`Description
`
`
`
`
`
`
`
`
`
`'¥"NARY Rid: R
`GfiRAl NG ABBARAlUS
`
`Technical Field
`
`[0001]
`
`
`The present invention relates to a binary refrigerating
`
`
`apparatus including a refrig
`
`invention more particularly
`
`10
`
`composition that has a small
`
`erant mixture. The present
`
`
`re'ates to: a refrigerant
`
`
` global—warming potential
`
`
`
`
`(hereinafter, referred to as
`
`
`be used as a refrigerant cap
`
`
`
`a GWP)
`
`to be earth friendly, can
`
`
`able of achieving a low
`
`
`
`
`temperature of —80°C, and is
`
`
`excellent in refrigerating
`
`
`capacity and other performan
`
`15
`
`apparatus that includes the
`
`
`
`ce; and a binary refrigerating
`
`
`refrigerant composition and can
`
`
`
`actually achieve low tempera
`
`ture.
`
` Background Art
`
`[0002]
`
`20
`
`Conventionally used re
`
`include a non—azeotropic mix
`
`
`
`
`frigerants for refrigerators
`
`
`
`
`
` :ure (R4073) o di’luoromethane
`
`
`
`(132)
`
`
`
`/ pentaf'uoroethane (R125)
`
`
`l,l,l,2—tetrafluoroethane
`
`/
`
`(
`
`5 /
`
`5 / 70% by mass) and a non—azeotropic mixture
`
`
`
`(RlB-a)
`
`
`
`25
`
`
`
`
`
`(R40—A) of pentafluoroethane
`
`
`(Rl43a)/l,l,l,2—,etrafluoroethane (Rl34a)
`
`
`
`,l,l—trifluoroethane
`(R125)/
`
`
`
`(44/52/4% by mass).
`
`
`
`The boili
`
`
`
`point of
`
`
`qg point of
`
`
`R4073 is about —39°
`
`C, and the boiling
`
`and these are suitable for known
`
`R404A is about —46°C,
`
`refrigerating apparatuses.
`
`Furthermore,
`
`even when a compressor
`
`
`
`
`
`inlet temperature is relatively high,
`
`an outlet temperature
`
`does not increase to a degree that oil sludge is caused in a
`
`compressor.
`
`However,
`
`
`R404A has a relatively high GWP of 3920.
`
`[0003]
`
`On
`
`the other hand,
`
`
`range of
`
`—80°C or lower, R508A (an a7eotropic mixture 0'
`
`
`for obtaining a lower temperatire
`
`H
`
`10
`
`trifluorome'
`
` boiling poi
`
`low tempera
`
`[0004]
`
`
`
`:hane 123
`
`
`and hexafluoroethane Rll6)
`
`is used. The
`
`H
`
`qt 0; R508A is —85.7°C,
`
`and suitable
`
`
`for obtaining
`
`
`
`:ure.
`
`However,
`
`the above—described re:
`
`
`
`frigerants each have a
`
`15
`
`physical property that the global—warming potential
`
`(the GWP
`
`
`
`value)
`
`is extraordinarily high.
`
`This re
`
`composition i
`
`
`
`frigerant composition is er
`
`
`:her a re'
`
`Zrigerant
`
`
`
`qcluding an azeotropic mixtire (R508A, boiling
`
`
`
`
`point: —85.7°C) of 39% by weight 0’ tri"'
`
`uoromethane
`
`(R23)
`
`2O
`
`having a ra
`
`
`hexafluoroe
`
` :hane
`
`:her high speci:
`
`H
`
`fic heat ratio and 61% by weight or
`
`
`
`(R116)
`
`having a rather low speci:
`
`
`fic heat
`
`
`ratio, or a re'
`
`=rigerant composition including a mixture of
`
`this a7eotropic mixture and n—pentane or propane that is mixed
`
`
`
`in a ratio 0' :
`
`l4% or
`
`
`less with respect to a total weight of
`
`25
`
`
`
`trifluoromethane and hexafluoroethane.
`
`This re:
`
`
`
`Erigerant
`
`
`
`
`
`composition can achieve a low temperature 0:
`
`
`
`—80°C.
`
`[0005]
`
`However,
`
`
`the above—described R508A has a high GWP of
`
`l3200,
`
`which has been a problem.
`
`Carbon dioxide
`
`(R744)
`
`has a small GWP o
`
`f l,
`
`
`
`Jr due
`
`but
`
`has a
`
`
`
`problem that oil deteriora
`
`increase in pressure and o
`
`itlet temperatur
`
`
`
`:ion and sludge occ
`
`
`Th r for
`
`are proposed: a
`
`re
`
`
`frigeran:
`
`mixture in which carbohydrates
`
`such as propane,
`
`c
`
`yclopropane,
`
`isobu
`
`:ene,
`
`and butane are added
`
`10
`
`to carbon
`
`dioxide
`
`
`in a ratio 0:
`
`abou:
`
`30 to 70%
`
` of
`
`the whole;
`
`
`
`
`and a refrigera
`
`:ion cycle apparatus including the re:
`
`
`
`Erigerant
`
`mixture (see Pa
`
`:ent Literature 1).
`
`
`
`Furthermore,
`
`there are proposed: a
`
`re
`
`
`frigerant mixture
`
`containing isobutane in a ratio 0:
`
`
`
`f 40 to 60%
`
`and
`
`
`
`15
`
`tri
`
`fluoromethane (
`
`R23)
`
`as the remainder
`
`(see Patent Literature
`
`2);
`
`
`a refrigerant
`
`
`of 65%
`
`or
`
`more to
`
`mixture in which propane is mixed in a ratio
`
`
`
`di
`’iuoromethane and
`a mixture 0
`
`
`pentafluoroethane
`
`(see Patent Literature 3);
`
`and the like.
