EP2379848B1 - Dispositif de production d'électricité avec plusieurs pompes à chaleur en série - Google Patents

Dispositif de production d'électricité avec plusieurs pompes à chaleur en série Download PDF

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Publication number
EP2379848B1
EP2379848B1 EP09805750.8A EP09805750A EP2379848B1 EP 2379848 B1 EP2379848 B1 EP 2379848B1 EP 09805750 A EP09805750 A EP 09805750A EP 2379848 B1 EP2379848 B1 EP 2379848B1
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EP
European Patent Office
Prior art keywords
heat
transfer fluid
exchanger
heat exchanger
inlet
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Application number
EP09805750.8A
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German (de)
English (en)
French (fr)
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EP2379848A2 (fr
Inventor
Alberto Sardo
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Xeda International SA
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Xeda International SA
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Priority to PL09805750T priority Critical patent/PL2379848T3/pl
Publication of EP2379848A2 publication Critical patent/EP2379848A2/fr
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Publication of EP2379848B1 publication Critical patent/EP2379848B1/fr
Priority to HRP20150213AT priority patent/HRP20150213T1/hr
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K17/00Using steam or condensate extracted or exhausted from steam engine plant
    • F01K17/005Using steam or condensate extracted or exhausted from steam engine plant by means of a heat pump
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/08Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours

Definitions

  • the invention generally relates to power generation devices.
  • Electricity generation devices known to date contribute to atmospheric warming (fossil or plant-based power plant) or are neutral with respect to atmospheric heating (hydroelectric power station, wind turbine, nuclear power plant).
  • Solar power generation devices help reduce atmospheric warming by converting solar energy into electrical energy.
  • solar energy installations are generally not very powerful, because the heat of the sun is only available at low temperatures. To raise the temperature, it is necessary to concentrate the sun's rays, which is technically complex.
  • Solar energy is therefore useful for heating water or air, but is poorly suited to mass production of electrical energy.
  • Photovoltaic cells are currently able to provide only small amounts of electrical energy.
  • heat pumps allow the production of heat at a temperature higher than that of the ambient air.
  • the heat pump absorbs the energy of the ambient air and provides heat with a temperature difference generally of the order of 30 to 40 ° C relative to the ambient air.
  • Such machines are not suitable for the production of electrical energy because of the small difference in temperature between the hot and cold points of the heat pump.
  • DE 3433366 describes a device comprising two heat pumps in series, designed to heat a cleaning fluid.
  • GB 2,016,668 describes a low-temperature thermal energy recovery system in an industrial installation, with several heat pumps placed in series.
  • the invention aims to provide an electricity generating device that contributes to limiting atmospheric heating, and to produce electricity in large quantities with acceptable efficiency.
  • the invention relates to a device for producing electricity according to claim 1.
  • the device shown in the attached figure is intended for the production of electricity. It comprises a steam turbine, interposed on a water / steam circuit, the heat required to provide high pressure steam to the turbine being obtained through several heat pumps placed in series. Thus, the heat required for the production of high pressure steam is mainly taken from the atmosphere.
  • the first heat pump 3 comprises a first closed circuit 15 in which circulates a first heat transfer fluid, a first heat exchanger 17 between the first heat transfer fluid and the atmospheric air, a compressor 19, and an expansion valve 21.
  • the first heat transfer fluid essentially comprises propane.
  • the first heat transfer fluid is technically pure propane.
  • the first heat exchanger 17 has a first side in which the atmospheric air circulates, and a second side in which the propane circulates.
  • the device comprises means for forcing the flow of air on the first side of the heat exchanger 17. These means may for example comprise fans or any similar type of equipment.
  • the second heat pump 5 comprises a second closed circuit 23 in which a second heat transfer fluid circulates, a second heat exchanger 25 between the second heat transfer fluid and the fluid flowing in the water / steam circuit 9, a compressor 27 and a gas valve. expansion 29.
  • the second heat transfer fluid essentially comprises hexane.
  • the second heat transfer fluid is technically pure hexane.
  • the second heat exchanger 25 has a first side in which the second heat transfer fluid circulates, and a second side in which water circulates in liquid or vapor form. Water is a third heat transfer fluid.
  • the water circulating in the water / steam circuit 9 enters the heat exchanger 25 in vapor form through the inlet 31 and in liquid form through the inlet 33, receives the heat transferred by the second heat transfer fluid, and leaves the the heat exchanger 25 in the form of water vapor through the outlets 35 and 37.
  • the third heat pump 7 comprises a third closed circuit 39 in which circulates a fourth heat transfer fluid, a third heat exchanger 41 between said fourth heat transfer fluid and the first heat transfer fluid of the first heat pump 3, a fourth heat exchanger 43 between said fourth heat transfer fluid and the second heat transfer fluid of the second heat pump 5, a compressor 45 and an expansion valve 47.
  • the heat exchanger 41 has a first side in which the first heat exchange fluid circulates and a second side in which the fourth heat exchange fluid flows.
  • the fourth heat exchanger 43 has a first side in which the fourth heat exchange fluid circulates and a second side in which the second heat exchange fluid circulates.
  • the fourth heat exchange fluid preferably comprises essentially butane.
  • the fourth heat fluid is technically pure butane.
  • the water / steam circuit 9 comprises first and second loops 49 and 51.
  • the same heat transfer fluid circulates in both loops.
  • the first loop 49 comprises a first hot line 53 connecting the steam outlet 35 of the second heat exchanger to a high pressure inlet 55 of the turbine 11.
  • the first loop also comprises a return line 57 connecting a low pressure outlet 59 of the turbine at the steam inlet 31 of the second heat exchanger.
  • the first loop 49 further comprises a compressor 61 interposed on the first hot line 53.
  • the second loop 51 of the water / steam circuit comprises a second hot line connecting the second steam outlet 37 of the heat exchanger 25 to the high pressure inlet 55 of the steam turbine.
  • the second loop further comprises an intermediate heat exchanger 65 between the first heat transfer fluid and the third heat transfer fluid, an intermediate line 67 connecting the low pressure outlet 59 of the steam turbine to an inlet 69 of the intermediate heat exchanger, and a second return line connecting an outlet 73 of the intermediate exchanger to the liquid inlet 33 of the second heat exchanger 25.
  • the second loop further comprises a compressor 75 interposed on the return line 71.
  • the intermediate heat exchanger 65 comprises a first side in which the first heat transfer fluid circulates, and a second side in which the third heat transfer fluid circulates, from the inlet 69 to the outlet 73.
  • the closed circuit 15 connects a discharge outlet of the compressor 19 to an inlet on the first side of the heat exchanger 41.
  • the circuit 15 also connects the outlet of said first side to the inlet of the expansion valve 21.
  • outlet of the expansion valve 21 is connected by the circuit 15 to an inlet on the second side of the heat exchanger 17.
  • the circuit also connects the outlet of the second side of the exchanger 17 to the inlet of the first side of the exchanger 65 and the outlet of the first side of the exchanger 65 to the suction of the compressor 19.
