WO2019022140A1

WO2019022140A1 - Heat cycle system and heat cycle method using same

Info

Publication number: WO2019022140A1
Application number: PCT/JP2018/027905
Authority: WO
Inventors: 正人福島
Original assignee: Ａｇｃ株式会社
Priority date: 2017-07-26
Filing date: 2018-07-25
Publication date: 2019-01-31

Abstract

Provided is a heat cycle system that: achieves excellent economy by using, as is, a system that is for a heat cycle and is designed to use 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) as a working medium; but that has the same or better cycle performance, lower environmental burden, and greater stability compared to when HCFO-1233zd is used. Also provided is a heat cycle method that uses the abovementioned heat cycle system. A heat cycle system that comprises a working medium and a system for a heat cycle. The system for a heat cycle is adapted to using HCFO-1233zd as a working medium, and the working medium includes 1-chloro-2,3,3,3-tetrafluoropropene. A heat cycle method that uses the heat cycle system.

Description

Thermal cycle system and thermal cycle method using the same

The present invention relates to a thermal cycle system and a thermal cycle method using the thermal cycle system.

In the present specification, for halogenated hydrocarbons, the abbreviation of the compound is indicated in the parenthesis after the compound name, but in the present specification, the abbreviation is used in place of the compound name as necessary.

Conventionally, working media for heat cycle systems such as refrigerants for refrigerators, refrigerants for air conditioners, working media for power generation systems (waste heat recovery power generation etc), working media for latent heat transport devices (heat pipes etc), secondary cooling media etc. As chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been used. However, CFCs and HCFCs have been identified as having an effect on the stratospheric ozone layer, and are currently subject to regulation, and therefore, instead of CFCs and HCFCs, hydrofluorocarbons (HFCs) with less effect on the ozone layer. Has been used as a working medium for thermal cycling.

For example, in a centrifugal refrigerator used for a building cold water production plant for heating and cooling of a building, etc., the working medium used is trichlorofluoromethane (CFC-11) to 1,1,1,2-tetrafluoroethane (HFC) -134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), etc.

Here, in a centrifugal refrigerator, the filling amount of the working medium is larger than that of other refrigerators and heat pumps, and in the case where the working medium leaks due to an accident etc., a large amount of working medium is released into the atmosphere. It may be done. Accordingly, it is required that the working medium used in the centrifugal refrigerator, in particular, has a low global warming potential (GWP).

With such a demand, hydrofluoroolefin (HFO), hydrochloroolefin having a carbon-carbon double bond that is easily decomposed by OH radicals in the atmosphere as a working medium that has less influence on the ozone layer and low GWP. Expectations are focused on fluoroolefins (HCFO) and chlorofluoroolefins (CFO). In the present specification, unless otherwise specified, saturated HFC is referred to as HFC and is used separately from HFO. Also, HFC may be specified as a saturated hydrofluorocarbon.

Among them, HCFO and CFO are compounds in which the flammability is suppressed because the ratio of halogen in one molecule is large, and are considered as a working medium in which the load on the environment is small and the flammability is suppressed. Then, 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) has been proposed as a low GWP refrigerant for centrifugal refrigerators (see, for example, Patent Document 1). However, HCFO-1233zd has a problem in thermal stability although it has the same cycle performance as HFC-245fa etc., and a working medium with low GWP and thermal stability is required as an alternative working medium. It was being done.

In addition, as the HCFO, for example, Patent Document 2 describes a working medium using 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd). However, Patent Document 1 does not describe an example in which HCFO-1224yd is applied to a specific heat cycle system.

WO 2010/077898 International Publication No. 2012/157763

The present invention is excellent in economics by using a thermal cycle system designed to use HCFO-1233zd as the working medium as it is, and has cycle performance equal to or higher than that using HCFO-1233zd. The thermal cycle system with low load and excellent thermal stability and the economy using the thermal cycle system are excellent, and the cycle performance is equal to or higher than that of the case using HCFO-1233zd, and the thermal stability is low. To provide a thermal cycle method excellent in

The present invention provides a thermal cycle system and a thermal cycle method having the following configuration.
[1] A thermal cycle system comprising a working medium and a system for thermal cycling, wherein the system for thermal cycling uses 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) as a working medium A thermal cycling system suitable for use in a thermal cycling system, the working medium comprising 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd).
[2] The heat cycle system according to [1], wherein the content of HCFO-1224yd is 40 to 100% by mass with respect to 100% by mass of the working medium.
[3] The thermal cycle system according to [1] or [2], wherein the working medium consists only of HCFO-1224yd.
[4] (Z) -1-Chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)) and (E) -1-chloro-2,3,3,3 in the HCFO-1224yd The ratio of 3-tetrafluoropropene (HCFO-1224yd (E)) is 50:50 to 100: 0 in the mass ratio shown by HCFO-1224yd (Z): HCFO-1224yd (E) [1] The thermal cycle system according to any one of [3].
[5] The thermal cycle system according to [4], wherein the HCFO-1224yd consists only of HCFO-1224yd (Z).
[6] The thermal cycle system according to any one of [1] to [5], wherein the thermal cycle system is a refrigeration / refrigerator, an air conditioner, a power generation system, a heat transport device or a secondary cooler.
[7] The heat cycle system according to any one of [1] to [5], wherein the heat cycle system is a centrifugal refrigerator.
[8] The heat cycle system according to any one of [1] to [5], wherein the heat cycle system is a low pressure centrifugal refrigerator.
[9] A thermal cycle method using the thermal cycle system according to any one of the above [1] to [8].

The thermal cycle system of the present invention is excellent in economy by using a thermal cycle system designed to use HCFO-1233zd as the working medium as it is, and has cycle performance better than when HCFO-1233zd is used. It is a thermal cycle system that is equal to or higher than that, has a low environmental impact, in particular, a low GWP, and is further excellent in thermal stability. The thermal cycle method of the present invention is excellent in economy by using the thermal cycle system of the present invention, and the cycle performance is equal to or higher than that of the case where HCFO-1233zd is used, and the environmental load, particularly GWP It is a thermal cycle method which is low and is further excellent in thermal stability.