`
`20
`
`Citation List
`
`
`
` Pa,ent Li cerature
`
`[0006]
`
`Patent Literature 1:
`
`Japanese Patent Application Laid—
`
`Open No.
`
`2005—15633
`
`25
`
`Patent Literature 2:
`
`Japanese Patent NO .
`
`5009530
`
`
`
`Patent Literature 3: Japanese Patent No. 4085897
`
`I]
`
` "nvention
`
`Summary 0'
`
`Technical Problem
`
`[0007]
`
`The above—described prior art contains carbohydrates such
`
`as propane, which are combustible,
`
`
`in an amount of about 30 to
`
`
`70% with respect to the whole refrigerant, and thus has a risk
`
`
`of explosion.
`
`
`
`
`An object of tie present invention is to provide a binary
`
`
`
`refrigerating apparatus employing a refrigerant composition
`
`that solves the existing problems, and that has a small GWP to
`
`
`
`
`
`be earth friendly. The refrigerant composition is a
`
`
`refrigerant mixture that has a high COP, does not cause oil
`
`deterioration and sludge, can return an oil to a compressor
`
`I]
`
`using n—pentane or propane as an oil carrier, has no risk or
`
`
`explosion, can achieve a low temperature of —80°C, and is
`
`excellent
`
`
`
`in refrigerating capacity and other performance.
`
`20
`
`Solution to Problem
`
`[0008]
`
`For solving the above—described problems,
`
`the inventor
`
`
`
`
`has conducted extensive studies, and foand that the problems
`
`can be solved by using: as a refrigerant to be filled in a
`
`25
`
`
`
`
`
`low—temperature—side refrigerant circuit, a miXture of a non—
`
`
`
`
`
`
`
`
`
`
`
`
`a7eotropic mixture in which 20% by mass or less of
`
`carbon
`
`dioxide
`
`(R744)
`
`
`is mixed to di"'
`uoroethylene
`
`(RllBZa)
`
`or a HOD—
`
`
`
`
`6
`is Fur
`cher added to achieve
`a7eotropic mixture in whicq R
`
`
`
`
`a mixture or a
`
`non—combustible composition and a prede
`
`:ermined amoun
`
`: or less
`
` of n—pentane
`
`or propane; and,
`
`
`as a refrigerant to be
`
`
`Sil—
`ed in
`
`a high—temperature—side re'
`
`=rigerant circuit,
`
` re
`
`frigerant mixture of
`
`
`R4073 or an R404A alternative having a
`
`GWP of
`
`1500 or less and a predetermined amount or less of
`
`n—
`
`invention has been accomplisted.
`
`
`
`pentane.
`
`Thus,
`
`the present
`
`10
`
`[0009]
`
`An invention according to claim 1
`
`
`
`to solve the above—
`
`
`
`described problems is a binary re:
`
`frigerating apparatus
`
`
`including a high—temperature—side re'
`
`=rigeration circuit and a
`
`
`low—temperature—side re'
`
`:rigeration circuit,
`
`which achieves a
`
`15
`
`re
`
`
`frigerating capacity 0:
`
`—80°C or lower by condensing a
`
`re
`
`
`frigerant in the low—temperature—side retrigeration
`
`circuit
`
`wi
`
`
`:h a refrigerant passing through a cascade condenser in the
`
`
`high—temperature—side re'
`
`:rigeration circuit,
`
`wherein a
`
` re
`
`fluoroethylene (
`frigerant composition containing di:
`
`20
`
`
`and hexafluoroethane
`
`(Ril6)
`
`
`is used as the refrigeran
`
`
`
`RllBZa)
`
`:
`
`in the
`
`1 qan both
`
`low—temperat
`
`evaporation
`
`boiling poin
`
`
`hexafluoroet
`
`25
`
`[0010]
`
`Jre—side retrigeration circur
`
`temperature reaches a tempera
`
`
`F di
`
`,s o
`
`"iuoroethylene
`
`
`
`qane (Rli6).
`
`
`
`:,
`
`so that a
`
` :ure lower t
`
`(RllBZa)
`
`and
`
`
`
`An invention according to claim 2 is a binary
`
`refrigerating apparatus comprising a high—temperature—side
`
`
`
`
`
`
`
`
`refrigeration circuit and a low—temperature—side refrigeration
`
`
`circuit, which achieves a refrigerating capacity of —80°C or
`
`
`
`lower by condensing a refrigerant in the low—temperature—side
`
`
`
`refrigeration circuit with a refrigerant passing through a
`
`
`
`cascade condenser in the high—temperature—side refrigeration
`
`
`
`
`
`circuit, wherein a refrigerant composition containing
`
`
`difluoroethylene (R1132a) and more than 0% by mass and 20% by
`
`10
`
`
`mass or less of carbon dioxide (R744)
`
`is used as the
`
`
`
`refrigerant in the low—temperature—side refrigeration circuit,
`
`so that an evaporation temperature reaches a temperature lower
`
`
`
`than both boiling points 0’ di’luoroethylene (R1132a) and
`
`
`
`
`
`
`carbon dioxide (R744).
`
`15
`
`[0011]
`
`An invention according to claim 3 is the binary
`
`refrigerating apparatus according to claim 1, wherein a
`
`
`further mixed is used as the refrigerant in the low—
`
`is
`
`20
`
`25
`
` refrigerant composition in which carbon dioxide (R744)
`
`
`
`
`
`temperature—side refrigeration circuit,
`
`so that an evaporation
`
`temperature reaches a temperature lower than any boiling
`
`
`
`
`
`points 0’ di’luoroethylene (R1132a), hexafluoroethane (R116),
`
`and carbon dioxide (R744).
`
`[0012]
`
`An invention according to claim 4 is the binary
`
`
`
`
`refrigerating apparatus according to claim 2, wherein
`
`hexaf1uoroethane (R116)
`
`is
`
`
`
`th Low t mp ratur
`
`sid r
`
`
`further mixed as the refrigerant in
`
` frigeration circuit.
