

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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
    • F25B15/02—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas
    • 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
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/06—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using mixtures of different fluids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/06—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using mixtures of different fluids
    • F01K25/065—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using mixtures of different fluids with an absorption fluid remaining at least partly in the liquid state, e.g. water for ammonia

Definitions

  • Heating and cooling in buildings use over 20% of the total energy consumed in the United States. Vehicle air conditioners also consume a significant portion of the transportation fuel. In addition, heating and cooling of process streams are also performed in the process industry, especially chemical industry and power generation industry. As the price of energy goes up, it becomes more desirable to run heating and cooling systems with solar thermal energy. Solar energy is plentiful during the hot summer days when the demand for air conditioning is greatest, and when the load on the electrical grid reaches its peak. Uses of solar water heaters are taking off in many places, including southern Europe and China. Such systems typically have a large excess supply of heat on hot summer days. It would be desirable to use this excess heat for air conditioning to meet the high demand for cooling at such time.
  • LiBr lithium bromide
  • TAHP thermally activated heat pump
  • LiBr-water absorption system is not suitable for winter heating when the ambient temperature is below water freezing temperature, because water freezes at 0° C.
  • LiBr-water absorption heat pumps are often called “LiBr chillers,” i.e., they are used for chilling only.
  • the LiBr-water absorption system typically needs heat of greater than 88° C in order to avoid freeze out issues, rendering the system unsuitable for many solar water heaters.
  • a TAHP can have a heating coefficient of performance (heating COP) significantly greater than 1 , while a conventional gas or oil furnace only has a heating COP of less than 1.
  • a good single-effect TAHP in theory can have a heating COP of greater than 1.7, while a double- effect TAHP in theory can have a heating COP of even greater. Therefore, by using a TAHP, the thermal energy needs for heating can be reduced more than 40% with a single effect TAHP system and even more with a double effect TAHP system. Considering the huge amount of energy consumed by heating, a TAHP for space heating is extremely attractive.
  • TAHPs based on LiBr-water absorption or its derivatives use pure water as the working fluid. They cannot be used when the space heating is most needed, i.e., when the ambient temperature is close to or below 0° C, because water freezes below 0° C.
  • ammonia can be used as a working fluid in both vapor compression heat pumps and thermally activated heat pumps.
  • one of the problems with ammonia is that it is highly toxic, therefore is not very desirable for residential and vehicular applications.
  • a secondary loop is needed in order to mitigate the toxicity issue, which adds to the cost of the system.
  • the heat of absorption of ammonia in water is much greater than the latent heat of ammonia vaporization. This requires large heat exchange duties for absorption cooling and distillation column boiling in an ammonia- water absorption heat pump system, which means a very large heat exchanger cost and significant thermal energy degradation in the heat exchangers. This in turn increases the cost and decreases the COP of such TAHPs.
  • the single effect heating COP of the ammonia-water system is only at about 1.6, or a cooling COP of about 0.6, which is significantly lower than that of the LiBr absorption system, whose cooling COP is on the order of 0.75.
  • Ammonia also has other problems such as its corrosivity with copper and aluminum, two of the best materials for making heat exchangers, and the needs for very clean, oil-free surface for heat transfer. These problems have greatly constrained the use of thermally activated heat pumps with ammonia as the working fluid for heating and for air conditioning.
  • TAHP for heating that can replace the fuel burning heaters and electrical resistive heaters to thereby greatly reduce the energy consumption for heating
  • a TAHP for cooling that can use the heat provided by solar water heaters or the cooling water coming from a vehicle engine to thereby drastically reduce the energy need for cooling.
  • the present invention meets such unmet needs by providing a thermally activated system for increasing the pressure of a gaseous working fluid, i.e., a thermally activated pressure booster, and its uses in applications such as a TAHP.
  • a thermally activated pressure booster for increasing the pressure of a gaseous working fluid
  • the present invention relates to a thermally activated system for increasing the pressure of a gaseous working fluid.
