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WO1999009359A1 - Installation refrigerante fonctionnant a l'energie solaire - Google Patents

Installation refrigerante fonctionnant a l'energie solaire Download PDF

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Publication number
WO1999009359A1
WO1999009359A1 PCT/EP1998/005081 EP9805081W WO9909359A1 WO 1999009359 A1 WO1999009359 A1 WO 1999009359A1 EP 9805081 W EP9805081 W EP 9805081W WO 9909359 A1 WO9909359 A1 WO 9909359A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
solar
cooling system
solar thermal
substances
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.)
Ceased
Application number
PCT/EP1998/005081
Other languages
German (de)
English (en)
Inventor
Werner Siol
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.)
Etc Energietechnik und Chemie & Co KG GmbH
Original Assignee
Etc Energietechnik und Chemie & Co KG GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Etc Energietechnik und Chemie & Co KG GmbH filed Critical Etc Energietechnik und Chemie & Co KG GmbH
Priority to EP98946314A priority Critical patent/EP1012512A1/fr
Priority to AU93411/98A priority patent/AU9341198A/en
Publication of WO1999009359A1 publication Critical patent/WO1999009359A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/047—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for absorption-type refrigeration systems
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B27/00—Machines, plants or systems, using particular sources of energy
    • F25B27/002—Machines, plants or systems, using particular sources of energy using solar energy
    • F25B27/007—Machines, plants or systems, using particular sources of energy using solar energy in sorption type systems
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D5/00—Devices using endothermic chemical reactions, e.g. using frigorific mixtures

