EP2510069A1 - Fluide de travail pour machine frigorifique à absorption - Google Patents
Fluide de travail pour machine frigorifique à absorptionInfo
- Publication number
- EP2510069A1 EP2510069A1 EP10784762A EP10784762A EP2510069A1 EP 2510069 A1 EP2510069 A1 EP 2510069A1 EP 10784762 A EP10784762 A EP 10784762A EP 10784762 A EP10784762 A EP 10784762A EP 2510069 A1 EP2510069 A1 EP 2510069A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- working medium
- ionic liquid
- lithium bromide
- carbon atoms
- water
- 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.)
- Withdrawn
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
-
- 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
- F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type
- F25B15/10—Sorption machines, plants or systems, operating continuously, e.g. absorption type with inert gas
-
- 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
- F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type
- F25B15/02—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas
- F25B15/06—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas the refrigerant being water vapour evaporated from a salt solution, e.g. lithium bromide
Definitions
- the invention is directed to a working medium for an absorption chiller with reduced friction.
- Refrigerant the evaporator and the condenser of a classic chiller nor a sorbent, an absorber and a desorber.
- the vaporized refrigerant is absorbed at the pressure of evaporation in the sorbent and then desorbed in the desorber at the higher pressure of the condensation by supplying heat back from the sorbent.
- Sorbent requires less mechanical energy than the compression of the refrigerant vapor in a classic chiller, in place of the consumption of mechanical energy occurs for the desorption of the refrigerant
- Absorption chillers use a working medium that uses water as a refrigerant and lithium bromide as
- Working medium can come.
- a working medium of water and lithium bromide also acts corrosive to many materials and causes high friction and thus accelerated wear on moving parts of the
- Example VII a describes in Example VII a) the use of the ionic liquids 1-ethyl-3-methylimidazoliummethylsulfonat, 1-ethyl-3-methylimidazoliumacetat, and 1-ethyl-3-methylimidazoliumhydroxid as additives for a
- Lithium bromide an increased coefficient of friction, so that they can not solve the problem of high friction.
- Lithium bromide is selected in a suitable range.
- the invention therefore relates to a working medium for an absorption chiller comprising 5 to 30 wt .-% water and 65 to 95 wt .-% of a sorbent consisting of lithium bromide and at least one ionic liquid, wherein the sorbent ionic liquid and lithium bromide in a weight ratio from 0.5: 1 to 5: 1.
- the invention is also a
- Absorption chiller containing an absorber, a
- Desorber an evaporator, a condenser, a
- the working medium according to the invention comprises from 5 to 30% by weight of water and from 65 to 95% by weight of a sorbent consisting of lithium bromide and at least one ionic liquid.
- a sorbent consisting of lithium bromide and at least one ionic liquid.
- Water. water and Sorbents taken together are preferably more than 90% by weight of the working medium, and more particularly
- the sorbent of the working medium according to the invention consists of lithium bromide and at least one ionic liquid.
- ionic liquid refers to a salt or a mixture of salts of anions and cations, wherein the salt or the mixture of salts has a melting point of less than 100 ° C.
- ionic liquid refers to salts or mixtures of salts free of nonionic substances or additives.
- the ionic liquid refers to salts or mixtures of salts free of nonionic substances or additives.
- the ionic liquid refers to a salt or a mixture of salts of anions and cations, wherein the salt or the mixture of salts has a melting point of less than 100 ° C.
- ionic liquid refers to salts or mixtures of salts free of nonionic substances or additives.
- the ionic liquid preferably, the ionic
- Liquid of one or more salts of organic cations with organic or inorganic anions Liquid of one or more salts of organic cations with organic or inorganic anions.
- Particularly suitable organic cations are cations of the general formulas (I) to (V): R R N * (I)
- R X , R 2 , R 3 , R 4 are the same or different and
- Hydrogen a linear or branched aliphatic or olefinic hydrocarbon radical having 1 to 30
- Carbon atoms an aromatic hydrocarbon radical having from 6 to 40 carbon atoms, an alkylaryl radical having from 7 to 40 carbon atoms, a radical represented by one or more groups -O-, -NH-, -NR'-, -OC (O) -, - (O) CO-, -NH- C (O) -, - (O) C -NH-, - (CH 3 ) NC (O) -, - (O) CN (CH 3 ) -, -S (O 2 ) -O-,
- R ' is an aliphatic or olefinic
- Hydrocarbon radical having 1 to 30 carbon atoms
- R 5 is a linear or branched hydrocarbon radical containing 2 to 4 carbon atoms, n is from 1 to 200, preferably from 2 to 60,
- R 6 is hydrogen, a linear or branched aliphatic or olefinic hydrocarbon radical having 1 to 30
- Carbon atoms an aromatic hydrocarbon radical having 6 to 40 carbon atoms, an alkylaryl radical having 7 to 40 carbon atoms or a radical -C (O) -R 7 ,
- R 7 is a linear or branched aliphatic or olefinic hydrocarbon radical having 1 to 30
- Carbon atoms an aromatic hydrocarbon radical having 6 to 40 carbon atoms or an alkylaryl radical having 7 to 40 carbon atoms, wherein at least one and preferably each of R, R 2 , R 3 and R 4 is other than hydrogen.
