Stabilization of 1-chloro-3,3,3-trifluoropropene

Abstract

The present invention relates to the use of a C3-C6 alkene compound containing only one double bond in combination with at least one molecular sieve to limit or prevent the isomerization of trans-1-chloro-3,3,3-trifluoropropene to cis-1-chloro-3,3,3-trifluoropropene and / or to limit or prevent the decomposition of trans-1-chloro-3,3,3-trifluoropropene. The present invention also relates to methods for heating or cooling fluids or objects, methods for generating electricity, and heat transfer equipment. [Selection diagram] None

Description

[Technical Field]

[0001] The present invention relates to compounds for stabilizing 1-chloro-3,3,3-trifluoropropene, more precisely to compounds for limiting or preventing the isomerization of the compound from the trans form to the cis form, or decomposition thereof. The present invention also relates to the use of such compounds in heat transfer applications. [Background technology]

[0002] Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zdE) is a product with a low global warming potential (GWP). Its thermodynamic and thermophysical properties make it well suited for use as a heat transfer fluid in refrigeration, air conditioning, power generation (especially using organic Rankine cycles), and high-temperature heat pump applications.

[0003] HCFO-1233zdE exhibits instability, manifested primarily at relatively high temperatures, consisting of partial isomerization of the initial feedstock, leading to the formation of cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zdZ).

[0004] However, HCFO-1233zdZ is a less volatile product than HCFO-1233zdE. The boiling points are approximately 40°C for the Z isomer and 18.3°C for the E isomer. This difference is accompanied by changes in the thermodynamic and thermophysical properties of the products in the plant, resulting in reduced performance if isomerization occurs.

[0005] WO 2016 / 146,940 describes the use of C3-C6 alkene compounds to stabilize 1-chloro-3,3,3-trifluoropropene.

[0006] French Patent No. 3,041,632 describes a process for purifying and drying a stream comprising hydrofluoroolefins selected from HFO-1234yf and HCFO-1233zd, water and impurities based on halocarbon compounds, characterized in that said stream is placed in contact with an adsorbent.

[0007] French Patent No. 2,973,809 relates to the use of zeolites to improve the thermal stability of any kind of oil, in particular oils or oil-based formulations included in the composition of refrigerant fluids.

[0008] French Patent No. 2,973,717 relates to a method for reducing the acidity of refrigerant fluids, in particular refrigerant fluids used in chillers and air conditioners, which method comprises contacting the refrigerant fluid with at least one zeolite adsorbent.

[0009] French Patent No. 3,032,131 describes the use of certain zeolitic adsorbent materials for the separation and / or drying of gases, especially hydrofluorocarbons or hydrofluoroolefins.

[0010] French Patent No. 3,041,632 relates to a method for drying and purifying a hydrofluoroolefin stream containing hydrofluoroolefins, water and impurities based on halocarbon compounds, characterized in that said stream is placed in contact with an adsorbent, in particular a molecular sieve.

[0011] WO 2012 / 067,980 relates to a process for producing HFO-1234yf via dehydrohalogenation of a 2-chloro-1,1,1,2-tetrafluoropropane stream that is free of impurities such as halogenated propanes, halogenated propenes, and halogenated propynes.

[0012] WO 2017 / 031,046 describes a method for removing acidic impurities present in haloolefins such as HFO-1234ze, HFO-1234yf, HCFO-1233zd, HCFO-1233xf, which method comprises passing the olefin stream through a solid adsorbent, which may in particular be a molecular sieve.

[0013] EP 2,035,117 relates to a method for drying a fluid containing fluoropropenes, which method comprises contacting the fluid with a dehydrating agent comprising a molecular sieve.

[0014] Improved methods for limiting or preventing the isomerization of HCFO-1233zdE to HCFO-1233zdZ are needed, particularly in vapor compression systems such as air conditioning, refrigeration, heat pumps, and organic Rankine cycle systems, most particularly in systems containing flooded evaporators. Summary of the Invention

[0015] First, the present invention relates to the use of a C3-C6 alkene compound containing only one double bond in combination with at least one molecular sieve to limit or prevent the isomerization of trans-1-chloro-3,3,3-trifluoropropene to cis-1-chloro-3,3,3-trifluoropropene and / or to limit or prevent the decomposition of trans-1-chloro-3,3,3-trifluoropropene.

[0016] In certain embodiments, the alkene compound is butene or pentene.

