CN102686957A - Cascade refrigeration system with fluoroolefin refrigerant - Google Patents

Abstract

The present invention relates to a cascade refrigeration system which circulates a refrigerant comprising a fluoroolefin therethrough. The cascade refrigeration system includes a low temperature refrigeration loop and a medium temperature refrigeration loop. The fluoroolefin circulates through either loop, or both. In a particular embodiment, the fluoroolefin circulates through the medium temperature loop. In a particular embodiment, where the cascade refrigeration system includes a first and a second cascade heat exchanger, and a secondary heat transfer loop which extends between the first and second cascade heat exchangers, either the first and/or second refrigerant may be, but need not necessarily be, a fluoroolefin.

Description

Cascade refrigeration system with fluoroolefins refrigerant

Background of invention

1. invention field

This disclosure relates to make the cascade refrigeration system that the refrigerant circulation comprising fluoroolefins passes through.Specifically, such cascade system includes middle temperature loops and low-temperature circuit and the fluoroolefins refrigerant available for any one in two loops or both.

2. background technology

Cascade refrigeration system is known in the art, see, for example, ICR07-B2-358, " CO₂- DX Systems for Medium-and Low-Temperature Refrigeration in Supermarket Applications "; T.Sienel, O.Finckh, International Congress of Refrigeration (International refrigeration conference); 2007 years, Beijing.Such system generally uses refrigerant in middle temperature loops, and such as HFA 134a (R134a) or its blend with HFC-125 and HFC-143a (i.e. R404A) simultaneously use carbon dioxide (CO in low-temperature circuit₂) with for example in supermarket to showcase provide cooling.

Since the past few decades, refrigerating industry be directed to always find alternative refrigerant for substitute Montreal Protocol in regulation by be phased out loss ozone layer CFC (CFC) and HCFC (HCFC).The solution of most of refrigerant manufacturers is all by the commercialization of HFC (HFC) refrigerant.Current most widely used new HFC refrigerants HFC-134a has zero ozone depletion potential, therefore not by current《Montreal Protocol》It is phased out defined influence.

Other environmental regulations, which may be ultimately resulted in, is globally phased out some HFC refrigerants.At present, car industry is faced with the regulations relevant with the global warming up trend of the refrigerant for mobile air conditioner.Therefore, mobile air conditioner market reduces the novel refrigerant of global warming up trend in the urgent need to finding at present.If the regulations to for example fixed air-conditioning and refrigeration system are more widely implemented in future, even more urgent will be felt to the demand available for refrigeration and the refrigerant of Air Conditioning Industry all spectra.

The alternative refrigerants of HFC-134a proposed at present include HFC-152a, pure hydrocarbon such as butane or propane or " natural " refrigerant such as CO₂.Many is poisonous, inflammable and/or low-energy-efficiency in the substitute of these suggestions.Also the new substitute using HCFC-22, R404A, R407C and R410A etc. is proposed.Because it have been observed that these substitutes, people are look for the new application of such alternative refrigerant to utilize their low or zero ozone depletion potentials and lower global warming up trend.

Summary of the invention

The purpose of the disclosure is to provide cascade refrigeration system, and it is using the refrigerant composition earl august eugene lund ian robert with specific characteristic to meet low compared with existing refrigerant or zero ozone depletion potential and lower global warming up trend requirement.

In addition to the advantage of lower global warming up trend, cascade refrigeration system of the invention can have the energy efficiency and capacity higher than currently used cascade refrigeration system.

Therefore, according to the invention provides the cascade refrigeration system with least two refrigerating circuits, each loop is circulated a refrigerant through, and the refrigeration system includes：

(a) it is used to reduce the first expansion gear of the pressure and temperature of the first refrigerant liquid；

(b) there is the evaporator of entrance and exit, wherein the first refrigerant liquid from the first expansion gear enters evaporator by evaporator inlet and evaporated in evaporator to form the first refrigerant vapour, so as to produce cooling, and outlet is recycled to；

(c) there is the first compressor of entrance and exit, the first refrigerant vapour for wherein carrying out flash-pot is recycled to the entrance of the first compressor and compressed, so as to improve the pressure and temperature of the first refrigerant vapour, and the first refrigerant vapour compressed is recycled to the outlet of the first compressor；

(d) cascade heat exchanger system, it includes：

(i) first entrance and first outlet, wherein the first refrigerant vapour is recycled to first outlet from first entrance and is condensed in heat exchanger system to form the first refrigerant liquid, so that heat is discharged, and

(ii) second entrance and second outlet, wherein second refrigerant liquid are recycled to second outlet from second entrance and absorb the heat discharged by the first refrigerant, and form second refrigerant steam；

(e) there is the second compressor of entrance and exit, wherein the second refrigerant steam from cascade heat exchanger system is inhaled into compressor and compressed, so as to improve the pressure and temperature of second refrigerant steam；

(f) there is the condenser of entrance and exit, it is used to pass through second refrigerant vapour-cycling, and for condensing second refrigerant steam from compressor to form second refrigerant liquid, wherein second refrigerant liquid leaves condenser by condensator outlet；With

(g) the second expansion gear, it is lowered from condenser and enters the pressure and temperature of the second refrigerant liquid of the second entrance of cascade heat exchanger system.

First refrigerant or second refrigerant, or both, fluoroolefins can be included.

In one particular embodiment, cascade heat exchanger system may include the first and second cascade heat exchangers, and the second heat transfer circuit extended between the first and second cascade heat exchangers.In this embodiment, second refrigerant liquid absorbs the heat discharged by the first refrigerant vapour by heat transfer fluid indirectly, and the heat transfer fluid is circulated between the first cascade heat exchanger and the second cascade heat exchanger by the second heat transfer circuit.First cascade heat exchanger has first entrance and first outlet and second entrance and second outlet, wherein the first refrigerant vapour is recycled to first outlet from first entrance and discharges heat and be condensed, and the second heat transfer fluid is recycled to second outlet from second entrance and absorbs the heat discharged from the first refrigerant vapour, and is recycled to the second cascade heat exchanger.Second cascade heat exchanger has first entrance and first outlet and second entrance and second outlet, the second outlet of wherein heat transfer fluid from the first cascade heat exchanger is recycled to the first entrance of the second cascade heat exchanger and is recycled to the first outlet of the second cascade heat exchanger, and discharges the heat from the first refrigerant suction.Second refrigerant liquid is recycled to the second outlet of the second cascade heat exchanger from second entrance, and absorbs the heat discharged by heat transfer fluid, and forms second refrigerant steam.In this embodiment, first and/or second refrigerant can be but not be necessarily fluoroolefins.

The method that heat exchange between at least two refrigerating circuits is provided always according to the present invention, including：

(a) from the absorbent body heat to be cooled and by the heat dissipation to the second refrigerating circuit in the first refrigerating circuit；And

(b) heat from the first refrigerating circuit is absorbed in the second refrigerating circuit and by the heat dissipation into environment, wherein the refrigerant at least one refrigerating circuit includes fluoroolefins.

Brief description

The present invention may be better understood in conjunction with the following drawings, wherein：

Fig. 1 is the schematic diagram of the cascade refrigeration system according to one embodiment of the invention.

Fig. 2 is the schematic diagram of another embodiment of the cascade refrigeration system of the present invention.

Fig. 3 is the schematic diagram of another embodiment of the invention, and it shows the cascade refrigeration system with the second heat transfer circuit, and the system is from lower temperature loop to higher temperature loop heat transfer.

Fig. 4 is the schematic diagram of another embodiment of the cascade refrigeration system of the present invention, and the refrigeration system has multiple low-temperature circuits.

Fig. 5 is cooling capacity and on figure of the refrigerant composition earl august eugene lund ian robert coefficient of performance comprising HFO-1234yf and HFC-134a to HFO-1234yf percentage by weights in the composition.

Detailed description of the invention

Before addressing details of embodiments described below, some terms are first defined or clarified.

Refrigerating capacity (also referred to as cooling capacity) is the term for defining refrigerant enthalpy change per unit mass circulating refrigerant in evaporator, or the term (volume capacity) of the refrigerant vapour of evaporator is left in definition by heat/unit volume that the refrigerant in evaporator is removed.Refrigerating capacity is measuring for refrigerant or heat transfer composition refrigerating capacity.Therefore capacity is higher, bigger for the cooling produced by giving refrigerant circulation speed.Cooldown rate refers to the heat removed in time per unit by the refrigerant in evaporator.

The coefficient of performance (COP) is the amount divided by the energy input needed for given time interval scope is used to operate the circulation of the heat removed from the main body to be cooled.COP is higher, and energy efficiency is higher.COP and energy efficiency ratio (EER) are directly related, and the energy efficiency ratio is the level of efficiency of refrigeration plant or air-conditioning equipment under one group of specific interior gentle outer temperature.

Global warming up trend (GWP) is the specific greenhouse gases of one kilogram of airborne release assess relative influenced by global warming index obtained by compared with discharging one kilogram of carbon dioxide.The GWP of different time scope can be calculated, it shows the atmospheric lifetime effect of designated gas.The GWP of 100 year scopes is typically reference value.For mixture, weighted average can be calculated according to the independent GWP of every kind of component.

Stratospheric ozone loss potentiality (ODP) is the numerical value for being related to the ozone depletion amount caused by material.ODP is the produced ratios for influenceing to compare of CFC-11 (Arcton 11) of influence and analog quantity of the chemical substance to stratospheric ozone.Therefore, CFC-11 ODP is defined as 1.0.Other CFC and HCFC have the ODP in the range of 0.01-1.0.Because they do not include chlorine, HFC has zero odp.

As used herein, term "comprising", " comprising ", " having " or their any other modification are intended to and cover including for nonexcludability.For example, composition, step, method, product or equipment comprising series of elements are not necessarily limited to those elements, and other not expressly listed elements can be included, or such composition, step, method, product or the intrinsic element of equipment.In addition, unless expressly stated to the contrary, "or" refers to the "or" of inclusive, without referring to exclusive "or".For example, following any one situation is satisfied by condition A or B：A is real (or presence) and B is false (or non-existent), and A is false (or non-existent) and B is real (or presence), and A and B are real (or presence).

Conjunctive phrase " Consists of " does not include any element do not specified, step or composition.If in the claims, then such word limitation claim is not with not comprising except in addition to adjoint impurity being therewith generally the material of those.When in the clause that phrase " Consists of " appears in the main body of claim, rather than immediately preamble when, it is only limited in the key element mentioned in the clause；Other key elements are excluded not as entirety from claim.

Conjunctive phrase "consisting essentially of ..." is used to limit composition, method or equipment in addition to according to literal those disclosed; also include material, step, part, component or element, precondition is that these material comprised additionally in, step, part, component or elements largely influence one or more essential characteristics and novel feature of claimed invention really.Term ' substantially by ... constitute ' occupy "comprising" and ' by ... constitute ' between.

When applicant limits invention or part thereof using open-ended term (such as "comprising"), it should be readily appreciated that should be interpreted that also using term "consisting essentially of ..." or " Consists of " describes this invention to (unless otherwise specified) explanation.

Key element as described herein and component are equally described using " one " or " one kind ".So do merely for convenience and provide general meaning to the scope of the present invention.This description should be read to include one or at least one, and the odd number also includes plural number, unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technologies used herein and the implication of scientific terminology are as those skilled in the art are generally understood that.Although similar or equivalent method and material are used equally in the practice or test of disclosed composition embodiment with those described herein, suitable method and material is described below.Except non-quoted physical segment falls, all publications, patent application, patent and the other bibliography full texts being mentioned above are herein incorporated by reference.If conflict occurs, by this specification and its including definition be defined.In addition, material, method and embodiment are only exemplary, it is no intended to limited.