  • the first coolant is gaseous between the outlet of the exchanger 17 and the inlet of the exchanger 41. It is liquid between the outlet of the exchanger 41 and the inlet of the exchanger 17. In the exchanger 17 , the first coolant is in thermal contact with the air flowing from the first side of this exchanger. The air gives up heat to the first heat transfer fluid. The first heat transfer fluid is vaporized during its passage in the first heat exchanger 17.
  • the first coolant circulating on the first side of the exchanger is in thermal contact with the water vapor flowing on the second side of the exchanger.
  • the water vapor is at least partially condensed through the intermediate heat exchanger and gives heat to the first heat transfer fluid.
  • the first heat transfer fluid flowing on the first side of the heat exchanger 41 is in thermal contact with the fourth heat transfer fluid circulating on the second side of the exchanger 41.
  • the first heat transfer fluid is condensed through the exchanger 41 and yields the heat to the third heat transfer fluid.
  • the third closed circuit 39 connects the discharge of the compressor 45 to an inlet on the first side of the heat exchanger 43. It also connects the outlet of said first side of the heat exchanger 43 to an inlet of the expansion valve 47 The closed circuit 39 further connects the outlet of the expansion valve 47 to an inlet on the second side of the heat exchanger 41. Finally, the circuit 39 connects an outlet of said second side of the exchanger 41 to the suction compressor 45.
  • the fourth heat transfer fluid is in thermal contact with the first heat transfer fluid through the heat exchanger 41 and receives heat therefrom.
  • the fourth heat transfer fluid is vaporized in the heat exchanger 41.
  • the fourth heat transfer fluid passing through the first side of the heat exchanger 43 is in thermal contact with the second heat transfer fluid circulating on the second side of the heat exchanger 43. heat transfer fluid is condensed through the heat exchanger heat 43 and gives heat to the second heat transfer fluid.
  • the fourth heat transfer fluid is in the gaseous state between the outlet of the second side of the heat exchanger 41 and the inlet of the first side of the heat exchanger 43. It is in the liquid state between the outlet of the first side of the exchanger 43 and the inlet of the second side of the exchanger 41.
  • the second closed circuit 23 connects the discharge of the compressor 27 to an inlet on the first side of the heat exchanger 25. It also connects an outlet of the first side of the heat exchanger 25 to an inlet of the expansion valve 29 The circuit 23 further connects the outlet of the expansion valve 29 to the inlet of the second side of the exchanger 43, and the outlet of said second side to the suction of the compressor 27.
  • the second heat transfer fluid through the second side of the exchanger 43 is in thermal contact with the fourth heat transfer fluid. It receives heat from the fourth heat transfer fluid through the exchanger 43 and is vaporized.
  • the second heat transfer fluid is in thermal contact with the third heat transfer fluid in the heat exchanger 25. Crossing the first side of the heat exchanger 25, it is condensed and gives heat to the third heat transfer fluid.
  • the second heat transfer fluid is in the gaseous state between the outlet of the second side of the exchanger 43 and the inlet of the first side of the heat exchanger 25. It is in the liquid state between the outlet of the first side of the heat exchanger 25 and the inlet of the second side of the heat exchanger 43.
  • the heat exchanger 25 is for example a two-zone exchanger, a first zone for heating the water vapor flowing in the first loop, and a second zone for vaporizing the water flowing in the second loop.
  • the second heat transfer fluid flowing from the first side of the heat exchanger 25 is first brought into thermal contact with the fluid flowing in the second loop, and then placed in thermal contact with the fluid flowing in the first loop.
  • the second side of the heat exchanger 25 comprises two separate circuits, one between the inlet 33 and the outlet 37 and the other between the inlet 31 and the outlet 35. These two circuits are fluidly separated.
  • the water is in the vapor state in the first loop between the outlet 35 and the high pressure inlet 55 of the turbine. It is in the vapor state, close to the saturation temperature, between the low pressure outlet 59 of the turbine and the inlet 31 of the second heat exchanger.
  • the water is in the vapor state between the outlet 37 of the second heat exchanger and the high pressure inlet 55 of the turbine. It is in the vapor state, close to the saturation temperature, between the low pressure outlet 59 of the turbine and the inlet 69 of the intermediate exchanger 65.
  • the vapor is at least partially condensed in the exchanger 65.
  • the water is in liquid form between the discharge of the compressor 75 and the inlet 33 of the second heat exchanger.
  • the atmospheric air flowing from the second side of the heat exchanger 17 transfers its heat to the first heat transfer fluid.
  • the atmospheric air has a temperature difference of 12 ° C between the inlet and the outlet of the exchanger 17.
  • the flow of atmospheric air is about 1 million m 3 / h.
  • the air at the inlet of exchanger 17 has a temperature of 12 ° C. and a temperature of 0 ° C. at the outlet of exchanger 17.
  • the propane flow rate in the first closed circuit 15 is about 40 t / h.
  • Propane is vaporized in the exchanger 17. It has a pressure of 4 bar and a temperature of about 0 ° C at the inlet of the exchanger 17, and a temperature of 10 ° C at the outlet of the exchanger 17.
  • the propane is heated in the intermediate exchanger 65. It has a pressure of 4 bar and a temperature of about 179 ° C at the outlet of the intermediate exchanger 65.
  • the propane is compressed by the compressor 19 and has a pressure of 20 bar and a temperature of about 245 ° C at the discharge of the compressor 19. Through the heat exchanger 41, the propane is condensed.
  • the butane flowing in the fourth closed circuit 39 has a pressure of 4 bar and a temperature of about 50 ° C. at the inlet of the heat exchanger 41. It is vaporized while passing through this exchanger and presents at the outlet a pressure of 4 bar and a temperature of about 240 ° C.