  • the system comprises a working fluid having a bubble point of less than 20° C when the working fluid is at 1 atm pressure, and a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • the thermally activated system comprises:
  • an absorber in which a lower pressure, substantially gaseous stream of a working fluid is absorbed into a lower pressure, liquid stream of an absorbent to form a liquid solution
  • a pressure boosting device that increases the pressure of the liquid solution to obtain a higher pressure liquid solution
  • a generator that separates the higher pressure liquid solution into at least a higher pressure, substantially vaporized stream of the working fluid and a higher pressure, liquid stream of the absorbent
  • the working fluid has a bubble point of less than 20° C when the working fluid is at 1 atm pressure; and the absorbent comprises components of the working fluid and a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • the present invention relates to a thermally activated system for increasing the pressure of a gaseous working fluid, comprising:
  • an absorber in which a lower pressure, substantially gaseous stream of a working fluid is absorbed into a lower pressure, liquid stream of an absorbent to form a liquid solution
  • the working fluid is selected from the group consisting of R134a, dimethyl ether, R152a, CH 3 I (R13I1), propane, isopropane, propylene, isobutane, n-butane, HF01234yf, and a combination thereof
  • the absorbent comprises components of the working fluid and a solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and a combination thereof;
  • a pressure boosting device that increases the pressure of at least a portion of the liquid solution to obtain a higher pressure liquid solution
  • a generator that separates the higher pressure liquid solution into at least a higher pressure, substantially vaporized stream of the working fluid and a higher pressure, liquid stream of the absorbent
  • a condenser that substantially condenses at least a portion of the higher pressure, substantially vaporized stream of the working fluid to obtain a substantially condensed stream of the working fluid
  • a heat exchanger that cools at least a portion of the substantially condensed stream of the working fluid to obtain a sub-cooled stream of the working fluid, while heating another stream,
  • a pressure reducing device that reduces the pressure of at least a portion of the sub- cooled stream of the working fluid to obtain a lower pressure stream of the working fluid
  • an evaporator that at least partially vaporizes at least a portion of the lower pressure stream of the working fluid to obtain an at least partially vaporized stream of the working fluid, while removing heat from another heat source, wherein the other heat source is heat from environment of an enclosed space or a process stream when the thermally activated system is used for heating the enclosed space or the process stream, or heat from an enclosed space or a process stream when the thermally activated system is used for cooling the enclosed space or the process stream, and
  • the other stream in the heat exchanger comprises at least a portion of the at least partially vaporized stream of the working fluid, heating of which results in the lower pressure, substantially gaseous stream of the working fluid, at least a portion of which is fed to the absorber;
  • a second heat exchanger that cools at least a portion of the higher pressure, liquid stream of the absorbent to obtain a sub-cooled, liquid stream of the absorbent
  • a second pressure reducing device that reduces the pressure of at least a portion the sub-cooled, liquid stream of the absorbent to obtain the lower pressure, liquid stream of the absorbent, at least a portion of which is fed to the absorber.
  • the present invention relates to a thermally activated process for increasing the pressure of a gaseous working fluid.
  • the process comprises using a working fluid having a bubble point of less than 20° C when the working fluid is at 1 atm pressure, and a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • a working fluid having a bubble point of less than 20° C when the working fluid is at 1 atm pressure
  • a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent
  • the thermally activated process comprises:
  • the working fluid has a bubble point of less than 20° C when the working fluid is at 1 atm pressure; and the absorbent comprises components of the working fluid and a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • the present invention relates to a thermally activated process for increasing the pressure of a gaseous working fluid, comprising:
  • the working fluid is selected from the group consisting of R134a, dimethyl ether, R152a, CH 3 I (R13I1), propane, isopropane, propylene, isobutane, n-butane, HF01234yf, and a combination thereof
  • the absorbent comprises components of the working fluid and a solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and a combination thereof;
  • the other heat source in the vaporizing step is heat from environment of an enclosed space or a process stream when the thermally activated process is used for heating the enclosed space or the process stream, or heat from an enclosed space or a process stream when the thermally activated process is used for cooling the enclosed space or the process stream
  • the other stream in the heat exchanger comprises the at least partially vaporized stream of the working fluid from the evaporator, heating of which results in the lower pressure, substantially gaseous stream of the working fluid; feeding at least a portion of the lower pressure, substantially gaseous stream of the working fluid to the absorber;
  • FIG 1 shows an example of a single effect system according to an embodiment of the present invention
  • FIG. 1 shows an example of a double effect system according to an embodiment of the present invention.
  • Figure 3 shows an example of a power generation system according to an
  • an absorbent is a liquid that absorbs a gas to form a liquid solution in an absorber, typically accompanied by heat removal.
  • Absorber an absorber is a piece of a process equipment in which a gas is dissolved in an absorbent, forming a liquid solution.
