EP0130908B1 - Wärmeübertragungsverfahren mittels einer monovarianten Dreiphasen-Reaktion - Google Patents

Wärmeübertragungsverfahren mittels einer monovarianten Dreiphasen-Reaktion Download PDF

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Publication number
EP0130908B1
EP0130908B1 EP84401360A EP84401360A EP0130908B1 EP 0130908 B1 EP0130908 B1 EP 0130908B1 EP 84401360 A EP84401360 A EP 84401360A EP 84401360 A EP84401360 A EP 84401360A EP 0130908 B1 EP0130908 B1 EP 0130908B1
Authority
EP
European Patent Office
Prior art keywords
gas
process according
phase
calories
reaction
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
Application number
EP84401360A
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English (en)
French (fr)
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EP0130908A1 (de
Inventor
Didier Payre
Georges Crozat
Bernard Spinner
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.)
Societe National Elf Aquitaine
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Societe National Elf Aquitaine
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Publication date
Application filed by Societe National Elf Aquitaine filed Critical Societe National Elf Aquitaine
Priority to AT84401360T priority Critical patent/ATE29578T1/de
Publication of EP0130908A1 publication Critical patent/EP0130908A1/de
Application granted granted Critical
Publication of EP0130908B1 publication Critical patent/EP0130908B1/de
Expired 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
    • F25B30/00—Heat pumps
    • F25B30/04—Heat pumps of the sorption type
    • 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

Definitions

  • the present invention relates to a thermochemical process for carrying out calorie transfers between a first source of calories and a second source of calories.
  • the process is implemented according to an intermittent cycle of heat storage and destocking.
  • thermochemical processes having either continuous operation or intermittent operation, which can operate to supply calories - heating or to take off - cooling.
  • the invention provides, on the contrary, a method which implements a monovariant system, that is to say a system for which the relationship between the logarithm of the pressure and I / T is unique and almost linear.
  • thermochemical heat pumps a process implementing a three-phase monovariant system for which the absorption of gas by a saturated solution corresponds to a single equilibrium, c that is to say that one has only one reaction, whereas Mar considered that the heat exchange takes place during two distinct reactions each concerning a different solid compound.
  • the invention provides a thermochemical process for transferring calories from a first heat source to a second heat source by using a reaction medium.
  • This process is characterized in that the exchange of calories between one of the two sources and the said reaction medium takes place during a reaction between a gas and a liquid phase constituted by a solution saturated with solid whereas the exchange of calories between the second source and the reaction medium takes place during a gas-liquid phase change reaction of said gas or of absorption of the gas on a solid, the two reactions taking place in a closed medium and being monovariant.
  • the gas may consist of water vapor or ammonia, or alternatively chosen from methanol, ethanol, butanol, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, fluoroalkanes , chlorinated fluoroalkanes, difluoromethylsilane, chlorodifluorosilane, disiloxane, propane, butane, acetone and acetaldehyde, the fluoroalkanes themselves being chosen from CC1 3 F, CCl 2 F 2 , CHCI 2 F, CHCIF 2 , C1 3 C 2 F 3 , C1 2 C 2 F 4 , C 2 HCIF 4 , C 2 H 2 CIF 3 , CH 2 CIF and C 2 H 2 F 4 .
  • the heat pump comprises a saturated solution, in the liquefied gas, of a solid chosen from CaCI 2 , KOH, LiCI, LiBr, ZnCl 2 , ZnBr 2 and the gas, in these cases, is H 2 0.
  • a solid chosen from CaCI 2 , KOH, LiCI, LiBr, ZnCl 2 , ZnBr 2 and the gas, in these cases, is H 2 0.
  • the heat pump comprises a reactor (1) and a reactor (2), interconnected by the pipe (3).
  • Each reactor is provided with a heat exchanger (4) to (5) allowing the exchange of calories between the reaction medium and the external sources of calories.
  • the reactor (1) contains the liquid in equilibrium with its vapor phase
  • the reactor (2) contains the saturated solid solution.
  • the gas coming from the reactor (1) condenses at the saturated solution and releases its latent heat of condensation ⁇ H while diluting the solution.
  • the differential heat of dilution of the saturated solution is ⁇ H D , it is an exothermic reaction.
  • excess solid dissolves to maintain the concentration at saturation, with a heat ⁇ H S of dissolution of the salt in the saturated solution.
  • the gas evaporates from the solution contained in the reactor (2) to go to the reactor (1) which then plays the role of condenser.
  • the solution is concentrated and the solid must crystallize.
  • the enthalpies involved are the same as before, in opposite sign.
  • FIG. 4 shows a heating installation allowing the implementation of the method according to the invention, and in which the heating period corresponds only to the destocking phase. It is understood that, as mentioned above, the installation could also be used for heating during the storage period.
  • Part A of Figure 4 represents the storage phase while part B represents the destocking phase.
  • the heat pump is symbolized by its two reactors (1) and (2) and by the gas line (3).
  • the reactor (1) is connected to a hot source constituted, in the installation shown, by a solar collector (12).
  • the calories given up in the reactor (2) during the condensation of the gas are released into the atmosphere, but they could as well be used for heating or even be stored.
  • the reactor (2) is supplied with calories by a cold source, symbolized by the arrow (11). The calories are recovered in the reactor (1) and used for heating.
  • the three-phase system used was the saturated solution of lithium chloride, water vapor and lithium chloride monohydrate.
  • the range of existence of the hydrate in solid form with the saturated solution is between 19 and 95 ° C.
  • the mass storage capacity, measured between a storage operation at 90 ° C and a destocking operation at 45 ° C, was 146 Wh / kg.
  • a temperature rise of approximately 41 ° C. (AT) was obtained.
  • phase rule shows that the system is monovariant.
  • FIG. 3 shows the LiCI / LiCI H 2 0 absorption curve, referenced by the reference (9). This curve is located to the right of the curve corresponding to the saturated solution.
  • the assembly works as in the previous example, with a storage phase and a destocking phase and gives identical results.
  • a compressor can be provided on the tube (3) so as to improve the reaction kinetics or else to place a stirring device inside the reactor (1).