- heteroaromatic cations having at least one quaternary nitrogen atom in the ring, which carries a radical R 1 as defined above, preferably substituted on the nitrogen atom derivatives of pyrrole, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyrazine, indole , Quinoline, isoquinoline, cinnoline, quinoxaline or phthalazine.
- R a OS03 are ⁇ , R a S0 3 ", R a OP0 3 2" (R a O) 2 P0 2 ", R a P0 3 2", R a COO "(R a CO ) 2 N " ,
- the ionic liquid comprises one or more 1,3-dialkylimidazolium salts, the alkyl groups being particularly preferably selected independently of one another from methyl, ethyl, n-propyl, n-butyl and n-hexyl. Particularly preferred ionic
- Liquids are salts of one or more of
- the ionic liquid comprises one or more quaternary
- R 1 is an alkyl radical having 1 to 20 carbon atoms
- R 2 is an alkyl radical having 1 to 4 carbon atoms
- R 4 is an alkyl radical having 1 to 4 carbon atoms or a radical (CH 2 CHRO) n -H where n is from 1 to 200 and R is H or CH 3 .
- ionic liquids are used which are immiscible with water, stable to hydrolysis and thermally stable up to a temperature of 150 ° C.
- the sorbent of the working medium according to the invention contains ionic liquid and lithium bromide in a weight ratio of 0.5: 1 to 5: 1.
- the weight ratio of 0.5: 1 to 2: 1 and more preferably from 1: 1 to 2: 1.
- Lithium bromide in the sorbent chosen so that the
- Working medium of 30 wt .-% remains single phase.
- Particularly preferred is the ionic liquid and the
- Lithium bromide in the sorbent chosen so that the working medium in a desorption of water to a water content in the working medium of 5 wt .-% and at an absorption of water to a water content in the
- the working medium may contain other additives besides the sorbent and water.
- the working medium contains as additive nor one or more corrosion inhibitors. It can all from the prior art than for in the
- Absorption chiller used materials suitably known, non-volatile corrosion inhibitors can be used. Further preferred additives are wetting-requiring
- Additives which can be used in an amount of 0.01 to 10 wt .-% based on the working medium.
- An absorption refrigeration machine comprises an absorber, a desorber, an evaporator, a condenser, a circulation pump and a circulating pump with absorber and desorber with the circulating pump
- Composition has.
- the working media of the invention show a clear compared to the known from the prior art working media of water and lithium bromide, and water, lithium bromide and 1-butyl-3-methylimidazoliumbromid
- the working media according to the invention thus enable the use of pumps whose bearings are in contact with the
- the working media according to the invention can be used not only in absorption chillers in which the absorption of heat by the coolant in the evaporator is used for cooling, but can also in
- Absorption heat pumps are used, in which the i absorber and released in the condenser heat is used for heating.
- Diameter as friction partners both made of polished stainless steel 1.3505 with a surface roughness of 0.01 ym, with a force of 30 N, a contact pressure of 947.8 MPa and a sliding-roll ratio of 50%.
- Table 1 summarizes the composition of the working media tested in Examples 1 to 6.
- Example 1 is a working medium of water
- Lithium bromide without a proportion of ionic liquid as used in commercially available absorption chillers.
- Examples 2 and 3 are working media according to the prior art of K.-S. Kim et al. , in Korean J. Chem. Eng., 23 (2006) 113-116, with a weight ratio of
- Examples 4 to 6 are working media according to the invention with 1-butyl-3-methylimidazolium bromide as ionic liquid.
- composition of the investigated working media Composition of the investigated working media
- Fig. 1 the Stribeck curve (friction coefficient ⁇ against velocity difference v between the friction surfaces in mm / s) is plotted at 40 ° C for the working media of Examples 1 to 3 (Example 1: empty circles;
- Example 2 empty triangles
- Example 3 empty squares
- Fig. 2 shows the corresponding Stribeck curves at 70 ° C.