  • Bubble point the temperature at which a liquid starts to vaporize. For a pure component, the bubble point at 1 atm is its boiling point.
  • Coefficient of performance (COP) or cooling COP the amount of heat lifted divided by the amount of energy used in the heat pumping process.
  • Pleating COP the amount of heat available for heating divided by the amount of energy used.
  • Cooling water in the context of the present invention refers to a heat transfer medium. It comprises mainly of water, and can contain other components such as ethylene glycol, alcohols, salt, etc.
  • Countercurrent heat exchanger a heat exchanger in which the stream being heated flows in the opposite direction from that being cooled, wherein the streaming being heated and the stream being cooled are separated by a thermally conductive solid material, such as a sheet material.
  • Dew point of a fluid the temperature at which a gas starts to condense.
  • the dew point of a pure component at 1 atm is the same as the boiling point for the pure component.
  • Generator a piece of process equipment in which a mixture is separated into two (or more) streams of different compositions.
  • the fundamental behind separation in a generator in the context of this patent is the volatility difference between the different components of the mixture.
  • a process unit operating on the same principle of the generator in the context of the present invention can also be called desorber or distillation unit or evaporation unit or evaporator in some other places. It differs from an electric generator which refers to an electro-mechanical device that converts mechanical energy to electrical energy.
  • Heat pump a process system that can move heat from a lower temperature to a higher temperature.
  • a conventional air conditioner is considered an example of a heat pump in the context of the present invention, as is a conventional refrigerator and a conventional heat pump that is used for space heating when the outdoor temperature is below that of the space to be heated.
  • Heat pumping a process that moves heat from a lower temperature to a higher temperature.
  • HFC fluorohydrocarbon, a chemical compound comprising hydrogen (H), carbon (C), and fluorine (F) in its molecule.
  • Organic oxygenate an organic compound comprising one or more oxygen (O) atoms in its molecule.
  • Polyol an alcohol comprising multiple -OH groups in its molecule.
  • examples of polyol include, but are not limited to, ethylene glycol, diethylene glycol, and propylene glycol.
  • Solvent a liquid that can dissolve a liquid and/or a gas component.
  • Subcooler a heat exchanger that cools a liquid to a temperature lower than its dew point.
  • Thermally activated heat pump a heat pump that is principally driven by the heat flow from a higher temperature heat source to a lower temperature heat sink.
  • TAHP Thermally activated heat pump
  • Working fluid a fluid in a heat pump, power generation system, or heat activated pressure booster that changes its phase. In heating, air conditioning, and refrigeration
  • a working fluid is also called refrigerant.
  • the working fluid may contain up to 5% of a solvent in certain embodiments in this patent.
  • Embodiments of the present invention relate to a non-ozone depleting or essentially non-ozone depleting working fluid and a solvent that improves the performance of a heat activated pressure booster, which can be used in applications such as a TAHP or a power generator.
  • the present invention relates to a lower cost, highly efficient thermally activated heat pump and air conditioning system that works at a higher pressure than the conventional LiBr chillers. They are capable of working at below sub water freezing temperatures, and can be thermally activated, especially with low level of heat, such as that from commercial solar water heaters and the cooling water from vehicle engines.
  • the heat activated pressure booster according to embodiments of the present invention does not use corrosive materials, and has no potential issue of absorbent freeze out during operation.
  • the present invention relates to a thermally activated system for increasing the pressure of a gaseous working fluid.
  • the thermally activated system comprises:
  • an absorber in which a lower pressure, substantially gaseous stream of a working fluid is absorbed into a lower pressure, liquid stream of an absorbent to form a liquid solution
  • a pressure boosting device that increases the pressure of at least a portion of the liquid solution to obtain a higher pressure liquid solution
  • a generator that separates at least a portion of the higher pressure liquid solution into at least a higher pressure, substantially vaporized stream of the working fluid and a higher pressure, liquid stream of the absorbent;
  • the working fluid has a bubble point of less than 20° C when the working fluid is at 1 atm pressure; and the absorbent comprises components of the working fluid and a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • the thermally activated system further comprises:
  • a condenser that substantially condenses at least a portion of the higher pressure, substantially vaporized stream of the working fluid to obtain a substantially condensed stream of the working fluid
  • a pressure reducing device that reduces the pressure of at least a portion of the substantially condensed stream of the working fluid to obtain a lower pressure stream of the working fluid
  • an evaporator that at least partially vaporizes at least a portion of the lower pressure stream of the working fluid to obtain an at least partially vaporized stream of the working fluid, while removing heat from another heat source
  • the other heat source in the evaporator is heat from environment of an enclosed space or a process stream when the thermally activated system is used for heating the enclosed space or the process stream, or heat froman enclosed space or a process stream when the thermally activated system is used for cooling the enclosed space or the process stream.