`
`[0013]
`
`An invention according to claim 5 is the binary
`
`refrigerating apparatus according to claim 4, wherein a
`
`
`refrigerant composition in which dif1uoroethy1ene (R1132a)
`
`/
`
`
`hexaf1uoroethane (R116)
`
`/ carbon dioxide (R744) = 27.6 to
`
`
`
`
`
`29.2% by mass / 56.8
`
`10
`
`are mixed is used as
`
` :he re:
`
`:o 68.4% by mass / 4.0 to 14.0% by mass
`
`
`
`Erigerant
`
`in the low—temperature—
`
`
`side refrigeration circuit.
`
`[0014]
`
`An invention according to claim 6 is the binary
`
`refrigerating apparatus according to claim 4, wherein a
`
`
`
`
`refrigerant composition in which dif1uoroethy1ene (R1132a)
`
`/
`
`
`hexaf1uoroethane (R116)
`
`/ carbon dioxide (R744) = 54.8 to
`
`58.3% by mass / 25.2
`
`are mixed is used as
`
` :he re:
`
`:o 35.7% by mass / 8.0 to 18.0% by mass
`
`
`
`Erigerant
`
`in the low—temperature—
`
`
`
`
`side refrigeration circuit.
`
`20
`
`[0015]
`
`An invention according to claim 7 is the binary
`
`
`refrigerating appara
`
`
`:us according to any one of claims 1
`
`to 6,
`
`
`
`wherein a refrigeran
`
`
`in a ratio 0'
`
`
`
`
`
`15
`
`25
`
`composition in which n—peqtane is mixed
`
`
`4% by mass or less with respect
`
`so the ,otal
`
`
`
`
`
`mass of the refrigerant composition in th low : mp ra:ur
`
`
`
`
`side refrigeration circuit is used.
`
`[0016]
`
`An invention according to claim 8 is the binary
`
` re
`
`frigerating appara:us according to any one of
`
`claims 1
`
`to 6,
`
`
`wherein a refrigeran
`I]
`
`
`mixed in a ratio 0'
`
`
`
`composition in which propane
`
`(R290)
`
`is
`
`4% by mass or less with respect to the
`
`:ion in the low—
`
` Erigerant composi
`
`
`
`total mass of
`
`the re:
`
` temperature—side re
`
`
`
`=rigeration circui:
`
`is used.
`
`[0017]
`
`An invention according to claim 9 is the binary
`
` re
`frigerating appara
`
`
`:us according to any one of
`
`claims 1
`
`to 8,
`
`
`wherein a refrigera
`
`mixture comprising
`
`composition,
`
`
`1e refrigerant
`
`containing a
`
`
` _ d15—
`uoromethane
`
`group o
`
`
`
`pentaf'uoroe
`
`(132),
`
` (1134a), and
`
`
`
`
`
`,1,3—
`
`(R125),
`
`1,1,
`
`
`",2—tetraf'
`
`
` (R143a), and
`
`non—azeotropic
`
` uoroethane
`
`1,1,1,2,3—
`
`T qane
` ri ’iuoroethane
`
`pentafluoropentene
`
`(HFO—1234ze),
`
`and having a Global—warming
`
`potential
`
`(GWP) of
`
`1500 or less,
`
`is used as the
`
`
`refrigerant in
`
`
`
`
`the high—temperature—side re'
`
`=rigeration circuit.
`
`[0018]
`
`binary
`
`claims 1
`
`to 8,
`
`non—azeotropic
`
`containing a
`
`
`
`uoromethane
`_ d15—
`
`group o
`
`
`
` (R143a), and 1, 1,1,2—
`
`a
`
`
`refrigerating appar
`
`
`wherein a refrigera
`
`mixture comprising
`
`
`
`pentaf'uoroe
`
`(132),
`
` (1134a), and
`
`
`
`T qane
`
`
`
`ri ’iuoroethane
`
`,1,3—
`
`composition,
`
`
`1e refrigerant
`
`An invention according to claim 10 is the
`I]
`
`:us according to any one or
`
`(R125),
`
`1,1,
`
`
`",2—tetraf' uoroethane
`
`10
`
`15
`
`20
`
`25
`
`
`
`tetrafluoropentene
`
`
`(HFO—1234yf),
`
`and having a Global—warming
`
`
`
`
`
`
`
`potential
`
`(GWP) of 1500 or less,
`
`
`is used as the refrigerant in
`
`
`
`
`the high—temperatire—side refrigeration circuit.
`
`
`
`
`A
`
`
`
`’ects o
` "nvention
`
`Advantageous
`
`[0019]
`
`The invention according to claim 1 of
`
`the present
`
`
`
`invention is a binary refrigerating apparatus including a
`
`
`
`
`
`
`
`high—temperature—side refrigeration circuit
`
`and a low—
`
`10
`
`
`temperature—side refrigeration circuit,
`
`which achieves a
`
`
`
`
`refrigerating capacity 0:
`
`—80°C or lower by condensing a
`
`
`
`refrigerant in the low—temperature—side refrigeration circuit
`
`
`with a refrigerant passing through a cascade condenser in the
`
`
`
`
`high—temperature—side refrigeration circuit,
`
`and wherein a
`
`
`
`refrigerant composition containing difluoroethylene (RllB2a)
`
`
`and hexafluoroethane
`
`"16)
`
`
`is used as the refrigerant
`
`in the
`
`
`
`frigeration circuit. Since
`
`low—temperature—side re'
`I]
`
`di'" uoroethylene
`
`
`
`
`boiling point of —85.7°C,
`
`(RllBZa)
`
`
`has a small GWP of
`
`10 and a low
`
`
`the refrigerant composition has a
`
`small GWP to be earth
`
`
`friendly,
`
`and can achieve a low
`
`
`Therefore,
`
`
`
`
`
` ’ect
`in which
`a significant e
`
`
`temperature of —80°C.