According to the present invention there is provided the cascade refrigeration system with least two refrigerating circuits, the system is used to circulate a refrigerant through each loop.In general, showing such cascade system in Fig. 1 with 10.The cascade refrigeration system of the present invention has at least two refrigerating circuits, including the first or relatively low loop 12 as shown in Figure 1, and it is low-temperature circuit；With the second or higher loop 14 as shown in Figure 1, it is middle temperature loops 14.Each loop is circulated a refrigerant through.

As shown in figure 1, the cascade refrigeration system of the present invention includes the first expansion gear 16.First expansion gear has entrance 16a and outlet 16b.The reduction of first expansion gear cycles through the pressure and temperature of the first refrigerant liquid of first or low-temperature circuit.

The cascade refrigeration system of the present invention also includes evaporator 18 as shown in Figure 1.Evaporator has entrance 18a and outlet 18b.The first refrigerant liquid from the first expansion gear enters evaporator by evaporator inlet and evaporated in evaporator to form the first refrigerant vapour.Cooling is produced at this food in the main body to be cooled such as low-temperature display cabinet in first or low-temperature circulating circuit.Then the first refrigerant vapour is recycled to the outlet of evaporator.

The cascade refrigeration system of the present invention also includes the first compressor 20.First compressor has entrance 20a and outlet 20b.The first refrigerant vapour for carrying out flash-pot is recycled to the entrance of the first compressor and compressed, so as to improve the pressure and temperature of the first refrigerant vapour.Then the first refrigerant vapour compressed is recycled to the outlet of the first compressor.

The cascade refrigeration system of the present invention also includes cascade heat exchanger system 22.Heat exchanger has first entrance 22a and first outlet 22b.The first refrigerant vapour from the first compressor enters the first entrance of heat exchanger and is condensed in heat exchanger to form the first refrigerant liquid, so as to discharge heat.Then the first refrigerant liquid is recycled to the first outlet of heat exchanger.Heat exchanger also includes second entrance 22c and second outlet 22d.Second refrigerant liquid is recycled to the second outlet of heat exchanger from second entrance and evaporated to form second refrigerant steam, so as to absorb the heat by the first discharge refrigerant (when it is condensed).The heat is disposed in environment.Then second refrigerant vapour-cycling to heat exchanger second outlet.Therefore, in the implementation of figure 1, directly absorbed and be disposed in environment by second refrigerant by the heat of the first discharge refrigerant.

The cascade refrigeration system of the present invention also includes the second compressor 24 as shown in Figure 1.Second compressor has entrance 24a and outlet 24b.Second refrigerant steam from cascade heat exchanger is inhaled into compressor and compressed by entrance, so as to improve the pressure and temperature of second refrigerant steam.Then second refrigerant vapour-cycling is to the outlet of the second compressor.

The cascade refrigeration system of the present invention also includes the condenser 26 with entrance 26a and outlet 26b.Second refrigerant from the second compressor is circulated and is condensed within the condenser to form second refrigerant liquid from entrance.Second refrigerant liquid leaves condenser by outlet.

The cascade refrigeration system of the present invention also includes the second expansion gear 28 with entrance 28a and outlet 28b.Second refrigerant liquid passes through the second expansion gear, and second expansion gear is lowered from the second refrigerant fluid pressure and temperature of condenser.The liquid can be part evaporation during the expansion.The second refrigerant liquid of reduction pressure and temperature is recycled to the second entrance of cascade heat exchanger system from expansion gear.

It should be pointed out that in the case where not departing from spirit and scope of the invention, various forms of modifications can be made to embodiment as shown in Figure 1.For example, it perhaps potentially includes multiple cascade heat exchangers rather than a cascade heat exchanger, and multiple first compressors rather than the first single compressor, as in the entitled " shown in Price Chopper Remodel Features Hill Phoenix Next Generation Refrigeration System " (on May 5th, 2008) cascade refrigeration system chart of announcement.In addition, use the second heat transfer fluid, the second heat transfer circuit of such as glycol, as shown in the chart, can with the present invention system be used together with from the main body to be cooled (for example, food display cabinet of supermarket) transmit heat to high or low refrigerating circuit or both.In the case, the second heat transfer circuit is used to be used between refrigerating circuit transmit heat from the main body to be cooled transmission heat to refrigerating circuit, rather than the second heat transfer circuit, as follows for described in Fig. 3.

According to the present invention, in the cascade system of Fig. 1 embodiment, the first refrigerant or second refrigerant can include fluoroolefins.Specifically, at least second refrigerant, i.e., include fluoroolefins by the refrigerant that middle temperature loops are circulated.However, the first refrigerant in scope of the invention, i.e., the refrigerant in low-temperature circuit includes fluoroolefins.In addition the first and second refrigerants comprising fluoroolefins also in scope of the invention.In addition, in some embodiments, first or second refrigerant can for the mixture or fluoroolefins and additional refrigerant as described herein of any fluoroolefins or fluoroolefins mixture.

Such fluoroolefins may be selected from：

(i) formula E- or Z-R¹CH=CHR²Fluoroolefins, wherein R¹And R²It independently is C₁-C₆Perfluoroalkyl；

(ii) formula ring-[CX=CY (CZW)_n-] ring-type fluoroolefins, wherein X, Y, Z and W independently is H or F, and n is 2-5 integer；And

(iii) it is selected from following fluoroolefins：Tetrafluoroethene (CF₂=CF₂), hexafluoropropene (CF₃CF=CF₂), 1,2,3,3,3- five fluoro- 1- propylene (CHF=CFCF₃), 1,1,3,3,3- five fluoro- 1- propylene (CF₂=CHCF₃), 1,1,2,3,3- five fluoro- 1- propylene (CF₂=CFCHF₂), 1,2,3,3- tetrafluoro-1-propene (CHF=CFCHF₂), 2,3,3,3- tetrafluoro-1-propene (CH₂=CFCF₃), 1,3,3,3- tetrafluoro-1-propene (CHF=CHCF₃), 1,1,2,3- tetrafluoro-1-propene (CF₂=CFCH₂F), 1,1,3,3- tetrafluoro-1-propene (CF₂=CHCHF₂), 1,2,3,3- tetrafluoro-1-propene (CHF=CFCHF₂), 3,3,3- tri- fluoro- 1- propylene (CH₂=CHCF₃), 2,3,3- tri- fluoro- 1- propylene (CHF₂CF=CH₂), 1,1,2- tri- fluoro- 1- propylene (CH₃CF=CF₂), 1,2,3- tri- fluoro- 1- propylene (CH₂FCF=CF₂), 1,1,3- tri- fluoro- 1- propylene (CH₂FCH=CF₂), 1,3,3- tri- fluoro- 1- propylene (CHF₂CH=CHF), 1,1,1,2,3,4,4,4- octafluoro -2- butylene (CF₃CF=CFCF₃), 1,1,2,3,3,4,4,4- octafluoro -1- butylene (CF₃CF₂CF=CF₂), 1,1,1,2,4,4,4- seven fluoro- 2- butylene (CF₃CF=CHCF₃), 1,2,3,3,4,4,4- seven fluoro- 1- butylene (CHF=CFCF₂CF₃), 1,1,1,2,3,4,4- seven fluoro- 2- butylene (CHF₂CF=CFCF₃), 1,3,3,3- tetra- fluoro- 2- (trifluoromethyl) -1- propylene ((CF₃)₂C=CHF), 1,1,3,3,4,4,4- seven fluoro- 1- butylene (CF₂=CHCF₂CF₃), 1,1,2,3,4,4,4- seven fluoro- 1- butylene (CF₂=CFCHFCF₃), 1,1,2,3,3,4,4- seven fluoro- 1- butylene (CF₂=CFCF₂CHF₂), 2,3,3,4,4,4- hexafluoro -1- butylene (CF₃CF₂CF=CH₂), 1,3,3,4,4,4- hexafluoro -1- butylene (CHF=CHCF₂CF₃), 1,2,3,4,4,4- hexafluoro -1- butylene (CHF=CFCHFCF₃), 1,2,3,3,4,4- hexafluoro -1- butylene (CHF=CFCF₂CHF₂), 1,1,2,3,4,4- hexafluoro -2- butylene (CHF₂CF=CFCHF₂), 1,1,1,2,3,4- hexafluoro -2- butylene (CH₂FCF=CFCF₃), 1,1,1,2,4,4- hexafluoro -2- butylene (CHF₂CH=CFCF₃), 1,1,1,3,4,4- hexafluoro -2- butylene (CF₃CH=CFCHF₂), 1,1,2,3,3,4- hexafluoro -1- butylene (CF₂=CFCF₂CH₂F), 1,1,2,3,4,4- hexafluoro -1- butylene (CF₂=CFCHFCHF₂), 3,3,3- tri- fluoro- 2- (trifluoromethyl) -1- propylene (CH₂=C (CF₃)₂), 1,1,1,2,4- five fluoro- 2- butylene (CH₂FCH=CFCF₃), 1,1,1,3,4- five fluoro- 2- butylene (CF₃CH=CFCH₂F), 3,3,4,4,4- five fluoro- 1- butylene (CF₃CF₂CH=CH₂), 1,1, Isosorbide-5-Nitrae, the fluoro- 2- butylene (CHF of 4- five₂CH=CHCF₃), 1,1,1,2,3- five fluoro- 2- butylene (CH₃CF=CFCF₃), 2,3,3,4,4- five fluoro- 1- butylene (CH₂=CFCF₂CHF₂), 1,1,2,4,4- five fluoro- 2- butylene (CHF₂CF=CHCHF₂), 1,1,2,3,3- five fluoro- 1- butylene (CH₃CF₂CF=CF₂), 1,1,2,3,4- five fluoro- 2- butylene (CH₂FCF=CFCHF₂), 1,1,3,3,3- five fluoro- 2- methyl-1-propylenes (CF₂=C (CF₃)(CH₃)), 2- (difluoromethyl) -3,3,3- tri- fluoro- 1- propylene (CH₂=C (CHF₂)(CF₃)), 2,3,4,4,4- five fluoro- 1- butylene (CH₂=CFCHFCF₃), 1,2,4,4,4- five fluoro- 1- butylene (CHF=CFCH₂CF₃), 1,3,4,4,4- five fluoro- 1- butylene (CHF=CHCHFCF₃), 1,3,3,4,4- five fluoro- 1- butylene (CHF=CHCF₂CHF₂), 1,2,3,4,4- five fluoro- 1- butylene (CHF=CFCHFCHF₂), 3,3,4,4- tetra- fluoro- 1- butylene (CH₂=CHCF₂CHF₂), fluoro- 2- (the difluoromethyl) -1- propylene (CF of 1,1- bis-₂=C (CHF₂)(CH₃)), 1,3,3,3- tetra- fluoro- 2- methyl-1-propylenes (CHF=C (CF₃)(CH₃)), fluoro- 2- (the difluoromethyl) -1- propylene (CH of 3,3- bis-₂=C (CHF₂)₂), 1,1,1,2- tetra- fluoro- 2- butylene (CF₃CF=CHCH₃), 1,1,1,3- tetra- fluoro- 2- butylene (CH₃CF=CHCF₃), 1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylenes (CF₃CF=CFCF₂CF₃), 1,1,2,3,3,4,4,5,5,5- ten fluoro- 1- amylenes (CF₂=CFCF₂CF₂CF₃), 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCF₃), 1,1,1,2,4,4,5,5,5- nine fluoro- 2- amylenes (CF₃CF=CHCF₂CF₃), 1,1,1,3,4,4,5,5,5- nine fluoro- 2- amylenes (CF₃CH=CFCF₂CF₃), 1,2,3,3,4,4,5,5,5- nine fluoro- 1- amylenes (CHF=CFCF₂CF₂CF₃), 1,1,3,3,4,4,5,5,5- nine fluoro- 1- amylenes (CF₂=CHCF₂CF₂CF₃), 1,1,2,3,3,4,4,5,5- nine fluoro- 1- amylenes (CF₂=CFCF₂CF₂CHF₂), 1,1,2,3,4,4,5,5,5- nine fluoro- 2- amylenes (CHF₂CF=CFCF₂CF₃), 1,1,1,2,3,4,4,5,5- nine fluoro- 2- amylenes (CF₃CF=CFCF₂CHF₂), 1,1,1,2,3,4,5,5,5- nine fluoro- 2- amylenes (CF₃CF=CFCHFCF₃), 1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CHF=CFCF (CF₃)₂), 1,1,2,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CFCH (CF₃)₂), 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene (CF₃CH=C (CF₃)₂), 1,1,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CHCF (CF₃)₂), 2,3,3,4,4,5,5,5- octafluoro -1- amylenes (CH₂=CFCF₂CF₂CF₃), 1,2,3,3,4,4,5,5- octafluoro -1- amylenes (CHF=CFCF₂CF₂CHF₂), 3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CH₂=C (CF₃)CF₂CF₃), 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CF₂=CHCH (CF₃)₂), 1,3,4,4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCF (CF₃)₂), 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CF₂=C (CF₃)CH₂CF₃), 3,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene ((CF₃)₂CFCH=CH₂), 3,3,4,4,5,5,5- seven fluoro- 1- amylenes (CF₃CF₂CF₂CH=CH₂), 2,3,3,4,4,5,5- seven fluoro- 1- amylenes (CH₂=CFCF₂CF₂CHF₂), 1,1,3,3,5,5,5- seven fluoro- 1- butylene (CF₂=CHCF₂CH₂CF₃), 1,1,1,2,4,4,4- seven fluoro- 3- methyl-2-butenes (CF₃CF=C (CF₃)(CH₃)), 2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂=CFCH (CF₃)₂), Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCH (CF₃)₂), 1,1, fluoro- 2- (the trifluoromethyl) -2- butylene of Isosorbide-5-Nitrae-four (CH₂FCH=C (CF₃)₂), 1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH₃CF=C (CF₃)₂), 1,1,1- tri- fluoro- 2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCH₃), 3,4,4,5,5,5- hexafluoro -2- amylenes (CF₃CF₂CF=CHCH₃), 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- methyl-2-butenes (CF₃C(CH₃)=CHCF₃), 3,3,4,5,5,5- hexafluoro -1- amylenes (CH₂=CHCF₂CHFCF₃), 4,4,4- tri- fluoro- 2- (trifluoromethyl) -1- butylene (CH₂=C (CF₃)CH₂CF₃), 1,1,2,3,3,4,4,5,5,6,6,6- ten two fluoro- 1- hexenes (CF₃(CF₂)₃CF=CF₂), 1,1,1,2,2,3,4,5,5,6,6,6- ten two fluoro- 3- hexenes (CF₃CF₂CF=CFCF₂CF₃), 1,1, Isosorbide-5-Nitrae, double (trifluoromethyl) -2- butylene ((CF of 4,4- hexafluoros -2,3-₃)₂C=C (CF₃)₂), 1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylenes ((CF₃)₂CFCF=CFCF₃), 1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- amylenes ((CF₃)₂C=CHC₂F₅), 1,1,1,3,4,5,5,5- octafluoro -4- (trifluoromethyl) -2- amylenes ((CF₃)₂CFCF=CHCF₃), 3,3,4,4,5,5,6,6,6- nine fluoro- 1- hexenes (CF₃CF₂CF₂CF₂CH=CH₂), double (the trifluoromethyl) -1- butylene (CH of 4,4,4- tri- fluoro- 3,3-₂=CHC (CF₃)₃), 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -3- methyl -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=C (CH₃)(CF₃)), 2,3,3,5,5,5- hexafluoro -4- (trifluoromethyl) -1- amylenes (CH₂=CFCF₂CH(CF₃)₂), 1,1,1,2,4,4,5,5,5- nine fluoro- 3- methyl -2- amylenes (CF₃CF=C (CH₃)CF₂CF₃), 1,1,1,5,5,5- hexafluoro -4- (trifluoromethyl) -2- amylenes (CF₃CH=CHCH (CF₃)₂), 3,4,4,5,5,6,6,6- octafluoro -2- hexenes (CF₃CF₂CF₂CF=CHCH₃), 3,3,4,4,5,5,6,6- octafluoro -1- hexenes (CH₂=CHCF₂CF₂CF₂CHF₂), 1,1, Isosorbide-5-Nitrae, fluoro- 2- (trifluoromethyl) -2- the amylenes ((CF of 4- five₃)₂C=CHCF₂CH₃), 4,4,5,5,5- five fluoro- 2- (trifluoromethyl) -1- amylenes (CH₂=C (CF₃)CH₂C₂F₅), 3,3,4,4,5,5,5- seven fluoro- 2- Methyl-1-pentenes (CF₃CF₂CF₂C(CH₃)=CH₂), 4,4,5,5,6,6,6- seven fluoro- 2- hexenes (CF₃CF₂CF₂CH=CHCH₃), 4,4,5,5,6,6,6- seven fluoro- 1- hexenes (CH₂=CHCH₂CF₂C₂F₅), 1,1,1,2,2,3,4- seven fluoro- 3- hexenes (CF₃CF₂CF=CFC₂H₅), 4,5,5,5- tetra- fluoro- 4- (trifluoromethyl) -1- amylenes (CH₂=CHCH₂CF(CF₃)₂), 1,1,1,2,5,5,5- seven fluoro- 4- methyl -2- amylenes (CF₃CF=CHCH (CF₃)(CH₃)), 1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- amylenes ((CF₃)₂C=CFC₂H₅), 1,1,1,2,3,4,4,5,5,6,6,7,7,7- ten four fluoro- 2- heptene (CF₃CF=CFCF₂CF₂C₂F₅), 1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten four fluoro- 3- heptene (CF₃CF₂CF=CFCF₂C₂F₅), 1,1,1,3,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CH=CFCF₂CF₂C₂F₅), 1,1,1,2,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CF=CHCF₂CF₂C₂F₅), 1,1,1,2,2,4,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CH=CFCF₂C₂F₅) and 1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CF=CHCF₂C₂F₅)。