It is a schematic block diagram which shows an example of the refrigerating-cycle system which evaluates the working medium used for the heat-cycling system of this invention. FIG. 2 is a cycle diagram in which a change in the state of a working medium in the refrigeration cycle system of FIG. 1 is described on a pressure-enthalpy diagram. It is the schematic block diagram which showed the centrifugal refrigerator which is an example of the heat cycle system of this invention.

Hereinafter, embodiments of the present invention will be described.
In the present specification, “a system for thermal cycling” means that a working medium flows in the system so that heat exchange (thermal cycle) can be performed between the working medium and other substances other than the working medium. Refers to a designed system for thermal cycling. Moreover, a "thermal cycle system" means the system provided with the working medium and the system for thermal cycling with which the working medium was supplied to the system for thermal cycling and the thermal cycle was made executable.

Thermal cycle system
The thermal cycle system of the present invention adopts a thermal cycle system suitable for using HCFO-1233zd as a working medium as a thermal cycle system in a thermal cycle system including a working medium and a system for thermal cycling, and the working medium It is a thermal cycle system using a working medium containing HCFO-1224yd. The thermal cycle system of the present invention is, for example, a thermal cycle system obtained by replacing HCFO-1233zd as a working medium with a working medium containing HCFO-1224yd in a thermal cycle system containing HCFO-1233zd as a working medium. is there.

The system for thermal cycling used in the present invention is not particularly limited as long as it is a system for thermal cycling designed to be applicable to HCFO-1233zd as a working medium. When a working medium containing HCFO-1224yd is used as a working medium in place of HCFO-1233zd in a system for thermal cycling to which HCFO-1233zd can be applied as a working medium, the resulting thermal cycle system is HCFO as described below. It is possible to exhibit the same or more cycle performance as in the case of using −1233 zd. Furthermore, since HCFO-1224yd used as the working medium has a low GWP, the load on the environment is small even when the working medium leaks. In addition, HCFO-1224yd is superior in thermal stability to HCFO-1233zd.

<Operating medium>
In the thermal cycle system of the present invention, the working medium contains HCFO-1224yd. The working medium may contain, in addition to HCFO-1224yd, if necessary, optional components described later. 40 to 100 mass% is preferable, 60 to 100 mass% is more preferable, 80 to 100 mass% is more preferable, and the content ratio of HCFO-1224 yd to 100 mass% of a working medium consists only of HCFO 12 24 yd. Is most preferred. However, depending on the manufacturing process, HCFO-1224yd may contain a slight amount of impurities. In the present invention, such a case is also in the category of “consisting only of HCFO-1224yd”. The content ratio of the impurities is, for example, preferably less than 1% by mass with respect to 100% by mass in total of HCFO-1224yd and the impurities.

(HCFO-1224yd)
HCFO-1224yd has halogen which suppresses flammability and a carbon-carbon double bond which is easily decomposed by OH radicals in the atmosphere in its molecule. Properties of HCFO-1224yd as a working medium, specifically, boiling point, cycle performance, GWP, and thermal stability are shown in Table 1 in comparison with HCFO-1233zd. The cycle performance of HCFO-1224yd is a relative value when the value of HCFO-1233zd is 1.00.

There are two geometric isomers of E-form (HCFO-1224yd (E)) and Z-form (HCFO-1224yd (Z)) in HCFO-1224yd. In the present specification, HCFO-1224yd without (E) or (Z) is HCFO-1224yd (E) or HCFO-1224yd (Z), or HCFO-1224yd (E) and HCFO-1224yd ( Z) shows a mixture of any proportions. Hereinafter, the same applies to other compounds having double bonds in the molecule and in which E form and Z form are present. Table 1 describes the properties of HCFO-1224yd (Z) as representative of HCFO-1224yd.

Similarly, in HCFO-1233zd, two geometric isomers, an E-form and a Z-form, exist. Table 1 describes the characteristics of HCFO-1233zd (E) as representative of HCFO-1233zd.

The cycle performance is indicated by the coefficient of performance and the refrigeration capacity determined by the method described later. The coefficient of performance and the freezing capacity of each compound are shown as relative values based on HCFO-1233zd (E) (1.00) (hereinafter referred to as "relative coefficient of performance" or "relative freezing capacity" respectively). The thermal stability is indicated by the amount of acid generated (the amount of generated acid relative to the amount of sample before heating; mass ppm) measured by the neutralization titration method after heating at 175 ° C. for 14 days. GWP is a 100-year value shown in the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (2014) or measured according to the method. In the present specification, GWP refers to this value unless otherwise noted.

It can be seen from Table 1 that the GWP and relative coefficient of performance of HCFO-1224yd (Z) are approximately equivalent to HCFO-1233zd (E). In addition, the relative refrigeration capacity of HCFO-1224yd (Z) is superior to HCFO-1233zd (E). If the relative coefficient of performance is substantially equal, it is possible to use a working medium containing HCFO-1224yd instead of HCFO-1233zd as a working medium, as a working medium, for a thermal cycle system to which HCFO-1233zd can be applied. In addition, HCFO-1224yd (Z) is significantly superior to HCFO-1233zd (E) in thermal stability.

HCFO-1224yd (Z) has higher chemical stability than HCFO 1224yd (E) and is preferable as a working medium. Therefore, the ratio of HCFO-1224yd (Z) and HCFO-1224yd (E) in HCFO-1224yd is such that the mass ratio represented by HCFO-1224yd (Z): HCFO-1224yd (E) is 50:50 to 100: 0. And preferably 70:30 to 100: 0. It is particularly preferred that HCFO-1224yd be composed only of HCFO-1224yd (Z).

HCFO-1224yd (Z): HCFO-1224yd (E) is equal to or higher than the above lower limit, that is, the ratio of HCFO-1224yd (Z) to the total 100 mass% of HCFO-1224yd (Z) and HCFO-1224yd (E) is 50 If the content is more than% by mass, the HCFO-1224yd contains a large amount of HCFO-1224yd (Z), so that a stable working medium can be obtained for a longer period of time.

