US20210253974A1

US20210253974A1 - Use of tetrafluoropropene based compositions

Info

Publication number: US20210253974A1
Application number: US17/164,888
Authority: US
Inventors: Wissam Rached
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2016-10-10
Filing date: 2021-02-02
Publication date: 2021-08-19
Also published as: MX2019004098A; KR20230052996A; EP3523390A1; CN109804037B; JP2019534936A; CN109804037A; WO2018069621A1; KR102605414B1; EP3523390B1; JP2023039989A; US10954467B2; FR3057271A1; KR20190060815A; US20190284500A1; FR3057271B1

Abstract

The use of a composition including a polyol ester-based lubricant and a refrigerant F including at least one tetrafluoropropene and at least one hydrofluorocarbon, in a heat transfer system containing a vapour compression circuit including an oil separator. A heat transfer system including a vapour compression circuit containing a composition including a polyol ester lubricant, and a refrigerant F including at least one tetrafluoropropene and at least one hydrofluorocarbon, as a heat transfer composition, said vapour compression circuit including an oil separator.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. application Ser. No. 16/339,956, filed on Apr. 5, 2019, which is a U.S. National Stage of International Application No. PCT/FR2017/052765, filed on Oct. 9, 2017, which claims the benefit of French Application No. 1659747, filed on Oct. 10, 2016. The entire contents of each of U.S. application Ser. No. 16/339,956, International Application No. PCT/FR2017/052765, and French Application No. 1659747 are hereby incorporated herein by reference in their entirety.

FIELD OF INVENTION

The present invention relates to the use of a composition based on tetrafluoropropene and at least one lubricant, in refrigeration, air conditioning and heat pump.

TECHNICAL BACKGROUND

The problems posed by substances that deplete the atmospheric ozone layer were discussed in Montreal, where the protocol imposing a reduction in the production and use of chlorofluorocarbons (CFCs) was signed. This protocol has been amended to eliminate the use of CFCs and extend the regulation to include other products, including hydrochlorofluorocarbons (HCFCs).
The refrigeration and air-conditioning industry has invested heavily in the substitution of these refrigerants and hydrofluorocarbons (HFCs) have thus been marketed.
In the automotive industry, the air conditioning systems of vehicles marketed in many countries have moved from a chlorofluorocarbon (CFC-12) refrigerant to hydrofluorocarbon (1,1,1,2-tetrafluoroethane: HFC-134a) refrigerant, less harmful for the ozone layer. However, in view of objectives set by the Kyoto Protocol, HFC-134a (GWP=1430) is considered to have a high warming potential. The contribution to the greenhouse effect of a fluid is quantified by a criterion, GWP (Global Warming Potential) which summarizes the warming power by taking a reference value of 1 for carbon dioxide.
Hydrofluoroolefins (HFOs) have a low warming potential and therefore meet the objectives set by the Kyoto Protocol. JP 4-110388 discloses hydrofluoropropenes as a heat transfer agent.
In the industrial field, the most widely used refrigeration machines are based on evaporative cooling of a liquid refrigerant. After vaporization, the fluid is compressed and then cooled in order to return to liquid state and thus continue the cycle.
Lubricating oils are necessary to ensure the proper functioning of the moving mechanical parts, and especially to ensure the lubrication of the compressor bearings. However, the refrigerant fluid, which is in contact with the lubricant present on the moving parts, at each passage through the compressor, tends to carry a certain amount, which accompanies the refrigerant in its cycle, and is therefore found in the evaporator. To overcome this problem of oil migration, it is common to use an oil separation system, capable of purging the accumulated oil from the high pressure at the compressor outlet towards the low pressure (at the compressor inlet).
Thanks to their thermal stability and their miscibility with HFOs, especially HFO-1234, POE oils are commonly used in heat transfer systems, especially in refrigeration and/or air conditioning.
However, due to good solubility of HFO-1234 in POE oils, a problem is found on heat transfer systems having an oil separator: a relatively large amount of refrigerant remains trapped by the oil. Draining the oil induces the return of trapped refrigerant from the compressor outlet directly to the inlet of the latter. This results in a net loss of efficiency for the system, since the entire refrigerant does not perform the refrigeration cycle in its entirety, and also results in a deterioration of the lubrication of compressors, especially of screw compressors, due to lower amount of oil.
There is therefore a need to find new compositions making it possible, in particular, to overcome at least one of the aforementioned drawbacks.

DESCRIPTION OF THE INVENTION

The present invention relates to the use of a composition comprising a polyol ester-based lubricant, and a refrigerant F comprising at least one tetrafluoropropene and at least one hydrofluorocarbon, in a heat transfer system containing a circuit vapour compression apparatus comprising an oil separator.
Unless otherwise stated, throughout the application, the proportions of compounds indicated are given in weight percentages.
The compositions of the invention advantageously make it possible to improve the efficiency of heat transfer systems comprising an oil separator, particularly with respect to HFO-1234/POE oil compositions which are devoid of hydrofluorocarbons. The compositions according to the invention also reduce the deterioration of the lubrication of compressors compared with HFO-1234yf alone, particularly due to the recovery of a higher quantity of lubricating oil in the separator.
In the context of the invention, the term “composition of the invention” is intended to mean a composition comprising a polyol ester-based lubricant and a refrigerant F comprising at least one tetrafluoropropene and at least one hydrofluorocarbon. The various compounds and ratios of said compounds in the composition according to the invention are described below.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 depicts a diagram of the mixture R134a/Triton oil SE 55 representing the temperature (in ° C.) on the abscissa and, on the ordinate, the pressure (in bar).

DETAILED DESCRIPTION

Refrigerant Fluid

The refrigerant F according to the invention comprises at least one tetrafluoropropene (HFO-1234) and at least one hydrofluorocarbon.
Examples of the tetrafluoroprenes, include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,2,3,3-tetrafluoropropene (HFO-1234ye).
The tetrafluoropropene is preferably HFO-1234yf or HFO-1234ze.
The refrigerant F according to the invention can be prepared by any known method, for example by simply mixing the different ingredients together.
In the context of the invention, “HFO-1234ze” refers to 1,3,3,3-tetrafluoropropene, regardless of whether it is cis (Z) or trans (E). The term “HFO-1234ze” therefore covers cis-HFO-1234ze, trans-HFO-1234ze, and all mixtures of the two isomeric forms in all proportions.
In the context of the invention, “HFO-1234yf” refers to 2,3,3,3-tetrafluoropropene,
In the context of the invention, “HFO-1234ye” refers to 1,2,3,3-tetrafluoropropene, regardless of whether it is cis (Z) or trans (E). The term “HFO-1234ye” therefore covers cis-HFO-1234ye, trans-HFO-1234ye, and all mixtures of the two isomeric forms in all proportions.
According to one embodiment, hydrofluorocarbon is chosen from the group consisting of difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1-trifluoropropane (HFC-263fb), and mixtures thereof.
According to one embodiment, the refrigerant F according to the invention comprises at least one tetrafluoropropene (HFO-1234) selected from HFO-1234yf and HFO-1234ze, and at least one hydrofluorocarbon selected from the group consisting of difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1-trifluoropropane (HFC-263fb), and mixtures thereof.
According to one embodiment, the refrigerant F comprises two tetrafluoropropenes, especially HFO-1234yf and HFO-1234ze.
According to specific embodiments, the refrigerant F according to the invention is a binary composition (consisting of two heat transfer compounds) or ternary (consisting of three heat transfer compounds) or quaternary (consisting of four transfer compounds of heat) or quinternary (consisting of five heat transfer compounds).
Impurities may or may not be present in such refrigerants F. When present, they may represent less than 1%, preferably less than 0.5%, preferably less than 0.1%, preferably less than 0.05% and preferably less than 0.01% of said fluid.
According to one embodiment, the refrigerant F essentially consists of two, three, four or five heat transfer compounds.
Preferred refrigerant fluid F compositions according to the invention comprise, or preferably consist of, the following mixtures:


	HFO-1234yf	HFC-32
	HFO-1234yf	HFC-152a
	HFO-1234yf	HFC-134a
	HFO-1234yf	HFC-125
	HFO-1234ze	HFC-32
	HFO-1234ze	HFC-152a
	HFO-1234ze	HFC-134a
	HFO-1234ze	HFC-125

Preferred refrigerant fluid F compositions according to the invention comprise, or preferably consist of, the following mixtures:


HFO-1234yf	HFC-32	HFC-125
HFO-1234yf	HFC-152a	HFC-125
HFO-1234yf	HFC-152a	HFC-32
HFO-1234yf	HFC-134a	HFC-152a
HFO-1234yf	HFC-134a	HFC-32
HFO-1234yf	HFC-134a	HFC-125
HFO-1234ze	HFC-134a	HFC-152a
HFO-1234ze	HFC-134a	HFC-32
HFO-1234ze	HFC-134a	HFC-125
HFO-1234ze	HFC-152a	HFC-32
HFO-1234ze	HFC-152a	HFC-125
HFO-1234ze	HFC-32	HFC-125
HFO-1234yf	HFO-1234ze	HFC-134a
HFO-1234yf	HFO-1234ze	HFC-152a
HFO-1234yf	HFO-1234ze	HFC-134
HFO-1234yf	HFO-1234ze	HFC-32
HFO-1234yf	HFO-1234ze	HFC-125


HFO-1234yf	HFC-134a	HFC-152a	HFC-32
HFO-1234yf	HFC-134a	HFC-152a	HFC-125
HFO-1234yf	HFO-1234ze	HFC-134a	HFC-32
HFO-1234yf	HFO-1234ze	HFC-134a	HFC-152a
HFO-1234yf	HFO-1234ze	HFC-134a	HFC-125
HFO-1234ze	HFC-134a	HFC-152a	HFC-32
HFO-1234ze	HFC-134a	HFC-152a	HFC-125

Other preferred compositions of refrigerant F according to the invention comprise, or preferably consist of, the following mixtures:


HFO-1234yf	HFC-134a	HFC-152a	HFC-125	HFC-32
HFO-1234ze	HFC-134a	HFC-152a	HFC-125	HFC-32