[0017] In certain embodiments, the alkene compound is a boiling point of less than or equal to 100°C, preferably less than or equal to 75°C, and even more preferably less than or equal to 50°C, and / or a freezing temperature below 0°C, preferably below -25°C, even more preferably below -50°C, It has.

[0018] In certain embodiments, the alkene compound is 2-methyl-2-butene.

[0019] In certain embodiments, the at least one molecular sieve is at least one zeolite adsorbent.

[0020] In certain embodiments, the at least one zeolite adsorbent is selected from A-type zeolite, faujasite-type zeolite, Y-type zeolite, and mixtures thereof.

[0021] In certain embodiments, the at least one zeolite adsorbent is selected from zeolite 3A, zeolite 5A, zeolite 13X, and mixtures thereof.

[0022] In certain embodiments, at least one molecular sieve for adsorbing air and at least one molecular sieve for adsorbing water are used, preferably arranged in successive layers within the cartridge.

[0023] The present invention also relates to a method for heating or cooling a fluid or object by a vapor compression circuit containing a heat transfer fluid, the method comprising, in succession, evaporating the heat transfer fluid, compressing the heat transfer fluid, condensing the heat transfer fluid, and expanding the heat transfer fluid, the heat transfer fluid comprising trans-1-chloro-3,3,3-trifluoropropene and a C3-C6 alkene compound, the heat transfer fluid being disposed in contact with a molecular sieve.

[0024] The present invention also relates to a method for generating electricity by a heat engine comprising a heat transfer fluid, the method comprising, in sequence, vaporizing the heat transfer fluid, expanding the heat transfer fluid in a power-generating turbine, condensing the heat transfer fluid, and compressing the heat transfer fluid, wherein the heat transfer fluid comprises trans-1-chloro-3,3,3-trifluoropropene and a C3-C6 alkene compound, and the heat transfer fluid is disposed in contact with a molecular sieve.

[0025] In certain embodiments, the heat transfer fluid reaches a temperature of 100°C or greater, preferably 150°C or greater, more preferably 200°C or greater, more preferably 220°C or greater.

[0026] The present invention also relates to a heat transfer system comprising a vapor compression circuit containing a heat transfer fluid comprising trans-1-chloro-3,3,3-trifluoropropene and a C3-C6 alkene compound and equipped with a molecular sieve.

[0027] In certain embodiments, the equipment is selected from heat pumps, mobile or stationary equipment for heating, air conditioning, refrigeration or freezing, and heat engines.

[0028] In certain embodiments, the alkene compound is 2-methyl-2-butene.

[0029] In certain embodiments, the molecular sieve is a zeolite adsorbent, or preferably at least two zeolite adsorbents arranged in layers.

[0030] The present invention fulfills the above-mentioned needs, and more particularly provides an improved means for stabilizing HCFO-1233zdE, especially in vapor compression systems such as air conditioning, refrigeration, heat pump and heat engine systems, most particularly in systems containing flooded evaporators, most particularly in high temperature applications.

[0031] Specifically, the inventors observed that the isomerization and decomposition of HCFO-1233zeE at high temperatures is accelerated by the presence of air and humidity, or even acidity, and therefore occurs to some extent despite the presence of stabilizers. The use of molecular sieves limits or prevents the presence of air and humidity in the cooling circuit and, surprisingly, does not affect the C3-C6 alkene stabilizer. DETAILED DESCRIPTION OF THE INVENTION

[0032] The invention will now be explained in more detail and in a non-limiting manner in the following description.

[0033] Unless otherwise stated, the proportions of indicated compounds are given as mass percentages throughout this patent application.

[0034] The present invention stabilizes HCFO-1233zdE, i.e., limits or prevents isomerization of HCFO-1233zdE to HCFO-1233zdZ, particularly at elevated temperatures, especially in the presence of traces of humidity and / or air and / or acidity, by contacting HCFO-1233zdE with a C3-C6 alkene compound containing only one double bond and at least one molecular sieve. This contacting also stabilizes HCFO-1233zdE while avoiding its decomposition. The term "decomposition" refers to the conversion of HCFO-1233zd molecules into other species. The decomposition of HCFO-1233zdE can be significantly reflected by an increase in the concentrations of fluoride and chloride ions present in a composition containing HCFO-1233zdE.

[0035] The alkene compounds according to the invention are propene, butene, pentene and hexene. Butene and pentene are preferred. Pentene is even more particularly preferred.