As described above, from the viewpoint of performance as a working medium, HCFO-1224yd is preferably composed only of HCFO-1224yd (Z). However, from the viewpoint of suppressing an increase in production cost due to distillation separation of Z form and E form of HCFO-1224yd, 5 mass per 100 mass% in total of HCFO 1224yd (Z) and HCFO 1224yd (E) % Or less of HCFO-1224 yd (E) may be contained.

(Evaluation method of cycle performance)
The cycle performance (coefficient of performance (COP), refrigeration capacity (Q)) of the working medium can be evaluated, for example, using a refrigeration cycle system whose schematic configuration is shown in FIG.

The refrigeration cycle system 10 shown in FIG. 1 cools and liquefies the working medium vapor B discharged from the compressor 11 by compressing the working medium vapor A into a high temperature and high pressure working medium vapor B and the working medium vapor B discharged from the compressor 11. A condenser 12 as a working medium C of low temperature and high pressure, an expansion valve 13 of expanding the working medium C discharged from the condenser 12 to a working medium D of low temperature and low pressure, and a working medium D discharged from the expansion valve 13 And a pump 15 for supplying the load fluid E to the evaporator 14 and a pump 16 for supplying the fluid F to the condenser 12. System.

In the refrigeration cycle system 10, the following cycles (i) to (iv) are repeated.
(I) The working medium vapor A discharged from the evaporator 14 is compressed by the compressor 11 to be a high temperature and high pressure working medium vapor B (hereinafter referred to as "AB process").
(Ii) The working medium vapor B discharged from the compressor 11 is cooled by the fluid F in the condenser 12 and liquefied to form a working medium C of low temperature and high pressure. At this time, the fluid F is heated to become fluid F ′ and discharged from the condenser 12 (hereinafter referred to as “BC process”).

(Iii) The working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to form a low-temperature low-pressure working medium D (hereinafter referred to as "CD process").
(Iv) The working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to be a high-temperature low-pressure working medium vapor A. At this time, the load fluid E is cooled to be a load fluid E ′ and discharged from the evaporator 14 (hereinafter referred to as “DA process”).

The refrigeration cycle system 10 is a cycle system consisting of adiabatic and isentropic changes, isenthalpy changes and isobaric changes. The change in state of the working medium can be represented as a trapezoid with vertices A, B, C, and D, when it is described on the pressure-enthalpy line (curve) diagram shown in FIG.

The AB process is a process in which adiabatic compression is performed by the compressor 11 to make the high temperature and low pressure working medium vapor A into a high temperature and high pressure working medium vapor B, which is shown by an AB line in FIG. As described later, the working medium vapor A is introduced into the compressor 11 in a superheated state, and the resulting working medium vapor B is also a superheated vapor.

The BC process is a process of performing isobaric cooling in the condenser 12 and making the high temperature / high pressure working medium vapor B into a low temperature / high pressure working medium C, and is shown by a BC line in FIG. The pressure at this time is the condensation pressure. Pressure - an intersection T ₁ of the high enthalpy side condensing temperature of the intersection of the enthalpy and BC line, the low enthalpy side intersection T ₂ is the condensation boiling temperature.

The CD process is a process in which isenthalpy expansion is performed by the expansion valve 13 to make the working medium C of low temperature and high pressure into the working medium D of low temperature and low pressure, which is shown by a CD line in FIG. Incidentally, if Shimese the temperature in the working medium C of low temperature and high pressure at _{T _{_3,} T} 2 -T ₃ is (i) ~ supercooling degree of the working medium in the cycle of (iv) (SC).

The DA process is a process in which isobaric heating is performed by the evaporator 14 to return the low-temperature low-pressure working medium D to the high-temperature low-pressure working medium vapor A, which is shown by a DA line in FIG. The pressure at this time is the evaporation pressure. Pressure - intersection T ₆ of the high enthalpy side of the intersection of the enthalpy and DA line is evaporating temperature. If Shimese the temperature of the working medium vapor A in _{T _7, T 7} -T ₆ is (i) ~ superheat of the working medium in the cycle of (iv) (SH). Incidentally, _{T 4} denotes the temperature of the working medium D.

The refrigeration capacity (Q) and coefficient of performance (COP) of the working medium are the working medium A (evaporation, high temperature and low pressure), B (compression, high temperature and high pressure after compression), C (condensed, low temperature and high pressure), D (after expansion) When each enthalpy, h _A , h _B , h _C , h _D in each state of low temperature and low pressure) is used, it can be respectively obtained from the following formulas (1) and (2). There shall be no loss due to equipment efficiency, and no pressure loss in piping and heat exchangers.

The thermodynamic properties required to calculate the cycle performance of the working medium can be calculated based on the generalized equation of state (Soave-Redlich-Kwong equation) based on the corresponding state principle, and thermodynamic relations. If the characteristic value can not be obtained, calculation is performed using an estimation method based on the group contribution method.

Q = h _A −h _D (1)
COP = Q / compression work = (h _A −h _D ) / (h _B −h _A ) (2)

The compression work indicated by (h _B -h _A ) corresponds to the output (kW) of the refrigeration cycle, and the Q shown by (h _A -h _D ) above is required to operate the compressor, for example The amount of power corresponds to the consumed power (kW). Also, Q means the ability to freeze the load fluid, and a higher Q means more work can be done in the same system. In other words, if it has a large Q, it indicates that the desired performance can be obtained with a small amount of working medium, and the system can be miniaturized.

The above description is based on numerical values when the temperature conditions of the refrigeration cycle are evaluated at the following temperatures.
Evaporation temperature; 5 ° C (however, in the case of non-azeotropic mixture, the average temperature of the evaporation start temperature and the evaporation completion temperature)
Condensation completion temperature; 40 ° C (however, in the case of non-azeotropic mixture, average temperature of condensation start temperature and condensation completion temperature)
Degree of supercooling (SC); 5 ° C
Degree of superheat (SH); 0 ° C
Compressor efficiency: 0.8

(Optional ingredient)
The working medium used in the present invention may optionally contain a compound generally used as a working medium, in addition to HCFO-1224yd, as long as the effects of the present invention are not impaired. Such optional compounds (optional components) include, for example, HFC, HFO, HCFO other than HCFO-1224yd, and other optional components which are vaporized and liquefied together with HCFO-1224yd. Preferred optional components are HFC, HFO, and HCFO other than HCFO-1224yd.