In some embodiments, fluoroolefins is the compound for including carbon atom, fluorine atom and optional hydrogen or chlorine atom.In one embodiment, the compound with 2-12 carbon atom is included for the fluoroolefins in the present composition.In another embodiment, fluoroolefins includes the compound with 3-10 carbon atom, and in another embodiment, fluoroolefins includes the compound with 3-7 carbon atom.Representational fluoroolefins includes but is not limited to all compounds listed in table 1, table 2 and table 3.

In one embodiment of the invention, the first refrigerant, which is selected from, has formula E- or Z-R¹CH=CHR²The fluoroolefins of (formula (i)), wherein R¹And R²It independently is C₁-C₆Perfluoroalkyl.R¹And R²The example of group includes but is not limited to：CF₃, C₂F₅CF₂CF₂CF₃, CF (CF₃)₂, CF₂CF₂CF₂CF₃, CF (CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C (CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C (CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF (CF₃)CF₂CF₂C₂F₅, and C (CF₃)₂CF₂C₂F₅.In one embodiment, the fluoroolefins of formula (i) has at least four carbon atom in the molecule.In another embodiment, the fluoroolefins of the first refrigerant formula (i) with least five carbon atom in molecule.In another embodiment, the fluoroolefins of the first refrigerant formula (i) with least six carbon atom in molecule.The compound of exemplary non-limiting formula (i) is shown in table 1.

Table 1

By making formula R¹Perfluoroalkyl iodides and formula R²CH=CH₂The hydrogen alkene of perfluoroalkyl three contact to form formula R¹CH₂CHIR²Three hydrogen iodo perfluoro alkane, formula (i) compound can be made.Then, the three hydrogen iodo perfluoro alkane dehydroiodination can be made to form R¹CH=CHR².Alternatively, by making formula R²I perfluoroalkyl iodides and formula R¹CH=CH₂The hydrogen olefine reaction of perfluoroalkyl three, then by the formula R of formation¹CHICH₂R²Three hydrogen iodo perfluoro alkane dehydroiodinations, alkene R can be made¹CH=CHR²。

Reactant is mixed in suitable reaction vessel (can be worked under the self-generated pressure of reaction temperature and reactant with product), so as to make perfluoroalkyl iodides and the contact of the hydrogen alkene of perfluoroalkyl three be carried out with batch mode.Suitable reaction vessel is included by stainless steel (specifically by austenitic stainless steels) and by well known Langaloy such as Monel

Monel, Hastelloy

Nickel-base alloy and Inconel

Nichrome be made those.

Alternatively, can half batch mode reacted, wherein at the reaction temperatures, the hydrogen olefin reactant of perfluoroalkyl three is added in perfluoroalkyl iodides reactant by suitable charging (feeding) equipment (such as pump).

The ratio of perfluoroalkyl iodides and the hydrogen alkene of perfluoroalkyl three should be between about 1: 1 to about 4: 1, between 1.5: 1 to 2.5: 1.Ratio less than 1.5: 1 tends to substantial amounts of 2: 1 adduct of generation, such as Jeanneaux et al. "Journal of Fluorine Chemistry" volume 4, reported in the 261-270 pages (1974).

The preferable temperature that the perfluoroalkyl iodides are contacted with the hydrogen alkene of perfluoroalkyl three is preferably in the range of about 150 DEG C to 300 DEG C, preferably from about 170 DEG C to about 250 DEG C, and most preferably from about 180 DEG C to about 230 DEG C.

The suitable contact time of full-fluorine alkyl iodide and the hydrogen olefine reaction of perfluoroalkyl three is about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours.

The three hydrogen iodo perfluoro alkane prepared by perfluoroalkyl iodides with the reaction of the hydrogen alkene of perfluoroalkyl three can be directly used for dehydroiodination step or preferably be reclaimed and purified by distilling before dehydroiodination step.

Dehydroiodination step can be carried out by the way that three hydrogen iodo perfluoro alkane are contacted with alkaline matter.Suitable alkaline matter includes the mixture (such as soda lime) of alkali metal hydroxide (such as NaOH or potassium hydroxide), alkali metal oxide (such as sodium oxide molybdena), alkaline earth metal hydroxide (such as calcium hydroxide), alkaline earth oxide (such as calcium oxide), alkali metal alcoholates (such as sodium methoxide or caustic alcohol), ammoniacal liquor, Sodamide or alkaline matter.It is preferred that alkaline matter be NaOH and potassium hydroxide.

The contact of three hydrogen iodo perfluoro alkane and alkaline matter can be carried out in the liquid phase, be carried out preferably at least one of solvent that can dissolve two kinds of reactants.Solvent suitable for dehydroiodination step includes one or more of polar organic solvents, such as alcohol (such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol and the tert-butyl alcohol), nitrile (such as acetonitrile, propionitrile, butyronitrile, cyanophenyl or adiponitrile), dimethyl sulfoxide (DMSO), N, dinethylformamide, DMA or sulfolane.Solvent can be selected according to the complexity of trace solvent is separated in boiling product and purge process from product.Generally, ethanol or isopropanol are the good solvents of the reaction.

Generally, dehydroiodination reaction can be carried out by adding one kind (alkaline matter or three hydrogen iodo perfluoro alkane) in reactant in another reactant in suitable reaction vessel.The reaction vessel can be made up of glass, ceramics or metal, and preferably use impeller or rabbling mechanism is stirred.

The temperature for being adapted for dehydrogenation iodination reaction is about 10 DEG C to about 100 DEG C, preferably from about 20 DEG C to about 70 DEG C.Dehydroiodination reaction can be carried out in environmental pressure or under the pressure or elevated pressure of reduction.It is worth noting that the dehydroiodination that formula (i) compound is distilled out when it is formed from reaction vessel reacts.