`
`
`
`the COP does not decrease,
`
`oil deterioration and sludge do not
`
`15
`
`20
`
`25
`
`occur,
`
`the addition of
`
`
`
`
`caused is exerted. Also,
`and a risk of explosion is nOt
`
`
`an appropriate amount o_
`
`
`
`
`
`’ect of
`significant e
`
`
`Rll6 exerts a further
`
`solving concerns on combustibility.
`
`
`
`
`
`10
`
`Since R116 has an extraordinari:
`
`
`_y high GWP value of 12200,
`
`
`
`
`
`the added amount of
`R116 i
`s preferab'y configured
`
`to be a
`
`
`minimum for achieving non— combustion,
`
`thereby suppressing the
`
`GWP value to be low while maintaining non—combustion.
`
`[0020]
`
`The invention according to claim 2 is a binary
`
`
`
`frigerating apparatus comprising a high—temperature—side
`
`re:
`
`
`
` refrigeration circuit
`
`
`and a low—temperature—side refrigeration
`
`circuit, which achieves a
`
`
`refrigerating capacity of —80°C or
`
`
`
`lower by condensing a re:
`
`
`refrigeration circuit with
`
`Erigerant
`
`in the low—temperature—side
`
`
`a refrigerant passing
`
`through a
`
`
`
`the high—temperature—side refrigeration
`
`cascade condenser in
`
`circuit, wherein a refrigerant composition containing
`
`
`
`10
`
`15
`
`
`
`
`difluoroethylene (R1132a) and carbon dioxide (R744)
`
`is used as
`
`
`
`the refrigerant in the low—temperature—side refrigeration
`
`
`
`
`
`
`
`
`circuit. Since dif'uoroethylene (R1132a) has a small GWP of 10
`
`
`and a low boiling point of —85.7°C, and carbon dioxide (R744)
`
`
`
`has a GWP O"
`
`,
`
`
`
`
`
`the refrigerant composition has a small GWP to
`
`
`
`
`be earth friendly, and can achieve a low temperature of —80°C.
`
`20
`
`Furthermore, since carbon dioxide (R744)
`
`is added,
`
`the outlet
`
`
`
`pressure and the outlet temperature are inhibited from
`
`
`
`
`
`
`increasing. Therefore, a further signi’icant effect in which
`
`
`
`the COP does not decrease,
`
`oil deterioration and sludge do not
`
`OCCUI‘,
`
`
`and a risk of explosion is not caused is exerted.
`
`25
`
`[0021]
`
`
`
`ll
`
`The non—a7eotropic mixture in which 20% by mass or less
`
`
`is mixed to difluoroethylene (Rli32a)
`
`
`
`
`of carbon dioxide (R744)
`
`
`
`
`A2 refrigerant
`
`
`
`
`
`
`
`is used as the low—temperature—side refrigerant. R1132a is an
`I]
`
`(combustible refrigerant), and the mixture or
`
`
`
`R1132a and R744 is still an A2. refrigerant (slightly
`
`
`combustible refrigerant).
`
`To address this concern,
`
`
`the addition of R116 can solve
`
`concerns on combustibility.
`
`[0022]
`
`
`
`The invention according to claim 3 o_ the present
`
`invention is the binary refrigerating apparatus according to
`
`
`
`claim 1, wherein the use of a refrigerant composition in which
`
`
`
`
`
`carbon dioxide (R744)
`
`
`
`is further mixed as the refrigerant in
`
`
`
`th low t mp ratur
`sid r :rigeration circuit,
`
`so that an
`
`evaporation temperature reaches a temperature lower than any
`
`
`
`
`
`
`
`
`
`
`
`boiling points 0" di"luoroethylene (R1132a), hexafluoroethane
`
`(Rli6), and carbon dioxide (R744). R116 can solve concerns on
`
`
`
`combustibility while the addition of an appropriate amount of
`
`carbon dioxide (R744)
`
`
`
`
`outlet temperature "rom increasing. Therefore, a further
`
`inhibits the outlet pressure and the
`
`significant e
`
`
`
`’ect
`in which the COP does not decrease, oil
`
`
`
`
`
`deterioration and sludge do not occur, and a risk of explosion
`
`is not caused is exerted.
`
`[0023]
`
`The invention according to claim 4 is the binary
`
`10
`
`15
`
`2O
`
`25
`
`
`
`12
`
` re
`frigerating apparatus according to claim 2,
`
`wherein
`
`hexafluoroethane
`
`(R116)
`
`is
`
`
`
`
`
` further mixed as the refrig
`
`:rigeration circuit.
`
`Tre addition
`
`erant in
`
`
`sid r
`low t mp ratur
`
`
`
`th
`
` of
`
`
`an appropriate amount 0:
`
`R116 can solve concerns on
`
`combustibility.
`
`Furthermore,
`
`since carbon dioxide
`
`(R744)
`
`is
`
`added,
`
`the outle
`
`: pressure and the outlet temperature are
`
`inhibi
`
`ted :rom
`
`
`
`
`
` e ’ect
`in which
`
`increasing.
`
`
`Therefore,
`
`a
`
`
`
`
`=icant
`:urther signi'
`
`the COP does not decrease,
`
`oil deterio
`
`ration
`
` occur, and a risk 0'
`
`and sludge do no:
`
`
`: explosion is not caused
`
`10
`
`is exe
`
`rted.