As an optional component, when the working medium is combined with HCFO-1224yd, the relative coefficient of performance is within the range where the working medium can be applied instead of HCFO-1233zd to a thermal cycle system designed for HCFO-1233zd. Preferred are compounds capable of keeping the GWP within an acceptable range while having the effect of further enhancing the relative freezing capacity. When the working medium contains such a compound in combination with HCFO-1224yd, better cycle performance is obtained while keeping the GWP low.

(HFC)
The HFC as an optional component is preferably selected from the above viewpoint. Here, HFC is known to have a higher GWP than HCFO-1224yd. Therefore, it is preferable that the HFC to be combined with HCFO-1224yd be appropriately selected from the viewpoint of improving the cycle performance as the working medium and keeping the GWP within the allowable range.

Specifically, HFCs having 1 to 5 carbon atoms are preferable as HFCs that have a small impact on the ozone layer and a small impact on global warming. The HFC may be linear, branched or cyclic.

As HFC, difluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane and the like can be mentioned.

Among them, as HFC, 1,1,2,2-tetrafluoroethane (HFC-134), HFC-134a, HFC-245fa, 1 from the viewpoint of little influence on the ozone layer and excellent refrigeration cycle characteristics. 1,1,1,3,3-pentafluorobutane (HFC-365mfc) is more preferable, and HFC-134a, HFC-245fa, and HFC-365mfc are more preferable. One of HFCs may be used alone, or two or more thereof may be used in combination.

In the case of HFC-245fa, for example, the content of HFC in the working medium (100% by mass) used in the present invention causes a large decrease in the coefficient of performance of the working medium by setting it in the range of 1 to 60% by mass. The refrigeration capacity can be improved without Here, since the GWP of HFC-245fa is as high as 1030, the content ratio is appropriately adjusted in consideration of the GWP as the working medium within the range of the content ratio. Even in the case of using HFCs other than HFC-245fa, the content thereof can be appropriately controlled according to the cycle performance required for the GWP and the working medium.

(HFO)
The HFO is also preferably selected from the same viewpoint as the above-mentioned HFC. In the case of HFO, GWP is orders of magnitude lower than HFC. Therefore, it is preferable that the HFO to be combined with the HCFO-1224yd be appropriately selected in consideration of improving the cycle performance as the working medium rather than considering the GWP.

As HFOs, 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf), 1,1,2-triphenyl Fluoropropene (HFO-1243yc), (E) -1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), (Z) -1,2,3,3,3-pentafluoro Propene (HFO-1225ye (Z)), (E) -1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), (Z) -1,3,3,3-tetrafluoropropene ( HFO-1234ze (Z)), 3,3,3-trifluoropropene (HFO-1243zf), (E) -1,1,1,4,4,4-hexafluoro-2-b Down (HFO-1336mzz (E)), it includes (Z)-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (Z)).

As HFO, HFO-1234yf, HFO-1234ze (E), HFO-1234ze (Z), HFO-1336mzz (Z), HFO-1243zf are preferable, and HFO-1234yf, HFO-1234ze (E), HFO-1234ze ( Z), HFO-1336mzz (Z) is more preferred. The HFO may be used alone or in combination of two or more.

(HCFO other than HCFO-1224yd)
The HCFO as an optional component other than HCFO-1224yd is also preferably selected from the same viewpoint as the above-mentioned HFC. In addition, even if it is HCFO other than HCFO-1224yd, GWP is orders of magnitude lower than HFC. Therefore, HCFOs other than HCFO-1224yd in combination with HCFO-1224yd are preferably selected appropriately in consideration of improving the cycle performance as the working medium rather than considering GWP.

HCFO other than HCFO-1224yd is 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-dichlorofluoroethylene (HCFO-1121), 1-chloro-2-fluoroethylene (HCFO-1131) And 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) and HCFO-1233zd.

Among them, HCFO other than HCFO-1224yd is preferably HCFO-1233zd from the viewpoint of having high critical temperature and being excellent in durability and coefficient of performance. One HCFO other than HCFO-1224yd may be used alone, or two or more HCFOs may be used in combination.

In the case of HCFO-1233zd, the content ratio of HCFO other than HCFO-1224yd in the working medium (100% by mass) used in the present invention is, for example, in the range of 1 to 60% by mass to generate temperature glide. Maintain a high coefficient of performance. Here, since HCFO-1233zd is inferior in thermal stability, the content ratio thereof is appropriately adjusted while taking into consideration the stability as a working medium within the above content ratio range.

(Other optional ingredients)
The working medium used in the heat cycle system of the present invention may contain carbon dioxide, hydrocarbons, chlorofluoroolefin (CFO), trans-1,2-dichloroethylene, etc. in addition to the above-mentioned optional components. As another optional component, a component which has less influence on the ozone layer and has less influence on global warming is preferable.

As a hydrocarbon, propane, propylene, cyclopropane, butane, isobutane, pentane, isopentane and the like can be mentioned. The hydrocarbon may be used alone or in combination of two or more.

When the said working medium contains a hydrocarbon, less than 10 mass% is preferable with respect to 100 mass% of working media, as for the content rate, 5 mass% or less is more preferable, and 3 mass% or less is more preferable. When containing a hydrocarbon, the solubility of the mineral lubricating oil in the working medium is better.

Examples of CFO include chlorofluoropropene and chlorofluoroethylene. As CFO, 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1 as a CFO, because the flammability of the working medium can be easily suppressed without significantly reducing the cycle performance of the working medium. Preferred is 3, 3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb) or 1,2-dichloro-1,2-difluoroethylene (CFO-1112). The CFO may be used alone or in combination of two or more.