[0036] The alkene compounds according to the present invention may have a straight or branched chain, preferably a branched chain.

[0037] Preferably, the compound has a boiling point of 100°C or less, more preferably 75°C or less, even more preferably 50°C or less.

[0038] The term "boiling point" means the boiling point at a pressure of 101.325 kPa as measured in accordance with standard NF EN 378-1 of April 2008.

[0039] Preferably, the compound has a freezing temperature of 0°C or less, preferably -25°C or less, and even more particularly preferably -50°C or less.

[0040] The freezing temperature is measured in accordance with Test No. 102: Melting point / Melting range (OECD guidelines for the testing of chemical products, Section 1, OECD, Paris, 1995 (address: http: / / dx.doi.org / 10.1787 / 9789264069534-fr)).

[0041] Alkene compounds according to the invention are in particular the following compounds: - 1-butene, - cis-2-butene, - trans-2-butene, - 2-methyl-1-propene, - 1-pentene, - cis-2-pentene, - trans-2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and - 3-methyl-1-butene.

[0042] A preferred compound is 2-methyl-2-butene of formula (CH3)2C=CH-CH3 (boiling point of about 39°C).

[0043] Two or more of the above compounds may be used in combination.

[0044] Thus, the alkene compounds according to the present invention are advantageously used in combination with HCFO-1233zd, and more particularly mixed with HCFO-1233zdE, to provide heat transfer fluids for use in heat transfer applications.

[0045] The mass proportion of the above-mentioned alkene compounds in the heat transfer fluid is in particular 0.01% to 0.05%, or 0.05% to 0.1%, or 0.1% to 0.2%, or 0.2% to 0.3%, or 0.3% to 0.4%, or 0.4% to 0.5%, or 0.5% to 0.6%, or 0.6% to 0.7%, or 0.7% to 0.8%, or 0.8% to 0.9%, or 0.9% to 1%, or 1% to 1.2%, or 1.2% to 1.5%, or 1.5% to 2%, or 2% to 3%, or 3% to 4%, or 4% to 5%.

[0046] The heat transfer fluid may include HCFO-1233zdE and optionally HCFO-1233zdZ. Advantageously, the proportion of HCFO-1233zdE relative to the total amount of HCFO-1233zd is 90% or more, or 91% or more, or 92% or more, or 93% or more, or 94% or more, or 95% or more, or 97% or more, or 98% or more, or 99% or more, or 99.1% or more, or 99.2% or more, or 99.3% or more, or 99.4% or more, or 99.5% or more, or 99.6% or more, or 99.7% or more, or 99.8% or more, or 99.9% or more, or 99.91% or more, or 99.92% or more, or 99.93% or more, or 99.94% or more, or 99.95% or more, or 99.96% or more, or 99.97% or more, or 99.98% or more, or 99.99% or more.

[0047] The presence of the alkene compound makes it possible to limit or prevent the increase in the proportion of HCFO-1233zdZ in the composition over time and / or in the case of relatively high temperature applications. The presence of the alkene compound also makes it possible to limit the concentrations of fluoride and chloride ions present in the composition and, more generally, the decomposition of HCFO-1233zdE.

[0048] Additionally, the alkene compounds may also have heat transfer properties similar to those of HCFO-1233zdE and any other heat transfer compounds, and in certain embodiments may form azeotropes or near-azeotropes with HCFO-1233zdE (and, where applicable, with other heat transfer compounds that may be present).

[0049] The heat transfer fluid can optionally be combined with various additives to form a heat transfer composition therewith, which may be selected from lubricants, nanoparticles, stabilizers (different from the stabilizer compounds of the present invention), surfactants, tracing agents, fluorescent agents, odorants, and solubilizers.

[0050] Stabilizers, when present, preferably represent 5% by weight or less in the heat transfer composition and include nitromethane, ascorbic acid, terephthalic acid, tromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, phosphites, phosphonates, thiols, epoxides (optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic) such as limonene, limonene oxide, and lactones.

[0051] As lubricants, in particular mineral-derived oils, silicone oils, naturally occurring paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-α-olefins, polyalkene glycols, polyol esters and / or polyvinyl ethers may be used.

[0052] However, in certain advantageous embodiments of the present invention, the compositions of the present invention do not contain a lubricant.

[0053] As nanoparticles, in particular carbon nanoparticles, metal oxides (copper, aluminum), TiO2, Al2O3, MoS2, etc. may be used.

