WO2020152714A1

WO2020152714A1 - Compositions comprising 1,3,3,3-tetrafluoropropene

Info

Publication number: WO2020152714A1
Application number: PCT/IN2020/050075
Authority: WO
Inventors: Prashant Yadav; Manoj Kumar Mishra; Aditya Sharma
Original assignee: Srf Limited
Priority date: 2019-01-24
Filing date: 2020-01-23
Publication date: 2020-07-30
Also published as: MX2021008926A

Abstract

The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises of 1,3,3,3-tetrafluoropropene, difluoromethane and at least one other compound. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

Description

COMPOSITIONS COMPRISING 1,3,3,3-TETRAFLUOROPROPENE

FIELD OF THE INVENTION

The present invention relates to compositions comprising 1 ,3,3,3-tetrafluoropropene, difluoromethane and at least one other compound. The compositions of the present invention are useful as refrigerants, heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

BACKGROUND OF THE INVENTION

The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the regulatory phase out as a result of the Montreal Protocol.

Currently, industry is facing regulations relating to global warming potential of refrigerants used in air-conditioning. Industry in general and the heat transfer industry in particular are continually seeking new fluorocarbon based mixtures that offer alternatives to, and are considered environmentally safer substitutes for, CFCs and HCFCs. It is generally considered important, with respect to heat transfer fluids, that any potential substitute must possess properties such as excellent heat transfer properties, chemical stability, low- or no-toxicity, non-flammability and/or lubricant compatibility etc. Furthermore, it is generally considered desirable for CFC refrigerant substitutes to be effective without major engineering changes to conventional vapor compression technology currently used with CFC refrigerants. Flammability is another important property for many applications. It is particularly important in heat transfer applications, to use compositions which are non flammable. As used herein, the term“nonflammable” refers to compounds or compositions which are determined to be nonflammable as determined in accordance with ASTM standard E-681, dated 2002, which is incorporated herein by reference.

U.S. Patent Pub. No. 2004/0061091 discloses a refrigerant composition comprising 45-50 weight percent R134a, 45-50 weight percent R125, 3-5 weight percent R32, and 1 -4 weight percent of the hydrocarbon component, the hydrocarbon component comprising one or more hydrocarbons selected from Group A and one or more hydrocarbons selected from Group B, wherein the Group A hydrocarbon comprises R290 and the Group B hydrocarbon comprises R600a.

U.S. Patent No. 9982180 discloses a heat transfer composition consisting of: (a) about 10% by weight of R32; (b) about 69% by weight of R125; (c) about 8% by weight of HF01234yf and (d) about 13% by weight of trans HF01234ze, with the weight percent being based on the total of the components (a)-(d) in the composition. All the above composition have significant amount of R 125 which contributes to higher GWP of these compositions. Applicants have thus come to appreciate a need for compositions, and particularly heat transfer compositions, that are highly advantageous in heating and cooling systems and methods, particularly vapor compression heating and cooling systems, and even more particularly low temperature refrigerant systems, including systems which are used with and/or have been designed for use with R-404A.

The present invention provides a refrigerant composition comprising R1234ze, R32 and at least one compound selected from a group consisting of tetrafluoroethane, R125, R1234yf, heptafluoropropane, difluoroethane and C02.

OBJECT OF THE INVENTION

The main object of the present invention is to provide a composition for use in refrigeration, air-conditioning, and heat pump systems comprising a 1, 3,3,3- tetrafluoropropene, difluoromethane and at least one other compound.

SUMMARY OF THE INVENTION

The present invention provides a refrigerant composition comprising:

10% by weight to 38% by weight of R32;

0% to 50% by weight of tetrafluoroethane;

10% by weight to 38% by weight of R1234ze;

0% to 15% by weight of R125;

0% to 20% by weight of R1234yf;

0% to 10% by weight of heptafluoropropane;

0% to 15% by weight of difluoroethane; and

0% to 5% by weight of C02. The present invention provides a refrigerant composition comprising R1234ze, R32, tetrafluoroethane and at least one compound selected from a group consisting of R125, R1234yf, heptafluoropropane, difluoroethane and C02.

The present invention provides a refrigerant composition comprising:

10% by weight to 38% by weight of R32;

20% by weight to 50% by weight of tetrafluoroethane;

10% by weight to 38% by weight of R1234ze;

0% to 15% by weight of R125;

0% to 20% by weight of R1234yf;

0% to 10% by weight of heptafluoropropane;

0% to 15% by weight of difluoroethane; and

0% to 5% by weight of C02.