  • thermally activated system when used for heating an enclosed space or process stream, it can be used to heat the enclosed space or a process stream directly, or indirectly by heating a stream or medium that is used to heat the enclosed space or process stream.
  • the other heat source in the evaporator can be heat directly or indirectly from the environment.
  • thermally activated system when used for cooling an enclosed space or process stream, it can be used to cool the enclosed space or a process stream directly, or indirectly by cooling a stream or medium that is used to cool the enclosed space or process stream.
  • the other heat source in the evaporator can be heat directly or indirectly from the enclosed space or process stream.
  • Examples of the enclosed space or a process stream include, but are not limited to, the space within a room or a building, or the space within a vehicle, or a process stream in an industrial plant or installation.
  • the environment of an enclosed space or a process stream can be the space outside of the enclosed space or process stream.
  • the thermally activated system further comprises a heat exchanger that cools at least a portion of the substantially condensed stream of the working fluid to obtain a sub-cooled stream of the working fluid, while heating another stream. At least a portion of the sub-cooled stream of the working fluid is then fed to the pressure reducing device to obtain the lower pressure stream of the working fluid.
  • the other stream heated in the heat exchanger comprises at least a portion of the at least partially vaporized stream of the working fluid from the evaporator, heating of which results in the lower pressure, substantially gaseous stream of the working fluid, at least a portion of which is used in the absorber.
  • the thermally activated system further comprises: a second pressure reducing device in fluid communication with the absorber, wherein the second pressure reducing device reduces the pressure of at least a portion of the higher pressure, liquid stream of the absorbent from the generator to obtain the lower pressure, liquid stream of the absorbent, at least a portion of which is used in the absorber.
  • the thermally activated system further comprises a second heat exchanger in fluid communication with the pressure boosting device, an intermediate location of the generator, the bottom section of the generator, and the second pressure reducing device, wherein the second heat exchanger cools at least a portion of the higher pressure, liquid stream of the absorbent from the bottom section of the generator to obtain a sub-cooled liquid stream of the absorbent, while heating and partially vaporizing at least a portion of the higher pressure, liquid solution from the pressure boosting device to obtain a higher pressure, two-phase stream, which is subsequently fed to the intermediate location of the generator; and at least a portion of the sub-cooled liquid stream of the absorbent is then fed to the second pressure reducing device to obtain the lower pressure, liquid stream of the absorbent.
  • the intermediate location of the generator can be any location of the generator that is in between of the top and the bottom sections of the generator.
  • the thermally activated system comprises more than one generator.
  • a thermally activated system according to an embodiment of the present invention can comprise a higher pressure generator, and a medium pressure generator having an operating pressure lower than that of the higher pressure generator, wherein there is thermal communication between the top section of the higher pressure generator and the medium pressure generator.
  • the present invention relates to a power generation system, which comprises the thermally activated system according to an embodiment of the present invention and an expander, wherein at least a portion of the higher pressure, substantially vaporized stream of the working fluid from the generator is expanded in the expander to generate mechanical energy, and at least a portion of the exhaust stream of the working fluid from the expander is absorbed into the lower pressure, liquid stream of the absorbent in the absorber.
  • the present invention relates to a thermally activated process for increasing the pressure of a gaseous working fluid.
  • the method comprises:
  • the working fluid has a bubble point of less than 20° C when the working fluid is at 1 atm pressure; and the absorbent comprises components of the working fluid and a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • a solvent comprising an organic oxygenate containing in its molecule at least one oxygen atom (O) and at least one atom selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), fluorine (F), and a combination thereof, and the dew point of the solvent is greater than 130° C when the solvent is at 1 atm.
  • the thermally activated process further comprises:
  • the other heat source in the vaporizing step is heat from environment of an enclosed space or a process stream when the thermally activated process is used for heating the enclosed space or process stream, or heat from the enclosed space or a process stream when the thermally activated process is used for cooling the enclosed space or process stream.