[0054] Tracing agents (which may be detected) include deuterated or non-deuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide, and combinations thereof. Tracing agents are distinct from the heat transfer compounds that make up the heat transfer fluid.

[0055] Solubilizing agents include hydrocarbons, dimethyl ethers, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. The solubilizing agent is distinct from the heat transfer compounds that make up the heat transfer fluid.

[0056] Fluorescent agents include naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins and derivatives thereof and combinations thereof.

[0057] Odorants include alkyl acrylates, allyl acrylates, acrylic acids, acrylic esters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allyl isothiocyanates, alkanoic acids, amines, norbornene, norbornene derivatives, cyclohexene, heterocyclic aromatic compounds, ascaridole, o-methoxy(methyl)phenol, and combinations thereof.

[0058] The heat transfer fluid (and heat transfer compositions containing same) may also include at least one other heat transfer compound in addition to HCFO-1233zd. Such optional other heat transfer compound may be, among others, a hydrocarbon compound, an ether, a hydrofluoroether, a hydrofluorocarbon, a hydrochlorofluorocarbon, a hydrofluoroolefin, a hydrochloroolefin, or a hydrochlorofluoroolefin.

[0059] By way of example, said other heat transfer compounds may be 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz, E or Z isomer), 3,3,4,4,4-pentafluoro-1-butene (HFO-1345fz), 2,4,4,4-tetrafluoro-1-butene (HFO-1354mfy), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), difluoromethane ( The fluorocarbon may be selected from HFC-32, 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1-difluoroethane (HFC-152a), pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), methoxynonafluorobutane (HFE7100), butane (HC-600), 2-methylbutane (HC-601a), pentane (HC-601), ethyl ether, methyl acetate, and combinations thereof.

[0060] In the heat transfer fluid, HCFO-1233zd may represent, in particular, by mass, 50% to 55% of the fluid, 55% to 60% of the fluid, or 60% to 65% of the fluid, or 65% to 70% of the fluid, or 70% to 75% of the fluid, or 75% to 80% of the fluid, or 80% to 85% of the fluid, or 85% to 90% of the fluid, or 90% to 95% of the liquid, or 95% to 99% of the liquid, or 99% to 99.5% of the liquid, or 99.5% to 99.9% of the liquid, or more than 99.9% of the fluid. The HFO-1233zd content may also vary within some of the above intervals, for example, between 50% and 55% and between 55% and 60%, i.e., between 50% and 60%.

[0061] The heat transfer composition / heat transfer fluid described above is, according to the present invention, placed in contact with at least one molecular sieve which is preferably disposed in a cartridge.

[0062] The molecular sieve is preferably a zeolite adsorbent.

[0063] The zeolitic adsorbents, or more simply zeolites, that may be used in the context of the present invention may be of any type known to those skilled in the art, in particular type A zeolites, faujasite type zeolites, i.e., type X and LSX ("low silica X") zeolites, and type Y zeolites. It is understood that these various zeolites may be used alone or in mixtures of two or more.

[0064] Zeolites are typically crystalline and porous aluminosilicate-based compounds with a three-dimensional crystal structure consisting of SiO₄ and AlO₄ tetrahedra linked together by sharing one or more oxygen atoms. Thus, these compounds form a crystalline network containing nanometer-sized pores.

[0065] These structures generally contain cations to make the system electrically neutral, and these cations are usually cations containing sodium, potassium or calcium, but also barium, rare earth metals or mixtures of two or more of these cations in any proportion.

[0066] Generally, the zeolites used are synthetic zeolites obtained in powder form from a process of nucleation and crystallization of an aluminosilicate gel. Naturally occurring zeolites, such as those of the clinoptilolite, mordenite or chabazite type, which are generally used primarily in purification or dehydration procedures, can also be used.

[0067] According to a preferred embodiment of the present invention, the zeolites used include A-type zeolites, faujasite-type zeolites, ie, X-type zeolites, LSX-type zeolites, and Y-type zeolites.

[0068] Zeolites have the general formula: M x / n [(AlO2) x (SiO2) y ].wH2O In the above formula, M represents one or more cations with a total valence of n, w represents the number of water molecules, the ratio (y / x) is between 1 and 5 according to the zeolite structure, and the sum (x+y) represents the number of tetrahedra per unit cell.

[0069] The structure and properties of type A zeolites are known and have been extensively described in the literature, in particular in Donald W. Breck, "Zeolite Molecular Sieves", John Wiley & Sons Eds (1974), pp. 83 ff., as well as in U.S. Pat. No. 2,882,243 and French Patent No. 1,257,034.