- FIG. 3 the Stribeck curve (coefficient of friction ⁇ against velocity difference v between the friction surfaces in mm / s) at 40 ° C. is plotted for the working media of Examples 3 to 6 (Example 3: empty squares, Example 4: filled circles, Example 5: filled triangles, Example 6: stars).
- Fig. 4 shows the corresponding
- Fig. 5 is for the working media of Examples 1, 7 and 8, the Stribeck curve (friction coefficient ⁇ against
- Example 7 filled squares
- Example 8 filled
- Fig. 6 shows the corresponding Stribeck curves at 70 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (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)
- Sorption Type Refrigeration Machines (AREA)
- Lubricants (AREA)
Abstract
La présente invention concerne un milieu de travail destiné à machine frigorifique à absorption. Ce fluide est constitué d'eau, représentant de 5% à 30% de son poids, et d'un sorbant, lui-même constitué de bromure de lithium et d'un liquide ionique. Dans le sorbant, le rapport pondéral entre liquide ionique et bromure de lithium se situe dans une plage allant de 0,5:1 à 5:1. Ce fluide de travail présente un coefficient de frottement réduit par rapport à un fluide de travail fait d'eau et de bromure de lithium.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102009047564A DE102009047564A1 (de) | 2009-12-07 | 2009-12-07 | Arbeitsmedium für eine Absorptionskältemaschine |
PCT/EP2010/068090 WO2011069822A1 (fr) | 2009-12-07 | 2010-11-24 | Fluide de travail pour machine frigorifique à absorption |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2510069A1 true EP2510069A1 (fr) | 2012-10-17 |
Family
ID=43602756
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10784762A Withdrawn EP2510069A1 (fr) | 2009-12-07 | 2010-11-24 | Fluide de travail pour machine frigorifique à absorption |
Country Status (13)
Country | Link |
---|---|
US (1) | US8696928B2 (fr) |
EP (1) | EP2510069A1 (fr) |
JP (1) | JP5479611B2 (fr) |
KR (1) | KR20120120161A (fr) |
CN (1) | CN102639667A (fr) |
AU (1) | AU2010330188A1 (fr) |
BR (1) | BR112012013583A2 (fr) |
CA (1) | CA2783679A1 (fr) |
DE (1) | DE102009047564A1 (fr) |
RU (1) | RU2012131105A (fr) |
SG (1) | SG181463A1 (fr) |
WO (1) | WO2011069822A1 (fr) |
ZA (1) | ZA201204139B (fr) |
Families Citing this family (29)
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EP2088389B1 (fr) * | 2008-02-05 | 2017-05-10 | Evonik Degussa GmbH | Machine de refroidissement à absorption |
EP2087930A1 (fr) * | 2008-02-05 | 2009-08-12 | Evonik Degussa GmbH | Procédé d'absorption d'une matière volatile dans un produit d'absorption liquide |
DE102009000543A1 (de) | 2009-02-02 | 2010-08-12 | Evonik Degussa Gmbh | Verfahren, Absorptionsmedien und Vorrichtung zur Absorption von CO2 aus Gasmischungen |
EP2638123B1 (fr) * | 2010-11-08 | 2016-08-31 | Evonik Degussa GmbH | Fluide de travail pour pompes à chaleur à absorption |
DE102011077377A1 (de) | 2010-11-12 | 2012-05-16 | Evonik Degussa Gmbh | Verfahren zur Absorption von sauren Gasen aus Gasmischungen |
WO2013072147A1 (fr) | 2011-11-14 | 2013-05-23 | Evonik Degussa Gmbh | Procédé et dispositif servant à séparer des gaz acides à partir d'un mélange gazeux |
DE102012200907A1 (de) | 2012-01-23 | 2013-07-25 | Evonik Industries Ag | Verfahren und Absorptionsmedium zur Absorption von CO2 aus einer Gasmischung |
DE102012207509A1 (de) | 2012-05-07 | 2013-11-07 | Evonik Degussa Gmbh | Verfahren zur Absorption von CO2 aus einer Gasmischung |
EP2735820A1 (fr) * | 2012-11-21 | 2014-05-28 | Evonik Industries AG | Pompe à chaleur à absorption et sorbant pour une pompe à chaleur à absorption comprenant de l'acide méthanosulfonique |