When the working fluid contains CFO, the content thereof is preferably less than 10% by weight, more preferably 8% by weight or less, and still more preferably 5% by weight or less based on 100% by weight of the working fluid. By containing CFO, it is easy to suppress the combustibility of the working medium. If the content rate of CFO is below an upper limit, favorable cycle performance will be easy to be obtained.

When the working medium contains other optional components as described above, the content ratio of the total of the other optional components in the working medium is preferably less than 10% by mass and 100% by mass or less with respect to 100% by mass of the working medium More preferably, 5% by mass or less is more preferable.

<Working medium composition>
The working medium can be used as a working medium composition, usually mixed with a lubricating oil, for application to a thermal cycling system. The working vehicle composition may further contain known additives such as stabilizers and leak detection substances in addition to these.

(Lubricant)
As the lubricating oil, a known lubricating oil used in the working medium composition can be adopted without particular limitation, together with the working medium conventionally composed of halogenated hydrocarbons. Specific examples of the lubricating oil include oxygen-containing synthetic oils (ester-based lubricating oils, ether-based lubricating oils and the like), fluorine-based lubricating oils, mineral-based lubricating oils, hydrocarbon-based synthetic oils and the like.

As ester-based lubricating oils, dibasic acid ester oils, polyol ester oils, complex ester oils, polyol carbonate oils and the like can be mentioned.

Examples of ether-based lubricating oils include polyvinyl ether oils and polyoxyalkylene oils such as polyglycol oils.

Examples of fluorine-based lubricating oils include compounds in which hydrogen atoms of synthetic oils (mineral oil, poly α-olefin, alkylbenzene, alkylnaphthalene, etc. described later) are substituted with fluorine atoms, perfluoropolyether oils, fluorinated silicone oils, etc. Be

As a mineral-based lubricating oil, a lubricating oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil is subjected to purification treatment (solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation The paraffinic mineral oil, the naphthenic mineral oil, etc. which refine | purified and refine | purified by appropriate | suitably refine | purifying, clay treatment etc. are mentioned.

Examples of hydrocarbon synthetic oils include poly α-olefins, alkylbenzenes and alkylnaphthalenes.

The lubricating oils may be used alone or in combination of two or more.
The lubricating oil is preferably at least one selected from polyol ester oils, polyvinyl ether oils and polyglycol oils from the viewpoint of compatibility with the working medium.

The addition amount of the lubricating oil may be in a range that does not significantly reduce the effects of the present invention, and is preferably 10 to 100 parts by mass, and more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the working medium.

(Stabilizer)
Stabilizers are components that improve the stability of the working medium against heat and oxidation. As the stabilizer, there are no particular limitations on known stabilizers conventionally used in thermal cycle systems, such as oxidation resistance improvers, heat resistance improvers, metal deactivators, etc., together with the working medium conventionally made of halogenated hydrocarbons. It can be adopted.

As the oxidation resistance improver and heat resistance improver, N, N'-diphenyl phenylene diamine, p-octyl diphenylamine, p, p'-dioctyl diphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine N- (p-dodecyl) phenyl-2-naphthylamine, di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothiazine, 6- (t-butyl) phenol, 2,6-di- (t-butyl) And the like) phenol, 4-methyl-2,6-di- (t-butyl) phenol, 4,4'-methylenebis (2,6-di-t-butylphenol) and the like. As the oxidation resistance improver and the heat resistance improver, one type may be used alone, or two or more types may be used in combination.

Examples of metal deactivators include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimethylcaptothiadiazole, salicylidine-propylenediamine, pyrazole, benzotriazole, toltriazole, 2-methylbenzamidazole, 3,5- Dimethylpyrazole, methylenebis-benzotriazole, organic acids or their esters, primary, secondary or tertiary aliphatic amines, amine salts of organic acids or inorganic acids, heterocyclic nitrogen-containing compounds, alkyl acid phosphates Amine salts or derivatives thereof.

The addition amount of the stabilizer may be within a range not significantly reducing the effects of the present invention, and is preferably 5 parts by mass or less, and more preferably 1 part by mass or less with respect to 100 parts by mass of the working medium.

(Leakage detection substance)
As a leak detection substance, an ultraviolet fluorescent dye, an odor gas, an odor masking agent and the like can be mentioned.
Ultraviolet fluorescent dyes are described in U.S. Pat. No. 4,249,412, JP-A-10-502737, JP-A-2007-511645, JP-A-2008-500437, and JP-A-2008-531836. Known ultraviolet fluorescent dyes used in thermal cycle systems, as well as working media conventionally comprising halogenated hydrocarbons, such as those described in U.S. Pat.

As odor masking agents, known perfumes used in heat cycle systems together with working media conventionally comprising halogenated hydrocarbons such as those described in JP-A-2008-500437 and JP-A-2008-531836 are known. It can be mentioned.

When a leak detection substance is used, a solubilizer may be used to improve the solubility of the leak detection substance in the working medium.

Examples of solubilizers include those described in JP-A-2007-511645, JP-A-2008-500437, and JP-A-2008-531836.

The addition amount of the leak detection substance may be within the range not significantly reducing the effects of the present invention, preferably 2 parts by mass or less and more preferably 0.5 parts by mass or less with respect to 100 parts by mass of the working medium.

<Thermal cycle system>
The thermal cycle system of the present invention is obtained by applying a working medium containing HCFO-1224yd instead of HCFO-1233zd to a thermal cycle system designed to be applicable to HCFO-1233zd. There is no change in the system for thermal cycling on application of the working medium containing HCFO-1224yd to the system for thermal cycling to which HCFO-1233zd is designed to be applicable. The working medium containing HCFO-1224yd may be contained in the thermal cycle system as the working medium composition. By applying a working medium containing HCFO-1224yd to a system for thermal cycling designed to be applicable to HCFO-1233zd, cycle performance can be made equal to or better than when using HCFO-1233zd, and thermal stability is further enhanced. Is enhanced.