[0070] The Si / Al ratio in type A zeolites is always close to 1. The presence of sodium cations ensures the electroneutrality of the structure.

[0071] Modification of the nature of the cations by total or partial exchange can be accompanied by changes in selectivity through changes in pore size or creation of specific interactions with adsorbed molecules, thus changing the adsorption properties.

[0072] Thus, in the as-synthesized sodium form, for an A-type zeolite with a pore opening of 4A, various cation exchanges A can be carried out to give the desired properties.

[0073] This often involves lithium (Li + ), potassium (K + ), Cesium (Cs + ), magnesium (Mg 2+ ), calcium (Ca 2+ ), strontium (Sr 2+ ), barium (Ba 2+ ), cerium (Ce 3+ cations of alkali metals or alkaline earth metals such as lanthanum (La 2+ / La 3+ ), silver (Ag + ), copper (Cu 2+ ), Nickel (Ni 2+ ), rare earth metals or metals such as zinc, iron, chromium, etc.

[0074] Thus, depending on the type of cation exchange carried out, the A-type zeolite may, for example, be converted into: - calcium form through exchange with calcium salts in aqueous solution to obtain zeolites with pores having an effective opening of 5A; - potassium form via exchange with potassium salts in aqueous solution to obtain zeolites with pores having an effective opening of 3A - Various forms, for example by mixing aqueous solutions of lithium, calcium or potassium salts.

[0075] The term "zeolite 4A" as used herein refers to a zeolite in which essentially all exchangeable cationic sites are sodium cations, Na +(sodium form after synthesis)

[0076] The term "zeolite 5A" as used herein means a zeolite having at least 40% (by equivalent) of the cationic sites of Ca. 2+ cations, and the remaining sites are occupied by sodium cations Na + Although it would not depart from the context of the present invention if other cations were present as previously mentioned.

[0077] The term "zeolite 3A" is used herein to mean a type A zeolite in which 20% to 70% (in equivalents) of the exchangeable cationic sites are occupied by potassium cations, although it would not depart from the context of the present invention if other cations were present as stated above.

[0078] Faujasites are a group of mineral species characterized by their crystallographic topography and are described in the book "Zeolite Molecular Sieves" by Donald W. Breck, edited by John Wiley & Sons (1974), pp. 92 ff. (Non-Patent Document 2).

[0079] Lowenstein's law requires a Si / Al molar ratio of at least 1. The following are usually distinguished: - Standard X-type faujasite with Si / Al ratio >1.15, - LSX ("low silica X") faujasite, which is of the X-type zeolite species, having an Si / Al atomic ratio of less than or equal to 1.15, preferably 1±0.05 (values ​​lower than 1 reflect the analytical uncertainty in the measurement of this ratio, values ​​higher reflect either the same uncertainty or an acceptable deviation in the purity of the product); - Y-type faujasite with Si / Al ratio >1.5.

[0080] The basic cell of type X zeolite is a tetrahedron, the vertices of which are occupied by polyhedra of the same type present in type A zeolites, each connected to four others through octahedral substructures formed by double rings containing eight oxygen atoms. The center of each edge is always occupied by an oxygen atom, while silicon and aluminum atoms occupy the vertices of the polyhedron. A preferred form of type X zeolite is zeolite 13X, which has the following chemical formula: Na 86 [(AlO2) 86 (SiO2) 106 ].H2O

[0081] X and Y zeolites are in their post-synthetic sodium forms: NaX, NaY, and post-synthetic LSX zeolite is in the NaKLSX form.

[0082] These zeolites may also be subjected to exchange or modification treatments and generally involve exchanging, for example, protons, alkali metal ions, alkaline earth metal ions, rare earth metals or alkali metal cations (Na, K) with ions of the aforementioned metals, for example.

[0083] The zeolite of the present invention may be in the form of a powder or an aggregate. The term "aggregate" refers to the shaping of zeolite powder with a mineral and / or organic binder. The shaping of the aggregate can be carried out according to any method known to those skilled in the art. For example, the aggregate can be in the form of platelets, beads having an average diameter of a few nanometers to a few millimeters, chains or extrudates, bars, rods, or moldings of various sizes and shapes, commonly referred to as "cores."