`
`[0024]
`
`The invention according to claim 5 is the binary
`
`re
`
`frigerating apparatus according to claim 4,
`
`wherein
`
`a
`
` re
`
`frigerant composition in which di
`
`
`:luoroe
`
`:hylene (Rll
`
`32a)
`
`/
`
`15
`
`
`hexafluoroethane
`
`(R116)
`
`/ carbon dioxide (
`
`27.6
`
`to
`
` R744)
`
`29.2% by mass / 56.8
`
`are mixed is used as :he re:
`
`:o 68.4% by mass / 4.0 to 14.0% by mass
`
`
`
`Erigerant
`
`in the low—temperature—
`
`
`side resrigeration circuit.
`
`
`The added amount of
`
`
`hexafluoroethane
`
`(R116)
`
`is high to be non—combustible;
`
`20
`
`is as small as about 8000;
`
`80°C can be achieved.
`
`the COP does not decrease,
`
`Furthermore,
`
`and a low temperature lower than —
`
`
`a
`
`:urther e"*eco in which
`
`oil deterioration ard
`
`
`
`sludge do not
`
`occur,
`
`
`and a risk 0'
`
`: explosion is not caused is more surely
`
`exerte
`
`d.
`
`25
`
`When the
`
`
`
` formulated amounts 0 di
`’luoroethylene
`
`(R1132a)
`
`:he GWP
`
`
`
`
`
`13
`
`
`/ hexafluoroethane (R116)
`
`/ carbon dioxide
`
`(R744)
`
`
`fall within
`
`
`the ranges of
`
`27.6 to 29.2% by mass / 56.8 to 68.4% by mass /
`
`4.0 to 14.0% by mass respectively,
`
` preferably when
`
`
`difluoroethylene (R1132a)
`
`
`
`dioxide (R744) 2 28.
`
`
`
`described operation and e
`
`/ 67.0 / 4.9% by mass,
`
`
`
`
`’ect can be surely exerted.
`
`the above—
`
`
`/ hexafluoroethane
`
`(R116)
`
`/ carbon
`
`[0025]
`
`The invention according to claim 6 is the binary
`
`refrigerating apparatus according to claim 4,
`
`wherein a
`
` refrigerant composition in which di
`
`
`fiuoroethylene (R1132a)
`
`/
`
`
`
`
`hexafluoroethane (R116)
`
`/ carbon dioxide (R744) =
`
`54.8 to
`
`58.3% by mass / 25.2
`
`are mixed is used as
`
`
`the refrigerant in the low—temperature—
`
`:o 35.7% by mass / 8.0 to 18.0% by mass
`
`side refrigeration circuit.
`
` Although :he added amount
`
`
`low to be slightly combustible,
`
`
`of hexafluoroethane (R116)
`
`is
`
`tie GWP is as extraordinarily
`
`
`
`small as about 3800,
`
`be achieved. Furthermore, a
`
`and a low temperature lower than —80°C can
`
`
`
`
` ’ect
`further e
`in which the COP
`
`10
`
`15
`
`2O
`
`does not decrease,
`
`oil deterioration and sludge do not occur,
`
`
`
`and a risk of explosion is no:
`
`
`When difluoroethylene (Rl
`
`/ carbon dioxide (R744) = 54.8
`
`caused is more surely exerted.
`
`
`/ hexafluoroethane (1116)
`
`
`
`132a)
`
`
`
`:o 58.3% by mass / 25.2 to
`
`35.7% by mass / 8.0 to 18.0% by mass,
`
`
`as a preferred example,
`
`
`when difluoroethylene (R1132a)
`
`25
`
`carbon dioxide (R744) =
`
`55.4 / 30.5 /
`
`
` uoroethane (R116)
`/ hexaf'
`
`/
`
` 14.0% by mass,
`
`the
`
`
`
`above—described operation and e
`
`
`
`
` ’ect can be surely exerted.
`
`14
`
`[0026]
`
`The invention according to claim 7 is the binary
`
`
`refrigerating appara
`
`
`:us according to any one of claims 1
`
`to 6,
`
`
`
`: composition,
`
`in which n—pentane is mixed
`
`
`mass or less with respect
`
`to the total
`
`
`
`
`
`frigerant composition in th low t mp ratur
`
`:ion circuit,
`
`is used. When n—pentane is mixed
`
`wherein a refrigeran
`H
`
`in a ratio 0'
`
`4% by
`
`
`mass 0:
`
`the re:
`
`
`side refrigera'
`
`
`in a ratio 0.
`
`
`
`: 14% by
`
`
`mass of the non—azeotropic mixture, n—pentane e
`
`mass or less with respect to the total
`
`
`
`’ectively acts
`
`as an oil carrier even within an extremely low temperature
`
`
`
`
`range, and thus plays a role of clearing clogging due to oil.
`
`
`
`since the added amount of n—pentane is as sma'"
`
`
`
`
`
`’ect
`in which a risk or
`as "4% by mass or less, a further e
`
`Furthermore,
`
`
`
`explosion is not caused is exerted.
`
`
`
` H
`
`
`
`[0027]
`
`The invention according to claim 8 is the binary
`
`
`refrigerating appara
`
`
`:us according to any one of claims 1
`
`to 6,
`
`10
`
`15
`
`20
`
` : composition,
`
`wherein a re:
`
`frigeran
`H
`
`
`mixed in a ratio 0'
`
`4% by mass or less with respect to the
`
`in which propane (1290)
`
`is
`
`
`
`
`
`
`
`
`
`total mass 0:
`
`
`
`
`temperature—side re'
`
`the refrigerant composition in the low—
`
`frigeration circuit,
`
`is used. When propane
`
`
`
`
`is mixed in a ratio 0'
`
`14% by mass or less with respect to the
`
`total mass 0:
`
`
`
`
`f the refrigerant composition, propane also acts
`
`25
`
`as an oil carrier in a similar manner to the above—described
`
`
`
`
`n—pentane. Furthermore, since the added amOLrt of propane is
`
`
`
`as small as 14% by mass or less, a further e”ect in which a
`
`
`
`
`
`
`
`
`
`risk of explosion is not caused is exerted.