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Sorption Type Refrigeration Machines (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Compression-Type Refrigeration Machines With Reversible Cycles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

1. Verfahren zum Wärmeübergang zwischen einer ersten Wärmequelle und einer zweiten Wärmequelle durch Verwendung eines Reaktionsmediums, dadurch gekennzeichnet, daß der Wärmeübergang zwischen einer der Wärmequellen und dem Reaktionsmedium eine Reaktion zwischen einem Gas und einer Flüssigphase ist, die aus einer mit Feststoff gesättigten Lösung besteht, und der Wärmeübergang zwischen der zweiten Wärmequelle und dem Reaktionsmedium bei einer Gas-Flüssigumwandlung des Gases oder einer Absorption des Gases an einem Feststoff stattfindet, wobei beide Reaktionen in geschlossenem Medium stattfinden und monovariant sind.
2. Verfahren nach Anspruch 1, gekennzeichnet durch Verwendung von Wasserdampf als Gas.
3. Verfahren nach Anspruch 1, gekennzeichnet durch Verwendung von Ammoniak als Gas.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Gas unter Methanol, Ethanol, Butanol, Methylamin, Dimethylamin, Trimethylamin, Ethylamin, Diethylamin, Fluoralkanen, chlorierten Fluoralkanen, Difluormethylsilan, Chlordifluorsilan, Disiloxan, Propan, Butan, Aceton und Acetaldehyd gewählt wird.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die chlorierten Fluoralkane unter CCl3F, CCl2F2, CHCl2F, CHClF2, Cl3C2F3, Cl2CzF4, C2HClF4, C2H2ClF3, CH2ClF und C2H2F4 gewählt werden.
6. Verfahren nach Anspruch 1, gekennzeichnet durch Verwendung einer gesättigten Lösung eines Feststoffs, gewählt unter CaCl2,. KOH, LiCI, LiBr, ZnCl2 und ZnBr2, in dem verflüssigten Gas als Flüssigphase.
7. Verfahren nach Anspruch 1, gekennzeichnet durch Verwendung von Wasser als verflüssigtes Gas.
EP84401360A 1983-07-01 1984-06-26 Wärmeübertragungsverfahren mittels einer monovarianten Dreiphasen-Reaktion Expired EP0130908B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84401360T ATE29578T1 (de) 1983-07-01 1984-06-26 Waermeuebertragungsverfahren mittels einer monovarianten dreiphasen-reaktion.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8310955A FR2548340B1 (fr) 1983-07-01 1983-07-01 Pompe a chaleur triphasique
FR8310955 1983-07-01

Publications (2)

Publication Number Publication Date
EP0130908A1 EP0130908A1 (de) 1985-01-09
EP0130908B1 true EP0130908B1 (de) 1987-09-09

Family

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Family Applications (1)

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EP84401360A Expired EP0130908B1 (de) 1983-07-01 1984-06-26 Wärmeübertragungsverfahren mittels einer monovarianten Dreiphasen-Reaktion

Country Status (7)

