WO2007144306A1 - Réfrigérant et système de réfrigération - Google Patents

Réfrigérant et système de réfrigération Download PDF

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Publication number
WO2007144306A1
WO2007144306A1 PCT/EP2007/055617 EP2007055617W WO2007144306A1 WO 2007144306 A1 WO2007144306 A1 WO 2007144306A1 EP 2007055617 W EP2007055617 W EP 2007055617W WO 2007144306 A1 WO2007144306 A1 WO 2007144306A1
Authority
WO
WIPO (PCT)
Prior art keywords
refrigerant
refrigeration system
refrigeration
mixed gas
hydrocarbons
Prior art date
Application number
PCT/EP2007/055617
Other languages
English (en)
Inventor
Gert Prang Jensen
Original Assignee
Elcold Frysere Hobro Aps
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 Elcold Frysere Hobro Aps filed Critical Elcold Frysere Hobro Aps
Priority to JP2009514759A priority Critical patent/JP2009540262A/ja
Publication of WO2007144306A1 publication Critical patent/WO2007144306A1/fr
Priority to DKPA200801842A priority patent/DK177364B1/da

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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
    • C09K5/042—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 comprising compounds containing carbon and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/10—Aliphatic saturated hydrocarbons with one to four carbon atoms with four carbon atoms
    • C07C9/12—Iso-butane
    • 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
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • F25B9/006—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
    • 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
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • 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
    • F25B40/00—Subcoolers, desuperheaters or superheaters