`
`The invention according to claim 9 is the
`
`binary
`
`tus according
`
`to any one o:
`
`
`
`3 claims 1
`
`to 8,
`
`
`
`t composition containing a
`
`
`
`
`'uoromethane
`1e refrigerant group 0’ di
`
`non—azeotropic
`
`
`qane (R125), 1,1,1,2—tetra'"uoroethane
`
`
`
`[0028]
`
` re
`frigerating appara
`
`
`wherein a refrigera
`
`mixture comprising
`
`’1
`
`
`
`(132),
`
`
`
`10
`
`(1134a) and
`
`
`
`pentafluoroe
`
`
`
`,1,3—trifluoroethane
`
`
`
`(R143a), and
`
`I1!
`
`[2/3—
`
`
`and having a G"
`oba'—warming
`
`
`
`pentafluoropentene
`
`(HFO—1234ze),
`
`
`
`potential
`
`(GWP) of
`
`1500 or less,
`
`
`is used as a refrigerant in
`
`the high—temperature—side re
`
`
`
` re
`frigerating apparatus exerts a
`
`frigeration circuit.
`
`
`
`’icant e
`Further signi
`
`The binary
`
`
`
`in
`’ect
`
`
`
` friendly,
`
`15
`
`which
`
`the GWP is as small as 1500 or less to be earth
`
`
`
`the outlet pressure and the outlet temperature are inhibited
` from increasing,
`
`the COP does not decrease,
`
`oil deterioration
`
`and slidge do not occur,
`
`
`and a risk of expiosi
`
`on is not caused.
`
`[0029]
`
`The invention according to claim 10 is the binary
`
` re
`frigerating appara
`
`tus according to any one o:
`
` 3 claims 1
`
`to 8,
`
`
`wherein a refrigera
`
`mixture comprising
`
`t composition containing a
`
`
`
`
`'uoromethane
`1e refrigerant group 0’ di
`
`non—azeotropic
`
` qane (R125), 1,1,1,2—tetra' "uoroethane
` ",l,l,2—
`
`pentafluoroet
`
`(132),
`
`
`
`(1134a) and
`
`
`
`
`
`,1,3—trifluoroethane (R143a),
`
`
`
`and
`
`’1
`
`
`
`20
`
`25
`
`
`
`
`
`16
`
`te,raf1uoropentene (HFO—1234y:
`
`
`
`
`
`
`po,en,ia1 (GWP) of 1500 or less,
`
`
`
`f), and having a Global—warming
`
`
`is used as the refrigerant in
`
`the high—:emperature—side refrigeration circait. The binary
`
`
`
`refrigerating apparatus exerts a urcher sigqi’icant e
`
`
`
`
`
`’ect
`
`in
`
`
`
`
`
`
`
`
`
`which even the use of
`
`
`
`iFO—1234ze can
`
`
`
`
`F0 123 lyf instead of
`
`
`
`
`
`’ect as those in the refrigerant
`
`
`
`
`
`have the same operatiO” and e
`
`
`lz
`composition inc1uding F0 123
`
`I]
`
`
` Drie'
`
`
`
`
`Description of the Drawing
`
`10
`
`[0030]
`
`Fig.
`
`1
`
`is a refrigerant
`
`
`circuit diagram of a binary
`
`
`
`
`refrigerating apparatus in which refrigerant compositions of
`
`
`the present invention are filled.
`
`
`
`15
`
`
`
`
`
`Description of Embodiments
`
`[0031]
`
`
`
`Hereinafter, an embodiment of the present
`
`invention will
`
`be described in detail on the
`
`
`basis of the drawing.
`
`Fig.
`
`1
`
`is a refrigerant
`
`
`circuit diagram of a binary
`
`20
`
`
`
`
`refrigerating apparatus in which refrigerant compositions of
`
`
`the present invention are filled.
`
`"81" indicates a high—
`
`
`
`
`
`:emperature—side refrigerant cycie, and "S2" indicates a low—
`
`
`
`
`
`
`
`
`
`:emperature—side refrigerant cycie.
`
`[0032]
`
`25
`
`
`An out1et—side pipe 2 o:f a compressor 1 constituting the
`
`
`
`l7
`
`high—temperature—
`
`auxiliary condens
`
`
`side reSrigeran: cycle 81 is connected to an
`
`er 3. The auxiliary condenser 3 is connected
`
`
`
`to a cascade cond
`
`
`enser ll via an oil cooler 4 of the
`
`compressor 1, an
`
`
`auxiliary condenser 5, an oil cooler 7 of a
`
`compressor 6 cons
`
`cycle S2, a conde
`
`and is connected
`
`
`:ituting the low—temperature—side retrigerant
`
`qser 8, a dryer 9, and a capillary tube 10,
`
` :o the compressor 1 via a liquid receiver 12
`
`through an inlet—
`
`for the condenser
`
` 20033]
`
`10
`
`
`side pipe 13. Numeral "14" is a cooling fan
`
`s 3,
`
`5 and 8.
`
`An outlet—s
`
`
`ide pipe 15 o:
`
`the compressor 6
`
`in the low—
`
`temperature—side
`
`
`retrigerant cycle S2 is connected to an oil
`
`separator i6, and
`
`
`
`
`
`separator i6 is returned to the compressor 6
`
`a compressor oil separated in the oil
`
`through a return
`
`15
`
`
`
`
`pipe 17. On the other hand, a retrigerant Slows into a pipe 18
`
`and exchanges heat with an inlet—side heat exchanger 19, and
`
`
`thereafter passes through a pipe 20 within the cascade
`
`condenser ll to condense. Then,
`
`
`
`
`the reSrigerant Slows into an
`
`
`evaporator 24 from an entrance pipe 23 via a dryer 21 and a
`
`2O
`
`capillary tube 22 , and exits through an exit pipe 25 and
`
`returns to the compressor 6
`
`
`
`
`from an inlet—side pipe 26 0:
`
`,he
`
`
`
`compressor 6 via th inl t sid h at
`
`xchanger l9. Numeral
`
`"27" is an expansion tank connected to the inlet—side pipe 26
`
`via a capillary tube 28.