In refrigerant F according to the invention, the weight proportion of tetrafluoropropene (s), and especially of HFO-1234yf and/or HFO-1234ze, can represent, for example, from 1 to 5% of the fluid; or from 5 to 10% of the fluid; or from 10 to 15% of the fluid; or 15 to 20% of the fluid; or from 20 to 25% of the fluid; or 25 to 30% of the fluid; or 30 to 35% of the fluid; or 35 to 40% of the fluid; or 40 to 45% of the fluid; or from 45 to 50% of the fluid; or from 50 to 55% of the fluid; or from 55 to 60% of the fluid; or from 60 to 65% of the fluid; or from 65 to 70% of the fluid; or from 70 to 75% of the fluid; or from 75 to 80% of the fluid; or from 80 to 85% of the fluid; or from 85 to 90% of the fluid; or from 90 to 95% of the fluid; or from 95 to 99% of the fluid; or from 99 to 99.5% of the fluid; or from 99.5 to 99.9% of the fluid; or more than 99.9% of the fluid, based on the total weight of said fluid. The content of tetrafluoropropene, and especially of HFO-1234yf and/or HFO-1234ze, in the refrigerant F may also vary in several of the above ranges: for example from 50 to 55% and from 55 to 60%, meaning, 50 to 60%, etc.
According to a preferred embodiment, the weight proportion of tetrafluoropropene (s), and in particular of HFO-1234yf and/or HFO-1234ze, in the refrigerant F is greater than 70%, preferably between 70% and 95%, preferably between 75% and 90%, and especially between 75% and 78%.
In the refrigerant according to the invention, the weight proportion of hydrofluorocarbon (s) may represent in particular from 1 to 5% of the fluid; or from 5 to 10% of the fluid; or from 10 to 15% of the fluid; or 15 to 20% of the fluid; or from 20 to 25% of the fluid; or 25 to 30% of the fluid; or 30 to 35% of the fluid; or 35 to 40% of the fluid; or 40 to 45% of the fluid; or from 45 to 50% of the fluid; or from 50 to 55% of the fluid; or from 55 to 60% of the fluid; or from 60 to 65% of the fluid; or from 65 to 70% of the fluid; or from 70 to 75% of the fluid; or from 75 to 80% of the fluid; or from 80 to 85% of the fluid; or from 85 to 90% of the fluid; or from 90 to 95% of the fluid; or from 95 to 99% of the fluid; or from 99 to 99.5% of the fluid; or 99.5 to 99.9% of the fluid, based on the total weight of said fluid. The content of hydrofluorocarbon (s) in the refrigerant F may also vary in several of the above ranges: for example 50 to 55% and 55 to 60%, hence, 50 to 60%, etc.
According to a preferred embodiment, the weight proportion of hydrofluorocarbon (s) in the refrigerant F is less than 70%, preferably less than 50%, preferably from 10% to 30%, and especially 18% to 27%, in relation to the total weight of said fluid.
Preferred compositions of refrigerant F are as follows:


	Concentration ranges
	(weight proportion in %)

						More	Most
					Preferred	preferred	preferred
V	W	X	Y	Z	(V/W/X/Y/Z)	(V/W/X/Y/Z)	(V/W/X/Y/Z)

HFO-1234yf	HFC-32		60-85/15-40	63-79/37-21	64-79/21-36
HFO-1234yf	HFC-152a		10-95/5-90	50-95/5-50	80-95/5-20
HFO-1234yf	HFC-134a		10-95/5-90	40-60/40-60	50-60/40-50
HFO-1234yf	HFC-125		10-95/5-90	50-95/5-50	80-95/5-20
HFO-1234ze	HFC-32		10-95/5-90	10-40/60-90	25-35/65-75
HFO-1234ze	HFC-152a		10-95/5-90	35-95/5-65	45-95/5-55
HFO-1234ze	HFC-134a		10-95/5-90	40-60/40-60	50-60/40-50
HFO-1234ze	HFC-125		10-95/5-90	50-95/5-50	80-95/5-20
HFO-1234yf	HFC-134a	HFC-152a	1-98/1-98/1-98	50-98/1-49/1-49	56-80/5-22/5-22
HFO-1234ze	HFC-134a	HFC-152a	1-98/1-98/1-98	50-98/1-49/1-49	56-80/5-22/5-22

The preferred refrigerants F are those comprising the aforementioned mixtures in the amounts mentioned in the table above.
According to one embodiment, the preferred refrigerant compositions are as follows:

- HFO-1234yf and HFC-134a;
- HFO-1234ze and HFC-134a; and
- HFO-1234yf and HFC-152a and HFC-134a.

According to one embodiment, the preferred refrigerants comprise the following mixtures:

According to a preferred embodiment, the refrigerant F is that comprising (preferably constituted): from 75.5 to 79.5% weight of HFO-1234yf, from 12 to 16% weight of HFC-152a, and from 6.5 to 10.5% weight of HFC-134a. In particular, the refrigerant F comprises (preferably consists of) 77.5% weight of HFO-1234yf, 14% weight of HFC-152a and 8.5% weight of HFC-134a, based on the total weight of said fluid F.
According to a preferred embodiment, the refrigerant F is that comprising (preferably consisting) from 74 to 81.5% weight of HFO-1234yf, from 6.5 to 10.5% weight of HFC-134a, and from 12 to 16% weight of HFC-152a, based on the total weight of said fluid F.
Azeotropic or quasi-azeotropic mixture can be identified from the liquid and vapour saturations at a given temperature.
Within the scope of the invention, the term “vapour saturation pressure” or “Psat yap”, refers to the pressure at which the first drop of liquid begins to form in a fluid in vapour state. This pressure is also called Dew pressure.
In the context of the invention, the term “liquid saturation pressure” or “Psat liq”, refers to the pressure at which the first vapour bubble begins to form in a liquid state fluid. This pressure is also known as bubble pressure.
In the context of the invention, the R_Ppercentage, calculated from the vapour and liquid saturation pressures, corresponds to the following equation:
$Rp = [\frac{(Psat liq - Psat vap)}{Psat liq}] \times 1 0 0$
In the context of the invention, a mixture is considered azeotropic when the R_Ppercentage defined above is between 0 and 0.5%.
In the context of the invention, “between x and y” refers to an interval wherein the x and y terminals are included. For example, the range “between 0 and 0.50%” includes in particular, the values 0 and 0.5%.
In the context of the invention, a mixture is almost azeotropic when the R_Ppercentage defined above is strictly greater than 0.5% and strictly less than 10.0%.
By way of example and in accordance with ASHRAE STANDARD 34-2013 “Design and safety classification of refrigerants”, the mixtures of the table below are classified as azeotropic, according to this standard (the components, compositions and temperatures are indicated by the same standard, and the pressures are calculated by Refrop 9 (Reference fluid Properties): Software developed by NIST (National Institute of Standards and Technology) for the calculation of the properties of refrigerants):


						RP (value
				Psat Liq	Psat vap	rounded to
			Temperature	(bar abs)	(bar abs)	the nearest
Product	Components	weight %	(° C.)	(±0.5%)	(±0.5%)	tenth)

R500	R12/R152a	73.8/26.2	0.0	3.643	3.638	0.1
R501	R22/R12	75/25	−41.0	0.996	0.992	0.4
R502	R22/R115	48.8/51.2	19.0	9.803	9.800	0.0
R504	R32/R115	48.2/51.8	17.0	15.240	15.229	0.1
R507A	R125/R143a	50/50	−40.0	1.386	1.386	0.0
R508A	R23/R116	39/61	−86.0	1.111	1.111	0.0
R512A	R134a/R152a	5/95	10.0	3.728	3.728	0.0

This table describes in particular, azeotropically classified refrigerants showing a relative difference in saturation pressures of less than 0.5%.
Some of the refrigerants F according to the invention, have the advantage of being azeotropic or quasi-azeotropic. The following mixtures may especially be mentioned:


					RP (value
			Psat Liq	Psat vap	rounded to
		Temperature	(bar abs)	(bar abs)	the nearest
		(° C.)	(±0.5%)	(±0.5%)	tenth)	type

R1234yf	R134a

60.0	40.0	30.00	8.208	8.208		azeotrope
56.0	44.0	30.00	8.211	8.211		azeotrope
50.0	50.0	30.00	8.205	8.204		azeotrope
45.0	55.0	30.00	8.191	8.187		azeotrope
40.0	60.0	30.00	8.169	8.161		azeotrope

R1234ze	R134a

58	42.0	30.00	6.830	6.705		quasi-azeotrope
50	50.0	30.00	6.983	6.870		quasi-azeotrope
45	55.0	30.00	7.072	6.969		quasi-azeotrope
40	60.0	30.00	7.157	7.066	1.3	quasi-azeotrope

R1234yf	R152a

95.0	5.0	−20.00	1.512	1.512	0.0	azeotrope
90.0	10.0	5.00	3.748	3.748	0.0	azeotrope
85.0	15.0	25.00	6.882	6.882	0.0	azeotrope
80.0	20.0	30.00	7.902	7.902	0.0	azeotrope

R1234ze	R152a

95	5.0	30.00	5.998	5.947	0.9	quasi-azeotrope
90	10.0	30.00	6.172	6.097	1.2	quasi-azeotrope
85	15.0	30.00	6.314	6.232	1.3	quasi-azeotrope
80	20.0	30.00	6.431	6.352	1.2	quasi-azeotrope
75	25.0	30.00	6.528	6.458	1.1	quasi-azeotrope

						RP (value
				Psat Liq	Psat vap	rounded to
			Temperature	(bar abs)	(bar abs)	the nearest
			(° C.)	(±0.5%)	(±0.5%)	tenth)	type

R1234yf	R134a	R152a

81.5	8.5	10.0	30.00	7.972	7.968	0.1	azeotrope
77.5	8.5	14.0	26.97	7.319	7.316	0.0	azeotrope
76.5	8.5	15.0	30.00	7.955	7.952	0.0	azeotrope
71.5	8.5	20.0	30.00	7.928	7.923	0.1	azeotrope
66.5	8.5	25.0	30.00	7.894	7.883	0.1	azeotrope

R134a	R152a	R1234ze

2.0	10.0	88.0	30.00	6.216	6.136	1.3	quasi-azeotrope
5.0	10.0	85.0	30.00	6.280	6.195	1.4	quasi-azeotrope
8.5	10.0	81.5	30.00	6.353	6.263	1.4	quasi-azeotrope
2.0	15.0	83.0	30.00	6.352	6.268	1.3	quasi-azeotrope
5.0	15.0	80.0	30.00	6.407	6.323	1.3	quasi-azeotrope
8.5	15.0	76.5	30.00	6.470	6.385	1.3	quasi-azeotrope
2.0	20.0	78.0	30.00	6.464	6.385	1.2	quasi-azeotrope
5.0	20.0	75.0	30.00	6.511	6.435	1.2	quasi-azeotrope
8.5	20.0	71.5	30.00	6.565	6.492	1.1	quasi-azeotrope

According to a preferred embodiment, refrigerants F comprising (preferably constituted) from 74 to 81.5% weight of HFO-1324yf, from 6.5 to 10.5% weight of HFC-134a, and from 12 to 16% weight of HFC-152a, in relation to the total weight of the composition, are azeotropic compositions at a temperature between −40.00 and 70.00° C., and at a pressure between 0.5 and 21.0 bar abs (±0.5%).
According to a preferred embodiment, refrigerants F comprising (preferably constituted) from 75.5% to 79.5% weight of HFO-1324yf, from 6.5 to 10.5% weight of HFC-134a, and from 12 to 16% weight of HFC-152a, in relation to the total weight of the composition, are azeotropic compositions at a temperature between −40.00 and 70.00° C., and at a pressure between 0.5 and 21.0 bar abs (±0.5%).
Preferred refrigerant fluid F constitute the following azeotropic compositions:


						RP (value
				Psat Liq	Psat vap	rounded to
			Temperature	(bar abs)	(bar abs)	the nearest
R1234yf	R134a	R152a	(° C.)	(±0.5%)	(±0.5%)	tenth)