Country Link
US (2) US4682476A (de)
EP (1) EP0130908B1 (de)
JP (1) JPS6026261A (de)
AT (1) ATE29578T1 (de)
CA (1) CA1236312A (de)
DE (1) DE3466059D1 (de)
FR (1) FR2548340B1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2548340B1 (fr) * 1983-07-01 1986-03-21 Elf Aquitaine Pompe a chaleur triphasique
FR2582790B1 (fr) * 1985-06-04 1987-07-24 Elf Aquitaine Procede et dispositif thermochimiques de stockage et destockage de chaleur
EP0287319B1 (de) * 1987-04-14 1992-11-11 Uwe Rockenfeller Chemisches Energie-Speicher-System
US4993239A (en) * 1987-07-07 1991-02-19 International Thermal Packaging, Inc. Cooling device with improved waste-heat handling capability
US4974419A (en) * 1988-03-17 1990-12-04 Liquid Co2 Engineering Inc. Apparatus and method for simultaneously heating and cooling separate zones
US4759191A (en) * 1987-07-07 1988-07-26 Liquid Co2 Engineering, Inc. Miniaturized cooling device and method of use
US4901535A (en) * 1987-07-07 1990-02-20 Sabin Cullen M Temperature changing device improved evaporation characteristics
IN171470B (de) * 1987-07-07 1992-10-24 Int Thermal Packaging Inc
US4949549A (en) * 1987-07-07 1990-08-21 International Thermal Packaging, Inc. Cooling device with improved waste-heat handling capability
US4744224A (en) * 1987-07-27 1988-05-17 Erickson Donald C Intermittent solar ammonia absorption cycle refrigerator
FR2629575A1 (fr) * 1988-03-30 1989-10-06 Elf Aquitaine Caloduc chimique, procede de regeneration d'un tel caloduc et utilisation de ce caloduc
DE3837880A1 (de) * 1988-11-08 1990-05-10 Zeolith Tech Kuehlbehaelter fuer einen sorptionsapparat
US5048301A (en) * 1989-01-05 1991-09-17 International Thermal Packaging Vacuum insulated sorbent driven refrigeration device
US5197302A (en) * 1989-01-05 1993-03-30 International Thermal Packaging, Inc. Vacuum insulated sorbent-driven refrigeration device
US5018368A (en) * 1989-10-12 1991-05-28 International Thermal Packaging, Inc. Multi-staged desiccant refrigeration device
US5490398A (en) * 1993-03-15 1996-02-13 Airex Research And Development, Inc. High efficiency absorption cooling and heating apparatus and method
FR2723438B1 (fr) 1994-08-02 1996-09-20 Lorraine Carbone Reacteur de pompe a chaleur chimique a puissance amelioree
AUPM835894A0 (en) * 1994-09-22 1994-10-13 Thermal Energy Accumulator Products Pty Ltd A temperature control system for liquids
FR2748093B1 (fr) * 1996-04-25 1998-06-12 Elf Aquitaine Dispositif thermochimique pour produire du froid et/ou de la chaleur
SE515688C2 (sv) * 1998-12-18 2001-09-24 Suncool Ab Kemisk värmepump samt förfarande för kylning och/eller uppvärmning
WO2004055453A1 (ja) * 2002-12-13 2004-07-01 The Tokyo Electric Power Company, Incorporated ガスハイドレートを用いたヒートポンプ及び熱利用装置
SE527721C2 (sv) * 2003-12-08 2006-05-23 Climatewell Ab Kemisk värmepump arbetande enligt hybridpincipen
FR2878940A1 (fr) * 2004-12-06 2006-06-09 Guy Karsenti Dispositif de climatisation du genre pompe a chaleur par absorption, en particulier pour enceintes de faible volume, et enceinte le comportant
CN101737996B (zh) * 2008-11-17 2012-02-01 苏庆泉 热泵循环系统以及冷热联供方法
EP2759679A1 (de) * 2013-01-23 2014-07-30 Siemens Aktiengesellschaft Thermische Speichereinrichtung zur Nutzung von Niedertemperaturwärme
US20210325092A1 (en) * 2018-02-06 2021-10-21 John Saavedra Heat Transfer Device
CN113025281A (zh) * 2021-03-18 2021-06-25 天津大学 一种含有机硅的制冷剂

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BE380828A (de) *
US2144441A (en) * 1932-10-27 1939-01-17 Schlumbohm Peter Method of conditioning an absorption refrigerating system
US2138686A (en) * 1933-02-28 1938-11-29 Altenkirch Edmund Intermittent absorption refrigerating apparatus
US2182453A (en) * 1936-01-18 1939-12-05 William H Sellew Heat transfer process and apparatus
FR2172754A1 (en) * 1972-02-21 1973-10-05 Greiner Leonard Heating and cooling apparatus with absorption chemical - and fluid to be absorbed
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US4005584A (en) * 1975-04-10 1977-02-01 Allied Chemical Corporation Composition, method and apparatus for absorption heating
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FR2548340B1 (fr) * 1983-07-01 1986-03-21 Elf Aquitaine Pompe a chaleur triphasique

Also Published As

Publication number Publication date
FR2548340B1 (fr) 1986-03-21
EP0130908A1 (de) 1985-01-09
ATE29578T1 (de) 1987-09-15
DE3466059D1 (en) 1987-10-15
US4873842A (en) 1989-10-17
CA1236312A (fr) 1988-05-10
FR2548340A1 (fr) 1985-01-04
JPS6026261A (ja) 1985-02-09
US4682476A (en) 1987-07-28

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