`
`25
`
`[0034]
`
`
`
`18
`
`
`An HFC refrigerant mixture (GWP value:
`
`"500 or less)
`
`
`
`
`
`
`is Silled
`containing 1,1,1,2,3—pentafluoropentene (HFO— 2347e)
`
`
`
`in :he
`
`
`higq—temperature—side refrigerant cycle 81. This
`
`
`refrigerant mixture flows in the cascade condenser 11 to
`
`
`refrigeran: mixture, having a boiling point at atmospheric
`
`pressure of about —40°C, condenses in the condensers 3,
`
`5 and 8,
`
`and decompressed in the capillary tube 10. The decompressed
`
`
`
`evaporate. Here,
`
`the cascade condenser 11 becomes about —36°C.
`
`[0035]
`
`10
`
`A non—a7eo
`
`:ropic mixture in which carbon dioxide (R744)
`
`
`
`is mixed in a ra,io o
`
`
`
`
`20% by mass or less to difluoroethylene
`
`
`
`(R1132a), and n—pentane, are filled in th low t mp ratur
`
`
`side refrigerant cycle 82. Here, n—pentane is mixed in a ratio
`
`
`
`o: 14% by mass or less with respect to the total mass of the
`
`15
`
`
`non—azeotropic mixture. As a result, a refrigerant composition
`
`
`having a considerably low evaporation temperature of about —
`
`
`
`90°C comes to be fil'ed. Then,
`
`
`the refrigerant and compressor
`
`
`
`oil discharged from ,he compressor 6 flow into the oil
`
`
`
`separator 16.
`
`20
`
`are separated i
`
`
`
`In the oil separator 16,
`
`
`the refrigerant and oil
`
`qto a gas phase and a liquid phase through a
`
` filter.
`
`
`A large portion of the oil is in a liquid phase, and
`
`thus can return to the compressor 6
`
`through the return pipe 17.
`
`Erigerant and oil in a gas phase pass through the pipe
`
`exchange heat with th inl t sid h a:
`
`xchanger 19,
`
`
`
`25
`
`and furthermore,
`
`are cooled in the cascade condenser 11 due to
`
`The re:
`
`
`
`18 and
`
`
`
`
`
`19
`
`
`
`
`evaporation o_ the refrigerant within the high—temperature—
`
`
`
`
`
`
`side refrigerant cycle 81 to condense. Thereafter,
`
`the
`
`
`refrigerant and oil are decompressed in the capillary tube 22,
`
`
`and flow into the evaporator 24 to evaporate. This evaporator
`
`
`
`
`24 is disposed on a wall
`o
`a "ree7er, which is not shown,
`
`in
`
`
`
`a heat exchange relationship for cooling the inside of the
`
`
`z r.
`H r ,
`th
`
`
`;r
`
`vaporation temperature in the evaporator
`
`24 reaches about —90°C.
`
`[0036]
`
`
`
`
`In the binary refrigerating apparatus configured in this
`
`manner, a non—a7eotropic mixture in whicq 20% by mass or less
`
`
`of carbon dioxide (R744)
`
`
`is mixed to dit'uoroethylene (Rf132a),
`
`
`
`
`
`10
`
`15
`
`20
`
`
`
`
`which is a refrigerant composition to be filled in the low—
`
`temperature—side refrigerant cycle S2, has an evaporation
`
`
`
`
`
`
`
`this non—azeotropic
`
`
`
`temperature of about —90°C. Therefore,
`
`
`
`
`mixture can su "iciently exert refrigerating capacity as an
`
`
`alternative refrigerant to R508A.
`
`
`
`[0037]
`
`Furthermore, although the non—a7eotropic mixture in which
`
`carbon dioxide (R744)
`
`
`less to difluoroethylene (RllB2a) has poor compatibility with
`
`
`is mixed in a ratio 0" 20% by mass or
`
`oil,
`
`
`this can be solved by mixing 14% by mass or less of n—
`
`pentaqe.
`
`
`That is, n—pentane has a high boiling point of
`
`
`
`+36.07°C, but has good compatibility with a compressor oil.
`
`25
`
`
`Accordingly, when n—pentane is mixed in a range o; 14% by mass
`
`
`
`20
`
`or less,
`
`the oil can be returned to a compressor in a state of
`
`
`
`
`
`ul
`e
`’ect stcr
`blending in n—pentane. This can prevent a harm
`
`as locking due to oil loss in a compressor. As a result,
`
`
`tre
`
`oil can be returned to the compressor 6 without necessity of
`
`thoroughly separating the oil in the oil separator 16. Here,
`
`
`since n—pentane has a high boiling point, addition of n—
`
`pentane in an extremely large amount increases an evaporation
`
`
`temperature thereby failing to obtain an intended low
`
`
`
`
`
`
`temperature. However, when n—pentane is added in a ratio of
`
`10
`
`14% by mass or less,
`
`the evaporation temperature does not
`
`
`increase, and n p ntan
`nabl
`s th oil to return to a
`
`
`
`compressor while being maintained in a non—combustible range.
`
`[0038]
`
`
`
`Thus, according to the binary refrigerating apparatus of
`
`15
`
`the present example, oil
`
`return improves, hazards such as
`
`
`explosion are not caused, and a low temperature of about —90°C
`
`
`can be achieved in an evaporator. The binary refrigerating
`
`
`apparatus can be practically realized as a medial freezer such
`
`
`as a blood cooler without using regulated refrigerants.