JP6655063B2 (ja) * | 2015-03-20 | 2020-02-26 | 国立大学法人東京農工大学 | 吸収冷凍機および除湿機 |
DE102015004266A1 (de) | 2015-04-01 | 2016-10-06 | Hans-Jürgen Maaß | Verfahren und Vorrichtung zur Speicherung von Energie zur Wärme-und Kälteerzeugung mit Salzschmelzen |
DE102015212749A1 (de) | 2015-07-08 | 2017-01-12 | Evonik Degussa Gmbh | Verfahren zur Entfeuchtung von feuchten Gasgemischen |
CN105400496A (zh) * | 2015-11-30 | 2016-03-16 | 中国科学院青海盐湖研究所 | 一种离子液体基相变储能材料及其制备方法 |
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US10168080B2 (en) * | 2016-05-26 | 2019-01-01 | Yazaki Corporation | Eutectic mixtures of ionic liquids in absorption chillers |
DE102016210481B3 (de) | 2016-06-14 | 2017-06-08 | Evonik Degussa Gmbh | Verfahren zum Reinigen einer ionischen Flüssigkeit |
DE102016210484A1 (de) | 2016-06-14 | 2017-12-14 | Evonik Degussa Gmbh | Verfahren zur Entfeuchtung von feuchten Gasgemischen |
DE102016210483A1 (de) | 2016-06-14 | 2017-12-14 | Evonik Degussa Gmbh | Verfahren und Absorptionsmittel zur Entfeuchtung von feuchten Gasgemischen |
EP3257843A1 (fr) | 2016-06-14 | 2017-12-20 | Evonik Degussa GmbH | Procédé pour préparer un sel tres pur d'imidazolium |
DE102016210478A1 (de) | 2016-06-14 | 2017-12-14 | Evonik Degussa Gmbh | Verfahren zur Entfeuchtung von feuchten Gasgemischen |
EP3257568B1 (fr) | 2016-06-14 | 2019-09-18 | Evonik Degussa GmbH | Procede de deshumidification de melanges gazeux humides par des liquides ioniques |
CN107163917A (zh) * | 2017-06-20 | 2017-09-15 | 大连理工大学 | 离子液体溶液基纳米流体直接吸收太阳能空调/热泵方法和装置 |
JP6444556B1 (ja) * | 2018-05-25 | 2018-12-26 | 株式会社日立パワーソリューションズ | 吸収冷温水機、吸収冷温水機用追加液、吸収冷温水機用吸収液及びメンテナンス方法 |
WO2020114576A1 (fr) | 2018-12-04 | 2020-06-11 | Evonik Operations Gmbh | Processus pour déshumidifier des mélanges de gaz humides |
JP7189322B2 (ja) | 2019-01-15 | 2022-12-13 | 矢崎総業株式会社 | 吸収式冷凍機における吸収剤として使用するためのイオン液体添加剤 |
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2009
- 2009-12-07 DE DE102009047564A patent/DE102009047564A1/de not_active Withdrawn
-
2010
- 2010-11-24 AU AU2010330188A patent/AU2010330188A1/en not_active Abandoned
- 2010-11-24 EP EP10784762A patent/EP2510069A1/fr not_active Withdrawn
- 2010-11-24 CA CA2783679A patent/CA2783679A1/fr not_active Abandoned
- 2010-11-24 US US13/514,167 patent/US8696928B2/en not_active Expired - Fee Related
- 2010-11-24 CN CN2010800552986A patent/CN102639667A/zh active Pending
- 2010-11-24 SG SG2012040317A patent/SG181463A1/en unknown
- 2010-11-24 WO PCT/EP2010/068090 patent/WO2011069822A1/fr active Application Filing
- 2010-11-24 KR KR1020127014563A patent/KR20120120161A/ko not_active Application Discontinuation
- 2010-11-24 RU RU2012131105/05A patent/RU2012131105A/ru not_active Application Discontinuation
- 2010-11-24 BR BR112012013583A patent/BR112012013583A2/pt not_active IP Right Cessation
- 2010-11-24 JP JP2012542440A patent/JP5479611B2/ja not_active Expired - Fee Related
-
2012
- 2012-06-06 ZA ZA2012/04139A patent/ZA201204139B/en unknown
Non-Patent Citations (1)
Title |
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See references of WO2011069822A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP5479611B2 (ja) | 2014-04-23 |
CN102639667A (zh) | 2012-08-15 |
RU2012131105A (ru) | 2014-04-10 |
AU2010330188A1 (en) | 2012-05-31 |
WO2011069822A1 (fr) | 2011-06-16 |
JP2013513002A (ja) | 2013-04-18 |
US8696928B2 (en) | 2014-04-15 |
US20120247144A1 (en) | 2012-10-04 |
ZA201204139B (en) | 2013-02-27 |
CA2783679A1 (fr) | 2011-06-16 |
KR20120120161A (ko) | 2012-11-01 |
BR112012013583A2 (pt) | 2016-07-05 |
SG181463A1 (en) | 2012-07-30 |
DE102009047564A1 (de) | 2011-06-09 |
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