As a system for thermal cycling, for example, a system for thermal cycling including heat exchangers such as a compressor, a condenser, and an evaporator, to which HCFO-1233zd is applicable, can be mentioned. In a thermal cycle system, for example, a refrigeration cycle, a gaseous working medium is compressed by a compressor, cooled by a condenser to produce a high pressure liquid, reduced by an expansion valve, and vaporized at a low temperature by an evaporator for vaporization. Has a mechanism to take heat with heat. Since the working medium containing HCFO-1224yd has a coefficient of performance that is substantially the same as that of HCFO-1233zd as described above, in the present invention, the working is included in a system for thermal cycling to which HCFO-1233zd is designed to be applicable. The respective means such as a compressor for supplying the medium to the heat cycle, and a heat exchanger such as a condenser and an evaporator can be used without any change.

The thermal cycle system of the present invention is obtained by applying a working medium containing HCFO-1224yd instead of HCFO-1233zd to a thermal cycle system designed to be applicable to HCFO-1233zd. And a working medium containing HCFO-1224yd instead of HCFC-123 may be applied to a thermal cycle system designed to be applicable to 2-dichloro-1,1,1-trifluoroethane (HCFC-123) . In addition, a working medium including HCFO-1224yd may be applied instead of HFO-1336mzz (Z) to a thermal cycle system designed to be applicable to HFO-1336mzz (Z).

Hereinafter, a specific type of the thermal cycle system of the present invention in which the working medium containing HCFO-1224yd is applied to a thermal cycle system designed to be applicable to HCFO-1233zd will be described.

The thermal cycle system of the present invention may be a heat pump system that utilizes the heat obtained by the condenser, or may be a refrigeration cycle system that utilizes the cold obtained by the evaporator. The thermal cycle system of the present invention may be a flooded evaporator type or a direct expansion type. In the thermal cycle system of the present invention, water or air is preferable as the substance other than the working medium to be heat-exchanged with the working medium.

Specific examples of the thermal cycle system of the present invention include refrigeration and refrigeration equipment, air conditioners, power generation systems, heat transport devices, secondary coolers and the like. Among them, since the thermal cycle system of the present invention can stably exhibit cycle performance even in a higher temperature operating environment, it is preferably used as an air conditioner which is often installed outdoors or the like. Moreover, it is also preferable that the heat cycle system of this invention is used as a freezing / refrigerating apparatus.

The working medium recovery device for recovering the working medium from the thermal cycle system of the present invention can use a conventionally known working medium recovery device.

The power generation system is preferably a Rankine cycle system power generation system. As a power generation system, specifically, the working medium is heated by geothermal energy, solar heat, middle to high temperature range waste heat at about 50 to 200 ° C. in an evaporator, and the working medium that has become high-temperature high-pressure steam is expanded An example is a system in which adiabatic expansion is performed in a machine, and a work generated by the adiabatic expansion drives a generator to generate electric power.

The thermal cycle system of the present invention may be a heat transport device. As a heat transport device, a latent heat transport device is preferable. Examples of the latent heat transport device include a heat pipe that performs latent heat transport utilizing phenomena such as evaporation, boiling, and condensation of a working medium enclosed in the device, and a two-phase closed thermosiphon device. The heat pipe is applied to a relatively small cooling device such as a cooling device for a semiconductor element or a heat generating portion of an electronic device. Since the two-phase closed thermosyphon does not require a wig and has a simple structure, it is widely used for gas-to-gas heat exchangers, snow melting on roads, prevention of freezing, and the like.

Specific examples of the refrigeration / refrigeration equipment include showcases (built-in showcases, separately mounted showcases, etc.), commercial freezers / refrigerators, vending machines, ice makers, and the like.

As air conditioners, specifically, room air conditioners, package air conditioners (package air conditioners for buildings, package air conditioners for buildings, equipment package air conditioners, etc.), heat source equipment chilling units, gas engine heat pumps, train air conditioners, car air conditioners Etc.

Examples of the heat source equipment chilling unit include a volumetric compression type refrigerator and a centrifugal type refrigerator. Among them, the centrifugal refrigerator to be described next is preferable because the effect of the present invention can be more remarkably obtained because the filling amount of the working medium is large.

Here, the centrifugal refrigerator is a refrigerator using a centrifugal compressor. A centrifugal refrigerator is a type of vapor compression refrigerator, and is generally referred to as a turbo refrigerator. A centrifugal compressor includes an impeller and performs compression by discharging a working medium to the outer peripheral portion by the rotating impeller. Centrifugal refrigerators are used in office buildings, district heating and cooling, heating and cooling in hospitals, semiconductor factories, cold water production plants in the petrochemical industry, and the like.

The centrifugal refrigerator may be either a low pressure type or a high pressure type, but is preferably a low pressure type centrifugal refrigerator. In addition, with the low pressure type, for example, operation that does not receive the application of high pressure gas safety method such as 2, 2-dichloro-1,1,1-trifluoroethane (HCFC-123), HFC-245fa, HCFO-1233zd Medium, that is, "a liquefied gas which has a pressure of 0.2 MPa or more at ordinary temperature, and which has a pressure of 0.2 MPa or more at present, or a temperature of 35 ° C. or less when the pressure is 0.2 MPa or more This refers to a centrifugal refrigerator that uses a working medium that does not fall under the term "liquefied gas".

Hereinafter, an embodiment of a centrifugal refrigerator according to the present invention will be described with reference to FIG. The schematic block diagram of the centrifugal refrigerator 100 is shown by FIG. The centrifugal refrigerator 100 includes a centrifugal compressor (hereinafter referred to as "compressor") 21, a condenser 22 for condensing a high pressure gas working medium compressed by the compressor 21, and a condenser 22 for condensing the high pressure gas working medium. The expansion valve 23 expands the high pressure liquid working medium, and the evaporator 24 evaporates the low pressure liquid working medium expanded by the expansion valve 23.

The working medium contained in the centrifugal refrigerator 100 is a working medium containing the HCFO-1224yd described above. The working medium is a high pressure gas, a high pressure liquid, a low pressure liquid, and a working medium pipe 20 provided to connect the compressor 21, the condenser 22, the expansion valve 23, the evaporator 24, and the compressor 21 in this order. Etc. It circulates in the state of gas phase or liquid phase. The arrows shown with a solid line indicating the working fluid pipe 20 indicate the flow direction of the working fluid. The working medium may be introduced into the centrifugal refrigerator 100 as a working medium composition containing the same.

