EP0580848B1 - Dispositif pour la production de froid et/ou de chaleur par reaction solide-gaz - Google Patents

Dispositif pour la production de froid et/ou de chaleur par reaction solide-gaz Download PDF

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Publication number
EP0580848B1
EP0580848B1 EP93905379A EP93905379A EP0580848B1 EP 0580848 B1 EP0580848 B1 EP 0580848B1 EP 93905379 A EP93905379 A EP 93905379A EP 93905379 A EP93905379 A EP 93905379A EP 0580848 B1 EP0580848 B1 EP 0580848B1
Authority
EP
European Patent Office
Prior art keywords
reactors
gas
heat
reactor
heat transfer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93905379A
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German (de)
English (en)
French (fr)
Other versions
EP0580848A1 (fr
Inventor
Jean Castaing
Pierre Neveu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Original Assignee
Societe National Elf Aquitaine
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Publication of EP0580848A1 publication Critical patent/EP0580848A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
    • F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt

Definitions

  • the present invention relates to a device for producing cold and / or heat by solid-gas reaction.
  • the reaction is exothermic in direction 1, which means that in this direction, it produces heat and endothermic in direction 2, that is to say that in this direction it produces cold.
  • Such a system allows energy storage in chemical form and has various fields of application.
  • the system is called a "chemical heat pump”.
  • Such a system also allows the production, from a heat source at temperature T's, of heat at temperature T'u such that: You> You
  • the system is called "chemical thermo transformer”.
  • the use of the heat or cold produced is simultaneous with the consumption of energy at high temperature (Ts, T's, T "s) or delayed over time (storage effect).
  • Document EP-A-0.382.586 discloses a device for producing cold and / or heat by solid-gas reaction, comprising two reactors each containing a salt capable of reacting chemically with a gas, a condenser and an evaporator for gas.
  • the elements of the device are arranged so as to allow the gas to follow a path from one reactor to another passing through the condenser and the evaporator.
  • the gas-poor reactor is at a temperature higher than that of the reactor containing the gas which has just reacted with the salt, the two reactors being at different pressure levels.
  • Heat is sent by a heat transfer system, from the reactor at the upper temperature to the reactor are at the lower temperature in order to increase the temperature of the latter.
  • the chemical reaction then takes place in reverse, with part of the heat from one reactor serving as the heat source for desorption of the gas from the other reactor. This heat transfer between the two reactors serves to improve the efficiency of the system.
  • Document US-A-5,025,635 describes a device intended to produce cold and / or heat comprising two sets of reactors, each set containing several blocks of reagent each block of which contains a different salt.
  • the device further comprises a heat transfer circuit connecting the two assemblies through each block of reagent.
  • the present invention therefore aims to provide a device for the production of cold and / or heat by solid-gas reaction, in which the heat transfer between the various reaction chambers of the device is optimized.
  • the invention provides a device for producing cold and / or heat by chemical reaction comprising at least four reactors each containing a salt capable of reacting chemically with a gas, an enclosure intended to receive the gas from the reactors and an enclosure intended to deliver the gas to the reactors, the device being arranged so that, during the chemical reaction, two reactors are at the same higher pressure level and form a first assembly, and two reactors are at the same level of lower pressure and form a second assembly, the device further comprising a closed circuit of heat transfer fluid intended to transfer heat between the two assemblies, this circuit further comprising a cooler and a heating device for the heat transfer fluid, characterized in that the reactors at the same pressure level are arranged concentrically so that heat can pass between neighboring reactors only by conduction.
  • the operation of the device according to the invention is based on the reaction between a salt and a gas.
  • FIGS. 1A and 1B which include lines of equilibrium of the salts used.