Definitions

  • the present invention relates to a refrigerant for use in a refrigeration system. More particularly, the present invention relates to a refrigerant which is more environment friendly than prior art refrigerants, and a refrigerant which is capable of providing very low refrigeration temperatures. Furthermore, the present invention relates to a refrigeration system in which a refrigerant according to the invention can be used.
  • Conventional refrigeration systems comprise a refrigeration path in which a refrigerant is allowed to flow.
  • a number of components are positioned, normally a compressor, a condenser, an expansion element and an evaporator.
  • the refrigeration path is closed, i.e. the refrigerant circulates in the path.
  • the compressor may be replaced by a rack of parallelly connected compressors. This is usually the case in refrigeration systems with many refrigeration sites, e.g. the kind of refrigeration system which is normally installed in supermarkets.
  • a refrigeration system as defined above normally functions in the following manner.
  • Gaseous refrigerant enters the compressor where it is compressed.
  • the refrigerant enters the condenser where it at least partly condenses, i.e. at least part of the refrigerant is in a liquid state when it leaves the condenser.
  • the refrigerant passes an expansion element, e.g. in the form of an expansion valve controlling the flow of refrigerant in the system, where refrigerant is expanded, i.e. the pressure of the refrigerant decreases.
  • the refrigerant enters the evaporator where the liquid refrigerant evaporates. Since this is an energy consuming process, heat is drawn from the surroundings, and thereby a refrigerating effect is obtained at the position of the evaporator.
  • the gaseous refrigerant once again enters the compressor.
  • refrigerants such as R134a, R404A or R507
  • a disadvantage of such refrigerants is that they can only provide refrigeration within a limited temperature interval. Accordingly, they are normally used in refrigeration systems for use in households or supermarkets, i.e. refrigerators adapted to maintain a refrigeration temperature of approximately 5 0 C or freezers adapted to maintain a refrigeration temperature of approximately -18 0 C.
  • a somewhat lower refrigeration temperature is desired. This is, e.g., the case in medical applications, such as storing of certain kinds of vaccines, serum or tissue samples.
  • Such products normally have to be stored at temperatures below -79 0 C.
  • refrigeration temperatures of this order of magnitude are sometimes desired in the food industry, e.g. in order to ensure that none of the stored products obtain a temperature above a critical temperature during transportation, even if the products are shifted from one transporting means to another.
  • Another approach is the so-called mixed gas refrigeration system in which the refrigerant used in the system is a mixture of various gases with different boiling points.
  • the refrigerant used in the system is a mixture of various gases with different boiling points.
  • it is utilised that when one of the gases undergoes a phase transition it either consumes energy from or delivers energy to the surroundings, depending on the kind of phase transition.
  • the gas having the highest boiling point evaporates the energy consumption during the evaporation is used for refrigerating the remaining gases, preferably until they start condensing. This may take place in a heat exchanger.
  • a mixed gas refrigerant comprising two hydrocarbons and a hydrofluoride (HFC) has previously been used.
  • HFC hydrofluoride
  • a disadvantage of such mixed gas refrigerants is that the HFC gases are undesired in the environment, and the refrigerants are therefore not optimal from an environmental point of view.
  • an object of the invention to provide a refrigerant for providing low refrigeration temperatures, and which is more environment friendly than prior art refrigerants.
  • a refrigerant for use in a refrigeration system, the refrigerant comprising a mixed gas of at least three different hydrocarbons, including isobutane (C 4 H 10 ), ethene (C 2 H 4 ) and methane (CH 4 ), wherein the mixed gas comprises at least 70% by weight of isobutane (C 4 H 10 ).
  • a mixed gas comprising at least three different hydrocarbons can be used as a refrigerant capable of providing very low refrigeration temperatures in one refrigeration stage, i.e. without the need for cascade refrigeration systems. Thereby only one compressor is necessary, and energy is thereby conserved as compared to the prior art cascade refrigeration systems. Furthermore, since the desired refrigeration is obtained by means of the three or more hydrocarbons, the presence of a hydrofluoride in the mixed gas is not required. Accordingly, the refrigerant according to the invention is more environment friendly than the prior art mixed gas refrigerants.
  • the refrigerant according to the first aspect of the invention is capable of providing very low refrigeration temperatures in an environment friendly manner, partly because energy is conserved as compared to the prior art cascade systems, partly because hydrofluorides are avoided in the refrigerant. This is very advantageous.