Alternatively, can be by making the aqueous solution of the alkaline matter be contacted in one or more of low polar organic solvents with three hydrogen iodo perfluoro alkane solution to carry out dehydroiodination reaction in the case of there is phase transfer catalyst, the low polar organic solvent such as alkane (such as hexane, heptane or octane), aromatic hydrocarbon (such as toluene), halogenated hydrocarbon (such as dichloromethane, chloroform, carbon tetrachloride or perchloroethylene) or ether (such as ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, 2- methyltetrahydrofurans, dioxane, dimethoxy-ethane, diethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether).Suitable phase transfer catalyst includes quaternary ammonium halide (such as Tetrabutylammonium bromide, 4-butyl ammonium hydrogen sulfate, triethyl benzyl ammonia chloride, DTAC and methyl tricapryl ammonium chloride), season

Halide (such as methyltriphenylphospbromide bromide

And tetraphenylphosphonichloride chloride

) or this area be referred to as the cyclic polyether compound (such as 18- crown-s 6 and 15- crown-s 5) of crown ether.

Alternatively, dehydroiodination reaction can be carried out in the case of in the absence of solvent by the way that three hydrogen are added in solid or liquid basified material for iodine perfluoro alkane.

The suitable reactions time of dehydroiodination reaction is about 15 minutes to about six hours or longer time, and concrete condition depends on the solubility of reactant.Generally, dehydroiodination reaction is quick, and needs about 30 minutes to about three hours to complete.Formula (i) compound can be reclaimed by being separated after addition of water, by distillation or by combinations thereof from dehydroiodination reactant mixture.

In another embodiment of the present invention, the first refrigerant, which is selected from, includes ring-type fluoroolefins (ring-[CX=CY (CZW)_n-] fluoroolefins including (formula (ii)), wherein X, Y, Z and W are independently selected from H and F, and n is 2-5 integer).In one embodiment, there are at least about 3 carbon atoms in formula (ii) fluoroolefins molecule.In another embodiment, there are at least about 4 carbon atoms in formula (ii) fluoroolefins molecule.In another embodiment, there are at least about 5 carbon atoms in formula (ii) fluoroolefins molecule.In another embodiment, there are at least about 6 carbon atoms in formula (ii) fluoroolefins molecule.The representative ring-type fluoroolefins of formula (ii) is listed in Table 2 below.

Table 2

Ring-type fluoroolefins	Structure	Chemical name
			HFO-C1316cc	Ring-CF2CF2CF=CF-	1,2,3,3,4,4- hexafluoro cyclobutane
HFO-C1334cc	Ring-CF2CF2CH=CH-	3,3,4,4- tetrafluoro cyclobutanes
			HFO-C1436	Ring-CF2CF2CF2CH=CH-	3,3,4,4,5,5- hexafluoro cyclopentene
HFO-C1418y	Ring-CF2CF=CFCF2CF2-	1,2,3,3,4,4,5,5- octafluoro cyclopentene
			HFO-C151-10y	Ring-CF2CF=CFCF2CF2CF2-	1,2,3,3,4,4,5,5,6,6- ten fluorine hexamethylene

The first refrigerant of the present invention can include the compound of single formula (i) or formula (ii), for example, one kind of table 1 or the compound in table 2, can also include the combination of the compound of formula (i) or formula (ii).

In another embodiment, the first refrigerant is selected from the fluoroolefins including listed compound in table 3.

Table 3

Title	Structure	Chemical name
			HFO-1225ye	CF3CF=CHF	1,2,3,3,3- five fluoro- 1- propylene
HFO-1225zc	CF3CH=CF2	1,1,3,3,3- five fluoro- 1- propylene
			HFO-1225yc	CHF2CF=CF 2	1,1,2,3,3- five fluoro- 1- propylene
HFO-1234ye	CHF2CF=CHF	1,2,3,3- tetrafluoro-1-propene
			HFO-1234yf	CF3CF=CH 2	2,3,3,3- tetrafluoro-1-propenes
HFO-1234ze	CF3CH=CHF	1,3,3,3- tetrafluoro-1-propene
			HFO-1234yc	CH2FCF=CF 2	1,1,2,3- tetrafluoro-1-propene
HFO-1234zc	CHF2CH=CF2	1,1,3,3- tetrafluoro-1-propene
			HFO-1243yf	CHF2CF=CH 2	2,3,3- tri- fluoro- 1- propylene
HFO-1243zf	CF3CH=CH2	3,3,3- tri- fluoro- 1- propylene

Title	Structure	Chemical name
			HFO-1243yc	CH3CF=CF2	1,1,2- tri- fluoro- 1- propylene
HFO-1243zc	CH2FCH=CF2	1,1,3- tri- fluoro- 1- propylene
			HFO-1243ye	CH2FCF=CHF	1,2,3- tri- fluoro- 1- propylene
HFO-1243ze	CHF2CH=CHF	1,3,3- tri- fluoro- 1- propylene
			HCFO-1233xf	CF3CCl=CH2	2- chloro- 3,3,3- tri- fluoro- 1- propylene
HCFO-1233zd	CF3CH=CHCl	1- chloro- 3,3,3- tri- fluoro- 1- propylene
			HFO-1318my	CF3CF=CFCF3	1,1,1,2,3,4,4,4- octafluoro -2- butylene
HFO-1318cy	CF3CF2CF=CF2	1,1,2,3,3,4,4,4- octafluoro -1- butylene
			HFO-1327my	CF3CF=CHCF3	1,1,1,2,4,4,4- seven fluoro- 2- butylene
HFO-1327ye	CHF=CFCF2CF3	1,2,3,3,4,4,4- seven fluoro- 1- butylene
			HFO-1327py	CHF2CF=CFCF3	1,1,1,2,3,4,4- seven fluoro- 2- butylene
HFO-1327et	(CF3)2C=CHF	1,3,3,3- tetra- fluoro- 2- (trifluoromethyl) -1- propylene
			HFO-1327cz	CF2=CHCF2CF3	1,1,3,3,4,4,4- seven fluoro- 1- butylene
HFO-1327cye	CF2=CFCHFCF3	1,1,2,3,4,4,4- seven fluoro- 1- butylene
			HFO-1327cyc	CF2=CFCF2CHF2	1,1,2,3,3,4,4- seven fluoro- 1- butylene
HFO-1336yf	CF3CF2CF=CH2	2,3,3,4,4,4- hexafluoro -1- butylene
			HFO-1336ze	CHF=CHCF2CF3	1,3,3,4,4,4- hexafluoro -1- butylene
HFO-1336eye	CHF=CFCHFCF3	1,2,3,4,4,4- hexafluoro -1- butylene
			HFO-1336eyc	CHF=CFCF2CHF2	1,2,3,3,4,4- hexafluoro -1- butylene
HFO-1336pyy	CHF2CF=CFCHF2	1,1,2,3,4,4- hexafluoro -2- butylene
			HFO-1336qy	CH2FCF=CFCF3	1,1,1,2,3,4- hexafluoro -2- butylene
HFO-1336pz	CHF2CH=CFCF3	1,1,1,2,4,4- hexafluoro -2- butylene
			HFO-1336mzy	CF3CH=CFCHF2	1,1,1,3,4,4- hexafluoro -2- butylene
HFO-1336qc	CF2=CFCF2CH2F	1,1,2,3,3,4- hexafluoro -1- butylene
			HFO-1336pe	CF2=CFCHFCHF2	1,1,2,3,4,4- hexafluoro -1- butylene
HFO-1336ft	CH2=C (CF3)2	3,3,3- tri- fluoro- 2- (trifluoromethyl) -1- propylene
			HFO-1345qz	CH2FCH=CFCF3	1,1,1,2,4- five fluoro- 2- butylene
HFO-1345mzy	CF3CH=CFCH2F	1,1,1,3,4- five fluoro- 2- butylene
			HFO-1345fz	CF3CF2CH=CH2	3,3,4,4,4- five fluoro- 1- butylene
HFO-1345mzz	CHF2CH=CHCF3	1,1, Isosorbide-5-Nitrae, the fluoro- 2- butylene of 4- five
			HFO-1345sy	CH3CF=CFCF3	1,1,1,2,3- five fluoro- 2- butylene
HFO-1345fyc	CH2=CFCF2CHF2	2,3,3,4,4- five fluoro- 1- butylene
			HFO-1345pyz	CHF2CF=CHCHF2	1,1,2,4,4- five fluoro- 2- butylene
HFO-1345cyc	CH3CF2CF=CF2	1,1,2,3,3- five fluoro- 1- butylene
			HFO-1345pyy	CH2FCF=CFCHF2	1,1,2,3,4- five fluoro- 2- butylene
HFO-1345eyc	CH2FCF2CF=CHF	1,2,3,3,4- five fluoro- 1- butylene
			HFO-1345ctm	CF2=C (CF3)(CH3)	1,1,3,3,3- five fluoro- 2- methyl-1-propylenes
HFO-1345ftp	CH2=C (CHF2)(CF3)	2- (difluoromethyl) -3,3,3- tri- fluoro- 1- propylene
			HFO-1345fye	CH2=CFCHFCF3	2,3,4,4,4- five fluoro- 1- butylene
HFO-1345eyf	CHF=CFCH2CF3	1,2,4,4,4- five fluoro- 1- butylene
			HFO-1345eze	CHF=CHCHFCF3	1,3,4,4,4- five fluoro- 1- butylene

Title	Structure	Chemical name
			HFO-1345ezc	CHF=CHCF2CHF2	1,3,3,4,4- five fluoro- 1- butylene
HFO-1345eye	CHF=CFCHFCHF2	1,2,3,4,4- five fluoro- 1- butylene
			HFO-1354fzc	CH2=CHCF2CHF2	3,3,4,4- tetra- fluoro- 1- butylene
HFO-1354ctp	CF2=C (CHF2)(CH3)	1,1,3,3- tetra- fluoro- 2- methyl-1-propylenes
			HFO-1354etm	CHF=C (CF3)(CH3)	1,3,3,3- tetra- fluoro- 2- methyl-1-propylenes
HFO-1354tfp	CH2=C (CHF2)2	The fluoro- 1- propylene of 2- (difluoromethyl) -3,3- bis-
			HFO-1354my	CF3CF=CHCH3	1,1,1,2- tetra- fluoro- 2- butylene
HFO-1354mzy	CH3CF=CHCF3	1,1,1,3- tetra- fluoro- 2- butylene
			HFO-141-10myy	CF3CF=CFCF2CF3	1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylenes
HFO-141-10cy	CF2=CFCF2CF2CF3	1,1,2,3,3,4,4,5,5,5- ten fluoro- 1- amylenes
			HFO-1429mzt	(CF3)2C=CHCF3	1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene
HFO-1429myz	CF3CF=CHCF2CF3	1,1,1,2,4,4,5,5,5- nine fluoro- 2- amylenes
			HFO-1429mzy	CF3CH=CFCF2CF3	1,1,1,3,4,4,5,5,5- nine fluoro- 2- amylenes
HFO-1429eyc	CHF=CFCF2CF2CF3	1,2,3,3,4,4,5,5,5- nine fluoro- 1- amylenes
			HFO-1429czc	CF2=CHCF2CF2CF3	1,1,3,3,4,4,5,5,5- nine fluoro- 1- amylenes
HFO-1429cycc	CF2=CFCF2CF2CHF2	1,1,2,3,3,4,4,5,5- nine fluoro- 1- amylenes
			HFO-1429pyy	CHF2CF=CFCF2CF3	1,1,2,3,4,4,5,5,5- nine fluoro- 2- amylenes
HFO-1429myyc	CF3CF=CFCF2CHF2	1,1,1,2,3,4,4,5,5- nine fluoro- 2- amylenes
			HFO-1429myye	CF3CF=CFCHFCF3	1,1,1,2,3,4,5,5,5- nine fluoro- 2- amylenes
HFO-1429eyym	CHF=CFCF (CF3)2	1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene
			HFO-1429cyzm	CF2=CFCH (CF3)2	1,1,2,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene
HFO-1429mzt	CF3CH=C (CF3)2	1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene
			HFO-1429czym	CF2=CHCF (CF3)2	1,1,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene
HFO-1438fy	CH2=CFCF2CF2CF3	2,3,3,4,4,5,5,5- octafluoro -1- amylenes
			HFO-1438eycc	CHF=CFCF2CF2CHF2	1,2,3,3,4,4,5,5- octafluoro -1- amylenes
HFO-1438ftmc	CH2=C (CF3)CF2CF3	3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene
			HFO-1438czzm	CF2=CHCH (CF3)2	1, Isosorbide-5-Nitrae, 4,4- five fluoro- 3- (trifluoromethyl) -1- butylene
HFO-1438ezym	CHF=CHCF (CF3)2	1,3,4,4,4- five fluoro- 3- (trifluoromethyl) -1- butylene
			HFO-1438ctmf	CF2=C (CF3)CH2CF3	1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- (trifluoromethyl) -1- butylene
HFO-1447fzy	(CF3)2CFCH=CH2	3,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene
			HFO-1447fz	CF3CF2CF2CH=CH2	3,3,4,4,5,5,5- seven fluoro- 1- amylenes
HFO-1447fycc	CH2=CFCF2CF2CHF2	2,3,3,4,4,5,5- seven fluoro- 1- amylenes
			HFO-1447czcf	CF2=CHCF2CH2CF3	1,1,3,3,5,5,5- seven fluoro- 1- amylenes
HFO-1447mytm	CF3CF=C (CF3)(CH3)	1,1,1,2,4,4,4- seven fluoro- 3- methyl-2-butenes
			HFO-1447fyz	CH2=CFCH (CF3)2	2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene
HFO-1447ezz	CHF=CHCH (CF3)2	Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene
			HFO-1447qzt	CH2FCH=C (CF3)2	Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 2- (trifluoromethyl) -2- butylene
HFO-1447syt	CH3CF=C (CF3)2	2,4,4,4- tetra- fluoro- 2- (trifluoromethyl) -2- butylene
			HFO-1456szt	(CF3)2C=CHCH3	3- (trifluoromethyl) -4,4,4- tri- fluoro- 2- butylene
HFO-1456szy	CF3CF2CF=CHCH3	3,4,4,5,5,5- hexafluoro -2- amylenes
			HFO-1456mstz	CF3C(CH3)=CHCF3	1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- methyl-2-butenes