77.5	8.5	14.0	−40.00	0.616	0.614
77.5	8.5	14.0	−35.00	0.783	0.781
77.5	8.5	14.0	−30.00	0.984	0.982
77.5	8.5	14.0	−25.00	1.224	1.221
77.5	8.5	14.0	−20.00	1.507	1.504
77.5	8.5	14.0	−15.00	1.838	1.835
77.5	8.5	14.0	−10.00	2.223	2.221
77.5	8.5	14.0	−5.00	2.668	2.665
77.5	8.5	14.0	0.00	3.178	3.176
77.5	8.5	14.0	5.00	3.759	3.757
77.5	8.5	14.0	10.00	4.418	4.416
77.5	8.5	14.0	15.00	5.161	5.158
77.5	8.5	14.0	20.00	5.994	5.991
77.5	8.5	14.0	25.00	6.924	6.921
77.5	8.5	14.0	26.97	7.319	7.316
77.5	8.5	14.0	30.00	7.959	7.956
77.5	8.5	14.0	35.00	9.106	9.102
77.5	8.5	14.0	40.00	10.371	10.367
77.5	8.5	14.0	45.00	11.765	11.760
77.5	8.5	14.0	50.00	13.293	13.288
77.5	8.5	14.0	55.00	14.966	14.960
77.5	8.5	14.0	60.00	16.793	16.786
77.5	8.5	14.0	65.00	18.783	18.775
77.5	8.5	14.0	70.00	20.948	20.938

Preferred refrigerant fluid F constitute the following azeotropic compositions:

77.5	6.5	16.0	−40.00	0.615	0.613
77.5	6.5	16.0	−35.00	0.782	0.779
77.5	6.5	16.0	−30.00	0.982	0.979
77.5	6.5	16.0	−25.00	1.221	1.218
77.5	6.5	16.0	−20.00	1.504	1.501
77.5	6.5	16.0	−15.00	1.834	1.831
77.5	6.5	16.0	−10.00	2.219	2.216
77.5	6.5	16.0	−5.00	2.663	2.660
77.5	6.5	16.0	0.00	3.172	3.169
77.5	6.5	16.0	5.00	3.752	3.749
77.5	6.5	16.0	10.00	4.409	4.406
77.5	6.5	16.0	15.00	5.150	5.147
77.5	6.5	16.0	20.00	5.981	5.979
77.5	6.5	16.0	25.00	6.910	6.907
77.5	6.5	16.0	26.97	7.304	7.301
77.5	6.5	16.0	30.00	7.942	7.939
77.5	6.5	16.0	35.00	9.086	9.083
77.5	6.5	16.0	40.00	10.349	10.346
77.5	6.5	16.0	45.00	11.740	11.736
77.5	6.5	16.0	50.00	13.265	13.261
77.5	6.5	16.0	55.00	14.935	14.930
77.5	6.5	16.0	60.00	16.757	16.752
77.5	6.5	16.0	65.00	18.743	18.737
77.5	6.5	16.0	70.00	20.903	20.897

Preferred refrigerant fluid F constitute the following azeotropic compositions:

81.5	6.5	12.0	−40.00	0.619	0.618
81.5	6.5	12.0	−35.00	0.787	0.785
81.5	6.5	12.0	−30.00	0.988	0.986
81.5	6.5	12.0	−25.00	1.228	1.226
81.5	6.5	12.0	−20.00	1.511	1.509
81.5	6.5	12.0	−15.00	1.842	1.841
81.5	6.5	12.0	−10.00	2.228	2.226
81.5	6.5	12.0	−5.00	2.672	2.671
81.5	6.5	12.0	0.00	3.182	3.181
81.5	6.5	12.0	5.00	3.763	3.761
81.5	6.5	12.0	10.00	4.420	4.419
81.5	6.5	12.0	15.00	5.162	5.160
81.5	6.5	12.0	20.00	5.993	5.991
81.5	6.5	12.0	25.00	6.922	6.919
81.5	6.5	12.0	26.97	7.316	7.313
81.5	6.5	12.0	30.00	7.954	7.951
81.5	6.5	12.0	35.00	9.097	9.094
81.5	6.5	12.0	40.00	10.359	10.355
81.5	6.5	12.0	45.00	11.748	11.743
81.5	6.5	12.0	50.00	13.272	13.266
81.5	6.5	12.0	55.00	14.939	14.932
81.5	6.5	12.0	60.00	16.759	16.751
81.5	6.5	12.0	65.00	18.742	18.732
81.5	6.5	12.0	70.00	20.898	20.887

Preferred refrigerant fluid F constitute the following azeotropic compositions:

75.5	10.0	14.5	−40.00	0.615	0.612
75.5	10.0	14.5	−35.00	0.782	0.778
75.5	10.0	14.5	−30.00	0.983	0.979
75.5	10.0	14.5	−25.00	1.222	1.218
75.5	10.0	14.5	−20.00	1.505	1.501
75.5	10.0	14.5	−15.00	1.836	1.833
75.5	10.0	14.5	−10.00	2.222	2.218
75.5	10.0	14.5	−5.00	2.667	2.663
75.5	10.0	14.5	0.00	3.177	3.173
75.5	10.0	14.5	5.00	3.759	3.755
75.5	10.0	14.5	10.00	4.418	4.415
75.5	10.0	14.5	15.00	5.161	5.158
75.5	10.0	14.5	20.00	5.995	5.992
75.5	10.0	14.5	25.00	6.927	6.923
75.5	10.0	14.5	26.97	7.323	7.319
75.5	10.0	14.5	30.00	7.963	7.960
75.5	10.0	14.5	35.00	9.112	9.108
75.5	10.0	14.5	40.00	10.380	10.375
75.5	10.0	14.5	45.00	11.775	11.770
75.5	10.0	14.5	50.00	13.307	13.301
75.5	10.0	14.5	55.00	14.983	14.977
75.5	10.0	14.5	60.00	16.814	16.806
75.5	10.0	14.5	65.00	18.808	18.800
75.5	10.0	14.5	70.00	20.978	20.968

Preferred refrigerant fluid F constitute the following azeotropic compositions:

77.5	10.5	12.0	−40.00	0.618	0.615
77.5	10.5	12.0	−35.00	0.785	0.783
77.5	10.5	12.0	−30.00	0.987	0.984
77.5	10.5	12.0	−25.00	1.227	1.224
77.5	10.5	12.0	−20.00	1.510	1.508
77.5	10.5	12.0	−15.00	1.842	1.840
77.5	10.5	12.0	−10.00	2.229	2.226
77.5	10.5	12.0	−5.00	2.674	2.672
77.5	10.5	12.0	0.00	3.186	3.183
77.5	10.5	12.0	5.00	3.768	3.766
77.5	10.5	12.0	10.00	4.429	4.426
77.5	10.5	12.0	15.00	5.173	5.170
77.5	10.5	12.0	20.00	6.008	6.005
77.5	10.5	12.0	25.00	6.940	6.937
77.5	10.5	12.0	26.97	7.336	7.332
77.5	10.5	12.0	30.00	7.978	7.974
77.5	10.5	12.0	35.00	9.127	9.122
77.5	10.5	12.0	40.00	10.395	10.390
77.5	10.5	12.0	45.00	11.791	11.785
77.5	10.5	12.0	50.00	13.324	13.316
77.5	10.5	12.0	55.00	15.000	14.992
77.5	10.5	12.0	60.00	16.831	16.821
77.5	10.5	12.0	65.00	18.826	18.815
77.5	10.5	12.0	70.00	20.996	20.983

According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% (±0.2%) weight of HFO-1234yf, 14% (±0.2%) weight of HFC-152a and 8.5% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point of between −40.00° C. and 70.00° C. at a pressure of between 0.5 and 21.0 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% (±0.2%) weight of HFO-1234yf, 14% (±0.2%) weight of HFC-152a and 8.5% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point of 26.97° C. (±0.50° C.) at a pressure of 7.3 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% weight of HFO-1234yf, 16% weight of HFC-152a and 6.5% weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point between −40,00° C. and 70,00° C., at a pressure of between 0.5 and 21.0 bar abs (±0.5%), and preferably between 0.6 and 20.9 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% weight of HFO-1234yf, 16% weight of HFC-152a and 6.5% weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling temperature of 26.97° C. (±0.50° C.) at a pressure of 7.3 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% (±0.2%) weight of HFO-1234yf, 15.8% (±0.2%) weight of HFC-152a and 6.7% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point between −40.00° C. and 70.00° C., at a pressure between 0.5 and 21.0 bar abs (±0.5%), and preferably between 0.6 and 20.9 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% (±0.2%) weight of HFO-1234yf, 15.8% (±0.2%) weight of HFC-152a and 6.7% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point of 26.97° C. (±0.50° C.) at a pressure of 7.3 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 81.5% (±0.2%) weight of HFO-1234yf, 12% (±0.2%) weight of HFC-152a and 6.5% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point between −40.00° C. and 70.00° C., at a pressure between 0.5 and 21.0 bar abs (±0.5%), and preferably between 0.6 and 20.9 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 81.5% (±0.2%) weight of HFO-1234yf, 12% (±0.2%) weight of HFC-152a and 6.5% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point of 26.97° C. (±0.50° C.) at a pressure of 7.3 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 75.5% (±0.2%) weight of HFO-1234yf, 14.5% (±0.2%) weight of HFC-152a and 10% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point between −40.00° C. and 70.00° C., at a pressure between 0.5 and 21.0 bar abs (±0.5%), and preferably between 0.78 and 20.98 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 75.5% (±0.2%) weight of HFO-1234yf, 14.5% (±0.2%) weight of HFC-152a and 10% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point of 26.97° C. (±0.50° C.) at a pressure of 7.3 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% (±0.2%) weight of HFO-1234yf, 12% (±0.2%) weight of HFC-152a and 10.5% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition with a boiling point between −40.00° C. and 70.00° C., at a pressure between 0.5 and 21.0 bar abs (±0.5%), and preferably between 0.61 and 21.00 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% (±0.2%) weight of HFO-1234yf, 12% (±0.2%) weight of HFC-152a and 10.5% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point of 26.97° C. (±0.50° C.) at a pressure of 7.3 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% (±0.2%) weight of HFO-1234yf, 12.2% (±0.2%) weight of HFC-152a and 10.3% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition with a boiling point between −40.00° C. and 70.00° C., at a pressure between 0.5 and 21.0 bar abs (±0.5%), and preferably between 0.61 and 21.00 bar abs (±0.5%).
According to a preferred embodiment, the azeotropic composition according to the invention comprises (preferably consists of) 77.5% (±0.2%) weight of HFO-1234yf, 12.2% (±0.2%) weight of HFC-152a and 10.3% (±0.2%) weight of HFC-134a, in relation to the total weight of the composition, said composition having a boiling point of 26.97° C. (±0,50° C.) at a pressure of 7.3 bar abs (±0.5%).

Lubricant

In the context of the invention, the terms “lubricant”, “lubricant oil” and “lubricating oil” are used interchangeably.
According to the invention, the lubricant may comprise one or more polyol esters.
According to one embodiment, the polyol esters are obtained by reaction of at least one polyol with a carboxylic acid or with a mixture of carboxylic acids.
In the context of the invention, and unless otherwise indicated, the term “polyol” means a compound containing at least two hydroxyl groups (—OH).
Polyol Esters A)
According to one embodiment, the polyol esters according to the invention have the following formula (I):
R¹[OC(O)R²]_n (I)
wherein:

- R¹is a linear or branched hydrocarbon radical, optionally substituted with at least one hydroxyl group and/or comprising at least one heteroatom selected from the group consisting of —O—, —N—, and —S—;
- each R²is, independently of each other, selected from the group consisting of:
  - i) H;
  - ii) an aliphatic hydrocarbon radical;
  - iii) a branched hydrocarbon radical;
  - iv) a mixture of a radical ii) and/or iii) with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms; and
- n is an integer of at least 2.