The compressor 21 includes a centrifugal impeller that is rotationally driven by the electric motor 31. The centrifugal impeller is, for example, a two-stage compression type. However, it may be a one-stage compression type or a three or more-stage compression type. An inlet vane 32 is provided at the working medium inlet of the compressor 21 to adjust the working medium flow rate. The opening degree of the inlet vanes 32 is controlled by the controller 33.

The input frequency from the power supply 34 is changed by the inverter 35, whereby the rotational speed of the motor 31 is controlled. The instruction frequency sent from the inverter 35 to the electric motor 31 is changed by the rotation speed control unit 33 a provided in the control device 33. Here, the dashed-dotted line in FIG. 3 shows the path | route of an electrical signal, The arrow shown with this path | route (dashed-dotted line) shows direction of this signal.

The condenser 22 is provided with a pressure sensor 25 that measures the working medium pressure (condensing pressure) Pc in the condenser 22. The output of the pressure sensor 25 is input to the controller 33. Further, the condenser 22 is provided with a hot water acquisition means 26 a which exchanges heat with the working medium in the condenser 22 to obtain hot water. A hot water outlet temperature sensor 26b is provided at the hot water outlet of the hot water acquisition means 26a, and a hot water inlet temperature sensor 26c is provided at the hot water inlet. The output of the hot water outlet temperature sensor 26 b (hot water outlet temperature) and the output of the hot water inlet temperature sensor 26 c (hot water inlet temperature) are input to the control device 33.

The centrifugal refrigerator 100 uses water as a substance that is thus heat-exchanged with the working medium. In FIG. 3, the hot water acquisition means 26a is indicated by a dotted line, and the flow direction of the hot water flowing through the hot water acquisition means 26a is indicated by an arrow on the dotted line. Moreover, it displayed similarly also in the following cold-water acquisition means 30a.

The degree of opening of the expansion valve 23 is controlled by an expansion valve opening degree control unit 33 b provided in the control device 33. A hot gas bypass pipe 27 is provided between the condenser 22 and the evaporator 24. The hot gas bypass pipe 27 allows the high pressure working medium gas in the condenser 22 to flow to the evaporator 24. The hot gas bypass pipe 27 is provided with a hot gas bypass valve 28. By adjusting the opening degree of the hot gas bypass valve 28, the working medium flow rate flowing in the hot gas bypass piping 27 is adjusted, and the suction working medium gas flow rate to the compressor 21 at the low refrigeration capacity is secured.

The evaporator 24 is provided with a pressure sensor 29 that measures the working medium pressure (evaporation pressure) Pe in the evaporator 24. The output of the pressure sensor 29 is input to the controller 33. In addition, the evaporator 24 is provided with cold water acquisition means 30 a which exchanges heat with the working medium in the evaporator 24 to obtain cold water. A cold water outlet temperature sensor 30b is provided at the cold water outlet of the cold water acquisition means 30a, and a cold water inlet temperature sensor 30c is provided at the cold water inlet. The output of the cold water outlet temperature sensor 30 b (cold water outlet temperature) and the output of the cold water inlet temperature sensor 30 c (cold water inlet temperature) are input to the controller 33.

The operating point of the centrifugal refrigerator compressor is determined by the flow rate variable θ and the pressure variable Ω. Since the flow rate variable θ and the pressure variable Ω both include the speed of sound as a parameter, as described below, the speed of sound of the working medium affects the design of the compressor refrigerator impeller of the centrifugal refrigerator.
Flow rate variable θ = air volume [m ³ / s] / sound velocity [m / s] / (impeller diameter [m]) ²
Pressure variable Ω = adiabatic head [m] × gravitational acceleration [m / s ² ] ÷ (sound velocity [m / s]) ²

In the present invention, the working medium containing HCFO-1224yd, in particular, since the sound velocity of HCFO-1224yd is equivalent to that of HCFO-1233zd, the design of a centrifugal refrigerator designed for HCFO-1233zd as described above It can be used without changing it.

In addition, in order to avoid generation | occurrence | production of the malfunction by mixing of water, and mixing of noncondensable gas, such as oxygen, it is preferable to provide the means to suppress these mixing in the case of operation | movement of a thermal cycle system.

The inclusion of moisture in the thermal cycling system can cause problems, especially when used at low temperatures. For example, there are problems such as freezing in a capillary tube, hydrolysis of a working medium and lubricating oil, material degradation due to the acid component generated thereby, and generation of contamination. In particular, when the lubricating oil is polyglycol oil, polyol ester oil, etc., the hygroscopicity is extremely high, and the hydrolysis reaction is apt to occur, the characteristics as the lubricating oil deteriorate, and the long-term reliability of the compressor is impaired. It becomes a big cause. Therefore, in order to suppress the hydrolysis of lubricating oil, it is necessary to control the water concentration in the thermal cycle system.

As a method of controlling the water concentration in the heat cycle system, a method using a water removing means such as a desiccant (silica gel, activated alumina, zeolite, etc.) can be mentioned. It is preferable in terms of dewatering efficiency that the desiccant be in contact with a liquid working medium or a working medium composition containing the same. For example, it is preferable to place a desiccant at the outlet of the condenser or at the inlet of the evaporator to contact the working medium or the working medium composition containing it.

As the desiccant, a zeolitic desiccant is preferred in view of the chemical reactivity between the desiccant and the working medium or the working medium composition containing the same, and the hygroscopic ability of the desiccant.

When a lubricating oil having a high moisture absorption amount is used as a zeolite-based desiccant compared to a conventional mineral-based lubricating oil, the compound represented by the following formula (C) is the main component from the viewpoint of excellent moisture absorption capacity. Zeolite based desiccants are preferred.
M _{2 / n} O · Al ₂ O ₃ · x SiO ₂ · y H ₂ O (C)
However, M is an element of Group 1 such as Na and K or an element of Group 2 such as Ca, n is a valence of M, and x and y are values determined by the crystal structure. The pore size can be adjusted by changing M.