DETAILED DESCRIPTION OF THE INVENTION

The term tetrafluoroethane as used herein in the present invention refers to either 1,1,2,2-tetrafluoroethane or 1 , 1 , 1 ,2-tetrafluoroethane.

The term difluoroethane as used herein in the present invention refers to either 1, 1- difluoroethane or 1,2-difluoroethane.

The term heptafluoropropane as used herein in the present invention refers to either 1,1,1 ,2,3,3,3-heptafluoropropane or 1,1,1 ,2,2,3,3-heptafluoropropane.

The various refrigerants as used in the present invention are described in the table below. Table- 1

In an aspect, the present invention provides a refrigerant composition comprising:

10% by weight to 38% by weight of R32;

20% by weight to 50% by weight of tetrafluoroethane;

10% by weight to 38% by weight of R1234ze;

0% to 15% by weight of R125;

0% to 20% by weight of R1234yf;

0% to 10% by weight of heptafluoropropane;

0% to 15% by weight of difluoroethane; and

0% to 5% by weight of C02.

In another aspect, the present invention provides a refrigerant composition comprising:

20% by weight to 38% by weight of R32;

10% by weight to 15% by weight of R1234yf; 14% by weight to 38% by weight of R1234ze;

0% to 15% by weight of R125;

25% by weight to 48% by weight of tetrafluoroethane;

0% to 5% by weight of heptafluoropropane;

0% to 5% by weight of difluoroethane; and

0% to 2% by weight of C02.

In an embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32) and one or more compounds selected from pentafluoroethane (R125), 1,1,2,2-tetrafluoroethane (R134), 1 , 1 , 1 ,2-tetrafluoroethane (R134a), difluoroethane (R152), heptafluoropropane, difluoromethane (R32), 2,3,3,3-tetrafluoropropene (R1234yf) and C02.

In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane and one or more compounds selected from pentafluoroethane (R125), difluoroethane (R152a), heptafluoropropane, 2,3,3,3-tetrafluoropropene (R1234yf) and C02.

In another embodiment, the present invention provides a refrigerant composition comprising:

20% by weight to 50% by weight of tetrafluoroethane;

0% to 15% by weight of R125;

0% to 20% by weight of R1234yf;

0% to 10% by weight of heptafluoropropane; 0% to 15% by weight of difluoroethane; and

0% to 5% by weight of C02.

In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of R134a, 0% to 15% by weight of R125 and 0% to 10% by weight of 227ea. In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane, more than 0% to 15% by weight of R125, more than 0% to 10% by weight of R227ea.

In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane and more than 0% to 15% by weight of R125.

In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane, more than 0% to 15% by weight of R125 and more than 0% to 5% by weight of C02. In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane, more than 0% to 15% by weight of R125 and more than 0% to 10% by weight of R152a.

In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane, more than 0% to 10% by weight of R227ea.

In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane, more than 0% to 15% by weight of R125, more than 0% to 20% by weight of R1234yf.

In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane.

In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), 20% by weight to 50% by weight of tetrafluoroethane, more than 0% to 10% by weight of R152a. In another embodiment, the present invention provides a refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32), more than 0% to 20% by weight of R1234yf and more than 0% to 15% by weight of R125.

In an embodiment the said refrigerant compositions have global warming potential of less than 1500, preferably less than 1200. In another embodiment the said refrigerant compositions are used as replacement for R404A. In first embodiment, the present invention provides a refrigerant composition 1 , comprising:

30% by weight of R32;

15% by weight of R1234ze(E);

10% by weight of R 125; and

45% by weight of R 134a.

In second embodiment, the present invention provides a refrigerant composition 2, comprising:

28% by weight of R32;

15% by weight of R1234ze(E);

10% by weight of R125;

45% by weight of R134a; and

2% by weight of C02. In third embodiment, the present invention provides a refrigerant composition 3, comprising:

25% by weight of R32;

30% by weight of R1234ze(E); 15% by weight of R125;

25% by weight of R134a; and

5% by weight of difluoroethane. In fourth embodiment, the present invention provides a refrigerant composition 4, comprising:

33.7% by weight of R32;

14.7% by weight of R1234ze(E);

5% by weight of R227ea; and

46.6% by weight of R 134a.