  • the mixed gas may comprise further components, such as additional hydrocarbons, e.g. in the form of impurities in one or more of the hydrocarbons, or other kinds of gases or liquids.
  • the mixed gas comprises a mixture of isobutane (C 4 H 10 ), ethene (C 2 H 4 ) and methane (CH 4 ).
  • the inventors of the present invention have found that this mixed gas is particularly suitable as a refrigerant for providing very low refrigeration temperatures without the need for a cascade refrigeration system. Since isobutane has a relatively high boiling point at atmospheric pressure (approximately -16 0 C), while ethene and methane have relatively low boiling points at atmospheric pressure (approximately -105 0 C for ethene and approximately - 18O 0 C for methane), evaporation of isobutane provides refrigeration for the ethene and the methane present in the mixed gas.
  • the mixed gas comprises at least 70% by weight of isobutane (C 4 H 10 ), such as between 70% and 85%, such as between 70% and 80%, such as between 70% and 75%.
  • isobutane forms a major part of the mixed gas. Since isobutane provides refrigeration for the other hydrocarbons as described above, the amount of isobutane present in the mixed gas should be selected in such a manner that it is capable of providing the desired level of refrigeration. By selecting a relatively large percentage of isobutane a relatively high level of refrigeration of the other hydrocarbons can be obtained, and this is very advantageous for some applications.
  • One of the hydrocarbons may have a boiling point at atmospheric pressure which is higher than or equal to -4O 0 C, such as higher than or equal to -25 0 C, such as higher than or equal to -16 0 C.
  • At least one of the hydrocarbons may have a boiling point at atmospheric pressure which is lower than or equal to -100 0 C, such as lower than or equal to -12O 0 C, such as lower than or equal to -15O 0 C.
  • One of the hydrocarbons may have a boiling point within the temperature interval from -12O 0 C to -100 0 C, while another of the hydrocarbons has a boiling point which is lower than or equal to -15O 0 C.
  • the hydrocarbon with the higher boiling point may, when evaporating, be used for refrigerating the one with the lower boiling point.
  • one of the hydrocarbons has a boiling point at atmospheric pressure which is higher than or equal to -4O 0 C, and two of the hydrocarbons have boiling points at atmospheric pressure which are lower than or equal to - 100 0 C, i.e. one of the hydrocarbons has a relatively high boiling point and two of the hydrocarbons have a relatively low boiling point.
  • the hydrocarbon with the high boiling point when evaporating, provides refrigeration for the other two hydrocarbons as described above.
  • At least one of the hydrocarbons may be in a vapour-liquid region at a temperature within the temperature interval from -45 0 C to 13O 0 C, and at a pressure within the pressure interval from 0.2 bar to 35 bar.
  • This has the advantage that at least one of the hydrocarbons is in a vapour-liquid region under normal operating conditions. Thereby this hydrocarbon is capable of providing refrigeration for other hydrocarbons in the manner described above.
  • the mixed gas may comprise between 1% and 69% by weight of ethene (C 2 H 4 ), such as between 1% and 50%, such as between 5% and 40%, such as between 15% and 30%, such as between 20% and 25%.
  • ethene C 2 H 4
  • the mixed gas may comprise between 1% and 69% by weight of methane (CH 4 ), such as between 1% and 50%, such as between 2% and 30%, such as between 3% and 20%, such as between 5% and 10%.
  • the mixed gas comprises approximately 71% by weight of isobutane, approximately 24% by weight of ethene and approximately 5% by weight of methane.
  • a refrigeration system comprising:
  • compressor, the condenser, the heat exchanger, the expansion element and the evaporator are interconnected in a refrigerant path, and wherein the refrigeration system is adapted to have a refrigerant according to the first aspect filled into the refrigerant path.
  • the second aspect of the invention provides a refrigeration system which is adapted to apply the refrigerant according to the first aspect of the invention. Accordingly, the refrigeration system according to the second aspect of the invention is adapted to provide low refrigeration temperatures at low energy consumption and without imposing special requirements on the components of the refrigeration system in terms of durability, strength, etc.
  • the refrigeration system further comprises a heat exchanger.
  • the heat exchanger preferably functions in the following manner.
  • the heat exchanger is passed by refrigerant running in opposite directions, and heat is thereby exchanged between refrigerant running in one direction and refrigerant running in the opposite direction. This will be described in further detail below with reference to Fig. 1.
  • the refrigerant path forms a closed circuit as described previously.
  • the refrigerant path is at least substantially hermetically closed.
  • the refrigeration system may be a freezer.