The pore size and the breaking strength are important in the selection of the desiccant. When a desiccant having a pore diameter larger than the molecular diameter of the working medium or a component (hereinafter, "working medium etc.") contained in the working medium composition containing the same, the working medium etc. is adsorbed in the desiccant As a result, a chemical reaction between the working medium and the like and the desiccant occurs, which causes undesirable phenomena such as generation of noncondensable gas, reduction in strength of the desiccant, and reduction in adsorption capacity.

Therefore, as the desiccant, it is preferable to use a zeolite-based desiccant with a small pore size. In particular, a sodium-potassium A-type synthetic zeolite having a pore size of 3.5 angstroms or less is preferable. By applying the sodium-potassium A-type synthetic zeolite having a pore diameter smaller than the molecular diameter of the working medium or the like, it is possible to selectively adsorb and remove only the water in the heat cycle system without adsorbing the working medium or the like. In other words, since adsorption to the desiccant such as the working medium does not easily occur, thermal decomposition hardly occurs, and as a result, it is possible to suppress the deterioration of the materials constituting the thermal cycle system and the generation of contaminants.

If the size of the zeolitic desiccant is too small, it may cause clogging of valves and piping details of the thermal cycle system, and if it is too large, the drying ability may be reduced, so the particle size is preferably about 0.5 to 5 mm. The shape is preferably granular or cylindrical.

The zeolitic desiccant can be made into an arbitrary shape by solidifying powdered zeolite with a binder (bentonite, etc.). Other desiccants (silica gel, activated alumina, etc.) may be used in combination as long as the zeolite-based desiccant is mainly used.

Furthermore, if the non-condensable gas is mixed in the thermal cycle system, it has an adverse effect of poor heat transfer in the condenser and the evaporator and an increase in operating pressure, so it is necessary to suppress the mixing as much as possible. In particular, oxygen, which is one of the noncondensable gases, reacts with the working medium and the lubricating oil to promote decomposition.

The noncondensable gas concentration is preferably 1.5% by volume or less by volume ratio to the working medium in the gas phase portion of the working medium, and particularly preferably 0.5% by volume or less.

[Thermal cycle method]
The thermal cycling method of the present invention is performed using the thermal cycling system of the present invention in which a working medium containing HCFO-1224yd is used in place of HCFO-1233zd in a thermal cycling system designed to be applicable to HCFO-1233zd. It is a thermal cycle method.

As described above, since the working medium containing HCFO-1224yd has substantially the same coefficient of performance as HCFO-1233zd, the method of the present invention particularly changes the operating conditions when HCFO-1233zd is used as the working medium. It is possible to carry out thermal cycling without In addition, the cycle performance can be made equal to or higher than when HCFO-1233zd is used, and the thermal stability can be further improved.

For example, when thermal cycling is performed using the centrifugal refrigerator of the present invention as schematically shown in FIG. 3, the opening degree of the inlet vane 32 for adjusting the working medium flow rate, the inverter 35 to the motor 31 The HCFO-1233zd is used as the working medium by setting the sent instruction frequency, the control device 33 for controlling the opening degree of the expansion valve 23, and other settings substantially the same as when using the HCFO-1233zd as the working medium. Cycle performance similar to or better than that of the conventional case can be obtained, and the thermal stability is further improved.

In the thermal cycle system of the present invention described above and the thermal cycle method using the same, using the thermal cycle system designed to use HCFO-1233zd as it is is excellent in economy and HCFO-1233zd is used. The cycle performance equal to or more than that in the case of the present invention can be obtained. In addition, since HCFO-1224yd used as the working medium has a low GWP, the load on the environment is small even when the working medium leaks. Furthermore, HCFO-1224yd is superior in thermal stability to HCFO-1233zd.

DESCRIPTION OF SYMBOLS 10 ... Refrigeration cycle system, 11 ... Compressor, 12 ... Condenser, 13 ... Expansion valve, 14 ... Evaporator, 15, 16 ... Pump 100 ... Centrifugal refrigerator, 20 ... Piping for working media, 21 ... Centrifugal compressor , 22: Condenser, 23: Expansion valve, 24: Evaporator, 31: Electric motor, 32: Inlet vane, 33: Control device, 34: Power supply, 35: Inverter.

Claims

A thermal cycle system comprising a working medium and a system for thermal cycling, comprising:
The system for thermal cycling is a system for thermal cycling suitable for using 1-chloro-3,3,3-trifluoropropene as a working medium,
The working medium comprises 1-chloro-2,3,3,3-tetrafluoropropene,
Thermal cycle system.
The heat cycle system according to claim 1, wherein a content ratio of 1-chloro-2,3,3,3-tetrafluoropropene to 100% by mass of the working medium is 40 to 100% by mass.
The heat cycle system according to claim 1 or 2, wherein the working medium comprises only 1-chloro-2,3,3,3-tetrafluoropropene.
(Z) -1-chloro-2,3,3,3-tetrafluoropropene and (E) -1-chloro-2,3,3 in the above 1-chloro-2,3,3,3-tetrafluoropropene The proportion of 1, 3-tetrafluoropropene is (Z) -1-chloro-2,3,3,3-tetrafluoropropene: (E) -1-chloro-2,3,3,3-tetrafluoropropene The thermal cycle system according to any one of claims 1 to 3, wherein the mass ratio is 50:50 to 100: 0.
The heat cycle system according to claim 4, wherein the 1-chloro-2,3,3,3-tetrafluoropropene consists only of (Z) -1-chloro-2,3,3,3-tetrafluoropropene.
The thermal cycle system according to any one of claims 1 to 5, wherein the thermal cycle system is a refrigeration / refrigerator, an air conditioner, a power generation system, a heat transport device or a secondary cooler.
The thermal cycle system according to any one of claims 1 to 5, wherein the thermal cycle system is a centrifugal refrigerator.
The thermal cycle system according to any one of claims 1 to 5, wherein the thermal cycle system is a low pressure centrifugal refrigerator.
A thermal cycle method using the thermal cycle system according to any one of claims 1 to 8.