In fifth embodiment, the present invention provides a refrigerant composition 5, comprising:

30% by weight of R32;

15% by weight of R1234yf;

10% by weight of R125;

30% by weight of R134a; and

15% by weight of R1234ze(E). In sixth embodiment, the present invention provides a refrigerant composition 6, comprising:

25% by weight of R32;

30% by weight of R1234ze(E);

15% by weight of R125;

25% by weight of R134a; and

5% by weight of R227ea. In seventh embodiment, the present invention provides a refrigerant composition 7, comprising:

30% by weight of R32;

34.7% by weight of R1234ze(E);

5.3% by weight of R125; and

30% by weight of R134a.

In eighth embodiment, the present invention provides a refrigerant composition 8, comprising:

35.5% by weight of R32;

36% by weight of R1234ze(E); and

28.5% by weight of R134a.

In ninth embodiment, the present invention provides a refrigerant composition 9, comprising:

37% by weight of R32;

23.5% by weight of R1234ze(E);

29.5% by weight of R134a; and

10% by weight of R152a.

In tenth embodiment, the present invention provides a refrigerant composition 10, comprising:

36% by weight of R32;

22% by weight of R1234ze(E);

14% by weight of R125; and

28% by weight of R 134a. In eleventh embodiment, the present invention provides a refrigerant composition 11, comprising:

35% by weight of R32;

35% by weight of R1234ze(E);

10% by weight of R125; and

20% by weight of R1234yf.

As used herein, a refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and back again during a cycle used to transfer of heat. Non-azeotropic composition is a mixture of two or more substances that behaves as a simple mixture rather than a single substance. One way to characterize a non- azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a substantially different composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes with substantial composition change.

The composition of the present invention has lower molecular weight thus has large enthalpy of evaporation. The larger the enthalpy of evaporation, the lower will be energy loss across compression and thus higher will be coefficient of performance COP value. The comparative data for molar mass and enthalpy of evaporation is given below (Table-2).

Table-2

Coefficient of performance (COP) is the amount of heat removed divided by the required energy input to operate the cycle. The higher the COP, higher is the energy efficiency. COP is directly related to the energy efficiency ratio (EER) that is the efficiency rating for refrigeration or air conditioning equipment at a specific set of internal and external temperatures. The composition of the present invention have higher COP as compared to known compositions of the art.

Further the compositions of the present invention have higher cooling capacity (CC) which leads to better coefficient of performance (COP) and therefore low power consumption which results in better performance as compared with the prior art composition R-404A as shown below.

Table-3

Flammability is a term used to mean the ability of a composition to ignite and/or propagate a flame. Determination of whether a refrigerant compound or mixture is flammable or non-flammable can be done by testing under the conditions of ASTM- 681. The compositions of the present inventions are mainly non-flammable.

Global warming potential (GWP) is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100-year time horizon is commonly the value referenced. For mixtures, a weighted average can be calculated based on the individual GWPs for each compound. The standard GWP values for R22, R32, R125 and tetrafluoroethane has been taken from IIPCC 5th Assessment report 2014 (AR5). The GWP of the refrigerant mixture has been derived from mass fraction and the corresponding GWP values. The compositions of the present invention has lower GWP value as compared with R-404 shown in the below table.

Table-4

Ozone depletion potential (ODP) is a number that refers to the amount of ozone depletion caused by a substance. The ODP is the ratio of the impact on ozone of a chemical compared to the impact of a similar mass of CFC-11 (fluorotrichloromethane). Thus, the ODP of CFC-11 is defined to be 1.0. Other CFCs and HCFCs have ODPs that range from 0.01 to 1.0. HFCs have zero ODP because they do not contain chlorine or other ozone depleting halogens. The compositions of the present invention has zero ODP value.

In another embodiment of the present invention, the refrigerant compositions may contain optional components selected from the group consisting of lubricants, dyes (including Ultra Violet dyes), solubilizing agents, compatibilizers, stabilizers, tracers, perfluoropolyethers, anti-wear agents, extreme pressure agents, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity adjusters, and mixtures thereof. Indeed, many of these optional other components fit into one or more of these categories and may have qualities that lend themselves to achieve one or more performance characteristic.

In another embodiment of the present invention, the refrigerant compositions are non-azeotropic mixture.

In another embodiment of this aspect of the present invention, the refrigerant composition is preferably charged in liquid form. The refrigerant composition of the present invention has higher specific heat capacity.