  • the thermally activated process further comprises cooling at least a portion of the substantially condensed stream of the working fluid in a heat exchanger to obtain a sub-cooled stream of the working fluid, while heating another stream, wherein at least a portion of the sub-cooled stream of the working fluid is then fed to the pressure reducing device, and the other stream comprises at least a portion of the at least partially vaporized stream of the working fluid from the evaporator, heating of at least a portion of which results in the lower pressure, substantially gaseous stream of the working fluid, at least a portion of which is used in the absorber.
  • the thermally activated process further comprises:
  • the thermally activated process further comprises:
  • the thermally activated process utilizes more than one generators in the separating step.
  • a thermally activated process according to an embodiment of the present invention can comprise using a higher pressure generator, and a medium pressure generator having an operating pressure lower than that of the higher pressure generator in the separating step, wherein there is thermal
  • the thermally activated process is used for generate a power.
  • the process further comprises:
  • the working fluid comprises a component selected from the group consisting of R134a (1 ,1,1,2-tetrafiuoroethane), dimethyl ether, R152a
  • the solvent is selected from the group consisting of an organic oxygenate containing in its molecule at least one atom selected from the group consisting of nitrogen (N), phosphorus (P), fluorine (F), and sulfur (S), and a combination thereof, has a dew point of greater than 130° C when the solvent is at 1 atm, and has a viscosity of less than 2.5 cP at 20°C.
  • the solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and a combination thereof.
  • NMP N-methyl-2-pyrrolidone
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • the absorbent contains both the working fluid and the solvent.
  • the absorbent is also referred to as the working fluid lean solution in the present application.
  • the absorption of a working fluid into an absorbent in the absorber or the absorbing step forms a liquid solution rich in the working fluid.
  • the liquid solution is also referred to as the weak solution in the present application.
  • the higher pressure, liquid solution from the pressure boosting device is split into at least a major stream and a minor stream.
  • the minor stream constitutes 1-20% (mol) of the total flow of the higher pressure, liquid solution and is fed to the top of the generator.
  • the major stream is heated and partially vaporized in a heat exchanger to obtain a two-phase stream, i.e., liquid and vapor, which is fed to an intermediate location of the generator.
  • a subcooler is used to cool at least a portion of the substantially condensed working fluid from the condenser, and heat and further vaporize at least a portion of the at least partially vaporized stream of the working fluid from the evaporator, which can contain 0.1 -5% (mol) liquid.
  • Figure 1 shows an example of a single effect absorption heat pump process according to an embodiment of the present invention.
  • a lower pressure, substantially gaseous stream of a working fluid (306) and a lower pressure, liquid stream of an absorbent (314) are fed into an absorber (31) to obtain a liquid solution (308).
  • the resultant working fluid-rich solution or weak solution (308) is fed to a pump (32) to obtain a higher pressure weak solution (309), which is subsequently split into a major stream (310) and a minor stream (312).
  • the overhead higher pressure vapor working fluid (301) is condensed in condenser (35), releasing heat.
  • the resultant substantially condensed working liquid is split into two streams: the reflux (315), which flows back to the top of the generator (34); and the rest (303) to be subcooled in a substantially countercurrent heat exchanger or Subcooler (30).
  • the reflux stream (315) for this system is a very small fraction of the total working fluid coming out of the condenser, typically smaller than 10% (mol) of the total working fluid flow in the condenser.
  • Heat, Q g is supplied to the base or the bottom section of the generator (34) to provide the reboiling heat of the distillation column. This heat transfer can be carried out in a heat exchanger inside or outside the generator.
  • the substantially condensed working fluid (303) is cooled by the lower pressure, mostly vaporized stream (305a) of the working fluid from the evaporator (13) in a subcooler (30) that is a substantially counter-current heat exchanger.
  • the resultant sub-cooled or cooler working fluid (304) is reduced in pressure in throttle valve (12). This results in a two phase stream at a lower temperature (305).
  • This lower temperature, two phase stream (305) is heated and mostly vaporized in the evaporator (13).
  • External heat (1 10) which can be from the environment when the system is used for heating, or room air or a process stream to be cooled when the system is used for cooling, is used to vaporize most of the two phase stream (305).
  • Cooling of the external heat stream (110) results in a lower temperature stream (112).
  • the temperature of the lower temperature stream (1 12) is lower than that of stream 303.