In the context of the invention, the term “hydrocarbon radical” means a radical composed of carbon atoms and hydrogen.
According to one embodiment, the polyols have the following general formula (II):
R¹(OH)_n (II)
wherein:

- R¹is a linear or branched hydrocarbon radical, optionally substituted with at least one hydroxyl group, preferably with two hydroxyl groups, and/or comprising at least one heteroatom selected from the group consisting of —O—, —N—, and —S—; and
- n is an integer of at least 2.

Preferably, R¹is a hydrocarbon, linear or branched radical, comprising from 4 to 40 carbon atoms, preferably from 4 to 20 carbon atoms.
Preferably, R¹is a hydrocarbon, linear or branched radical comprising at least one oxygen atom.
Preferably, R¹is a branched hydrocarbon radical comprising from 4 to 10 carbon atoms, preferably 5 carbon atoms, substituted by two hydroxyl groups.
According to a preferred embodiment, the polyols comprise from 2 to 10 hydroxyl groups, preferably from 2 to 6 hydroxyl groups.
The polyols according to the invention may comprise one or more oxyalkylene groups, in this particular case polyether polyols.
The polyols according to the invention may also comprise one or more nitrogen atoms. For example, the polyols may be alkanol amines containing from 3 to 6 OH groups. Preferably, the polyols are alkanol amines containing at least two OH groups, and preferably at least three.
According to the present invention, the preferred polyols are selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, 1,2-butanediol, 1,4-butanediol, 1,3-butanediol, pentaerythritol, dipentaerythritol, tripentaerythritol, triglycerol, trimethylolpropane, sorbitol, hexaglycerol, and mixtures thereof.
According to the invention, carboxylic acids can satisfy the following general formula (III):
R²COOH (III)
wherein:

- R²is selected from the group consisting of:
  - i) H;
  - ii) an aliphatic hydrocarbon radical;
  - iii) a branched hydrocarbon radical;
  - iv) a mixture of a radical ii) and/or iii), with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms.

Preferably, R²is an aliphatic hydrocarbon radical comprising from 1 to 10, preferably from 1 to 7 carbon atoms, and especially from 1 to 6 carbon atoms.
Preferably, R²is a branched hydrocarbon radical comprising from 4 to 20 carbon atoms, especially from 5 to 14 carbon atoms, and preferably from 6 to 8 carbon atoms.
According to a preferred embodiment, a branched hydrocarbon radical has the following formula (IV):
—C(R³)R⁴)(R⁵) (IV)
wherein R³, R⁴and R⁵are, independently of each other, an alkyl group, and at least one of the alkyl groups contains at least two carbon atoms. Such branched alkyl groups, once bound to the carboxyl group, are known as “neo group”, and the corresponding acid as “neo acid”. Preferably, R³and R⁴are methyl groups and R¹⁰is an alkyl group comprising at least two carbon atoms.
According to the invention, the R²radical may comprise one or more carboxy groups, or ester groups such as —COOR⁶, with R⁶representing an alkyl radical, hydroxyalkyl radical or a hydroxyalkyloxy alkyl group.
Preferably, the acid R²COOH of formula (III) is a monocarboxylic acid.
Examples of carboxylic acids in which the hydrocarbon radical is aliphatic include: formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid and heptanoic acid.
Examples of carboxylic acids among which the hydrocarbon-based esterified radical include: 2-ethyl-n-butyric acid, 2-hexyldecanoic acid, isostearic acid, 2-methyl-hexanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neoheptanoic acid, and neodecanoic acid.
The third type of carboxylic acids which can be used in the preparation of the polyol esters of formula (I) are carboxylic acids comprising an aliphatic hydrocarbon radical containing from 8 to 14 carbon atoms. For example: decanoic acid, dodecanoic acid, lauric acid, stearic acid, myristic acid, behenic acid, etc. Examples of dicarboxylic acids, include maleic acid., succinic acid, adipic acid, sebacic acid . . . .
According to a preferred embodiment, the carboxylic acids used to prepare the polyol esters of formula (I) comprise a mixture of monocarboxylic and dicarboxylic acids, the proportion of monocarboxylic acids being the majority. The presence of dicarboxylic acids results especially in the formation of polyol esters of high viscosity.
In particular, the polyol ester-forming reaction of formula (I) by reaction between the carboxylic acid and the polyols is an acid-catalysed reaction. This is mostly a reversible reaction, which can be complete by using a large amount of acid or by removing the water formed during the reaction.
The esterification reaction can be carried out in the presence of organic or inorganic acids, such as sulphuric acid, phosphoric acid . . . .
Preferably, the reaction is carried out in the absence of a catalyst.
The amount of carboxylic acid and polyol in the mixture may vary depending on the desired results. In the particular case where all the hydroxyl groups are esterified, a sufficient amount of carboxylic acid must be added to react with all the hydroxyls.
According to one embodiment, when using mixtures of carboxylic acids, these can react sequentially with the polyols.
According to a preferred embodiment, when using a mixture of carboxylic acids, a polyol reacts first with a carboxylic acid, typically the highest molecular weight carboxylic acid, followed by reaction with the carboxylic acid with an aliphatic hydrocarbon chain.
According to one embodiment, the esters can be formed by reaction between the carboxylic acids (or their anhydride or ester derivatives) with the polyols, in the presence of acids at high temperature, while removing the water formed during the reaction. Typically, the reaction can be carried out at a temperature of 75 to 200° C.
According to another embodiment, the polyol esters formed may comprise unreactive hydroxyl groups, in this case they are esters of partially esterified polyols.
According to a preferred embodiment, the polyol esters are obtained from pentaerythritol alcohol, and from a mixture of carboxylic acids: isononanoic acid, at least one acid having an aliphatic hydrocarbon radical comprising from 8 to 10 carbon atoms, and heptanoic acid. The preferred polyol esters are obtained from pentaerythritol, and a mixture of 70% of isononanoic acid, 15% of at least one carboxylic acid with an aliphatic hydrocarbon radical comprising from 8 to 10 carbon atoms, and 15% heptanoic acid. For example, Solest 68 oil sold by CPI Engineering Services Inc.
Polyol Esters B)
According to another embodiment, the polyol esters of the invention comprise at least one ester of one or more branched carboxylic acids comprising at most 8 carbon atoms. The ester is mostly obtained by reacting said branched carboxylic acid with one or more polyols.
Preferably, the branched carboxylic acid comprises at least 5 carbon atoms. In particular, the branched carboxylic acid comprises from 5 to 8 carbon atoms, and preferably contains 5 carbon atoms.
Preferably, the above-mentioned branched carboxylic acid does not comprise 9 carbon atoms. In particular, said carboxylic acid is not 3,5,5-trimethylhexanoic acid.
According to a preferred embodiment, the branched carboxylic acid is selected from 2-methylbutanoic acid, 3-methylbutanoic acid, and mixtures thereof.
In a preferred embodiment, the polyol is selected from the group consisting of neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.
According to a preferred embodiment, the polyol esters are obtained from:

- i) a carboxylic acid selected from 2-methylbutanoic acid, 3-methylbutanoic acid, and mixtures thereof; and
- ii) a polyol selected from the group consisting of neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.

Preferably, the polyol ester is that obtained from 2-methylbutanoic acid and pentaerythritol.
Preferably, the polyol ester is that obtained from 2-methylbutanoic acid and dipentaerythritol.
Preferably, the polyol ester is that obtained from 3-methylbutanoic acid and pentaerythritol.
Preferably, the polyol ester is that obtained from 3-methylbutanoic acid and dipentaerythritol.
Preferably, the polyol ester is that obtained from 2-methylbutanoic acid and neopentyl glycol.
Polyol Esters C)
According to another embodiment, the polyol esters according to the invention are poly (neopentylpolyol) esters obtained by:

- i) reaction of a neopentylpolyol with the following formula (V):

wherein:

- each R represents, independently of each other, CH₃, C₂H₅or CH₂OH;
- p is an integer between 1 and 4;
- with at least one monocarboxylic acid containing 2 to 15 carbon atoms, and in the presence of an acid catalyst, the molar ratio between the carboxyl groups and the hydroxyl groups being less than 1:1, to form a composition of partially esterified poly (neopentyl) polyol; and
- ii) reacting the partially esterified poly (neopentyl) polyol composition obtained at the end of step i) with another carboxylic acid having from 2 to 15 carbon atoms, to form the final composition of poly (neopentyl polyol) ester (s).

Preferably, reaction i) is carried out with a molar ratio ranging from 1:4 to 1:2.
Preferably, neopentyl polyol has the following formula (VI):
wherein each R is, independently of each other, CH₃, C₂H₅or CH₂OH.
Preferred neopentyl polyols are those selected from pentaerythritol, dipentaerythritol, tripentaerythritol, tetraerythritol, trimethylolpropane, trimethylolethane, and neopentyl glycol. In particular, the neopentyl polyol is pentaerythritol.
Preferably, a single neopentyl polyol is used to produce the POE-based lubricant. In some cases, two or more neopentyl polyols are used. This is particularly the case when a commercial product of pentaerythritol includes small amounts of dipentaerythritol, tripentaerythritol, and tetraerythritol.
According to a preferred embodiment, the above mentioned monocarboxylic acid comprises from 5 to 11 carbon atoms, preferably from 6 to 10 carbon atoms.
Monocarboxylic acids have in particular, the following general formula (VII):
R′C(O)OH (VII)
in which R ′is a linear or branched C1-C12 alkyl radical, a C6-C12 aryl radical or a C6-C30 aralkyl radical. Preferably, R ′is a C4-C10 alkyl radical, and preferentially a C5-C9 alkyl radical.
In particular, the monocarboxylic acid is selected from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, 3-methylbutanoic acid, 2-methylbutanoic acid, 2,4-dimethylpentanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, benzoic acid, and mixtures thereof.
According to a preferred embodiment, the monocarboxylic acid is n-heptanoic acid, or a mixture of n-heptanoic acid with another linear monocarboxylic acid, in particular n-octanoic acid and/or n-decanoic acid. Such a mixture of monocarboxylic acid may comprise between 15 and 100 mol % of heptanoic acid and between 85 and 0 mol % of other monocarboxylic acid(s). In particular, the mixture comprises between 75 and 100 mol % of heptanoic acid, and between 25 and 0 mol % of a mixture of octanoic acid and decanoic acid in a molar ratio 3:2.
According to a preferred embodiment, polyol esters comprise:

- i) from 45% to 55% weight of a monopentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms;
- ii) less than 13% weight of a dipentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms;
- iii) less than 10% weight of a tripentaerythritol ester with at least one monocarboxylic acid having 2 to 15 carbon atoms; and
- iv) at least 25% weight of a tetraerythritol ester and other pentaerythritol oligomers, with at least one monocarboxylic acid having from 2 to 15 carbon atoms.

Polyol Esters D)

According to another embodiment, the polyol esters according to the invention have the following formula (VIII):
wherein:

- R⁷, R⁸, R⁹, R¹⁰, R¹¹and R¹²are, independently of each other, H or CH₃;
- a, b, c, y, x and z are, independently of each other, an integer;
- a+x, b+y, and c+z are, independently of each other, integers ranging from 1 to 20;
- R¹³, R¹⁴and R¹⁵are, independently of each other, selected from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls, cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryls and cycloalkylarylalkyls,
- R¹³, R¹⁴and R¹⁵, consisting 1 to 17 carbon atoms, and may be optionally substituted.