  • FIGS 2A and 2B a device for producing cold by solid-gas reaction.
  • the device comprises four reaction chambers 10, 12, 14, 16, called reactors, formed of an enclosure containing a mixture of a salt and of expanded graphite, possibly recompressed.
  • the device further comprises an evaporator 18 for the gas, as well as a condenser 20 which are arranged so as to be able to exchange heat with their environment.
  • the reactors 10 and 12 are connected, in the example illustrated in FIG. 2A, to the condenser 20 by conduits 22 and 24 which are provided with a valve 26 so as to be able to allow, selectively, the passage of gas between the reactors 10 , 12 and the condenser 20.
  • the reactors 14 and 16 are connected to the evaporator 18 by conduits 30 and 32 provided with a valve 34 so as to be able to allow, selectively, the passage of gas between the reactors 14 , 16 and the evaporator 18.
  • the reactors 10, 12, 14, 16 are at the temperatures and pressures shown in the diagram in FIG. 1A. As can be seen from the diagram, the reactor 10 is at a temperature higher than that of the reactor 12, and the reactor 14 is at a temperature lower than that of the reactor 16.
  • the reactors 10, 12, 14, 16 are each provided with an associated heat exchanger 38, 40, 42 and 44, these exchangers being connected together by a conduit 46, in order to form a heat transfer circuit 45.
  • a cooler 48 is mounted in the duct 46 between the reactors 12 and 14, and a heating device, for example a burner 50, is mounted in the duct 46 between the reactors 16 and 10.
  • the gas passes through the conduits 22, 24 and 30, 32 between the reactors, the condenser 20 and the evaporator 18 in accordance with the cycle shown in FIG. 1A.
  • the reactors 10, 12, 14 and 16 are at the temperatures and pressures illustrated in FIG. 1, the reactors 10 and 12 being at a high pressure and the reactors 14 and 16 being at a lower pressure.
  • the heat transfer circuit 45 is put into operation, the heat transfer fluid circulating, under the effect of a pump (not shown) in the direction of the arrows 52.
  • Heat from reactor 10, which is at a temperature T 1 is sent to reactor 12 which is at a lower temperature T 2 .
  • the heat transfer fluid cooled after its passage through the reactor 12, is then further cooled by the cooler 48 and leaves the latter at a temperature T 3 .
  • the cooled heat transfer fluid then passes through the reactor 14 and then through the reactor 16, which is at a temperature T4 before passing through the burner 50 in order to return to the starting temperature level T 1 .
  • the reaction between the salts used in the reactors and the gas, which is for example ammonia, is reversible, the reactions in the two directions forming together a cycle.
  • the reactors 10 and 12 are connected by conduits 52 and 54 to the evaporator 18 and the reactors 14 and 16 are connected to the condenser 20 by conduits 56 and 58 as shown in FIG. 2B.
  • the reactors 10 and 12 and the reactors 14 and 16 are in reversed positions with respect to those shown in FIG. 1A.
  • the heat transfer circuit is then started in the opposite direction, as shown by the arrows 60 in FIG. 1B.
  • the heat transfer effect caused by the passage of the heat transfer fluid is similar to that described above.
  • FIGS. 4A and 4B a second type of device for producing cold or heat by solid-gas reaction.
  • This device differs from that of FIG. 2 in that the condenser 20 and the evaporator 18 have been replaced by reactors.
  • the device thus comprises six reactors 80, 82, 84, 86, 88 and 90, four of which 82, 84, 88 and 90 are connected to a burner 92 and to a cooler 94 by a heat transfer circuit 96.
  • the reactors are at the temperatures and pressures illustrated in FIG. 3A, the reactors 80, 82 and 84 being at the same pressure level, but at different temperatures, the reactors 86, 88 and 90 being at the same lower pressure level, but also at different temperatures.
  • the heat transfer circuit 96 is then put into operation, the heat transfer fluid circulating in the direction of the arrows 98. As was the case for the device in FIG. 2, the heat transfer fluid successively transfers the heat between the reactors 84 and 82 being at the higher pressure level, the reactors being at associated temperatures T 1 and T 2 .
  • the heat transfer fluid then passes through the cooler 94 in order to reduce the temperature thereof to T 3 before passing successively through the reactors 88 and 90, the temperature of the fluid increasing from T 3 to T 4 during this passage. As in the example in FIG. 1, the heat transfer fluid is then reheated in the burner 92 to a temperature T 1 .