`
`20
`
`[0039]
`
`Furthermore, n—pentane is commercially available and can
`
`
`be easily obtained when used in freezers or the like, and is
`
`therefore practical.
`
`
`
`[0040:
`
`25
`
`Furthermore, propane has an advantage in that it can
`
`
`
`21
`
`enhance sealing workability and serviceability in a gas state.
`
`[0041]
`
`
`
`It is nOted that although the mixture of the non—
`
`
`a7eotropic mixture in which 20% by mass or less of carbon
`
`dioxide (R744)
`
`
`is mixed to difluoroethylene (RllB2a), and n—
`
`
`
`pentane, has been described in the present embodimert,
`I]
`
`0; R290 (propane, Cfih)
`
`
`
`
`
`the use
`
`in the same ratio in place of n—pentane
`
`
`
`can achieve a similar e
`
`ect. That is,
`
`propane also has good
`
`is mixed in an amount 0:
`
`compatibility with a compressor
`
`oil. Accordingly, when propane
`
`14% by mass or less,
`
`the oil can be
`
`returned to the compressor 6
`
`being dissolved in
`
`
`in a state of
`
`QC
`
`
`
`Jl
`
`e
`
`propane. This can inhibit a harm
`
`t such as locking due
`
` :hough propane has a
`
`to oil loss in the compressor 6.
`
`iere,
`
`al
`
`
`
`
`
`low boiling point 0: —42.75°C and
`
`
`
`evaporation temperature, it is com
`
`
`thus less influence on the
`
`I]
`
`bustible and has a risk or
`
`10
`
`15
`
`explosion, causing a problem in handling.
`
`However, when
`
`
`propane is contained in an amount of 14
`
`9O
`
`by weight or less,
`
`propane can be maintained in a non—combustible range. This
`
`eliminates concerns such as explosion.
`
`20
`
`[0042]
`
`
`
`It is noted that the embodiment described above is for
`
`
`
`explaining the present invention,
`
`and neither limits nor
`
`
`narrows the invention described in the claims. Configurations
`
`
`
`of the components of the present invention are not limited to
`
`25
`
`the embodiment described above,
`
`
`and can be variously modified
`
`
`
`22
`
`within the technical scope described in the claims.
`
` [Examples]
`
`[0043]
`
`Although
`
`
`
`5 with reference
`
`the present
`
` :o examples,
`
`invention will be described below
`
`the present
`
`invention is not
`
`limited to thes
`
`
`e examples as long as the gist of the present
`
`invention is not departed.
`
`[0044]
`
`
`(Example l)
`
`10
`
`A binary refrigerating apparatus illustrated in Fig.
`
`l
`
`was stably and
`
` continuously operated at an OLtSide air
`
`
`
`temperature 0"
`
`—10°C for a lorg time. Thereafter, a cycle 81
`
`and a cycle S2 were measured for temperatures at the points
`
`described below.
`
`15
`
`
`
`In the high—temperature—side refrigerant cycle 81, a
`
`
`refrigerant composition (GWP value: 1500 or less, boiling
`
`
`
`point: about —4
`
`0°C at atmospheric pressure) containing a non—
`
`
`azeo:ropic mixture comprising the refrigerant group of
`
`
`(R32), pentafluoroethane (R125),
`
`l,l,f,2—
`
`
`
`diflioromethane
`
`
`
`
`te,rafi uoroethane (Ri34a) and l,l,3—trifluoroethane (Ri43a),
`
`
`
`
`2O
`
`
`
`
`
`
`
`
`
`
`
`and l,f,l,2,3—pentaf'uoropentene (HFO—1234ze), was fil'ed.
`
`
`
`This refrigerant mixture condensed in each of condensers
`
`
`3,5 and 8, was decompressed in a capillary tube 10, and flowed
`
`into a cascade
`
`condenser ll to evaporate. The temperature at
`
`25
`
`
`an exit of the
`
`cascade condenser ll was —54.9°C.
`
`
`
`23
`
`On the other hand,
`
`in the low—temperature—side
`
` re
`frigerant cycle S2,
`
`
`a refrigerant composition
`
`(GWP
`
`value:
`
`
`
`about 8000),
`
`in which n—pentane was added as an oil carrier in
`
`
`an amount 0:
`
`to a non—
`
`combustible re:
`
`
`
`frigerant
`
`
` UO
`roethylene
`ng dif'
`composition includi
`
`6.8% by mass with respect to the whole
`
`
`(le32a
`
`)
`
`
`/ hexafluoroethane
`
`(R116)
`
`/ carbon dioxide
`
`(R744) =
`
`28.
`
`/ 67.0 / 4.9% by mass,
`
`was
`
`
`filled.
`
`
`
`
`temperature of
`
`an outlet—side pipe 15 at a
`
`The
`
` re
`frigeran
`
`10
`
`
`side refrigerant
`
`cycle S2 was 45.4°C;
`
` of
`
`the compressor 6
`
`in the low—temperature—
`
` an
`the temperature or
`
` , exit
`
`
`inlet—side pipe 26 at a re:
`
`
`
`frigerant inlet to the com
`
`pressor 6
`
`was —l5
`
`.8°C;
`
` an entrance
`the temperature of
`
`pipe 23
`
`:0 an
`
`evaporator 24 was —97.2°C;
`
`the temperature of
`
`an exi
`
`: pipe 25
`
`
`
`
`from the evaporator 24 was —90.3°C;
`
`and the
`
`15
`
` a freezer
`
`(not shown)
`
`was —95.3°C.
`
`[0045]
`
`
`
`(ixamp'e
`
`2)
`
`
`
`temperatire inside
`
`
`
`
`In the high—temperature—side re'
`
`frigerant cycle S1 and the
`
`
`low—temperature—side ref
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