Table-5

In another embodiment of this aspect, the present invention provides a refrigeration process using the refrigerant composition comprising the steps of:

a) condensing the refrigerant composition;

b) evaporating the refrigerant composition.

The vapor compression refrigeration cycle is given below.

T-S Diagram of Vapor Compression Cycle

Further, the refrigerant compositions of present invention have higher thermal conductivity. Table-6

The refrigerant compositions of the present invention find use in stationary or mobile air conditioning systems or heat exchanger systems. Preferably, the refrigerant compositions find use in domestic room air conditioning systems.

The present invention provides R404a replacement refrigerant compositions that are compatible with existing mineral oil and alike lubricants and do not require replacement of the expensive devices in the legacy system.

R32 is commercially available or may be prepared by methods known in the art, such as by dechlorofluorination of methylene chloride. R125 is commercially available or may be prepared by methods known in the art, such as dechlorofluorination of 2,2-dichloro-l,l,l-trifluoroethane as described in US Patent No. 5,399,549, incorporated herein by reference. Tetrafluoroethane is commercially available or may be prepared by methods know in the art, such as by the hydrogenation of 1 , 1 -dichloro- 1 ,2,2,2-tetrafluoroethane (i.e., CCI2FCF3 or CFC-114a) to 1 , 1 ,1 ,2-tetrafluoroethane.

Heptafluoropropane is commercially available or may be prepared by methods known in the art.

R1234yf and R1234ze(E) is commercially available or may be prepared by methods known in the art. It is against this and other backgrounds, which shall be filed in a detailed manner in complete specifications, in due course, the present invention is brought out and explained in following non-limiting examples.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention and specific examples provided herein without departing from the spirit and scope of the invention. Thus, it is intended that the present invention covers the modifications and variations of this invention that come within the scope of any claims and their equivalents. EXAMPLE

The refrigerant compositions according to the invention having components selected from the group consisting of R125, R134a, R32, R227ea, R1234yf, 1234ze(E) and R152a were prepared and tested with standard ASHRAE modeling program maintaining indoor at 5°C dry bulb temperature (DBT) and 4°C wet bulb temperature (WBT) and outdoor at 35 DBT and 24 WBT.

The properties of the various refrigerant compositions are shown in below tables. Table-7

Table-8

Table-9

Table- 10

Claims

WE CLAIM

1. A refrigerant composition comprising 10% by weight to 38% by weight of 1,3,3,3-tetrafluoropropene (R1234ze), 20% by weight to 38% by weight of difluoromethane (R32) and one or more additional compound selected from pentafluoroethane (R125), tetrafluoroethane (R134), difluoroethane (R152), heptafluoropropane (R227), 2,3,3,3-tetrafluoropropene (R1234yf) and C02.

2. The refrigerant composition, as claimed in claim 1, wherein said one or additional compounds are selected from the group comprising:

20% by weight to 50% by weight of tetrafluoroethane;

0% to 15% by weight of R125;

0% to 20% by weight of R1234yf;

0% to 10% by weight of heptafluoropropane;

0% to 15% by weight of difluoroethane; and

0% to 5% by weight of C02.

3. The refrigerant composition, as claimed in claim 1, wherein said additional compound is essentially 20% by weight to 50% by weight of R 134a.

4. The refrigerant composition, as claimed in claim 1, wherein said additional compounds essentially consist of 20% by weight to 50% by weight of R134a, more than 0% to 15% by weight of R 125 and more than 0% to 5% by weight of CO2.

5. The refrigerant composition, as claimed in claim 1, wherein said additional compounds essentially consist of 20% by weight to 50% by weight of R134a, 0% to 15% by weight of R 125 and 0% to 10% by weight of 227ea.

6. The refrigerant composition, as claimed in claim 1, wherein said additional compounds essentially consist of 20% by weight to 50% by weight of R134a, 0% to 15% by weight of R125 and 0% to 15% by weight of difluoroethane.

7. The refrigerant composition, as claimed in claim 1, wherein said additional compounds essentially consist of 0% to 50% by weight of R134a, more than 0% to 15% by weight of R125 and more than 0% to 20% by weight of R1234yf.

8. The refrigerant composition as claimed in claim 1, has global warming potential of less than 1500, preferably less than 1200.

9. The refrigerant compositions as claimed in previous claims are non- azeotropic compositions.

10. The refrigerant compositions as claimed in previous claims are used as replacement for R404A.