The compound listed in table 2 and table 3 is commercially available, can also be prepared by methods known in the art or method described herein.

1,1, Isosorbide-5-Nitrae, the fluoro- 2- butylene of 4- five can be by 1,1,1,2,4,4- hexafluoro butane (CHF₂CH₂CHFCF₃) prepared in the gas phase by the dehydrofluorination on solid KOH at room temperature.The synthesis of 1,1,1,2,4,4- hexafluoro butane is described in US 6,066,768.1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene can make 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- iodobutanes (CF by using phase transfer catalyst at about 60 DEG C₃CHICH₂CF₃) react to prepare with KOH.1,1, Isosorbide-5-Nitrae, the synthesis of 4,4- hexafluoro -2- iodobutanes can pass through perfluoro-methyl iodine (CF₃I) with 3,3,3- trifluoro propene (CF₃CH=CH₂) react about 8 hours under about 200 DEG C, self-generated pressure to carry out.

3,4,4,5,5,5- hexafluoro -2- amylenes can be by carrying out 1,1,1,2,2,3,3- seven amyl fluoride (CF using solid KOH at 200-300 DEG C or on C catalyst₃CF₂CF₂CH₂CH₃) dehydrofluorination prepare.1,1,1,2,2,3,3- seven amyl fluoride can pass through 3,3,4,4,5,5,5- seven fluoro- 1- amylenes (CF₃CF₂CF₂CH=CH₂) hydrogenization prepare.

1,1,1,2,3,4- hexafluoro -2- butylene can be by using solid KOH to 1,1,1,2,3,3,4- seven fluorine butane (CH₂FCF₂CHFCF₃) carry out dehydrofluorination to prepare.

1,1,1,2,4,4- hexafluoro -2- butylene can be by using solid KOH to 1,1,1,2,2,4,4- seven fluorine butane (CHF₂CH₂CF₂CF₃) carry out dehydrofluorination to prepare.

1,1,1,3,4,4- hexafluoro -2- butylene can be by using solid KOH to 1,1,1,3,3,4,4- seven fluorine butane (CF₃CH₂CF₂CHF₂) carry out dehydrofluorination to prepare.

1,1,1,2,4- five fluoro- 2- butylene can be by using solid KOH to 1,1,1,2,2,3- hexafluoro butane (CH₂FCH₂CF₂CF₃) carry out dehydrofluorination to prepare.

1,1,1,3,4- five fluoro- 2- butylene can be by using solid KOH to 1,1,1,3,3,4- hexafluoro butane (CF₃CH₂CF₂CH₂F dehydrofluorination) is carried out to prepare.

1,1,1,3- tetra- fluoro- 2- butylene can be by making 1,1,1,3,3- 3-pentafluorobutane (CF₃CH₂CF₂CH₃) react to prepare at 120 DEG C with the KOH aqueous solution.

1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- amylenes can by using phase transfer catalyst at about 60 DEG C by (CF₃CHICH₂CF₂CF₃) react to prepare with KOH.4- iodos -1,1, the synthesis of 1,2,2,5,5,5- octafluoro pentane can be by making perfluor iodoethane (CF₃CF₂I) react about 8 hours under about 200 DEG C, self-generated pressure to carry out with 3,3,3- trifluoro propenes.

1,1,1,2,2,5,5,6,6,6- ten fluoro- 3- hexenes can by using phase transfer catalyst at about 60 DEG C by 1,1,1,2,2,5,5,6,6,6- ten fluoro- 3- iodohexanes (CF₃CF₂CHICH₂CF₂CF₃) react to prepare with KOH.The synthesis of 1,1,1,2,2,5,5,6,6,6- ten fluoro- 3- iodohexanes can pass through perfluor iodoethane (CF₃CF₂I) with 3,3,4,4,4- five fluoro- 1- butylene (CF₃CF₂CH=CH₂) react about 8 hours under about 200 DEG C, self-generated pressure to carry out.

1,1, Isosorbide-5-Nitrae, 5,5,5- seven fluoro- 4- (trifluoromethyl) -2- amylenes can pass through 1,1,1,2,5,5,5- seven fluoro- 4- iodos -2- (trifluoromethyl)-pentane (CF₃CHICH₂CF(CF₃)₂) prepare with dehydrofluorinations of the KOH in isopropanol.CF₃CHICH₂CF(CF₃)₂By at high temperature, at e.g., from about 200 DEG C, by (CF₃)₂CFI and CF₃CH=CH₂Reaction prepare.

1,1, Isosorbide-5-Nitrae, 4,5,5,6,6,6- ten fluoro- 2- hexenes can pass through 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene CF₃CH=CHCF₃) and tetrafluoroethene (CF₂=CF₂) and antimony pentafluoride (SbF₅) reaction prepare.

2,3,3,4,4- five fluoro- 1- butylene can be prepared by the dehydrofluorination of under high temperature 1,1,2,2,3,3- hexafluoro butane on fluorided alumina.

2,3,3,4,4,5,5,5- octafluoro -1- amylenes can be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5- nine amyl fluorides on solid KOH.

1,2,3,3,4,4,5,5- octafluoro -1- amylenes can be prepared by the dehydrofluorination of under high temperature 2,2,3,3,4,4,5,5,5- nine amyl fluorides on fluorided alumina.

Formula 1, formula 2, table 1, many compounds of table 2 and table 3 exist with the isomers of various configuration or stereoisomer.When not specified specific isomers, it is contemplated that the isomers including all single configurations, single stereoisomer or any combination of them.For example, F11E is intended to represent any combinations or mixture of two kinds of isomers of E- isomers, Z- isomers or any ratio.And for example, HFO-1225ye is intended to represent any combinations or mixture of two kinds of isomers of E- isomers, Z- isomers or any ratio.

In addition, the first refrigerant can be any single fluoroolefins in formula (i), formula (ii), table 1, table 2 and table 3, or it is any combination of different fluoroolefins in formula (i), formula (ii), table 1, table 2 and table 3.

In some embodiments, first refrigerant can be single fluoroolefins or multiple fluoroolefins selected from formula (i), formula (ii), table 1, table 2 and table 3, with any combination of at least one other refrigerant, the refrigerant is selected from HFC, fluoro-ether, hydrocarbon, CF₃I, ammonia (NH₃), carbon dioxide (CO₂), nitrous oxide (N₂O) and their mixture, this refers to the mixture of i.e. any aforesaid compound.

In some embodiments, the first refrigerant can include HFC, and the HFC contains the saturated compounds of at least one carbon containing, hydrogen and fluorine.Especially useful is with 1-7 carbon atom and with the HFC of about -90 DEG C to about 80 DEG C of normality boiling point.HFC is can be from a variety of commercial products originated and obtained, or can be prepared with methods known in the art.Representational HFC compound includes but is not limited to fluomethane (CH₃F, HFC-41), difluoromethane (CH₂F₂, HFC-32), fluoroform (CHF₃, HFC-23), pentafluoroethane (CF₃CHF₂, HFC-125), 1,1,2,2- HFC-134a (CHF₂CHF₂, HFC-134), HFA 134a (CF₃CH₂F, HFC-134a), 1,1,1- HFC-143a (CF₃CH₃, HFC-143a), 1,1- Difluoroethanes (CHF₂CH₃, HFC-152a), fluoroethane (CH₃CH₂F, HFC-161), 1,1,1,2,2,3,3- heptafluoro-propane (CF₃CF₂CHF₂, HFC-227ca), HFC-227ea (CF₃CHFCF₃, HFC-227ea), 1,1,2,2,3,3 ,-HFC-236fa (CHF₂CF₂CHF₂, HFC-236ca), 1,1,1,2,2,3- HFC-236fa (CF₃CF₃CH₂F, HFC-236cb), 1,1,1,2,3,3- HFC-236fa (CF₃CHFCHF₂, HFC-236ea), 1,1,1,3,3,3- HFC-236fa (CF₃CH₂CF₃, HFC-236fa), 1,1,2,2,3- pentafluoropropane (CHF₂CF₂CH₂F, HFC-245ca), 1,1,1,2,2- pentafluoropropane (CF₃CF₂CH₃, HFC-245cb), 1,1,2,3,3- pentafluoropropane (CHF₂CHFCHF₂, HFC-245ea), 1,1,1,2,3- pentafluoropropane (CF₃CHFCH₂F, HFC-245eb), 1,1,1,3,3- pentafluoropropane (CF₃CH₂CHF₂, HFC-245fa), 1,2,2,3- tetrafluoropropane (CH₂FCF₂CH₂F, HFC-254ca), 1,1,2,2- tetrafluoropropane (CHF₂CF₂CH₃, HFC-254cb), 1,1,2,3- tetrafluoropropane (CHF₂CHFCH₂F, HFC-254ea), 1,1,1,2- tetrafluoropropane (CF₃CHFCH₃, HFC-254eb), 1,1,3,3- tetrafluoropropane (CHF₂CH₂CHF₂, HFC-254fa), 1,1,1,3- tetrafluoropropane (CF₃CH₂CH₂F, HFC-254fb), 1,1,1- trifluoro propane (CF₃CH₂CH₃, HFC-263fb), 2,2- difluoropropanes (CH₃CF₂CH₃, HFC-272ca), 1,2- difluoropropanes (CH₂FCHFCH₃, HFC-272ea), 1,3- difluoropropanes (CH₂FCH₂CH₂F, HFC-272fa), 1,1- difluoropropanes (CHF₂CH₂CH₃, HFC-272fb), 2- fluoro-propanes (CH₃CHFCH₃, HFC-281ea), 1- fluoro-propanes (CH₂FCH₂CH₃, HFC-281fa), 1,1,2,2,3,3,4,4- octafluorobutane (CHF₂CF₂CF₂CHF₂, HFC-338pcc), 1,1,1,2,2,4,4,4- octafluorobutane (CF₃CH₂CF₂CF₃, HFC-338mf), 1,1,1,3,3- 3-pentafluorobutane (CF₃CH₂CHF₂, HFC-365mfc), 1,1,1,2,3,4,4,5,5,5- Decafluoropentane (CF₃CHFCHFCF₂CF₃, HFC-43-10mee) and 1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten tetrafluoro heptane (CF₃CF₂CHFCHFCF₂CF₂CF₃, HFC-63-14mee).