  • the evaporator provides refrigeration to a refrigerated volume in which products of a desired kind may be stored. Since the provided refrigeration temperature is very low as described above, the storage temperature inside the refrigerated volume will be correspondingly low. Thus, the products are stored at a very low temperature. This is, e.g., suitable for storing medical products, such as certain kinds of vaccines, serum or tissue samples.
  • the freezer functions in a manner which is very similar to the function of an ordinary household freezer, and it is thereby very easy and simple to install and drive.
  • the refrigeration system may be a cooling device for a central processing unit (CPU).
  • CPU central processing unit
  • a CPU positioned in a computer device will often need cooling.
  • Such cooling may be provided by means of a refrigeration system according to the second aspect of the invention.
  • the evaporator should be positioned in the proximity, preferably in thermal contact with a heat generating part of the CPU.
  • Fig. 1 is a schematic drawing of a refrigeration system according to an embodiment of the invention.
  • Fig. 2 is a phase diagram illustrating the cycle of the refrigerant present in the refrigeration system of Fig. 1.
  • Fig. 1 is a schematic drawing of a refrigeration system 10 with a compressor 11, a first condenser 12, a filter drier 13, a second condenser 14, a heat exchanger 15, an expansion element 16, an evaporator 17, and an accumulator 18 connected in such a manner that a closed circuit is formed. Inside the closed circuit a refrigerant according to the first aspect of the invention is allowed to flow.
  • a refrigerant comprising a mixed gas of isobutane (C 4 H 10 ), ethene (C 2 H 4 ) and methane (CH 4 ) is used.
  • Gaseous refrigerant enters the compressor 11 where it is compressed.
  • the compressed refrigerant then enters the first condenser 12 in which the refrigerant at least partly condenses.
  • the refrigerant enters the filter drier 13, where moisture present in the system is absorbed and impurities present in the system are collected.
  • the refrigerant enters the second condenser 14 where the refrigerant undergoes further condensation.
  • the refrigerant Upon leaving the second condenser 14 the refrigerant enters the heat exchanger 15 where heat is exchanged with refrigerant flowing in the opposite direction in a separate tube. This will be described further below. From the heat exchanger 15 the refrigerant passes the expansion element 16 where the pressure of the refrigerant decreases, and the expanded refrigerant continues into the evaporator 17 where the refrigerant evaporates, thereby providing refrigeration, e.g. to a refrigerated volume. The evaporated refrigerant then enters the heat exchanger 15. Next, the refrigerant enters the accumulator 18. The accumulator functions as a 'refrigerant buffer' in the sense that it is capable of compensating for variations in the mass flow of the refrigerant as a consequence of variations in refrigeration load. Finally, the refrigerant once again enters the compressor 11.
  • the isobutane In the heat exchanger 15 the following takes place.
  • the isobutane In the refrigerant entering the heat exchanger 15 from the second condenser 14 the isobutane is undergoing a phase transition from a liquid phase to a gaseous phase, i.e. the isobutane of the refrigerant consumes energy from the surroundings, thereby providing refrigeration for the ethene and the methane of the refrigerant.
  • the ethene will reach its boiling point, and it will thereby start to undergo a phase transition from a gaseous to a liquid phase, i.e. it will start to condensate.
  • the methane will similarly start condensing.
  • the refrigerant flowing in the opposite direction i.e. the refrigerant entering the heat exchanger 15 from the evaporator 17 typically has a lower temperature than the refrigerant flowing in the direction from the second condenser 14 towards the expansion element 16. Since heat is exchanged between the two flows of refrigerant, this has the consequence that the refrigerant flowing from the evaporator 17 towards the accumulator 18 'helps' in cooling the ethene and the methane flowing in the opposite direction. Thus, the cooler refrigerant 'helps' the warmer refrigerant in reaching the condensations points of the ethene and the methane. Fig.
  • FIG. 2 is a phase diagram illustrating the cycle of the refrigerant present in the refrigeration system 10 of Fig. 1.
  • Reference numerals 1-5 indicate specific points in the refrigeration system. These points are also marked, using corresponding reference numerals, in Fig. 1.
  • the refrigerant passes the heat exchanger 15 in the direction from the second condenser 14 towards the expansion element 16. It is clear from Fig. 2 that this has the consequence that the temperature of the refrigerant decreases and the energy (enthalpy) decreases.
  • the curve defining the boundary between liquid phase and two phase is followed until point 2 is reached.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Devices That Are Associated With Refrigeration Equipment (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