  • the mostly vaporized working fluid (305a) is first substantially completely vaporized and further heated in the subcooler (30).
  • the resultant lower pressure, substantially gaseous working liquid (306) is then used for absorption by the absorbent (314) in the absorber 31, releasing heat (Qb) at a temperature higher than that of stream 1 12.
  • This heat removal can be carried out in one or more heat exchanger(s) inside the absorber.
  • the higher pressure absorbent (313) is cooled in the substantially counter-current heat exchanger (33), and let down in pressure in a throttle valve (36) to produce the lower pressure absorbent stream (314), which is used for absorption in the absorber (31).
  • the reflux stream (315) to the top of the generator (34) can be eliminated, and the minor feed stream (312) is fed to where reflux is typically fed in the generator (34).
  • the working fluid (301) will contain some small fraction of the solvent.
  • the working fluid (305a) coming out of the evaporator (13) is allowed to contains some liquid, typically in 0.1-5% (mol) range.
  • Embodiments of the present invention also include two or more effect heat pumps and their uses thereof.
  • Fig 2 shows an example of a double effect system. The difference between this process and that in Fig 1 described as follows.
  • the higher pressure liquid solution coming out of the pump (55) is split into two streams.
  • the stream (409) is let down in pressure in throttle valve (67) to a medium pressure that is higher than that of the solution (408) upstream of the pump (55).
  • the resultant medium pressure solution is further split into the major portion (410) and the minor portion (412).
  • the major portion (410) of the medium pressure solution is heated and partially vaporized in a substantially countercurrent medium pressure heat exchanger (56), and the resultant medium pressure two phase stream (41 1) is fed to the lower feeding port of a medium pressure generator (57).
  • the minor medium pressure stream (412) is fed directly to the higher feeding port of the medium pressure generator (57).
  • the medium pressure generator (57) generates an overhead, medium pressure, substantially vaporized stream (431) of the working fluid. It also generates a medium pressure absorbent (413), which is lean in the working fluid components, from the bottom.
  • the medium pressure absorbent (413) is then cooled in the medium pressure bottom subcooler (56), which is a substantially countercurrent heat exchanger.
  • the resultant subcooled medium pressure lean liquid is further let down in pressure in throttle valve (59).
  • Another portion of the high pressure solution (420) from the pump (55) is first heated in a substantially countercurrent high pressure heat exchanger (68).
  • a side stream (422) is taken out of the heat exchanger (68) and fed to a higher feeding port in a higher pressure generator (69).
  • the remaining portion of the heated higher pressure liquid solution is further heated and partially vaporized in the substantially countercurrent high pressure heat exchanger (68), and the resultant two phase high pressure stream (421), is fed to the lower feeding port of the higher pressure generator (69).
  • the higher pressure generator (69) is heated by heat Qg at the base or the lower section.
  • the higher pressure generator (69) produces a higher pressure vapor stream (423) that is substantially composed of the working fluid from the top, and a working fluid-lean stream or absorbent (425) from the bottom.
  • the resultant higher pressure condensate which is essentially pure working fluid, is split into two streams: the reflux (433), which is sent back to the top of the higher pressure generator (69), and the rest (424) is further subcooled in the subcooler (61).
  • This subcooler (61) can be a part of the medium pressure generator (57). That is to say, the higher pressure working fluid solution can be subcooled in the medium pressure generator (57) by the substantially countercurrent heat exchanger 61. The subcooled, higher pressure liquid working fluid is then let down in pressure in throttle valve 62, forming a two phase stream, and join the overhead working fluid vapor (431) from the medium pressure generator (57).
  • the combined medium pressure working fluid (401), formed from the vaporized working fluid from the top of the medium pressure column and the two phase mixture from valve (62) is fed to the condenser (58), releasing heat.
  • the resultant condensed liquid working fluid is split into two streams: the reflux (432), which is fed back to the top of the medium pressure generator (57), and the liquid working fluid (403), to be subcooled in a medium pressure top subcooler (50), which is a substantially countercurrent heat exchanger.
  • the absorbent stream (425) from the high pressure generator (69) is subcooled in a higher pressure, substantially countercurrent heat exchanger (68).
  • the resultant subcooled absorbent stream (426) is first let down in pressure higher pressure in throttle valve (63).
  • the thus resultant lower pressure absorbent stream (427) is then combined with the absorbent stream from throttle valve (59) and form a low pressure absorbent stream (428), which is then fed to the absorber (54) for reuse.