In some embodiments, the first refrigerant can also include fluoro-ether.Fluoro-ether includes at least one compound, and the compound contains carbon, fluorine, oxygen and optional hydrogen, chlorine, bromine or iodine.Fluoro-ether is commercially available, it is also possible to prepared by methods known in the art.Representational fluoro-ether includes but is not limited to Nonafluoromethoxybutcompositions (C₄F₉OCH₃, any or all possible isomers or their mixture), nine fluorine ethoxy butane (C₄F₉OC₂H₅, any or all possible isomers or their mixture), 2- difluoro-methoxies-HFA 134a (HFOC-236eaE β γ or CHF₂OCHFCF₃), 1,1- difluoro-2-methoxyls ethane (HFOC-272fbE β γ, CH₃OCH₂CHF₂), 1,1,1,3,3,3- hexafluoro -2- (fluorine methoxyl group) propane (HFOC-347mmzE β γ or CH₂FOCH(CF₃)₂), 1,1,1,3,3,3- hexafluoro -2- methoxy propanes (HFOC-356mmzE β γ or CH₃OCH(CH₃)₂), 1,1,1,2,2- five fluoro- 3- methoxy propanes (HFOC-365mcE γ δ or CF₃CF₂CH₂OCH₃), 2- ethyoxyls-HFC-227ea (HFOC-467mmyE β γ or CH₃CH₂OCF(CF₃)₂And their mixture.

In some embodiments, the first refrigerant can also include at least one hydrocarbon.Hydrocarbon is the compound only with carbon and hydrogen.Especially useful is the compound with 3-7 carbon atom.Many chemicals suppliers that can comform buy hydrocarbon.Representational hydrocarbon includes but is not limited to propane, normal butane, iso-butane, cyclobutane, pentane, 2- methybutanes, 2,2- dimethylpropanes, pentamethylene, n-hexane, 2- methylpentanes, 2,2- dimethylbutanes, 2,3- dimethylbutanes, 3- methylpentanes, hexamethylene, normal heptane, cycloheptane and their mixture.In some embodiments, disclosed composition, which can be included, contains heteroatomic hydrocarbon, such as dimethyl ether (DME, CH₃OCH₃).DME is commercially available.

In some embodiments, the first refrigerant can also include carbon dioxide (CO₂), it can be commercially available from various sources, or is made by methods known in the art.

In some embodiments, the first refrigerant can also include ammonia (NH₃), it can be commercially available from various sources, or is made by methods known in the art.

In some embodiments, the first refrigerant can also include CF3I (CF₃I), it can be commercially available from various sources, or is made by methods known in the art.

In specific embodiments, the first and second refrigerants can be as shown in Table 4 below.

Table 4

	The first refrigerant for cryogenic circuit	Second refrigerant for middle circuit temperature
			1	CO2Or N2O	HFO-1234yf
2	HFO-1234yf/HFC-32	HFO-1234yf
			3	Trans HFO-1234ze/HFC-32	HFO-1234yf
4	CO2Or N2O	HFO-1234yf/HFC-134a
			5	HFO-1234yf/HFC-32	HFO-1234yf/HFC-134a
6	Trans HFO-1234ze/HFC-32	HFO-1234yf/HFC-134a
			7	CO2Or N2O	HFO-1234yf/HFC-32
8	HFO-1234yf/HFC-32	HFO-1234yf/HFC-32
			9	Trans HFO-1234ze/HFC-32	HFO-1234yf/HFC-32

	The first refrigerant for cryogenic circuit	Second refrigerant for middle circuit temperature
			10	CO2Or N2O	Trans HFO-1234ze/HFC-32
11	HFO-1234yf/HFC-32	Trans HFO-1234ze/HFC-32
			12	Trans HFO-1234ze/HFC-32	Trans HFO-1234ze/HFC-32
13	CO2Or N2O	Trans HFO-1234ze/HFC-134a
			14	HFO-1234yf/HFC-32	Trans HFO-1234ze/HFC-134a
15	Trans HFO-1234ze/HFC-32	Trans HFO-1234ze/HFC-134a
			16	CO2Or N2O	Trans HFO-1234ze/HFC-125
17	HFO-1234yf/HFC-32	Trans HFO-1234ze/HFC-125
			18	Trans HFO-1234ze/HFC-32	Trans HFO-1234ze/HFC-125

In certain embodiments, second refrigerant can be substantially made up of HFO-1234yf.In other embodiments, second refrigerant can include HFO-1234yf and R134a.In another embodiment, second refrigerant can include HFO-1234yf and R32, or it can include trans HFO-1234ze and HFC-32, or trans HFO-1234ze and HFC-134a, or trans HFO-1234ze and HFC-125.

In the embodiment that second refrigerant is substantially made up of HFO-1234yf, the first refrigerant can include carbon dioxide (CO₂) or nitrous oxide (N₂O).Alternatively, in the embodiment that second refrigerant is substantially made up of HFO-1234yf, the first refrigerant can include HFO-1234yf and HFC-32.In another embodiment that second refrigerant is substantially made up of HFO-1234yf, the first refrigerant can include trans HFO-1234ze and HFC-32.

In embodiment of the second refrigerant comprising HFO-1234yf and HFC-134a, or when second refrigerant includes HFO-1234yf and HFC-32, the first refrigerant can include carbon dioxide or nitrous oxide.Alternatively, in second refrigerant includes HFO-1234yf and HFC-134a, or HFO-1234yf and HFC-32 embodiment, the first refrigerant can include HFO-1234yf and HFC-32.In second refrigerant includes HFO-1234yf and HFC-134a, or HFO-1234yf and HFC-32 another embodiment, the first refrigerant can include trans HFO-1234ze and HFC-32.

In second refrigerant comprising in the particular of HFO-1234yf and R134a and the first refrigerant comprising HFO-1234yf and HFC-32, second refrigerant can include 1-99% HFO-1234yf and 99-1% HFC-134a.In one embodiment, HFO-1234yf and 46.9-99% of the second refrigerant comprising 1-53.1% HFC-134a.Specifically, second refrigerant includes 53% HFO-1234yf and 47% HFC-134a.In one embodiment, HFO-1234yf and 41-99% of the second refrigerant comprising 1-59% HFC-134a.In this embodiment, second refrigerant is nonflammable at 100 DEG C or 60 DEG C.Said composition is nonflammable, and with the maximum capacity in the range of 40-59% 1234yf and 41-60% 134a.Specifically, second refrigerant can include 53% HFO-1234yf and 47% HFC-134a.

In particular of the second refrigerant comprising HFO-1234yf and HFC-32, the scope of these components can be 1-99% HFO-1234yf and 99-1% HFC-32.In one particular embodiment, second refrigerant can include 20-99% HFO-1234yf and 80-99% HFC-32.More particularly, second refrigerant can include 50-99% HFO-1234yf and 50-99% HFC-32, even more specifically, and second refrigerant can include 63% HFO-1234yf and 37% HFC-32.In this embodiment, second refrigerant can be used as R404A substitute.In another embodiment, second refrigerant can include 27.5% HFO-1234yf and 72.5% HFC-32.In this embodiment, second refrigerant can be used as R410A substitute.In second refrigerant comprising in the HFO-1234yf and any embodiment of HFC-32 foregoing embodiments in special scope, the first refrigerant can include CO₂Or N₂O, HFO-1234yf/HFC-32 blend, or trans HFO-1234ze/HFC-32 blend.

In embodiment of the second refrigerant comprising trans HFO-1234ze and HFC-32, the first refrigerant can include carbon dioxide or nitrous oxide.Alternatively, in embodiment of the second refrigerant comprising trans HFO-1234ze and HFC-32, the first refrigerant can include HFO-1234yf and HFC-32.In another embodiment of second refrigerant comprising trans HFO-1234ze and HFC-32, the first refrigerant can include trans HFO-1234ze and HFC-32.

In particular of the second refrigerant comprising trans HFO-1234ze and HFC-32, HFO-1234ze and 99-1% of the second refrigerant comprising 1-99% HFC-32.1234ze can be trans 1234ze or cis 1234ze.In second refrigerant comprising in the trans HFO-1234ze and any embodiment of HFC-32 foregoing embodiments in special scope, the first refrigerant can include CO₂Or N₂O, HFO-1234yf/HFC-32 blend, or trans HFO-1234ze/HFC-32 blends.

In embodiment of the second refrigerant comprising trans HFO-1234ze and HFC-134a, the first refrigerant can include CO₂Or N₂O.Alternatively, in embodiment of the second refrigerant comprising trans HFO-1234ze and HFC-32, the first refrigerant can include HFO-1234yf and HFC-134a.In another embodiment of second refrigerant comprising trans HFO-1234ze and HFC-32, the first refrigerant can include trans HFO-1234ze and HFC-134a.

In embodiment of the second refrigerant comprising trans HFO-1234ze and HFC-125, the first refrigerant can include carbon dioxide or nitrous oxide.Alternatively, in embodiment of the second refrigerant comprising trans HFO-1234ze and HFC-32, the first refrigerant can include HFO-1234yf and HFC-125.In another embodiment of second refrigerant comprising trans HFO-1234ze and HFC-32, the first refrigerant can include trans HFO-1234ze and HFC-125.

The various configurations of cascade system are also within the scope of the invention.For example with reference to Fig. 2, it shows the cascade system according to the present invention, wherein corresponding to element same drawing reference numeral and apostrophe (') expression of element shown in Fig. 1.The element for corresponding to element shown in Fig. 1 in fig. 2 is operated as described above for described in Fig. 1.In addition, Fig. 2 cascade system includes the second heat transfer circuit, it includes second fluid cooler 30 and second fluid heat exchanger 32.Second fluid heat exchanger is located near the main body to be cooled (food such as in middle temperature showcase).Second cooler cools down the second heat transfer fluid.The use of the second heat transfer circuit is in the embodiment of fig. 2 favourable, because the length for the pipeline that its amount and refrigerant for limiting the refrigerant that must be used must be cycled through, however, (remote location such as in the big supermarket) heat transfer between position that must be away from each other simultaneously.Minimize the amount of refrigerant and the length reduction refrigerant cost of refrigerant tubing, percolation ratio and the mitigation risk related to using inflammable and/or toxicity refrigerant.In addition, or as another option of configuration as shown in Figure 2, second servo loop can be used to from low-temperature display cabinet to low-temperature circuit transmit heat similar to the shown configuration on shown in high temperature or middle temperature loops in fig. 2.However, the selection of the second heat transfer fluid will be quite restricted, because at low temperature, the viscosity of liquid and related pumping cost increase.

Fig. 2 cascade refrigeration system also includes the cascade heat exchanger system being arranged between low temperature refrigeration circuit and middle temperature refrigeration loop.As in the above-described embodiment, cascade heat exchanger system has first entrance 22a ' and first outlet 22b ', wherein the first refrigerant vapour is recycled to first outlet from first entrance, and is condensed in heat exchanger system to form the first refrigerant liquid, so as to discharge heat.Cascade heat exchanger system also includes second entrance 22c ' and second outlet 22d ', wherein second refrigerant liquid is recycled to second outlet from second entrance, and absorb the heat discharged by the first refrigerant, and as being formed and will being explained in second refrigerant steam, following article.Therefore, in the embodiment of fig. 2, the heat discharged by the first refrigerant is directly absorbed by second refrigerant.