  • the butane is then compressed by compressor 45 to a pressure of 19 bar and a temperature of about 310 ° C. It is condensed through the heat exchanger 43, and has a pressure of about 19 bar and a temperature of about 116 ° C at the outlet of the heat exchanger 43. Butane then undergoes a relaxation through the expansion valve 47, up to a pressure of 4 bar and a temperature of about 50 ° C.
  • the butane flow rate in the fourth closed circuit is about 52 t / h.
  • the flow of hexane in the second closed circuit 23 is about 50t / h. It has a pressure of 2.5 bar and a temperature of 110 ° C at the inlet of the heat exchanger 43.
  • the hexane is vaporized in the heat exchanger 43 and has a pressure of 2.5 bar and a temperature of 305 ° C at the outlet of the exchanger 43.
  • the hexane is then compressed by the compressor 27 to a pressure of 15 bar and a temperature of 365 ° C.
  • the hexane is condensed through the heat exchanger 25 and then undergoes expansion through the expansion valve 29.
  • the flow of water in the third closed circuit 9 is in total about 65.2 t / h.
  • the water flow in the first loop is about 62 t / h and the water flow in the second loop is about 3.2 t / h.
  • the water vapor flowing in the first loop has a pressure of 9 bar and a temperature of about 180 ° C. It is superheated by passing through the heat exchanger 25, the steam having at the outlet 35 a pressure of 9 bar and a temperature of about 360 ° C.
  • the steam is compressed by the compressor 61 to a pressure of 30 bar and a temperature of 405 ° C.
  • the water flowing in the second loop has at the inlet 33 of the second heat exchanger a pressure of 30 bars and a temperature of about 180 ° C. This water is vaporized in the heat exchanger 25 to a temperature of about 370 ° C and a pressure of about 30 bar.
  • the first and second loops are connected to the same inlet 55 of the turbine. Alternatively, they can be connected to different inputs.
  • the water vapor drives the turbine and at the same time undergoes expansion. It has a pressure of 9 bar and a temperature of about 180 ° C at the low pressure outlet of the turbine.
  • the water vapor is subdivided into two streams and is partly directed towards the return line 57 of the first loop and partly towards the intermediate line 67 of the second loop.
  • the steam is condensed at least partially in the intermediate heat exchanger 65, the pressure and temperature remaining substantially constant.
  • the water present at the inlet of the compressor 75 a pressure of 9 bar and a temperature of 180 ° C and the discharge of said compressor, a pressure of 30 bar and a temperature of 180 ° C.
  • the energy balance of the device is as follows: atmospheric air yields propane about 3,700,000 kcal / hour. This receives in the intermediate exchanger 65 about 1,660,000 kcal / hour. It also receives during compression by the compressor 19 about 550 000 kcal / hour. Propane yields to butane in the heat exchanger 41 about 5,900,000 kcal / hour.
  • the hexane receives about 600 000 kcal / hour during compression by the compressor 27. It yields about 7000 100 kcal / hour to the water in the heat exchanger 25. Moreover, the water flowing in the first loop receives during compression by the compressor 61 about 550 000 kcal / hour. The energy received by the water circulating in the second loop during compression by the compressor 75 will be neglected.
  • the energy supplied to the turbine is about 6,000,000 kcal / hour, given the heat given off by the steam of the second loop in the intermediate heat exchanger 65.
  • the electrical efficiency of the turbo-generator assembly 11 and 13 is about 70%.
  • the alternator 13 thus produces approximately 4,000,200 kcal / hour of electricity, ie an electric power of 4,900 kW.
  • the power consumption of the various compressors 19, 27, 45, 61 and 75 are respectively 750 kW, 900 kW, 900 kW, 800 kW, 20 kW.
  • the consumption of the fans intended to force the flow of atmospheric air through the exchanger 17 is estimated at about 100 kW.
  • the electricity generating device therefore has a positive energy balance of about 1400 kW.
  • the power generation device described above has many advantages.
  • the heat transfer fluids are chosen so that the condensing temperature of the fluid of a given heat pump substantially corresponds to the boiling temperature of the heat transfer fluid of the next heat pump in the series.
  • each heat transfer fluid by a compressor and then condensing it by heat exchange with a more volatile fluid, this step being followed by expansion, it is possible to absorb the heat of each coolant by the less volatile fluid. used by the next heat pump in the series. This results in a gradual increase in temperature of the heat transfer fluid until reaching about 400 ° C.
  • Two heat pumps in series may be sufficient to produce electricity, but it is advantageous to use at least three to obtain sufficient energy efficiency.
  • propane, butane and hexane as heat transfer fluids in the three heat pumps placed in series is particularly advantageous because these fluids have characteristics well adapted to the desired purpose.
  • the electric bearing of the turbine / alternator assembly is thus greater than 60%, for example of the order of 70%.
  • the electricity generating device described above can have multiple variants.
  • It may comprise only two heat pumps or three heat pumps, or more than three heat pumps in series with each other, depending on the power to be obtained and the heat transfer fluids used.
  • the heat transfer fluids used in the various heat pumps can be of any type, provided that the condensation temperature of a heat transfer fluid used in a given heat pump substantially corresponds to the boiling temperature of the heat transfer fluid used in the pump. next heat in the series.
  • the pressure and temperature profiles may vary for each of the heat pumps, depending on the thermal power to be transferred and the heat transfer fluids used.
  • the water / steam circuit may have only one loop.
  • the heat exchanger 25 between the second heat transfer fluid and the water may consist of a multi-zone exchanger or may consist of several heat exchangers physically independent of each other.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Engine Equipment That Uses Special Cycles (AREA)
EP09805750.8A 2008-12-19 2009-12-18 Dispositif de production d'électricité avec plusieurs pompes à chaleur en série Active EP2379848B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL09805750T PL2379848T3 (pl) 2008-12-19 2009-12-18 Urządzenie do produkcji elektryczności z kilkoma pompami ciepła w układzie szeregowym
HRP20150213AT HRP20150213T1 (en) 2008-12-19 2015-02-24 Electricity generation device with several heat pumps in series