Definitions

  • the invention relates to a solar thermal cooling system and a system for combined heating and cooling with solar energy and a method for operating these systems
  • the principle of the compression refrigerator which is used for example in most household refrigerators, is based on the fact that a gaseous Refrigerant is liquefied under pressure. The heat that occurs is dissipated. During the subsequent expansion, the refrigerant evaporates and extracts the heat required for evaporation from the cooling chamber.
  • the absorption refrigerator operates like the compression refrigerator at 2 pressure levels but at 3 temperature levels.
  • the mechanical compressor is replaced by a thermal compressor.
  • Working fluid is a mixture of two substances, consisting of the working or refrigerant and the sorbent or solvent The ability of the sorbent to dissolve the refrigerant determines the mode of operation of this process
  • Such an absorption refrigerator has at least the following 4 main components
  • the sorption technology with the water / zeolite pair of substances is also investigated.
  • the high binding tendency of the zeolite for water is used.
  • the absorption of water vapor in the zeolite is so violent that the water evaporates with the formation of ice.
  • the regeneration of the zeolite, ie the water is expelled from the zeolite using solar energy at temperatures> 200 ° C see also DE-OS 3521448 and S Muller, S Zech, Sonnenenergie 6/96, 22-24
  • a cooling system based on activated carbon / ammonia is described by J Bougard et al, Be Tech Froid 1992 (1, Froid a Sorption solid), 302-7.
  • the heating and cooling system described in DE-OS 4340812 works with zeolite as a storage medium and Ethan as a tool
  • the zeolite / water system has found particular interest in the field of solar cooling. However, temperatures> 200 ° C are required to regenerate the zeolite, i.e. to drive off the water, which are difficult to achieve with the flat collectors currently in use of water, for example, special parabolic collectors are used. In addition, the handling of such a periodically operating zeolite / water chiller is quite complex (see Stefan Eichengrun et al, Ki Lucas- und Kältechn 1994, 30 (3) 1 12)
  • the solar-powered absorption chillers which work with the material pair lithium bromide / water, are limited in their area of application by the salt content
  • the invention also relates to a method for cooling by means of solar energy, which is characterized in that a liquid mixture consisting of at least 2 components which have a heat of mixing ⁇ H> 500 J / mol differ from the boiling point by more than 20 ° C. and from them at least one component one
  • the liquid components 1 and 2 are mixed in the mixing device with the absorption of energy and finally the mixture obtained is fed back to the expeller
  • the solar-powered cooling system according to the invention is therefore a very simple system.
  • This system essentially consists of the components shown in FIGS. 1 and 2, i.e. a solar-powered expeller, a condenser and a mixing device.
  • the difference to the solar-powered absorption chiller is that that the cooling takes place by mixing and not by evaporation at reduced pressure.
  • the system generally also works at a single (low) pressure level
  • the low-boiling component 1 is driven out in a temperature range, for example 40-180 ° C., or preferably 50-150 ° C., which is achieved without problems with the solar collectors according to the prior art.
  • a disadvantage is the fact that in the solar-powered cooling system according to the invention, the very high heat of vaporization is opposed by a heat of mixture, which usually only makes up a fraction of the heat of vaporization, for example 20%.
  • this cooling system according to the invention can be easily combined with a solar collector system for domestic water heating, the cooling being obtained as an additional benefit, for example for air conditioning
  • An essential component of the solar-powered cooling system according to the invention is a suitable mixture, ie a suitable pair of substances, consisting at least of components 1 and 2.
  • the mixture can also contain further components, which may be used to influence the separation process (Influencing an azeotrope) or the rheology of the mixture.
  • the mixture can also contain stabilizing additives such as anti-aging agents
  • a suitable pair of substances i.e. a suitable mixture, is characterized at least by the following features
  • Essential for the functioning of the cooling system according to the invention is the use of a pair of substances with a heat of mixing that is as high as possible, that is, the use of a pair of substances that cools significantly during mixing
  • a suitable pair of substances has a mixture warmth ⁇ H> 500 J / mol mixture or, preferably, ⁇ H> 1000 J / mol mixture.
  • mixture warmths ⁇ H> 1,500 J / mol mol mixture preferred
  • the heat of mixture of a suitable pair of substances should generally be ⁇ H> 10 kJ / kg of mixture.
  • a mixture heat of ⁇ H> 20 kJ / kg of mixture is preferred
  • the temperature change when mixing the substances can also be used directly as a criterion for the selection of a suitable pair of substances.
  • the cooling during mixing should be at least 4 ° C, better at least 6 ° C or preferably at least 8 ° C such are preferred
  • suitable material pairs can be obtained directly from standard reference works such as James J Christensen et al, Handbook of Heats of Mixing, John Wiley & Sons, New York or Christensen et al, Heats of Mixing Data Collection (Chemistry Data Series 3/1, 2), Frankfurt DECHEMA 1984, can be taken.
  • suitable mixing partners can also be calculated using incremental methods B UNIFAC (see also A Fredenslund et al, AICHE Journal, 21, 1086 (1975) or JW Barlow et al, Macromolecules 1988, 21, 2492-2502 and Macromolecules 1989, 22, 374-80)
  • inorganic and organic liquids are of interest.
  • Mixture components are of interest, for example, water.
  • Mixtures in which both components are organic liquids are of particular interest.
  • At least one of the components has a boiling point> 50 ° preferably> 80 ° C.
  • Particularly preferred are material pairs in which the higher-boiling component, hereinafter referred to as
  • Component 2 addressed has a boiling point> 1 20 ° C or even more favorably a boiling point> 160 ° C.
  • material pairs which have a mixture heat ⁇ H> 500 J / mol are, according to the invention, very particularly suitable are those material pairs which have a significantly higher mixture heat , eg show ⁇ H> 2000 J / mol
  • the substance class of the alkanes can be used both as volatile component 1 (e.g. pentane) and the more volatile component 2 (e.g. long-chain hydrocarbons such as dodecane)
  • volatile component 1 e.g. pentane
  • volatile component 2 e.g. long-chain hydrocarbons such as dodecane
  • Halogenated hydrocarbons eg fluoroalkanes, chlorinated hydrocarbons, - Compounds containing carbonyl groups such as
  • N, N-dialkylamides eg N, N-dimethylacetamide / heptane ⁇ H 1236 J / mol - carboxylic acids, eg acetic acid / cyclohexane ⁇ H approx. 1000 J / mol
  • Nitro compounds e.g. nitroethane / 2,2-dimethylbutane ⁇ H approx. 1610 J / mol
  • Alcohols are also of interest as mixing partners for alkanes.However, certain restrictions have to be observed. Alcohols / alkanes show a pronounced dependence of the heat of the mixture on the temperature and tend to have gaps in the mixture, especially at low temperatures