Specifically, referring to Fig. 2, the second heat transfer fluid enters the second cooler in first entrance 30a and leaves the second cooler in first outlet 30b.Second heat transfer fluid may include ethylene glycol, propane diols, carbon dioxide, salt solution or any number of other fluids or suspension known in the art.In some embodiments, the second heat transfer fluid can undergo phase transformation.In addition, the second cooler includes second entrance 30c and second outlet 30d.Second refrigerant enters second fluid cooler by second entrance 30c and evaporated, therefore causes the heat transfer fluid in cooler to be cooled.The heat transfer fluid of cooling leaves cooler 30 and the second fluid heat exchanger 32 being recycled near the main body to be cooled by first outlet 30b.The main body to be cooled can be the food in the showcase freezed in supermarket.Heat transfer fluid is heated by the main body, and in the second fluid cooler that cooled down again by evaporating second refrigerant to return to, the second refrigerant equally cycles through second fluid cooler.Liquid pump (not shown) is by heat transfer fluid from second fluid heat exchanger pumped back second fluid cooler.The heated heat transfer fluid causes second refrigerant to be evaporated in second fluid cooler.Separated expansion gear (not shown) can be placed in at the suction line of cascade heat exchanger 22 ', and suction line passes through cascade heat exchanger and the flow of second fluid cooler so as to control pressure and respectively into second fluid cooler 30.Although cascade heat exchanger 22 ' is shown as parallel connection with second fluid cooler 30, they or can be connected in series without departing from scope of the invention.

The second refrigerant liquid for leaving the part reduction pressure and temperature of condenser 26 ' enters cascade heat exchanger 22 ' in entrance 22c '.In cascade heat exchanger 22 ', in such as Fig. 1 the first embodiment, the first refrigerant is condensed, and second refrigerant evaporates and left in outlet 22d ' from heat exchanger 22 '.Second refrigerant is incorporated from the outlet 22d ' of cascade heat exchanger and be recycled to the second compressor 24 ' in the second outlet 30d second refrigerants for leaving second fluid cooler 30.By the circulation of middle temperature loops 14 ' and low-temperature circuit 12 ' in addition with above with respect to Fig. 1 discuss it is identical.

Another embodiment of the cascade refrigeration system of the present invention is shown in Figure 3.In Fig. 3 embodiment, corresponding to element the identical drawing reference numeral and double apostrophes (" of element shown in Fig. 1) represent.The element for corresponding to element shown in Fig. 1 in figure 3 is operated as described above for described in Fig. 1.Fig. 3 system includes the second heat transfer circuit, generally so that shown in 40, it includes two cascade heat exchangers rather than a cascade heat exchanger, as shown in the embodiment in Fig. 1 and 2.As in the embodiment of fig. 2, the use of the second heat transfer circuit is favourable in Fig. 3 embodiment, because the length for the pipeline that must be cycled through which limit the amount for the refrigerant that must be used and refrigerant, however, the heat transfer between position that must be away from each other simultaneously.

Fig. 3 embodiment includes cascade heat exchanger system, and it includes two cascade heat exchangers being connected to each other by the second heat transfer circuit.Cascade heat exchanger system in figure 3 has first entrance 42a and first outlet 42b, wherein the first refrigerant vapour is recycled to first outlet from first entrance and condensed in cascade heat exchanger system to form the first refrigerant liquid, so as to discharge heat.Cascade heat exchanger system also includes second entrance 44c and second outlet 44d, and wherein second refrigerant liquid is recycled to second outlet from second entrance and absorbed indirectly by the heat of the first refrigerant discharge, and forms second refrigerant steam.In Fig. 3 embodiment, second refrigerant liquid absorbs the heat discharged by the first refrigerant by the second heat transfer fluid indirectly, in other words, first refrigerant discharges heat to heat transfer fluid, and heat transfer fluid is recycled to the second cascade heat exchanger 44, wherein it shifts heat from the first refrigerant to second refrigerant, as will be described below.The heat is disposed in environment.

Referring to Fig. 3, cascade refrigeration system 10 " is included in the first cascade heat exchanger 42 in low-temperature circuit 12 ", and it has first entrance 42a and first outlet 42b, and second entrance 42c and second outlet 42d.Middle temperature loops 14 " include the second cascade heat exchanger 44, and it has first entrance 44a and first outlet 44b, and second entrance 44c and second outlet 44d.As shown in figure 3, the first refrigerant vapour of compression is recycled to the first entrance 42a of First Heat Exchanger 42 from the first compressor 20b " outlet.As shown in the implementation of figure 1, the refrigerant vapour of the compression is condensed in the first cascade heat exchanger to form the first refrigerant liquid, so as to discharge heat.Then the first refrigerant liquid is recycled to the first outlet 42b of the first cascade heat exchanger.Heat transfer fluid in the second heat transfer circuit between the second cascade heat exchanger 44 of the middle part of temperature loops 14 " in the first cascade heat exchanger and also to circulate.Specifically, heat transfer fluid enters First Heat Exchanger 42 by second entrance 42c and leaves First Heat Exchanger by second outlet 42d.The heat transfer fluid is absorbed by condensing the heat for entering the first refrigerant of that heat exchanger via entrance 42a and discharging, and is heated.Heated heat transfer fluid leaves First Heat Exchanger by second outlet 42d and is recycled to the second heat exchanger 44.Heat transfer fluid is cooled by the way that heat is drained into second refrigerant in the second heat exchanger, and the second condensing agent enters the second heat exchanger by second entrance 44c, and leaves the second heat exchanger by second outlet 44d.Second refrigerant evaporates in the second cascade heat exchanger, because it is heated by heat transfer fluid, and forms second refrigerant steam.The heat transfer fluid of condensation leaves the first outlet 44b of the second heat exchanger.By the circulation of low-temperature circuit 12 " and middle temperature loops 14 " it is other with above with respect to Fig. 1 discuss it is identical, the difference is that in this embodiment, first and/or second refrigerant can be but not be necessarily fluoroolefins.

Another embodiment of the cascade refrigeration system of the present invention is shown in Figure 4.In the embodiment of fig. 4, corresponding to element the identical drawing reference numeral and three apostrophes (" ' of element shown in Fig. 1) represent.The element for corresponding to element shown in Fig. 1 in Fig. 4 is operated as described above for described in Fig. 1.Fig. 4 system includes two low-temperature circuits, similar to the loop 12A and loop 12B of the low-temperature circuit 12 in Fig. 1.One in two low-temperature circuits, such as loop 12B there is provided being different from temperature, for example in the middle of to the refrigeration at a temperature of the refrigeration provided wherein by other low-temperature circuits and by middle temperature loops.The advantage of such system can be used for the refrigerator showcase for cooling down two different main bodys, such as two at two different temperature separation for the refrigerant in low-temperature circuit.

In the embodiment of fig. 4, cascade heat exchanger system is arranged between two loops.Cascade heat exchanger system has first entrance 22a " ' and second entrance 22b " ' and first outlet 52, wherein the first refrigerant vapour is recycled to first outlet from the first and second entrances and condensed in heat exchanger system to form the first refrigerant liquid, so as to discharge heat.Cascade heat exchanger system also includes the 3rd entrance 22c " ' and second outlet 22d " ', and wherein second refrigerant liquid is recycled to second outlet from the 3rd entrance and absorbed indirectly by the heat of the first refrigerant discharge, and forms second refrigerant steam.Therefore, in the embodiment of fig. 4, the heat discharged by the first refrigerant is directly absorbed by second refrigerant, and the heat is disposed in environment.

It should be pointed out that the embodiment described in Fig. 4 includes the cascade heat exchanger system of all heats of transmission in the above described manner within the scope of the invention.

It is split after in the system of Fig. 4 embodiment, the stream of the first refrigerant liquid 52 leaves cascade heat exchanger 22 " when it ' when or leave cascade heat exchanger 22 " '.A part is circulated by a low-temperature circuit 12A, and another part is circulated by other low-temperature circuit 12B.Additional expansion gear 54 is entered in entrance 54a by loop 12B the first refriger-ant sections circulated, and the pressure and temperature of the part of the first refrigerant liquid is lowered.Then the liquid refrigerant of the reduction pressure and temperature is circulated by the outlet 54b of additional expansion gear and is recycled to additional evaporator 56.It should be pointed out that the liquid can partly evaporate during the expansion.Additional evaporator 56 includes entrance 56a and outlet 56b.Refrigerant liquid from additional expansion device enters evaporator by evaporator inlet 56a and evaporated in evaporator to form refrigerant vapour, so as to form cooling, and is recycled to outlet 56b.Low-temperature circuit 12B is also wrapped includes additional compressor 58 with entrance 58a and outlet 58b.The first refrigerant vapour from additional evaporator 56 is recycled to the entrance 58a of additional compressor 58 and compressed, so as to improve the pressure and temperature of the first refrigerant vapour, and the first refrigerant vapour compressed is recycled to the outlet 58b of additional compressor and is recycled to cascade heat exchanger 22 " ' entrance 22b " '.By other low-temperature circuit 12A and middle temperature loops 14 " ' circulation in addition with above with respect to Fig. 1 discussed it is identical.Specifically, low-temperature circuit 12A also includes evaporator 18 " ', it can be encapsulated within refrigerator showcase, and additional evaporator 56 can be encapsulated within refrigerator showcase.Therefore, the system can provide cooling to two separated refrigerator showcases.

Always according to the present invention there is provided the method for the heat-shift between at least two refrigerating circuits, including：(a) heat is absorbed from the main body to be cooled in the first refrigerating circuit and by the heat dissipation to the second refrigerating circuit；In second refrigerating circuit absorb heat from first refrigerating circuit and by the heat dissipation into environment (b).Refrigerant in any one loop, the i.e. wherein absorbed loop of heat, or the loop that wherein heat is discharged, or both can include fluoroolefins.Heat from the first refrigerating circuit can directly be absorbed in the second refrigerating circuit, the embodiment as described in Fig. 1,2 and 4, or can directly be absorbed in the second refrigerating circuit, in embodiment as described in Figure 3.

Embodiment

Embodiment 1

The cooling performance of cascade system higher temperature circulation

Table 5 shows some example combinations physical performances and HFC-134a comparison.In table 5, Evap Pres are evaporator pressure, Cond Pres are condenser pressure, Comp Disch T are compressor discharge temperature, COP is the coefficient of performance (being similar to energy efficiency), CAP is capacity, and mean temperature sliding is the average value of the temperature glide in evaporator and condenser, and GWP is global warming up trend.The data are based on following condition.

Note：Evaporator superheat enthalpy is not included in cooling capacity and energy efficiency measure.

Table 5

^*GWP value on HFC-134a is derived from " Climate Change 2007-IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report on Climate Change ", from following part：Entitled " the Report of Working Group 1：" The Physical Science Basis ", the 2nd chapter, the 212-213 pages, table 2.14.Value on FO-1234yf is published in Papadimitriou et al. Physical Chemistry Chemical Physics, volume 9, the 1-13 pages in 2007.Specifically, using the horizontal GWP value of 100 years.The GWP value of composition comprising HFC-134a and HFO-1234yf is calculated by the weighted average of one pack system GWP value.

Data display 1234yf/134a compositions in table 5 are tight fit 134a according to COP in systems, capacity, pressure and temperature, and it has relatively low GWP value.In addition, all compositions have, low temperature is slid and specific composition can be selected based on management organization for GWP requirement, and this is not measured also at this moment.HFO-1234yf comprising 53 weight % and 47 weight % HFC-134a composition have particularly provide low GWP and in cooling capacity peak value beneficial effect.This is represented with diagram in Figure 5.