L'invention concerne un réfrigérant destiné à une utilisation dans un système de réfrigération. Le réfrigérant comprend un gaz mixte d'au moins trois hydrocarbures différents, comprenant de l'isobutane (C4H10), de l'éthène (C2H4) et du méthane (CH4). Le gaz mixte comprend au moins 70 % en poids d'isobutane (C4H10). En utilisant le réfrigérant, il est possible d'obtenir des températures de réfrigération basses, par exemple inférieures à -79 °C, sans nécessiter un système de réfrigération en cascade et sans nécessiter l'application d'un hydrofluorure au réfrigérant. Ainsi le réfrigérant est respectueux de l'environnement et l'énergie se conserve durant le processus de réfrigération. L'invention concerne en outre un système de réfrigération conçu pour présenter un chemin réfrigérant rempli du réfrigérant.
PCT/EP2007/055617 2006-06-15 2007-06-07 Réfrigérant et système de réfrigération WO2007144306A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2009514759A JP2009540262A (ja) 2006-06-15 2007-06-07 冷媒および冷凍システム
DKPA200801842A DK177364B1 (da) 2006-06-15 2008-12-29 Et kølemiddel og et kølesystem

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06012342 2006-06-15
EP06012342.9 2006-06-15

Publications (1)

Publication Number Publication Date
WO2007144306A1 true WO2007144306A1 (fr) 2007-12-21

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Application Number Title Priority Date Filing Date
PCT/EP2007/055617 WO2007144306A1 (fr) 2006-06-15 2007-06-07 Réfrigérant et système de réfrigération

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Country Link
JP (1) JP2009540262A (fr)
DK (1) DK177364B1 (fr)
TW (1) TW200817644A (fr)
WO (1) WO2007144306A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011150940A1 (fr) * 2010-06-03 2011-12-08 Arctiko A/S Système de refroidissement et mélange non azéotrope de fluides frigorigènes constitué de fluides frigorigènes respectueux de l'environnement

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116606632B (zh) * 2023-07-19 2023-10-20 中科美菱低温科技股份有限公司 制冷剂

Citations (7)

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Publication number Priority date Publication date Assignee Title
US5430223A (en) * 1991-08-19 1995-07-04 Linde Aktiengesellschaft Process for separating higher hydrocarbons from a gas mixture
WO1997020902A1 (fr) * 1995-12-01 1997-06-12 Gary Lindgren Melange refrigerant ameliore et son procede d'utilisation dans des systemes de refrigeration
CN1448677A (zh) * 2003-04-03 2003-10-15 上海交通大学 单级压缩冷藏低温箱
WO2004083752A1 (fr) * 2003-03-18 2004-09-30 Air Products And Chemicals, Inc. Processus de refrigeration integre et a boucles multiples pour liquefier les gaz
EP1514915A1 (fr) * 2003-09-09 2005-03-16 A.S. Trust & Holdings Inc. Composition d'hydrocarbures et réfrigérant et détergent la contenant
US20060065013A1 (en) * 2002-12-03 2006-03-30 Susumu Kurita Refrigerator system using non-azeotropic refrigerant, and non-azeotropic refrigerant for very low temperature used for the system
US20060075775A1 (en) * 2004-10-07 2006-04-13 Mikhail Boiarski Efficient heat exchanger for refrigeration process

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5430223A (en) * 1991-08-19 1995-07-04 Linde Aktiengesellschaft Process for separating higher hydrocarbons from a gas mixture
WO1997020902A1 (fr) * 1995-12-01 1997-06-12 Gary Lindgren Melange refrigerant ameliore et son procede d'utilisation dans des systemes de refrigeration
US20060065013A1 (en) * 2002-12-03 2006-03-30 Susumu Kurita Refrigerator system using non-azeotropic refrigerant, and non-azeotropic refrigerant for very low temperature used for the system
WO2004083752A1 (fr) * 2003-03-18 2004-09-30 Air Products And Chemicals, Inc. Processus de refrigeration integre et a boucles multiples pour liquefier les gaz
CN1448677A (zh) * 2003-04-03 2003-10-15 上海交通大学 单级压缩冷藏低温箱
EP1514915A1 (fr) * 2003-09-09 2005-03-16 A.S. Trust & Holdings Inc. Composition d'hydrocarbures et réfrigérant et détergent la contenant
US20060075775A1 (en) * 2004-10-07 2006-04-13 Mikhail Boiarski Efficient heat exchanger for refrigeration process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200404, Derwent World Patents Index; AN 2004-036055, XP002404993 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011150940A1 (fr) * 2010-06-03 2011-12-08 Arctiko A/S Système de refroidissement et mélange non azéotrope de fluides frigorigènes constitué de fluides frigorigènes respectueux de l'environnement

Also Published As

Publication number Publication date
TW200817644A (en) 2008-04-16
JP2009540262A (ja) 2009-11-19
DK200801842A (da) 2008-12-29
DK177364B1 (da) 2013-02-18

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