  • the refluxes (433) and (432) to the high and medium pressure generators, respectively can also be eliminated, and the minor feed streams (422) and (412) can be fed to the tops of the high and medium pressure generators, respectively.
  • the working fluid (431) and (423), coming out of the tops of the generators will contain some solvent, typically in 10 ppm - 5% range.
  • the working fluid stream (305a) leaving the evaporator (53) should preferably contains 0.1 - 5% (mol) liquid, and is then substantially completely vaporized in the subcooler (50).
  • systems and processes according to embodiments of the present invention can be used for heating or cooling an enclosed space or process stream, such as the interior of a building or a vehicle or a process stream in an industrial process.
  • the evaporator removes heat from the enclosed space or a process stream while heat from the condenser and the absorber is expelled to the environment.
  • the evaporator absorbs heat from the environment while the condenser and the absorber provide heat to the enclosed space or process stream.
  • a unitary system can be built such that the same system can be used for both winter heating and summer cooling, e.g., by switching the roles of the condenser and the evaporator as season changes.
  • the work fluid comprises a blend of one or more organic components, such as R134a, CF 3 I, DMF, or HF01234yf.
  • DME is selected in the example due to its excellent thermodynamic properties, low cost, non-toxicity, low GWP nature, and a slightly higher boiling point than that of R 134a.
  • R134a is used to make the working fluid inflammable. Due to the very close boiling points of the components, such mixtures behave very much like azeotropes.
  • CF 3 I has a GWP value of 1. Therefore, a mixture of CF 3 I and DME has a very low GWP value.
  • the mixture of CF 3 I and DME is considered to have some ozone depleting potential (ODP) although its ODP value is very small (less than 0.008, likely less than 0.0001 of Rl 1 ).
  • ODP ozone depleting potential
  • HF01234yf has a GWP of about 4, vs. the 1430 value for R134a, but is slightly flammable.
  • hydrocarbons and organic oxygenates have the desired properties of having a boiling point of greater than 130° C (or dew point of greater than 130°C at 1 atm for mixed solvents), that are relatively inexpensive and miscible with the above-mentioned working fluids, thus can be used as the solvent.
  • solvent examples include the base oil of lube oils, polyols such as ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glymes such as tetraglyme, or the products of the condensation reactions between glycols and ketones or aldehydes.
  • the base oils of lube oils, tetraglyme (or a combination of glymes such as that used in the Solexol process), ethylene glycol, and triethylene glycol are among the common commodity chemicals with relatively low unit price and low toxicity and therefore are among our initial candidates for study.
  • TOXICITY DATA 3,914 mg/kg oral-rat LD50
  • TOXICITY DATA Acute oral toxicity (LD50): 7920 mg/kg
  • TOXICITY DATA ORL-RAT LD50 2800 mg kg "1 IPR-RAT LD50 1400 mg kg "1
  • TOXICITY DATA Acute oral toxicity (LD50): 7920
  • NMP was chosen as the solvent in the description below because of its overall superior performance.
  • other components in the family can also have more desirable values on certain properties.
  • components including, but not limited to, DMSO, DMF, DMAc, NMP, or a combination of one or more of these components, can be the preferred solvent under certain specific conditions.
  • a heat pump system is suitable for living space cooling or heating in residential and vehicular applications as well as in commercial applications.
  • Use of such a system for heating can greatly decrease the fuel consumption, while for air conditioning applications it can use solar water heater or the cooling water coming out of the vehicle engines, thereby drastically reducing the electricity demand for air conditioning during the hot summer days when the demand for electricity reaches peaks, or that generated by burning liquid fuel, which is expensive and is becoming even more expensive.
  • a thermally activated system is based on the principle that such an absorption system can act as a thermally driven compressor.
  • an expander can be used for power generation in the placed of the condenser- vaporizer.
  • FIG. 3 shows such a process.
  • the absorption - separation parts are the same as those in the process in Figure 1.
  • the difference is that in this process a vapor stream (501) is directly taken out of the top of the generator (34), and expanded in an expander (70).
  • the work obtained from expander (70) can be used to generate electricity by an electric generator (72), which is mechanically connected to the expander (70).
  • the resultant low pressure vapor (502) is then sent to the absorber (31) for further use.
  • the vapor stream (501) coming out of the generator can be further heated before it is fed to the expander (70). This is not shown in Figure 3.