  • Acetic anhydride / cyclohexane This system is only slightly miscible at room temperature. However, at elevated temperature, e.g. 60 ° C, it is readily miscible and then shows a mixing temperature of ⁇ H approx. 3000 J / mol. Such a system is therefore only at an elevated temperature applicable
  • MTBE methyl t-butyl ether
  • the combinations alcohol / ketone, alcohol / ester and alcohol / nitrile are of particular interest.
  • the mixture shows isopropanol /
  • the mixing ratio of components 1 and 2 can be in the range 1 9 to 9 1 (parts by weight)
  • ketone / alkane pair For example, if you start from the ketone / alkane pair and choose the ketone as volatile component 1, a number of mixtures known from the literature are directly suitable. Examples include (boiling points of the components in parentheses) acetone (56 ° C) / decane (174 ° C), ⁇ H 1978 J / mol,
  • alkane as volatile component 1 and, accordingly, the ketone as the high-boiling component.
  • the various butanes, pentanes or hexanes are suitable as alkanes, for example, and the corresponding high-boiling compounds, for example, as ketones Diethyl ketone or cycloalkanone Only if the system is to work under increased pressure is acetone as component 2 of interest, for example in combination with butane as component 1
  • ester / alkane pair of substances can be seen quite analogously.
  • the ester as volatile component 1
  • the substance pairs based on low-boiling formates or acetates described in the literature can be used directly, for example the mixtures of methyl acetate (56 ° C.) / Dodecane (216 ° C), ⁇ H 2140 J / mol or ethyl acetate (77 ° C) / dodecane (216 ° C), ⁇ H 1 768 J / mol
  • the boiling point of a component can be reduced for a given mixture by, for example, choosing a component with a lower molecular weight in a homologous series, for example the mixture hexane (68 ° C.) / diethyl carbonate (121 ° C.) instead the mixture dodecane (216 ° C) / diethyl carbonate (121 ° C) described in the literature
  • the inverse procedure that is, starting from a known mixture to increase the molecular weight of a component, for example in order to raise the boiling point, is not always possible. Gaps in the mixture often occur here.
  • at least component 1 of the mixture should have a molecular weight ⁇ 100 g / mol
  • the high-boiling component 2 also has a relatively low molecular weight, for example ⁇ 400 g / mol
  • the alcohol / ketone and alcohol / ester substance pairs which generally show complete miscibility and very high heat of mixing even when using relatively high molecular weight components.
  • substances are to be mentioned
  • esters can be combined with higher alcohols, e.g. ethyl acetate (77 ° C) / 3-methyl-1-butanol (13 1 ° C), ⁇ H approx. 2700 J / mol or lower esters such as methanol, ethanol, propanol and isopropanol as component 1 and higher esters as component 2, for example
  • Isopropanol / dialkyl esters of dicarboxylic acids such as dialkyl succinates, dialkyl adipates. Esters of diols and high-boiling cyclic esters such as propylene carbonate are also of interest as component 1.
  • Isopropyl alcohol and a diisopropyl ester of a dicarboxylic acid as component 2 are preferred.
  • alkane / chlorohydrocarbon combinations in particular material pairs which contain chlorofluorocarbons, are less preferred.
  • fluorocarbon / alkane combinations are particularly suitable
  • components 1 and 2 can be mixed using an agitator. With a view to making the cooling system as simple as possible, however, a stirrer will generally be dispensed with. A simple merging of the components is often sufficient. Suitable mixing devices are, for example. described in Ullmann ' s Encyclopedia of
  • Static mixers are particularly suitable for mixing components 1 and 2 (see in particular Manfred H. Pahl and E. Musselknautz, Chem.-Ing. -Tech., 51 (1979), 347-64 and Chem.-Ing. -Tech ., 1980, 52: 285-91).
  • the solar collector can be used directly as an expeller (cooker).
  • the use of the solar collector is preferred as
  • a rectifier will be added to the expeller.
  • the rectification devices e.g. reflux coolers
  • the stripping and rectification techniques known from absorption chillers can be used
  • the solar-powered cooling system according to the invention has an extremely wide range of uses.This is due, among other things, to the fact that the temperatures for separating the components ideally match the working areas of the usual solar collectors, but it should also be emphasized that the cooling effect used here is achieved by mixing two liquids can be used not only at room temperature but also at higher temperatures and at low temperatures In general, a working range from z + 70 ° C to -80 ° C can be covered with a single pair of substances
  • the cooling system according to the invention can be used to operate a
  • Freezer temperature - 18 ° C
  • a cow cupboard temperature approx. 4 ° C
  • dehumidification or air conditioning cooling of rooms.
  • Refrigerators and freezers with suitable latent storage are known from DE-OS 2433499, EPA 0098052 or EPA 065 1214
  • a particularly preferred embodiment of the solar-powered cooling system according to the invention is the combined operation of a solar-powered heating system, in particular a solar-powered hot water preparation and a refrigeration system
  • the solar energy introduced in the expeller to evaporate component 1 is used in the condenser (heat of condensation) to produce hot water
  • the hot water tank can preferably be called a so-called
  • kite generation according to the invention is an additional benefit that is achieved without major additional effort
  • water is also of interest as component 1 (heat of vaporization 2253 kJ / kg).
  • Methanol, ethanol and isopropanol are also particularly suitable as component 1 in this heating / cooling combination
  • component 1 When used purely as a refrigeration system or as an air conditioning system, however, components 1 with a significantly lower heat of vaporization will be used as component 1
  • pentane shows a heat of evaporation of 383 kJ / kg.
  • the lower esters such as methyl acetate (heat of evaporation 406 kJ / kg) are also suitable
  • the particular benefit of the cooling system according to the invention lies particularly in the combination of solar hot water preparation / solar cooling.
  • the very simple structure is to be emphasized.
  • the entire system consists only of a number of pipes and heat exchangers that are particularly stressed
  • the system does not have any moving parts.
  • the system is usually driven by a pump, which pumps the mixture into the expeller, for example. This pump advantageously works photovoltaically. In general, there is no need for complex control
  • a pump can be used entirely In this case, a hydrostatic drive is possible
  • thermometer For the exact determination of the warmth of the mixture of footiness see e.g. Christensen et al (loc cit) For a quick, orientating examination it is completely sufficient to mix 20g of liquid in a glass flask equipped with a magnetic stirrer and thermometer and to observe the temperature change it is only necessary to bring the components to the same initial temperature and to use a fast responding thermometer or thermocouple
  • Example 1 Isopropanol and acetone are mixed in a ratio of 1 1 (data as
  • Example 2 Methyl acetate and dodecane are mixed in a ratio of 1 liter
  • Isopropanol and propylene carbonate are mixed in a ratio of 1 1
  • Example 7 (not according to the invention) ethylene glycol diacetate and acetone are mixed in a ratio of 1 liter
  • the pair of methyl acetate materials enables the construction of a solar-powered cooling system without complex temperature control