According to a preferred embodiment, R¹³, R¹⁴and R¹⁵each represents, independently of each other, a linear or branched alkyl group, an alkenyl group, a cycloalkyl group, said alkyl, alkenyl or cycloalkyl groups may comprise at least one heteroatom selected from N, O, Si, F or S. Preferably, R¹³, R¹⁴and R¹⁵have, each independently of each other, from 3 to 8 carbon atoms, preferably from 5 to 7 carbon atoms.
Preferably, a+x, b+y, and c+z are, independently of one another, integers ranging from 1 to 10, preferably from 2 to 8, and even more preferably from 2 to 4.
Preferably, R⁷, R⁸, R⁹, R¹⁰, R¹¹and R¹²represent H.
The polyol esters of formula (VIII) above can typically be prepared as described in paragraphs [0027] to [0030] of international application WO2012/177742.
In particular, the polyol esters of formula (VIII) are obtained by esterification of glycerol alkoxylates (as described in paragraph [0027] of WO2012/177742) with one or more monocarboxylic acids having from 2 to 18 carbon atoms.
According to a preferred embodiment, the monocarboxylic acids have one of the following formulas:
R¹³COOH
R¹⁴COOH and
R¹⁵COOH
wherein R¹³, R¹⁴and R¹⁵are as defined above. Derivatives of the carboxylic acids can also be used, such as anhydrides, esters and acyl halides.
Esterification can be carried out with one or more monocarboxylic acids. Preferred monocarboxylic acids are those selected from the group consisting of acetic acid, propanoic acid, butyric acid, isobutanoic acid, pivalic acid, pentanoic acid, isopentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, palmitoleic acid, citronellic acid, undecenoic acid, lauric acid, undecylenic acid, linolenic acid, arachidic acid, behenic acid, tetrahydrobenzoic acid, hydrogenated or non-hydrogenated abietic acid, 2-ethylhexanoic acid, furoic acid, benzoic acid, 4-acetylbenzoic acid, pyruvic acid, 4-tert-butyl-benzoic acid, naphthenic acid, 2-methyl benzoic acid, salicylic acid, their isomers, their methyl esters, and mixtures thereof.
Preferably, the esterification is carried out with one or more monocarboxylic acids selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, n-hexanoic acid, n-heptanoic acid, 3,3,5-trimethylhexanoic acid, 2-ethylhexanoic acid, n-octanoic acid, n-nonanoic acid and isononanoic acid.
Preferably, the esterification is carried out with one or more monocarboxylic acids selected from the group consisting of butyric acid, isobutyric acid, n-pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, n-nonanoic acid, decanoic acid, undecanoic acid, undecylenic acid, lauric acid, stearic acid, isostearic acid, and mixtures thereof.
According to another embodiment, the polyol esters according to the invention have the following formula (IX):
wherein:

- each of R¹⁷and R¹⁸, is, independently of each other, H or CH₃;
- each of m and n is, independently of each other, an integer, with m+n being an integer from 1 to 10;
- R¹⁶and R¹⁹are, independently of each other, selected from the group consisting of aliphatic or branched aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls, cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryls and cycloalkylarylalkyls,
- R¹⁶and R¹⁹, consisting 1 to 17 carbon atoms, and may be optionally substituted.

According to a preferred embodiment, each of R¹⁶and R¹⁹each represents, independently of one another, a linear or branched alkyl group, an alkenyl group, a cycloalkyl group, said alkyl, alkenyl or cycloalkyl groups may comprise at least one heteroatom selected from N, O, Si, F or S Preferably, each of R¹⁶and R¹⁹has, independently of each other, from 3 to 8 carbon atoms, preferably from 5 to 7 carbon atoms.
According to a preferred embodiment, R¹⁷and R¹⁸each represents H, and/or m+n is an integer ranging from 2 to 8, from 4 to 10, from 2 to 5, or from 3 to 5. In particular, m+n is 2, 3 or 4.
According to a preferred embodiment, the polyol esters of formula (IX) above are triethylene glycol diesters, tetraethylene glycol diesters, in particular with one or two monocarboxylic acids having from 4 to 9 carbon atoms.
The polyol esters of formula (IX) above may be prepared by esterifications of an ethylene glycol, a propylene glycol, or an oligo- or polyalkylene glycol, (which may be an oligo- or polyethylene glycol, oligo- or polypropylene glycol, or an ethylene glycol-propylene glycol block copolymer), with one or two monocarboxylic acids comprising 2 to 18 carbon atoms. The esterification can be carried out identically to the esterification reaction used to prepare the polyol esters of formula (VIII) above.
In particular, monocarboxylic acids identical to those used to prepare the polyol esters of formula (VIII) above can be used to form the polyol esters of formula (IX).
According to one embodiment, the lubricant based on polyol esters according to the invention comprises from 20 to 80%, preferably from 30 to 70%, and preferably from 40 to 60% weight of at least one polyol ester of formula (VIII), and from 80 to 20%, preferably from 70 to 30%, and preferably from 60 to 40% weight of at least one polyol ester of formula (IX).
In general, certain alcohol functional groups cannot be esterified during the esterification reaction, however, their proportion remains low. Thus, the POE can comprise between 0 and 5% relative molar ratio of CH₂OH in relation to —CH₂—O—C(═O)—.
Preferred POE lubricants according to the invention are those having a viscosity between 1 to 1000 centiStokes (cSt) at 40° C., preferably from 10 to 200 cSt, even more preferably from 20 to 100 cSt, and advantageously from 30 to 80 cSt.
The international classification of oils is provided by ISO3448-1992 (NF T60-141) and according to which oils are designated by their average viscosity class measured at a temperature of 40° C.

Composition

In the composition of the invention, the weight proportion of refrigerant F can represent especially, from 1 to 5% of the composition; or from 5 to 10% of the composition; or from 10 to 15% of the composition; or from 15 to 20% of the composition; or from 20 to 25% of the composition; or from 25 to 30% of the composition; or from 30 to 35% of the composition; or from 35 to 40% of the composition; or from 40 to 45% of the composition; or from 45 to 50% of the composition; or from 50 to 55% of the composition; or from 55 to 60% of the composition; or from 60 to 65% of the composition; or from 65 to 70% of the composition; or from 70 to 75% of the composition; or from 75 to 80% of the composition; or from 80 to 85% of the composition; or from 85 to 90% of the composition; or from 90 to 95% of the composition; or from 95 to 99% of the composition; or from 99 to 99.5% of the composition; or from 99.5 to 99.9% of the composition; or more than 99.9% of the composition. The content of hydrofluorocarbon (s) in the refrigerant F may also vary in several of the above ranges: for example 50 to 55% and 55 to 60%, hence, 50 to 60%, etc.
According to a preferred embodiment, the composition of the invention comprises more than 50% weight of refrigerant F, and in particular from 50% to 99% in weight, relative to the total weight of the composition.
In the composition of the invention, the weight proportion of lubricant based on polyol esters (POE) can represent especially, from 1 to 5% of the composition; or from 5 to 10% of the composition; or from 10 to 15% of the composition; or from 15 to 20% of the composition; or from 20 to 25% of the composition; or from 25 to 30% of the composition; or from 30 to 35% of the composition; or from 35 to 40% of the composition; or from 40 to 45% of the composition; or from 45 to 50% of the composition; or from 50 to 55% of the composition; or from 55 to 60% of the composition; or from 60 to 65% of the composition; or from 65 to 70% of the composition; or from 70 to 75% of the composition; or from 75 to 80% of the composition; or from 80 to 85% of the composition; or from 85 to 90% of the composition; or from 90 to 95% of the composition; or from 95 to 99% of the composition; or from 99 to 99.5% of the composition; or from 99.5 to 99.9% of the composition; or more than 99.9% of the composition. The lubricant content may also vary in several of the above ranges: for example from 50 to 55%, and from 55 to 60%, meaning from 50 to 60%, etc.
According to one embodiment, the composition according to the invention comprises:

- a refrigerant F selected from the group consisting of:
- HFO-1234WHFC-134a;
- HFO-1234ze/HFC-134a; and
- HFO-1234WHFC-134a/HFC-152a;

and

- at least one lubricant based on polyol esters (POE), especially selected from polyol esters A), B), C) or D) described above, especially polyol esters of formulas (I), (VIII) or (XI).

According to one embodiment, the composition according to the invention comprises:

- a refrigerant F comprising one of the following mixtures:
- HFO-1234WHFC-134a;
- HFO-1234ze/HFC-134a; or
- HFO-1234yf/HFC-134a/HFC-152a;

and

- a refrigerant F comprising (preferably consisting of) the mixture HFO-1234yf/HFC-134a/HFC-152a, in particular comprising from 75.5 to 79.5% weight of HFO-1234yf, from 12 to 16% weight of HFC-152a, and from 6.5 to 10.5% weight of HFC-134a, and preferably comprising 77.5% weight of HFO-1234yf, 14% weight of HFC-152a and 8.5% weight of HFC-134a

and

The composition according to the invention may comprise one or more additives (which are essentially not heat transfer compounds for the intended application).
The additives may especially be selected from nanoparticles, stabilizers, surfactants, tracer agents, fluorescent agents, odorants and solubility agents.
Preferably, the additives are not lubricants.
According to one embodiment, the composition of the invention is a heat transfer composition.
The stabilizer (s), when present, preferably represent at most 5% weight in the heat transfer composition. Examples of the stabilizers, include in particular, nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenol compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphonates, thiols and lactones.
As nanoparticles, it is possible to use nanoparticles of carbon, metal oxides (copper, aluminium), TiO₂, Al₂O₃, MoS₂. . . .
Examples of (detectable) tracer agents include deuterated or non-deuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof. The tracer agent is different from the one or more heat transfer compounds that constitute the heat transfer fluid (refrigerant F).
Examples of solubility agents, include hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalcanes. The solubility agent is different from the one or more heat transfer compounds composing the heat transfer fluid (refrigerant F).
Examples of fluorescent agents include naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanhthenes, fluoresceins and derivatives and combinations thereof.
Examples of odorants include alkyl acrylates, allyl acrylates, acrylic acids, acrylesters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulphides, allyl isothiocyanates and alkanoic acids, amines, norbornenes, norbornene derivatives, cyclohexene, heterocyclic aromatic compounds, ascaridole, o-methoxy (methyl) phenol and combinations thereof.
“Heat transfer compound”, respectively “heat transfer fluid” or “refrigerant” refers to a compound, respectively a fluid, capable of absorbing heat by evaporating at low temperature and low pressure and of rejecting heat by condensing at high temperature and high pressure, in a vapour compression circuit. In general, a heat transfer fluid may comprise one, two, three or more than three heat transfer compounds. In particular, the refrigerant F is a heat transfer fluid.
“Heat transfer composition” refers to a composition comprising a heat transfer fluid and optionally one or more additives that are not heat transfer compounds for the intended application. In particular, the composition according to the invention is a heat transfer composition.

Uses

The present invention also relates to a heat transfer method based on the use of a heat transfer system containing a vapour compression circuit which comprises the composition of the invention as a heat transfer composition, said circuit comprising an oil separator. The heat transfer process may be a method of heating or cooling a fluid or a body.
The invention also relates to the use of the composition described above as a heat transfer fluid in a vapour compression system comprising an oil separator, preferably said vapour compression system comprising a screw compressor.
According to one embodiment, the vapour compression system constitutes:

- an air conditioning system; or
- a refrigeration system; or
- a freezing system; or
- a heat pump system.