Embodiment LE2

The inflammability of HFO-1234yf/HFC-134a mixtures

Can be by according to ASTM (American Society Testing and Materials) E681-2004, being tested to differentiate combustible composition using electronic ignition source.Such inflammability test is on the composition comprising HFO-1234yf and HFC-134a, in 101kPa (14.7psia), 50% relative humidity, and carried out in atmosphere with various concentration at about 23 DEG C (room temperature), 60 DEG C and 100 DEG C, it is inflammable to determine whether, and if it does, find relatively low limit of flammability (LFL) and higher limit of flammability (UFL).As a result it is shown in Table 6.

Table 6

%HFO-1234yf	%HFC-134a	Room temperature		60℃	100℃
								LFL    UFL	LFL    UFL	LFL    UFL
50.00	50.00	It is nonflammable	It is nonflammable	It is nonflammable
					52.50	47.50	It is nonflammable	It is nonflammable	It is nonflammable
53.10	46.9	It is nonflammable	It is nonflammable	It is nonflammable
					53.75	46.25	It is nonflammable	It is nonflammable	10.0% (single-point)
55.00	45.00	It is nonflammable	It is nonflammable	9.0%10.5%
					57.50	42.50	It is nonflammable	It is nonflammable	8.0%12.0%
59.00	41.0	It is nonflammable	It is nonflammable	Do not test
					60.00	40.00	It is nonflammable	10.0% (single-point)	Do not test
60.63	39.37	It is nonflammable	10.0%11.0%	Do not test
					61.25	38.75	It is nonflammable	10.0%11.0%	Do not test
62.50	37.50	It is nonflammable	8.75%10.75%	Do not test
					65.00	35.00	It is nonflammable	8.0%12.0%	Do not test
66.25	33.75	It is nonflammable	Do not test	Do not test
					67.50	32.50	10.0% (single-point)	Do not test	Do not test
70.00	30.00	9.0%11.0%	Do not test	Do not test

At ambient temperature (about 23 DEG C), the composition with 66.25 weight % or lower HFO-1234yf will be considered as nonflammable in HFC-134a.At 60 DEG C, the composition with 60.00 weight % or lower HFO-1234yf will be considered as nonflammable in HFC-134a.At 100 DEG C, the composition containing 53.10 weight % or lower HFO-1234yf in HFC-134a will be considered as nonflammable.

Embodiment 3

For the cooling performance of cascade system low-temperature circulating

Table 7 shows certain combination thing relative to CO₂, R404A (for comprising HFC-125, HFC-134a and HFC-143a mixture ASHRAE name), R410A (for comprising HFC-32 and HFC-125 mixtures ASHRAE name) and HFC-32 performance.In table 7, Evap Pres are evaporator pressure, Cond Pres are condenser pressure, Comp Disch T are compressor discharge temperature, COP is the coefficient of performance (being similar to energy efficiency), CAP is capacity, and mean temperature sliding is the average value of the temperature glide in evaporator and condenser, and GWP is global warming up trend.The data are based on following condition.

Note：Evaporator superheat enthalpy is not included in cooling capacity and energy efficiency measure.

Table 7

^*GWP value on HFC is derived from " Climate Change 2007-IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report on Climate Change ", from sections below：Entitled " the Report of Working Group 1：" The Physical Science Basis ", the 2nd chapter, the 212-213 pages, table 2.14.Value on FO-1234yf is published in Papadimitriou et al. Physical Chemistry Chemical Physics, volume 9, the 1-13 pages in 2007.Specifically, using the horizontal GWP value of 100 years.GWP value comprising more than one components compositions is calculated by the weighted average of single component GWP value.

Composition comprising 63 weight %HFO-1234yf and 37 weight %HFC-32 actually shows the COP more improved relative to R404A, and also has significantly lower GWP.HFO-1234yf comprising 27.5 weight % and 72.5 weight % HFC-32 composition match the R410A coefficient of performance and capacity, and it has the sliding of very low temperature, show azeotrope-like behavior and equally have significantly lower GWP.

It should be noted that all compositions comprising HFO-1234yf and HFC-32 mixtures are relative to CO₂With the improved coefficient of performance (energy efficiency).

Embodiment 4

Total equivalent greenhouse effect

Total equivalent greenhouse effect (TEWI) for system as disclosed herein and conventional non-coupled Refrigeration System in Supermarkets are determined, and conventional cascade system compares.TEWI considers the effect of the energy efficiency of the system, is attributed to the contribution of the energy source for providing electric energy to described device, and fills the amount of refrigerant, and percolation ratio into system with the quantitative more complete ambient influnence using different refrigerants.

The embodiment using it is conventional it is usual in middle temperature (MT) and low temperature (LT) refrigeration system using R404A European direct expansion (DX) Refrigeration System in Supermarkets, be used as the basic condition for comparing.It is shown in Table 8 based on some hypothesis that typical European supermarket system is made.Additionally, it is desirable to equipment life be assumed 15 years, and from generate electricity discharge CO₂It is estimated as 0.616kg CO₂/kw-hr。

Table 8

^*Including mutability and unexpected release, independently of the selection of refrigerant.

Table 9 provides the condition that wherein systematic function (coefficient of performance, or the coefficient of performance, energy efficiency measure) is estimated.In table 9, temp is temperature, and evap is evaporator, and cond is condenser, and comp is compressor.

Table 9

Table 10 lists multiple different embodiments of the present invention relative to conventional non-coupled and cascade system, there is shown TEWI determination, and the performance demands numerical value estimated such as calculated based on condition listed in table 9 above.

Table 10

^*Estimate on these values of the coefficient of performance to match relative to energy ezpenditure (Sienel, the T. for using R404A systems in MT and LT loops；Finckh, O., " CO₂- DX Systems for Medium-and Low-Temperature Refrigeration in Supermarket Applications ", the international conference of refrigeration, Beijing, China in 2007).

TEWI values show indirect contribution, and it includes energy source and purposes, and due to the direct contribution of the GWP given from system the refrigerants discharged.Table 11 is according to the equivalent CO during device lifetime₂Discharge (with million kg), to list indirect and direct contribution, and the TEWI values on different system-computed described above from maximum to the order of minimum ambient influnence.

Table 11

Result displaying in table 11 can be than causing lower TEWI values using the refrigerant (such as in the middle temperature loops of cascade refrigeration system 3 and 4) of HFO bases using those non-coupled or cascade refrigeration systems of refrigerant known in the art.

Claims (15)

1. the cascade refrigeration system with least two refrigerating circuits, each loop is circulated a refrigerant through, the refrigeration system includes：

(a) it is used to reduce the first expansion gear of the pressure and temperature of the first refrigerant liquid；

(b) there is the evaporator of entrance and exit, the first refrigerant liquid wherein from first expansion gear enters the evaporator by evaporator inlet and evaporated in the evaporator to form the first refrigerant vapour, so as to produce cooling, and it is recycled to the outlet；

(c) there is the first compressor of entrance and exit, wherein the first refrigerant vapour from the evaporator is recycled to the entrance of the first compressor and compressed, so as to improve the pressure and temperature of first refrigerant vapour, and the first refrigerant vapour of the compression is recycled to the outlet of first compressor；

(d) cascade heat exchanger system, it has：

(i) first entrance and first outlet, wherein first refrigerant vapour is recycled to first outlet from first entrance and is condensed in the heat exchanger system to form the first refrigerant liquid, so that heat is discharged, and

(ii) second entrance and second outlet, wherein second refrigerant liquid are recycled to second outlet from second entrance and absorb the heat discharged by first refrigerant, and form second refrigerant steam；

(e) there is the second compressor of entrance and exit, wherein the second refrigerant steam from the cascade heat exchanger system is inhaled into the compressor and compressed, so as to improve the pressure and temperature of the second refrigerant steam；

(f) there is the condenser of entrance and exit, it is used to make second refrigerant vapour-cycling by and for condense the second refrigerant steam from the compressor to form second refrigerant liquid, wherein the second refrigerant liquid leaves the condenser by the outlet；With

(g) the second expansion gear, it is used for the pressure and temperature of the second refrigerant liquid for the second entrance for being lowered from the condenser and entering the cascade heat exchanger system；

At least one of wherein described first and second refrigerant includes fluoroolefins.

2. the system of claim 1, wherein the second refrigerant includes the fluoroolefins selected from HFO-1234yf, trans 1234ze and E-1234ze.

3. the system of claim 1, wherein the second refrigerant is substantially made up of HFO-1234yf.

4. the system of claim 2, wherein the second refrigerant also includes R134a.

5. the system of claim 2, wherein the second refrigerant also includes HFC-32.

6. the system of claim 3, wherein first refrigerant includes the composition selected from carbon dioxide and nitrous oxide.

7. the system of claim 3, wherein first refrigerant includes HFO-1234yf and HFC-32.

8. the system of claim 4, wherein first refrigerant includes the composition selected from carbon dioxide and nitrous oxide.

9. the system of claim 4, wherein first refrigerant includes HFO-1234yf and HFC-32.

10. the system of claim 5, wherein the second refrigerant includes HFO-1234yf.

11. the system of claim 5, wherein the second refrigerant includes trans 1234ze.

12. the system of claim 5, wherein first refrigerant includes carbon dioxide or nitrous oxide.

13. the system of claim 5, wherein first refrigerant includes HFO-1234yf and HFC-32.

14. the cascade refrigeration system with least two refrigerating circuits, each loop is circulated a refrigerant through, the refrigeration system includes：

First refrigerating circuit, it includes：

(a) it is used to reduce the first expansion gear of the pressure and temperature of the first refrigerant liquid；

(b) there is the evaporator of entrance and exit, the first refrigerant liquid wherein from first expansion gear enters the evaporator by the evaporator inlet and evaporated in the evaporator to form the first refrigerant vapour, so as to produce cooling, and it is recycled to the outlet；

(c) there is the first compressor of entrance and exit, wherein the first refrigerant vapour from the evaporator is recycled to the entrance of first compressor and compressed, so as to improve the pressure and temperature of first refrigerant vapour, and the first refrigerant vapour of the compression is recycled to the outlet of first compressor；

(d) cascade heat exchanger system, it includes：

(i) the first cascade heat exchanger, it has：

(A) first entrance and first outlet, wherein the first refrigerant vapour from the evaporator is recycled to the first outlet from the first entrance and is condensed in the First Heat Exchanger to form the first refrigerant liquid, so that heat is discharged, and

(B) second entrance and second outlet, heat transfer fluid wherein from the second entrance is recycled to the second outlet, wherein when first refrigerant vapour is condensed, the heat discharged by first refrigerant vapour is absorbed by the heat transfer fluid

(ii) the second cascade heat exchanger, it has：

(A) first entrance and first outlet, wherein the heat that the heat transfer fluid from first cascade heat exchanger is recycled to the first outlet from the first entrance and absorbed in being emitted on first cascade heat exchanger, and

(B) second entrance and second outlet, wherein second refrigerant liquid are recycled to the second outlet from the second entrance and absorb the heat discharged by the heat transfer fluid, and form second refrigerant steam；

(e) there is the second compressor of entrance and exit, wherein the second refrigerant steam from second cascade heat exchanger is inhaled into the compressor and compressed, so as to improve the pressure and temperature of the second refrigerant steam；

(f) there is the condenser of entrance and exit, it is used to make second refrigerant vapour-cycling by and for condense the second refrigerant steam from the compressor to form second refrigerant liquid, wherein the second refrigerant liquid leaves the condenser by the outlet；With

(g) the second expansion gear, it is used for the pressure and temperature of the second refrigerant liquid for the second entrance for being lowered from the condenser and entering second cascade heat exchanger.

15. the method for heat-shift between at least two refrigerating circuits, including：

(a) from the absorbent body heat to be cooled and by the heat dissipation to the second refrigerating circuit in the first refrigerating circuit；And

(b) heat from first refrigerating circuit is absorbed in second refrigerating circuit and by the heat dissipation into environment, wherein the refrigerant at least one described refrigerating circuit includes fluoroolefins.

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