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0858836A FR2940355B1 (fr) 2008-12-19 2008-12-19 Dispositif de production d'electricite avec plusieurs pompes a chaleur en serie
PCT/FR2009/052615 WO2010070242A2 (fr) 2008-12-19 2009-12-18 Dispositif de production d'électricité avec plusieurs pompes à chaleur en série

Publications (2)

Publication Number Publication Date
EP2379848A2 EP2379848A2 (fr) 2011-10-26
EP2379848B1 true EP2379848B1 (fr) 2014-11-26

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EP09805750.8A Active EP2379848B1 (fr) 2008-12-19 2009-12-18 Dispositif de production d'électricité avec plusieurs pompes à chaleur en série

Country Status (14)

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US (1) US8624410B2 (es)
EP (1) EP2379848B1 (es)
CN (1) CN102325965B (es)
AU (1) AU2009329431B2 (es)
BR (1) BRPI0918110B1 (es)
DK (1) DK2379848T3 (es)
ES (1) ES2528932T3 (es)
FR (1) FR2940355B1 (es)
HR (1) HRP20150213T1 (es)
MX (1) MX2011006529A (es)
PE (1) PE20120568A1 (es)
PL (1) PL2379848T3 (es)
PT (1) PT2379848E (es)
WO (1) WO2010070242A2 (es)