The composition of the invention may also be used in a method of producing mechanical work or electricity, in particular, in accordance with a Rankine cycle.
The invention also relates to a heat transfer system comprising a vapour compression circuit containing the composition according to the invention as a heat transfer composition, said circuit containing an oil separator, and preferably a screw compressor.
According to one embodiment, this system is selected from mobile or stationary refrigeration, heating (heat pump), air conditioning and freezing systems, and thermal engines.
This may concern in particular a heat pump system, in which case the fluid or body that is heated (usually air and possibly one or more products, objects or organisms) is located in a room or a vehicle interior (for a mobile system). According to a preferred embodiment, it is an air conditioning system, in which case the fluid or body that is cooled (generally air and possibly one or more products, objects or organisms) is located in a room or vehicle interior (for a mobile system). It can be a refrigeration plant or a freezing facility (or cryogenic system), in which case the fluid or body that is cooled generally comprises air and one or more products, objects or organisms, located in a room or container.
In particular, the heat transfer system is a heat pump, or an air conditioning system, for example a chiller.
The invention also relates to a method for heating or cooling a fluid or a body by means of a vapour compression circuit containing a heat transfer composition, said method comprising successively the evaporation of the heat transfer composition, compression of the heat transfer composition, condensation of the heat transfer composition and expansion of the heat transfer composition, wherein the heat transfer composition is the composition according to invention described above, said compression circuit comprising an oil separator, and in particular a screw compressor.
The invention also relates to a method for producing electricity by means of a heat engine, said method comprising successively evaporation of the heat transfer composition, the expansion of the heat transfer composition in a turbine allowing generating electricity, condensing the heat transfer composition and compressing the heat transfer composition, wherein the heat transfer composition is the composition described above, said method using an oil separator.
The vapour compression circuit containing a heat transfer composition comprises at least one evaporator, preferably a screw compressor, an oil separator, a condenser and an expander, and heat transfer composition transport lines. between these elements. The evaporator and the condenser comprise a heat exchanger for heat exchange between the heat transfer composition and another fluid or body.
The evaporator used in the context of the invention may be an overheating evaporator or an embedded evaporator. In an overheating evaporator, all of the heat transfer composition is evaporated at the evaporator outlet, and the vapour phase is superheated.
In a flooded evaporator, the heat transfer composition in liquid form does not evaporate completely. A flooded evaporator has a liquid phase and vapour phase separator.
Regarding a compressor, a single or multi-stage centrifugal compressor in particular or a mini centrifugal compressor may be used. Rotary, piston or screw compressors may also be used.
According to one embodiment, the vapour compression circuit comprises a centrifugal compressor, and preferably a centrifugal compressor and a flooded evaporator.
According to another embodiment, the vapour compression circuit comprises a screw compressor, preferably twin-screw or single-screw. In particular, the vapour compression circuit comprises a twin-screw compressor, which can implement a substantial flow of oil, for example up to 6.3 L/s.
A centrifugal compressor is characterized in that it uses rotating elements to accelerate radially the heat transfer composition; it typically comprises at least one rotor and a diffuser housed in an enclosure. The heat transfer composition is introduced into the centre of the rotor and flows towards the periphery of the rotor while undergoing acceleration. Thus, on the one hand, the static pressure increases in the rotor, and especially on the other hand at the level of the diffuser, the speed is converted into an increase of the static pressure. Each rotor/diffuser assembly constitutes a compressor stage. Centrifugal compressors may comprise from 1 to 12 stages, depending on the desired final pressure and the volume of fluid to be treated.
The compression ratio is defined as the ratio of the absolute pressure of the output heat transfer composition to the absolute pressure of said composition at the inlet.
The rotational speed for large centrifugal compressors ranges from 3000 to 7000 revolutions per minute. Small centrifugal compressors (or mini-centrifugal compressors) generally operate at a rotation speed ranging from 40000 to 70000 revolutions per minute and comprise a small rotor (generally less than 0.15 m).
A multi-stage rotor can be used to improve the efficiency of the compressor and to limit the energy cost (compared to a single-stage rotor). For a two-stage system, the output of the first stage of the rotor feeds the input of the second rotor. Both rotors can be mounted on a single axis. Each stage can provide a fluid compression ratio of about 4 to 1, i.e. the output absolute pressure can be about four times the absolute suction pressure. Examples of two-stage centrifugal compressors, particularly for automotive applications, are described in U.S. Pat. No. 5,363,674.
The centrifugal compressor can be driven by an electric motor or by a gas turbine (for example powered by the exhaust gas of a vehicle, for mobile applications) or by gearing.
The system may include coupling of the expander with a turbine to generate electricity (Rankine cycle).
The system may also optionally comprise at least one heat transfer fluid circuit used to transmit heat (with or without a change of state) between the circuit of the heat transfer composition and the fluid or body to be heated or cooled.
The system may also optionally include two or more vapour compression circuits containing identical or different heat transfer compositions. For example, the vapour compression circuits may be coupled together.
The vapour compression circuit operates in a conventional vapour compression cycle. The cycle comprises changing the state of the heat transfer composition from a liquid phase (or two-phase liquid/vapour) to a vapour phase at a relatively low pressure, and then compressing the vapour phase composition to a relatively high pressure, changing the state (condensation) of the heat transfer composition from the vapour phase to the liquid phase at a relatively high pressure, and reducing the pressure to restart the cycle.
In the case of a cooling process, heat from the fluid or the body that is cooled (directly or indirectly, via a coolant) is absorbed by the heat transfer composition, during the evaporation of the latter, and this at a relatively low temperature compared to the environment. Cooling processes include air conditioning processes (with mobile systems, for example in vehicles, or stationary), refrigeration and freezing or cryogenics. In the field of air conditioning, examples include domestic, commercial or industrial air conditioning, where the equipment used is either chillers or direct expansion equipment. In the field of refrigeration, examples include domestic and commercial refrigeration, cold rooms, the food industry, refrigerated transport (trucks, boats).
In the case of a heating process, heat is transferred (directly or indirectly via a heat transfer fluid) from the heat transfer composition, during the condensation thereof, to the fluid or to the body that it heats at a relatively high temperature relative to the environment. The system for implementing the heat transfer is called in this case “heat pump”. This can concern medium and high temperature heat pumps.
It is possible to use any type of heat exchanger for the implementation of the heat transfer compositions according to the invention, and in particular co-current heat exchangers or, preferably, counter-current heat exchangers.
However, according to a preferred embodiment, the invention anticipates that the cooling and heating processes, and the corresponding facilities, comprise a counter current heat exchanger, either the condenser or the evaporator. Indeed, the heat transfer compositions according to the invention are particularly effective with counter current heat exchangers. Preferably, both the evaporator and the condenser comprise a counter current heat exchanger.
According to the invention, the term “counter current heat exchanger” is understood to mean a heat exchanger wherein heat is exchanged between a first fluid and a second fluid, the first fluid at the inlet of the exchanger exchanging heat with the second fluid at the outlet of the exchanger, and the first fluid at the outlet of the exchanger exchanging heat with the second fluid at the inlet of the exchanger.
For example, counter current heat exchangers include devices wherein the flow of the first fluid and the flow of the second fluid are in opposite or almost opposite directions. The exchangers operating in cross current mode with counter current tendency are also included among the counter current heat exchangers within the meaning of the present application.
Under different operating conditions (air conditioning, refrigeration, heat pump, etc.), the compositions according to the invention can advantageously induce overheating at the outlet of the compressor (difference between temperature at the separator and temperature at the condenser) greater than that of HFO-1234yf and/or HFO-1234ze.
In “low temperature refrigeration” processes, the inlet temperature of the heat transfer composition to the evaporator is preferably −45° C. to −15° C., especially −40° C. to −20° C. ° C., more preferably from −35° C. to −25° C. and for example about −30° C.; and the temperature of the onset of condensation of the heat transfer composition at the condenser is preferably 25° C. to 80° C., especially 30° C. to 60° C., more preferably 35° C. to 55° C. and for example about 40° C.
In “moderate temperature cooling” processes, the inlet temperature of the heat transfer composition to the evaporator is preferably from −20° C. to 10° C., especially from −15° C. to 5° C. more preferably from −10° C. to 0° C. and for example about −5° C.; and the temperature of the onset of condensation of the heat transfer composition at the condenser is preferably 25° C. to 80° C., especially 30° C. to 60° C., more preferably 35° C. to 55° C. and for example about 50° C. These processes can be refrigeration or air conditioning processes.
In “moderate temperature heating” processes, the inlet temperature of the heat transfer composition to the evaporator is preferably from −20° C. to 10° C., especially from −15° C. to 5° C. more preferably from −10° C. to 0° C. and for example about −5° C.; and the temperature of the onset of condensation of the heat transfer composition at the condenser is preferably from 25° C. to 80° C., especially from 30° C. to 60° C., more preferably from 35° C. to 55° C. and for example about 50° C.
In “high temperature heating” processes, the inlet temperature of the heat transfer composition to the evaporator is preferably from −20° C. to 90° C., especially from 10° C. to 90° C., such as more preferably from 50° C. to 90° C. and for example about 80° C.; and the temperature of the onset of condensation of the heat transfer composition at the condenser is preferably from 70° C. to 160° C., especially from 90° C. to 150° C., more preferably from 110° C. to 140° C. and for example about 135° C.
The compositions according to the invention are particularly significant in refrigerated transport.
Refrigerated transport entails any movement of perishable products under refrigerated space. Food or pharmaceutical products are an important part of perishable products.
Refrigerated transport can be carried out by lorry, rail or boat, possibly using multi-platform containers that also fit on lorries, rails or boats.
In refrigerated transport, the temperature of refrigerated spaces is between −30° C. and 16° C. The refrigerant charge in transport by lorry, rail or multi-platform containers varies between 4 kg and 8 kg of refrigerant. The systems in the boats can contain between 100 and 500 kg.
The most used refrigerant to date is R404A.
The operating temperatures of the refrigerating plants depend on the refrigeration temperature requirements and the external climatic conditions. The same refrigeration system must be able to cover a wide temperature range of −30° C. to 16° C. and operate in both cold and hot climates.
The most restrictive condition at evaporation temperature is −30° C.

Oil Separator

According to the invention, the vapour compression circuit comprises an oil separator.
According to one embodiment, the oil separator is located between the compressor and the condenser.
According to the invention, the oil separator may be a tank or a cylinder comprising at least one deflector or screen for collecting the oil.
According to one embodiment, the oil separator comprises a float/valve/needle mechanism. In this particular case, the oil, recovered in the separator, is stored in the lower part containing the float/valve/pointer mechanism. When the oil level is high enough to lift the float mechanism, the valve-needle system opens and allows the oil to re-enter the compressor housing(s). The oil return is carried out thanks to the pressure difference between that of the oil separator and that of the compressor crank house (s).
The oil separator advantageously makes it possible to separate the lubricating oil (lubricant) from the refrigerant in the gaseous refrigerant mixture and the lubricating oil from the compressor. In particular, the oil separator allows the release of the refrigerant to the condenser, and the return of the separated lubricating oil, to the compressor.
The compression circuit according to the invention may comprise an oil return line between the oil separator and the inlet of the compressor.
In particular, the oil separator comprises an inlet valve (allowing in particular the entry of the composition of the invention), an outlet valve in the upper part of the separator (in particular for recovering a part of the refrigerant which will go to the condenser), and an outlet valve in the lower part of the separator (allowing in particular the exit of the oil for its return to the compressor).
Typically, the oil separators can implement at least one of the following techniques:

- coalescence: a phenomenon by which two identical but dispersed substances tend to reunite;
- centrifugation: this technique uses centrifugal force to separate fluids of different densities;
- speed reduction: this technique allows the heavier molecules to continue their trajectory, thanks to their inertia, while the lighter molecules disperse in the internal volume of the oil separator;
- change of direction: this technique associated with the previous one makes it possible to increase the separation efficiency of the oil droplets (heavy molecules) present in the vapour (light molecules). The oil droplets retain their initial trajectory, in particular because of their weight and their initial velocity, while the steam is directed towards the exit of the separator.