  • the reaction then takes place in the opposite direction, and, at a given instant in the cycle, the reactors are at the temperatures and pressures indicated in FIG. 3B.
  • the fluid coolant circulates in the opposite direction as indicated by the arrows 100.
  • a heat transfer circuit ensures the transfer of heat between reactors being at the same high pressure level, the heat passing from a reactor being at a given temperature to a reactor at a lower temperature.
  • the heat transfer fluid is heated during its passage through successive reactors, the heat transfer fluid passing from a reactor at a given temperature to a reactor at a higher temperature.
  • FIG. 5 shows a device according to the invention, in which the heat passes from one reactor to another of the same series only by conduction, that is to say without having recourse to a heat transfer circuit between the reactors.
  • a cylindrical reactor 112 is arranged inside a first annular reactor 114, itself arranged inside a second annular reactor 116, the three reactors being arranged in order to ensure good conductivity thermal between them.
  • a heat exchanger 118 connected to a heat transfer circuit shown schematically at 120 is disposed inside the cylindrical reactor 112.
  • This set of three reactors 112, 114 and 116 is connected, in the example illustrated, to a second similar set which is formed by three reactors 122, 124 and 126.
  • the heat transfer fluid after passing through the heat exchanger 118, passes through another heat exchanger 128 which is in thermal communication with the reactor 116.
  • the fluid then passes through a cooler 130, a heat exchanger 132 in thermal communication with the reactor 126, an exchanger 134 arranged inside the reactor 122, a burner 136 before passing through the exchanger 118.
  • the operation of this type of device is similar to that of the device of FIGS. 3 and 4.
  • the performance of a device for producing cold and / or heat by solid-gas chemical reaction can be evaluated using the economic concept of the coefficient of performance or COP.
  • the COP of a device corresponding to that of FIG. 2A is calculated.
  • reactors 12 and 14 each contain CaCl 2 reacting with 4 moles of ammonia, ie CaCl 2 .8NH 3 to 4NH 3
  • reactors 10 and 16 each containing NiCl 2 reacting with 4 moles of ammonia, or NiCl 2 .6NH 3 to 2NH 3 .
  • the temperature of the heat transfer fluid leaving the burner 50 is 285 ° C, the temperature T3 is 35 ° C, and at the outlet of the evaporator is 5 ° C.
  • the COP defined by the ratio of the cold energies produced compared to the high temperature energy is equal to 1.07, since the heating or cooling of the heat transfer fluid in a reactor during absorption, or desorption of the gas corresponds to 80% of the maximum possible rise, or of the maximum possible reduction. This corresponds to the difference between the inlet temperature of the heat transfer fluid and the equilibrium temperature of the reactant at the pressure considered.
  • the condenser is replaced by a reactor 80 containing BaCl 2 (8-ONH 3 ), and the evaporator is replaced by a reactor 86 containing the same salt, the COP is 1.60.
  • heat is transferred between reactors located, at an instant in the cycle, at the same given pressure level.
  • This heat transfer can be carried out by a heat transfer fluid or by simple conduction.
  • the reactors located at the same pressure level can be connected to an associated heat transfer circuit or to a circuit which is common to all the reactors of the device.
  • the device according to the invention comprises two sets of reactors, each set being formed of several reactors and being intended to be connected to a condenser or to an evaporator.
  • the condenser and evaporator can each be replaced by an associated reactor which is intended to receive or release the gas.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Sorption Type Refrigeration Machines (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Glass Compositions (AREA)
EP93905379A 1992-02-14 1993-02-10 Dispositif pour la production de froid et/ou de chaleur par reaction solide-gaz Expired - Lifetime EP0580848B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9201680A FR2687462A1 (fr) 1992-02-14 1992-02-14 Dispositif pour la production de froid et/ou de chaleur par reaction solide-gaz.
FR9201680 1992-02-14
PCT/FR1993/000135 WO1993016339A1 (fr) 1992-02-14 1993-02-10 Dispositif pour la production de froid et/ou de chaleur par reaction solide-gaz