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FR2981129B1 (fr) * 2011-10-07 2013-10-18 IFP Energies Nouvelles Procede et systeme perfectionne de conversion de l'energie thermique marine.
SE536432C2 (sv) * 2012-03-20 2013-10-29 Energihuset Foersaeljnings Ab Hardy Hollingworth Värmecykel för överföring av värme mellan medier och för generering av elektricitet
US10233788B1 (en) * 2012-04-10 2019-03-19 Neil Tice Method and apparatus utilizing thermally conductive pumps for conversion of thermal energy to mechanical energy
GB201208771D0 (en) 2012-05-17 2012-07-04 Atalla Naji A Improved heat engine
AU2012203556B2 (en) * 2012-06-19 2014-03-27 Ampro Systems Inc. Air conditioning system capable of converting waste heat into electricity
JP5949383B2 (ja) * 2012-09-24 2016-07-06 三浦工業株式会社 蒸気発生システム
WO2015041501A1 (ko) * 2013-09-23 2015-03-26 김영선 히트펌프 발전 시스템 및 그 운전방법
FR3012517B1 (fr) * 2013-10-30 2015-10-23 IFP Energies Nouvelles Procede d'une conversion d'une energie thermique en energie mecanique au moyen d'un cycle de rankine equipe d'une pompe a chaleur
CN104748592B (zh) * 2013-11-12 2020-10-30 特灵国际有限公司 具有流体流动以与不同的制冷剂回路串联地热交换的钎焊换热器
IL254492A0 (en) * 2017-09-13 2017-11-30 Zettner Michael System and process for converting thermal energy into kinetic energy
CN112901400A (zh) * 2021-01-26 2021-06-04 重庆中节能悦来能源管理有限公司 一种大高差取水系统水轮机组应用方法
EP4356050A2 (en) * 2021-06-16 2024-04-24 Colorado State University Research Foundation Air source heat pump system and method of use for industrial steam generation
EP4269758A1 (en) * 2022-04-28 2023-11-01 Borealis AG Method for recovering energy
EP4269757A1 (en) * 2022-04-28 2023-11-01 Borealis AG Method for recovering energy
US12071866B1 (en) * 2023-11-02 2024-08-27 Joel M. Levin Coupled orc heat pump electric generator system

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DE3433366A1 (de) * 1984-09-08 1986-03-20 Peter 2351 Hasenkrug Koch Verfahren zur waermeenergiezu- und -abfuhr sowie waermepumpeneinrichtung
US4724679A (en) * 1986-07-02 1988-02-16 Reinhard Radermacher Advanced vapor compression heat pump cycle utilizing non-azeotropic working fluid mixtures
US5042259A (en) * 1990-10-16 1991-08-27 California Institute Of Technology Hydride heat pump with heat regenerator
DE19925257A1 (de) * 1999-06-01 2001-02-22 Gerhard Von Hacht Multiples, solares-, Wärmepumpen-Pumpspeicher-Kombinations-Kraftwerk
US20050076639A1 (en) * 2003-10-14 2005-04-14 Shirk Mark A. Cryogenic cogeneration system
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CN200978686Y (zh) * 2006-09-05 2007-11-21 袁欢乐 动力机
TW200825280A (en) * 2006-12-05 2008-06-16 Wei Fang Power generating system driven by a heat pump

Also Published As

Publication number Publication date
CN102325965A (zh) 2012-01-18
BRPI0918110A2 (pt) 2015-11-24
PL2379848T3 (pl) 2015-04-30
FR2940355A1 (fr) 2010-06-25
WO2010070242A3 (fr) 2011-05-12
DK2379848T3 (en) 2015-01-26
MX2011006529A (es) 2011-09-29
EP2379848A2 (fr) 2011-10-26
FR2940355B1 (fr) 2011-07-22
US20110309635A1 (en) 2011-12-22
AU2009329431A1 (en) 2011-08-11
US8624410B2 (en) 2014-01-07
CN102325965B (zh) 2014-07-02
HRP20150213T1 (en) 2015-03-27
PE20120568A1 (es) 2012-06-06
WO2010070242A2 (fr) 2010-06-24
ES2528932T3 (es) 2015-02-13
BRPI0918110B1 (pt) 2020-01-28
AU2009329431B2 (en) 2014-08-14
PT2379848E (pt) 2015-03-02

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