Coalescence can be performed using metal screens or coalescent cartridges.
Centrifugation can be performed using turbulators, helical systems or special arrangements of the separators (cyclone).
An oil separator can especially implement several of the aforementioned techniques.
Examples of the oil separators that are useful according to the invention are CarlyTURBOIL range, Danfoss OUB, Emerson OS, Castel 5520 and 5540 series, Temprite separator and AC & R separators, Bitzer OAS separators for screw compressors.
The vapour compression circuit may further comprise an oil cooling system, and optionally an oil pump and/or an oil distribution system, located between the oil separator and the inlet of the compressor.
The oil pump can be used to remedy pressure losses and/or to allow the oil to reach a pressure higher than the discharge pressure of the compressor.
The oil cooling system can be used to cool the oil from the compressor and oil separator.
Flammability
The preferred refrigerants F of the present invention furthermore have the advantage of having a flame propagation velocity of less than 10 cm/s, preferably less than 8 cm/s or even 7 cm/s or even 3 cm/s following the measurement method developed by Jabbour T—2004. Some compositions are even non-flammable.
The experimental setup uses the vertical glass tube method (number of tube 2, length 150 cm, diameter 40 cm). The use of two tubes facilitates two tests with the same concentration at the same time.
The tubes are equipped with tungsten electrodes, which are placed at the bottom of each tube, 6.35 mm (¼ inch) apart and connected to a 15 kV and 30 mA generator.
The test method is developed in T. Jabbour's thesis, “Classification of flammability of refrigerants based on the fundamental flame velocity” under the direction of Denis Clodic. Thesis, Paris, 2004.
For example, the flame propagation speed for the composition HFO-1234yf/R134a/R152a: 78,9/7,0/14,1% by weight is 4.75 cm/s and that of the composition HFO-1234yf/R134a/R152a: 74,2/7,7/18,1% by weight is 6 cm/s.
All the embodiments described above can be combined with each other. Thus, each preferred refrigerant of the composition can be combined with each preferred polyol ester (esters A, B, C or D) in the various proportions mentioned. The various preferred compositions can be used in the various applications described above.

EXAMPLES

The following examples illustrate the invention but without limiting it.
FIG. 1: FIG. 1 is a diagram of the mixture R134a/Triton oil SE 55 representing the temperature (in ° C.) on the abscissa and on the ordinate the pressure (in bar), produced under the operating conditions of the example below. At 0% oil, 100% R134a, while 70% oil has a mixture comprising 30% R134a. This diagram shows that at constant pressure, the refrigerant concentration in the oil decreases as the temperature of the mixture Ts increases.
Supplier of POE Triton SE 55 d oil: FUCHS
In an oil separator integrated in a screw compressor, the oil is recovered in the lower part of the separator. In this example, the amounts of refrigerant trapped by the oil in the separator are analysed.
The coolant/oil mixture in the separator is at a temperature Ts (which is also the temperature of the refrigerant at the outlet of the compressor) and the pressure in the separator is equal to the refrigerant vapour saturation pressure at the condenser inlet (Pcond). Therefore, this results in a system that works at a condensing temperature (Tcond), which is the saturation temperature of the refrigerant alone at the corresponding Pcond pressure.
In general, the analysis of a typical refrigerant/oil diagram (as shown for example in FIG. 1 for R134a) indicates that, at constant pressure (Pcond), the refrigerant concentration in the oil decreases when the temperature of the mixture (oil/refrigerant, Ts) increases and moves away from the saturation temperature of the refrigerant alone (Tcond), the difference between Ts and Tcond representing the overheating at the outlet of the compressor.
Temperature Tcond, pressure Pcond and temperature Ts in the oil separator are defined by the operating needs of the system. The percentage of oil in the refrigerant will therefore be deduced from the corresponding refrigerant/oil diagram at the pressure Pcond and at temperature Ts. This method makes it possible to compare the refrigerants indirectly by watching overheating at the outlet of the compressor.
Let us consider an air conditioning system that operates under the following conditions in heating mode (heat pump):

- Condensation temperature Tcond=70° C.;
- Evaporation temperature: 0° C.;
- Overheating on the evaporator: 0° C.;
- Under cooling: 0° C.;
- Compressor efficiency: 75%;
- Reference case: R134a and POE Triton SE 55;

According to the diagram of FIG. 1, for a temperature (Ts) in the separator of 87° C. and a pressure of 21 bar abs, the superheat at the outlet of the compressor is 17° C. and the percentage of oil is 75% weight (25% weight of R134a in the oil).
For a HFO-1234yf/POE Triton SE 55 oil mixture, under the same operating conditions as described above, the condenser pressure is about 20.5 bar abs and the superheat at the compressor outlets about 4.8° C.
HFO-1234yf at saturation pressure very close to R134a but low overheating. As a result, the refrigerant concentration in the liquid phase of the oil separator will be greater than 30%, or even 35%, in weight.
Consequently, for the same oil/coolant liquid flow rate, increase of the percentage of refrigerant in the oil of the separator resulted in a decrease in the amount of lubricating oil circulating in the compressor and also in a decrease of the viscosity of the oil/refrigerant mixture. Therefore, direct replacement of R134a with HFO-1234yf may damage the compressor (lubrication problem, low viscosity) and decrease performance.
The table below provides the overheat value at the compressor output compared to the condensing temperature under the same operating conditions, described above for R134a and HFO-1234yf, for different mixtures:
The ratio A corresponds to the following relation:
$A = [\frac{overheating of compressor of the mixture - overheating of compressor of 1234 yf}{overheating of the compressor of 1234 yf}] \times 100$


	Temperature (° C.)

P (bar abs)

evaporator

compressor

condenser vapour

overheating

	condenser	evaporator	inlet	output	saturation	compressor	A

HFO-1234yf	20.45	3.16	0.0	74.8	70.0	4.8	0
HFO-1234ze	16.11	2.17	0.0	77.2	70.0	7.2	50
R134a	21.17	2.93	0.0	87.6	70.0	17.6	266

R1234yf	R134a

60.0	40.0	21.74	3.25	0.0	79.6	70.0	9.6	99
56.0	44.0	21.79	3.25	0.0	80.1	70.0	10.1	109
50.0	50.0	21.83	3.23	0.0	80.8	70.0	10.8	125
45.0	55.0	21.85	3.21	0.0	81.5	70.0	11.5	138
40.0	60.0	21.85	3.19	−0.1	82.1	70.0	12.1	152

R134a	R1234ze

42.0	58.0	18.77	2.53	−0.3	82.3	70.5	11.7	144
50.0	50.0	19.18	2.60	−0.3	83.0	70.5	12.6	161
55.0	45.0	19.42	2.64	−0.2	83.5	70.4	13.1	171
60.0	40.0	19.65	2.68	−0.2	84.0	70.4	13.6	182

R1234yf	R152a

85.0	15.0	20.74	3.17	0.0	79.1	70.0	9.1	89
80.0	20.0	20.77	3.16	0.0	80.6	70.0	10.6	119

R152a	R1234ze

5.0	95.0	16.61	2.23	−0.1	79.1	70.2	8.9	84
10.0	90.0	17.02	2.30	−0.2	80.7	70.3	10.4	116
15.0	85.0	17.36	2.36	−0.2	82.3	70.3	11.9	147
20.0	80.0	17.64	2.41	−0.2	83.7	70.3	13.4	177
25.0	75.0	17.88	2.45	−0.2	85.0	70.3	14.8	206

Temperature (° C.)

P (bar abs)

evaporator

compressor

condenser vapour

overheating

	condenser	evaporator	inlet	output	saturation	compressor

R1234yf	R134a	R152a

81.5	8.5	10.0	20.95	3.19	0.0	78.7	70.0	8.7	81
77.5	8.5	14.0	20.95	3.18	0.0	79.9	70.0	9.9	105
76.5	8.5	15.0	20.95	3.17	0.0	80.2	70.0	10.2	111
71.5	8.5	20.0	20.92	3.15	0.0	81.7	70.0	11.6	142
66.5	8.5	25.0	20.88	3.12	−0.1	83.1	70.0	13.1	173

R134a	R152a	R1234ze

2.0	10.0	88.0	17.13	2.31	−0.2	81.0	70.3	10.6	121
5.0	10.0	85.0	17.30	2.34	−0.2	81.3	70.4	11.0	127
8.5	10.0	81.5	17.49	2.36	−0.2	81.7	70.4	11.3	135
2.0	15.0	83.0	17.46	2.37	−0.2	82.5	70.3	12.1	152
5.0	15.0	80.0	17.61	2.39	−0.2	82.8	70.4	12.4	158
8.5	15.0	76.5	17.78	2.42	−0.2	83.1	70.4	12.8	165
2.0	20.0	78.0	17.73	2.42	−0.2	83.9	70.3	13.6	181
5.0	20.0	75.0	17.86	2.44	−0.2	84.2	70.3	13.9	188
8.5	20.0	71.5	18.01	2.46	−0.2	84.5	70.3	14.2	195

The mixtures according to the invention advantageously have a compressor overheating higher than the HFO-1234yf alone, and in particular a coefficient A, as defined above, greater than 50%, preferably greater than 80% in relation to HFO-1234yf.
Thus, the mixtures according to the invention advantageously can reduce (and/or avoid) the quantity of refrigerant trapped in the lubricating oil in relation to HFO-1234yf alone, and therefore increase the efficiency of the system due to higher refrigerant circulation in the system. In addition, with the mixtures of the invention, the amount of lubricating oil recovered by the separator being higher than with the HFO-1234yf, a better lubrication of the compressor is obtained.