  • the generator had 6 theoretical stages (2 stages in the rectifying section, and 4 in the stripping section including the feed stage), and the absorber had only one stage (i.e., it is a mixer).
  • Our later study showed that the number of stages in the generator could be reduced to 3 to 4 stages without significantly impacting the performance of the system when the working fluid coming out of the evaporator was allowed to contain a few percent of liquid, which was then substantially vaporized in the substantially countercurrent subcooler.
  • the pump work (60% pump efficiency and 95% motor efficiency were assumed) values were respectively 0.8%, 2.1 %, 1.4% %, and 2.3% of the generator reboiler duties of the respective cases.
  • a HCOP of 1.90 can be achieved for heating when the evaporator temperature is 40.4° F (4.7 0 C), the condenser and absorber cooler temperatures are about 81 0 F (27 0 C), and the generator reboiler temperature is 188 °F(87 0 C).
  • the ambient temperature is lower, such as when the evaporator temperature is 17 °F (- 8 °C)
  • the HCOP is reduced while the temperature of the generator reboiler is increased to 226.5 0 F (108 0 C).
  • the CCOP can be 0.83 if the generator reboiler is at 170 0 F (76.7 0 C), or 0.78 if the generator reboiler is at 160 0 F (71 0 C).

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  • Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne des systèmes activés thermiquement et des procédés apparentés permettant d'augmenter la pression d'un fluide de travail gazeux. Les systèmes et procédés peuvent être utilisés pour le chauffage en hiver et le refroidissement en été avec une efficacité accrue. Ils peuvent également être utilisés pour d'autres applications ayant besoin d'un compresseur entraîné thermiquement efficace, telles qu'un procédé de génération d'énergie.
PCT/US2012/026313 2011-02-23 2012-02-23 Dispositif d'amplification de pression activé thermiquement pour chauffage thermodynamique et génération d'énergie WO2012116174A1 (fr)

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US14/001,389 US20140053594A1 (en) 2011-02-23 2012-02-23 Thermally activated pressure booster for heat pumping and power generation

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CN103045174A (zh) * 2012-12-24 2013-04-17 广州市香港科大霍英东研究院 一种含有二甲醚和三氟碘甲烷的环保型中高温热泵工质
WO2014008531A3 (fr) * 2012-07-09 2016-06-23 Just Energy Solutions Pty Ltd Système de moteur thermique
EP3042135A4 (fr) * 2013-09-04 2017-07-05 Climeon AB Génération d'énergie à partir de chaleur perdue à l'aide d'un cycle thermodynamique de support de carbone
US10082030B2 (en) 2014-01-22 2018-09-25 Climeon Ab Thermodynamic cycle operating at low pressure using a radial turbine

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CN104061710A (zh) * 2014-06-23 2014-09-24 周永奎 一种提供蒸汽动力的方法及其装置
CN104048450A (zh) * 2014-06-23 2014-09-17 周永奎 一种吸收式热泵制冷与动力联供方法及其装置
CN104653423B (zh) * 2015-01-27 2017-01-11 华北电力大学 基于压缩空气储能与火电厂的联合控制系统及方法
CN106350016A (zh) * 2016-07-29 2017-01-25 长春弘海能源设备有限公司 一种超导热媒的制备方法
CN106595122B (zh) * 2016-12-07 2019-03-08 天津城建大学 串并联切换的燃气机压缩吸收复合热泵供热方法
CN110157383B (zh) * 2019-05-22 2020-12-18 山西省工业设备安装集团有限公司 一种供热热泵三元混合工质
CN112409992B (zh) * 2020-08-28 2021-12-14 珠海格力电器股份有限公司 三元环保混合制冷剂、其制备方法及制冷系统

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WO2014008531A3 (fr) * 2012-07-09 2016-06-23 Just Energy Solutions Pty Ltd Système de moteur thermique
CN103045174A (zh) * 2012-12-24 2013-04-17 广州市香港科大霍英东研究院 一种含有二甲醚和三氟碘甲烷的环保型中高温热泵工质
EP3042135A4 (fr) * 2013-09-04 2017-07-05 Climeon AB Génération d'énergie à partir de chaleur perdue à l'aide d'un cycle thermodynamique de support de carbone
US10082030B2 (en) 2014-01-22 2018-09-25 Climeon Ab Thermodynamic cycle operating at low pressure using a radial turbine

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