Publications (2)

Publication Number Publication Date
EP0580848A1 EP0580848A1 (fr) 1994-02-02
EP0580848B1 true EP0580848B1 (fr) 1996-09-18

Family

ID=9426648

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93905379A Expired - Lifetime EP0580848B1 (fr) 1992-02-14 1993-02-10 Dispositif pour la production de froid et/ou de chaleur par reaction solide-gaz

Country Status (11)

Country Link
US (1) US5445217A (ja)
EP (1) EP0580848B1 (ja)
JP (1) JP3114154B2 (ja)
AT (1) ATE143125T1 (ja)
CA (1) CA2107215C (ja)
DE (1) DE69304833T2 (ja)
DK (1) DK0580848T3 (ja)
ES (1) ES2094530T3 (ja)
FR (1) FR2687462A1 (ja)
GR (1) GR3021689T3 (ja)
WO (1) WO1993016339A1 (ja)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3341516B2 (ja) * 1994-09-19 2002-11-05 株式会社デンソー 吸着式冷凍機
FR2726282B1 (fr) 1994-10-28 1999-02-19 Elf Aquitaine Reactif pour systemes thermochimiques et systeme thermochimique destine a utiliser un tel reactif
US5768906A (en) * 1996-01-16 1998-06-23 Borst, Inc. Electrochemical heat exchanger
FR2748093B1 (fr) * 1996-04-25 1998-06-12 Elf Aquitaine Dispositif thermochimique pour produire du froid et/ou de la chaleur
FR2852676B1 (fr) * 2003-03-18 2017-10-06 Centre Nat De La Rech Scient (C N R S ) Procede et dispositif pour la production de froid rapide et de forte puissance
US9914337B2 (en) * 2015-03-05 2018-03-13 Toyota Motor Engineering & Manufacturing North America, Inc. Vehicle with adsorption-based thermal battery
FR3037072A1 (fr) * 2015-06-04 2016-12-09 Jean Louis Juillard Produit pour reacteur thermochimique

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR641486A (fr) * 1927-06-27 1928-08-04 Silica Gel Corp Procédé et appareil frigorifique à récupération
US2087939A (en) * 1933-08-28 1937-07-27 Sarnmark Axel Uno Process for producing cold and continuously operating absorption cold apparatus
GB1572737A (en) * 1977-01-17 1980-08-06 Exxon France Heat pump
US4439994A (en) * 1982-07-06 1984-04-03 Hybrid Energy Systems, Inc. Three phase absorption systems and methods for refrigeration and heat pump cycles
US4610148A (en) * 1985-05-03 1986-09-09 Shelton Samuel V Solid adsorbent heat pump system
US4694659A (en) * 1985-05-03 1987-09-22 Shelton Samuel V Dual bed heat pump
FR2590356B1 (fr) * 1985-11-19 1989-06-02 Jeumont Schneider Dispositif pour la production en continu de chaud et de froid
FR2615601B1 (fr) * 1987-05-22 1989-11-10 Faiveley Ets Dispositif et procede pour produire du froid et/ou de la chaleur par reaction solide-gaz
FR2642509B1 (fr) * 1989-01-11 1995-01-27 Elf Aquitaine Dispositif pour la production du froid et/ou de la chaleur par reaction solide-gaz
US5079928A (en) * 1989-07-07 1992-01-14 Rocky Research Discrete constant pressure staging of solid-vapor compound reactors
US5025635A (en) * 1989-11-14 1991-06-25 Rocky Research Continuous constant pressure staging of solid-vapor compound reactors

Also Published As

Publication number Publication date
JP3114154B2 (ja) 2000-12-04
CA2107215C (fr) 2001-04-17
GR3021689T3 (en) 1997-02-28
ATE143125T1 (de) 1996-10-15
DE69304833D1 (de) 1996-10-24
US5445217A (en) 1995-08-29
DK0580848T3 (ja) 1997-03-10
CA2107215A1 (fr) 1993-08-15
DE69304833T2 (de) 1997-04-03
EP0580848A1 (fr) 1994-02-02
WO1993016339A1 (fr) 1993-08-19
ES2094530T3 (es) 1997-01-16
JPH06507008A (ja) 1994-08-04
FR2687462A1 (fr) 1993-08-20

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