EMBODIMENTS

1. Use of a composition comprising a polyol ester lubricant, and a refrigerant F comprising at least one tetrafluoropropene and at least one hydrofluorocarbon, in a heat transfer system containing a vapour compression circuit comprising a vapour separator comprising ′oil.
2. Use according to embodiment 1, characterized in that the polyol esters have the following formula (I):

R¹[OC(O)R²]_n (I)

- wherein:
- R¹is a linear or branched hydrocarbon radical, optionally substituted with at least one hydroxyl group and/or comprising at least one heteroatom selected from the group consisting of —O—, —N—, and —S—;
- each R²is, independently of each other, selected from the group consisting of:
  - i) H;
  - ii) an aliphatic hydrocarbon radical;
  - iii) a branched hydrocarbon radical;
  - iv) a mixture of a radical ii) and/or iii), with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms; and
- n is an integer of at least 2.
3. Use according to embodiment 1, characterized in that the polyol esters are obtained from a polyol selected from the group consisting of neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.
4. Use according to embodiment 1 or 3, characterized in that the polyol esters are obtained from at least one branched carboxylic acid comprising from 5 to 8 carbon atoms.
5. Use according to embodiment 1, characterized in that the polyol esters are poly (neopentylpolyol) esters obtained by:
- i) reaction of a neopentylpolyol with the following formula (V):

- wherein:
  - each R represents, independently of each other, CH₃, C₂H₅or CH₂OH;
  - p is an integer between 1 and 4;
- with at least one monocarboxylic acid containing 2 to 15 carbon atoms, in the presence of an acid catalyst, the molar ratio between the carboxyl groups and the hydroxyl groups being less than 1:1, to form a composition of poly (neopentyl partially esterified poly; and
- ii) reacting the partially esterified poly (neopentyl) polyol composition obtained at the end of step i) with another carboxylic acid consisting from 2 to 15 carbon atoms, to form the poly (neopentyl polyol) ester composition.
6. Use according to embodiment 1, characterized in that the polyol esters have one of the following formulas (VIII) or (IX):

in which:

- R⁷, R⁸, R⁹, R¹⁰, R¹¹and R¹²are, independently of each other, H or CH₃;
- a, b, c, y, x and z are, independently of each other, an integer;
- a+x, b+y, and c+z are, independently of each other, integers ranging from 1 to 20;
- R¹³, R¹⁴and R¹⁵are, independently of each other, selected from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls, cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryls and cycloalkylarylalkyls,
- R¹³, R¹⁴and R¹⁵, consisting 1 to 17 carbon atoms, and may be optionally substituted.
- or

wherein:

- each of R¹⁷and R¹⁸, is, independently of each other, H or CH₃;
- each of m and n is, independently of each other, an integer, with m+n being an integer from 1 to 10;
- R¹⁶and R¹⁹are, independently of each other, selected from the group consisting of aliphatic or branched aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls, cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryls and cycloalkylarylalkyls, R¹⁶and R¹⁹, consisting 1 to 17 carbon atoms, and may be optionally substituted.
7. Use according to any one of embodiments 1 to 6, characterized in that the refrigerant F comprises at least one tetrafluoropropene chosen from HFO-1234yf and HFO-1234ze, and at least one hydrofluorocarbon selected from the group consisting of dichloromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1-trifluoropropane (HFC-263fb), and mixtures thereof.
8. Use according to any one of embodiments 1 to 7, characterized in that refrigerant F comprises one of the following mixtures:


HFO-1234yf	HFC-32
HFO-1234yf	HFC-152a
HFO-1234yf	HFC-134a
HFO-1234yf	HFC-125
HFO-1234ze	HFC-32
HFO-1234ze	HFC-152a
HFO-1234ze	HFC-134a
HFO-1234ze	HFC-125
HFO-1234yf	HFC-32	HFC-125
HFO-1234yf	HFC-152a	HFC-125
HFO-1234yf	HFC-152a	HFC-32
HFO-1234yf	HFC-134a	HFC-152a
HFO-1234yf	HFC-134a	HFC-32
HFO-1234yf	HFC-134a	HFC-125
HFO-1234ze	HFC-134a	HFC-152a
HFO-1234ze	HFC-134a	HFC-32
HFO-1234ze	HFC-134a	HFC-125
HFO-1234ze	HFC-152a	HFC-32
HFO-1234ze	HFC-152a	HFC-125
HFO-1234ze	HFC-32	HFC-125
HFO-1234yf	HFO-1234ze	HFC-134a
HFO-1234yf	HFO-1234ze	HFC-152a
HFO-1234yf	HFO-1234ze	HFC-134
HFO-1234yf	HFO-1234ze	HFC-32
HFO-1234yf	HFO-1234ze	HFC-125
HFO-1234yf	HFC-134a	HFC-152a	HFC-32
HFO-1234yf	HFC-134a	HFC-152a	HFC-125
HFO-1234yf	HFO-1234ze	HFC-134a	HFC-32
HFO-1234yf	HFO-1234ze	HFC-134a	HFC-152a
HFO-1234yf	HFO-1234ze	HFC-134a	HFC-125
HFO-1234ze	HFC-134a	HFC-152a	HFC-32
HFO-1234ze	HFC-134a	HFC-152a	HFC-125
HFO-1234yf	HFC-134a	HFC-152a	HFC-125	HFC-32
HFO-1234ze	HFC-134a	HFC-152a	HFC-125	HFC-32

9. Use according to any one of embodiments 1 to 8, characterized in that refrigerant F comprises from 75.5 to 79.5% weight of HFO-1234yf, from 12 to 16% weight of HFC-152a, and from 6.5 to 10.5% weight of HFC-134a.
10. Use according to any one of embodiments 1 to 9, characterized in that refrigerant F comprises 77.5% (±0.2%) weight of HFO-1234yf, 14% (±0.2%) weight of HFC-152a and 8.5% (±0.2%) weight of HFC-134a, said composition being azeotropic at a boiling point of between −40.00° C. and 70.00° C., at a temperature of pressure between 0.5 and 21.0 bar abs (±0.5%), and in particular a boiling point of 26.97° C. (±0.50° C.) at a pressure of 7.3 bar abs (±0.5%).
11. A heat transfer system comprising a vapour compression circuit containing a composition comprising a polyol ester lubricant, and a refrigerant F comprising at least one tetrafluoropropene and at least one hydrofluorocarbon, as a heat transfer composition, said vapour compression circuit comprising an oil separator.
12. System according to embodiment 11, selected from mobile or stationary heat pump heating, air conditioning, refrigeration, and freezing systems, and thermal engines.
13. A method of producing electricity by means of a heat engine, said method comprising successively evaporation of the heat transfer composition, expansion of the heat transfer composition in a turbine for generating electricity, condensation of the heat transfer composition, and compression of the heat transfer composition,
- wherein the process comprising using an oil separator, and
- said heat transfer composition being a composition comprising a lubricant based on polyol esters, and a refrigerant fluid F comprising at least one tetrafluoropropene and at least one hydrofluorocarbon.
14. A method of heating or cooling a fluid or a body by means of a vapour compression circuit containing a heat transfer composition, said method comprising successively evaporation of the heat transfer composition, compression of the heat transfer composition, the condensation of the heat transfer composition and the expansion of the heat transfer composition,
- said compression circuit comprising an oil separator, and
- said heat transfer composition being a composition comprising a lubricant based on polyol esters, and a refrigerant fluid F comprising at least one tetrafluoropropene and at least one hydrofluorocarbon.

Claims

1. A heat transfer system comprising a vapour compression circuit containing a composition comprising a polyol ester lubricant, and a refrigerant F comprising at least one tetrafluoropropene and at least one hydrofluorocarbon, as a heat transfer composition, said vapour compression circuit comprising an oil separator.

2. The system according to claim 1, wherein the polyol esters have the following formula (I):

R¹[OC(O)R²]_n (I)

wherein:

R¹is a linear or branched hydrocarbon radical, optionally substituted with at least one hydroxyl group and/or comprising at least one heteroatom selected from the group consisting of —O—, —N—, and —S—;

each R²is, independently of each other, selected from the group consisting of:

i) H;

ii) an aliphatic hydrocarbon radical;

iii) a branched hydrocarbon radical;

iv) a mixture of a radical ii) and/or iii), with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms; and

n is an integer of at least 2.

3. The system according to claim 1, wherein the polyol esters are obtained from a polyol selected from the group consisting of neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.

4. The system according to claim 1, wherein the polyol esters are obtained from at least one branched carboxylic acid comprising from 5 to 8 carbon atoms.

5. The system according to claim 1, wherein the polyol esters are poly (neopentylpolyol) esters obtained by:

i) reaction of a neopentylpolyol with the following formula (V):

wherein:

each R represents, independently of each other, CH₃, C₂H₅or CH₂OH;

p is an integer between 1 and 4;

with at least one monocarboxylic acid containing 2 to 15 carbon atoms, in the presence of an acid catalyst, the molar ratio between the carboxyl groups and the hydroxyl groups being less than 1:1, to form a composition of poly (neopentyl partially esterified poly; and

ii) reacting the partially esterified poly (neopentyl) polyol composition obtained at the end of step i) with another carboxylic acid consisting from 2 to 15 carbon atoms, to form the poly (neopentyl polyol) ester composition.

6. The system according to claim 1, wherein the polyol esters have one of the following formulas (VIII) or (IX):

in which:

R⁷, R⁸, R⁹, R¹⁰, R¹¹and R¹²are, independently of each other, H or CH₃;

a, b, c, y, x and z are, independently of each other, an integer;

a+x, b+y, and c+z are, independently of each other, integers ranging from 1 to 20;

R¹³, R¹⁴and R¹⁵are, independently of each other, selected from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls, cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryls and cycloalkylarylalkyls,

R¹³, R¹⁴and R¹⁵, consisting 1 to 17 carbon atoms, and may be optionally substituted.

or

wherein:

each of R¹⁷and R¹⁸, is, independently of each other, H or CH₃;

each of m and n is, independently of each other, an integer, with m+n being an integer from 1 to 10;

R¹⁶and R¹⁹are, independently of each other, selected from the group consisting of aliphatic or branched aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls, cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryls and cycloalkylarylalkyls,

R¹⁶and R¹⁹, consisting 1 to 17 carbon atoms, and may be optionally substituted.

7. The system according to claim 1, wherein the refrigerant F comprises at least one tetrafluoropropene chosen from HFO-1234yf and HFO-1234ze, and at least one hydrofluorocarbon selected from the group consisting of dichloromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1-trifluoropropane (HFC-263fb), and mixtures thereof.

8. The system according to claim 1, wherein refrigerant F comprises one of the following mixtures:

9. The system according to claim 1, wherein refrigerant F comprises from 75.5 to 79.5% weight of HFO-1234yf, from 12 to 16% weight of HFC-152a, and from 6.5 to 10.5% weight of HFC-134a.

10. The system according to claim 1, wherein refrigerant F comprises 77.5% (±0.2%) weight of HFO-1234yf, 14% (±0.2%) weight of HFC-152a and 8.5% (±0.2%) weight of HFC-134a, said composition being azeotropic at a boiling point of between −40.00° C. and 70.00° C., at a temperature of pressure between 0.5 and 21.0 bar abs (±0.5%).

11. The system according to claim 1, selected from mobile or stationary heat pump heating, air conditioning, refrigeration, and freezing systems, and thermal engines.

12. The system according to claim 1, wherein said vapour compression circuit further comprises a centrifugal compressor.

13. A method of producing electricity by means of a heat engine, said method comprising successively evaporation of the heat transfer composition, expansion of the heat transfer composition in a turbine for generating electricity, condensation of the heat transfer composition, and compression of the heat transfer composition,

wherein the process comprising using an oil separator, and

said heat transfer composition being a composition comprising a lubricant based on polyol esters, and a refrigerant fluid F comprising at least one tetrafluoropropene and at least one hydrofluorocarbon.

14. A method of heating or cooling a fluid or a body by means of a vapour compression circuit containing a heat transfer composition, said method comprising successively evaporation of the heat transfer composition, compression of the heat transfer composition, the condensation of the heat transfer composition and the expansion of the heat transfer composition,

said compression circuit comprising an oil separator, and