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Sorption Type Refrigeration Machines (AREA)

Abstract

L'invention concerne une installation réfrigérante comprenant un générateur fonctionnant à l'énergie solaire, un condenseur et un mélangeur dans lequel deux liquides, ayant une chaleur de mélange DELTA H > 500 J/mole, circulent en circuit. Le refroidissement est effectué par le mélange de ces liquides. Le générateur chauffé par l'énergie solaire sépare le mélange conformément aux différents points d'ébullition en une composante gazeuse 1 et une composante liquide 2. Après condensation de la composante 1 dans le condenseur, les deux liquides sont à nouveau renvoyés au mélangeur. Dans un mode de réalisation préféré, le condenseur est simultanément utilisé pour chauffer de l'eau sanitaire.
PCT/EP1998/005081 1997-08-14 1998-08-11 Installation refrigerante fonctionnant a l'energie solaire Ceased WO1999009359A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98946314A EP1012512A1 (fr) 1997-08-14 1998-08-11 Installation refrigerante fonctionnant a l'energie solaire
AU93411/98A AU9341198A (en) 1997-08-14 1998-08-11 Solar heat powered cooling plant

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19735334.7 1997-08-14
DE1997135334 DE19735334C2 (de) 1997-08-14 1997-08-14 Solarthermisch betriebene Kühlanlage

Publications (1)

Publication Number Publication Date
WO1999009359A1 true WO1999009359A1 (fr) 1999-02-25

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Family Applications (1)

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PCT/EP1998/005081 Ceased WO1999009359A1 (fr) 1997-08-14 1998-08-11 Installation refrigerante fonctionnant a l'energie solaire

Country Status (4)

Country Link
EP (1) EP1012512A1 (fr)
AU (1) AU9341198A (fr)
DE (1) DE19735334C2 (fr)
WO (1) WO1999009359A1 (fr)

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US7160947B2 (en) 2002-12-13 2007-01-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polymers and laundry detergent compositions containing them
US7160848B2 (en) 2002-12-13 2007-01-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polymers and laundry detergent compositions containing them

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DE19962644A1 (de) * 1999-12-23 2001-06-28 Hkf Heizungsbau Gmbh Solarautarkes Versorgungssystem für Inselbetrieb
DE10104900B4 (de) * 2001-02-03 2005-10-20 Mip Mittelstands Projekt Gmbh Solarkollektor zur Raumklimatisierung sowie mit solchen Solarkollektoren ausgestattete Klimaanlage
DE10347497B4 (de) * 2003-10-13 2006-03-30 MIWE-ÖKOKÄLTE GmbH Vorrichtung zum Kühlen von Gegenständen und Räumen und Verfahren zu deren Betrieb
DE102007016738A1 (de) * 2007-04-07 2008-10-09 pro Kühlsole GmbH Neuer Wärmeträger für Solaranlagen
DE102010019413A1 (de) 2010-05-04 2011-11-10 Solvis Gmbh & Co.Kg Anordnung zur Versorgung eines Gebäudes mit Wärme
DE102010017674B3 (de) * 2010-07-01 2011-11-24 Universität Stuttgart Solarkollektoranlage und Verfahren zu deren Steuerung
CN117157377A (zh) * 2021-04-26 2023-12-01 埃克森美孚技术与工程公司 具有协同热容量的热管理流体

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Cited By (2)

* Cited by examiner, † Cited by third party
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US7160947B2 (en) 2002-12-13 2007-01-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polymers and laundry detergent compositions containing them
US7160848B2 (en) 2002-12-13 2007-01-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polymers and laundry detergent compositions containing them

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DE19735334C2 (de) 2000-02-03

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