[0084] This shaping is carried out, for example, by mixing a paste-like mixture of zeolites, a binder, and optionally one or more additives to facilitate the handling of the paste, for example by modifying the rheology and / or viscosity. The binder, which is usually inert, is used to ensure the cohesion of the zeolites between their crystals.

[0085] Among the mineral binders, alumina, montmorillonite (bentonite), zeolitizable clays such as those selected from attapulgite, sepiolite, kaolin, kaolinite, nacrite, dickite, halloysite, metakaolin, colloidal clays such as naturally occurring Attagel type or other minerals, or naturally occurring zeolites (clinoptilolite, mordenite or chabazite), diatomaceous earth, talc, and other mineral binders known to those skilled in the art can be used alone or in mixtures of two or more.

[0086] Among the organic binders that can be used alone or in combination with the mineral binders described above, any polymer matrix known to those skilled in the art of polymers is contemplated. It can be composed of thermoplastic and / or thermosetting homopolymers and / or copolymers, as well as, in a non-limiting manner, polyurethanes, fluoropolymers such as PVDF, epoxy resins, etc. These polymers can be in any form, for example, in the form of expanded or semi-expanded foams.

[0087] Examples of polymer matrices include those described in WO 2010 / 063975, in which the polymer matrix comprises a polyolefin (e.g., of the polyethylene, polypropylene, etc. type), an elastomer (of the acrylate copolymer type, e.g., ethylene / butyl acrylate copolymer), a polyamide, a polyester, or a mixture of two or more of these polymers.

[0088] The polymer matrix may also comprise, in whole or in part, one or more polymers, homopolymers and / or copolymers capable of forming supramolecular assemblies. The term "supramolecular assemblies" refers to polymers, homopolymers and / or copolymers that are capable of associating with one another through hydrogen bonding.

[0089] "Supramolecular" polymers include, by way of non-limiting example, semi-crystalline polymers, particularly those formed by supramolecular assembly of compounds resulting from the condensation of fatty acids and / or fatty acid dimers and / or fatty acid trimers, at least one associated amine (capable of forming hydrogen bonds) selected from 1-(2-aminoethyl)imidazolidin-2-one (UDETA), 1-(2-[(2-aminoethyl)amino]ethyl)imidazolidone (UTETA), 1-(2-{2-[(2-aminoethylamino]ethyl}amino)ethyl]-imidazolidone (UTEPA), and N-(6-aminohexyl)-N'-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea (UPy), and mixtures thereof.

[0090] In addition to the mineral and / or organic binder, one or more additives commonly used and known to those skilled in the art can be added to the zeolite, such as additives selected from silica, colloidal silica, cellulose, corn starch or other types of pore formers.

[0091] In general, the zeolites used in the present invention may be any form of zeolite aggregates containing an organic binder, such as those described in WO 2010 / 063,975 for removing water in double glazing applications, or as described in U.S. Pat. No. 2,583,812, U.S. Pat. No. 4,013,566, U.S. Pat. Appl. Pub. No. 2001 / 0,014,707 and EP 1,566,600, which disclose zeolite and polymer-based solids for drying refrigerant fluids.

[0092] For the purposes of the present invention, zeolite aggregates based on organic binders are generally obtained from compounds (mixed and then formed, for example, by extrusion, molding, extrusion, injection extrusion, or any other technique known to those skilled in the art for obtaining articles in solid form from at least one molten polymer matrix).

[0093] In one embodiment, the sorbent material according to the present invention may also contain one or more additives commonly used in the formulation art. Non-limiting examples of such additives may be selected from UV stabilizers, pigments, colorants, antioxidants, impact modifiers, phase change materials (PCMs), flame retardants, odorants, cellulose, etc., either alone or in mixtures.

[0094] Zeolitic compounds may be used in the context of the present invention whether they are in agglomerated or powder form (i.e. non-agglomerated form), and may optionally be subjected to an impregnation treatment, such as, for example, via aqueous phase impregnation with hydroxides of alkali metals and / or alkaline earth metals, or impregnation of said hydroxides or salts of these hydroxides and / or carbonates and / or alkali metals and / or alkaline earth metals before, after or during the agglomeration step and / or before, after or during the shaping step.

[0095] The purpose of this impregnation operation is to impregnate the zeolite or zeolite aggregates with one or more metals, non-metals and / or rare earth metals, for example selected from aluminum, scandium, gallium, iron(III), chromium(III), indium, yttrium, lanthanides or, more generally, rare earth metals, alone or in mixtures, and / or divalent ions selected from calcium, strontium, zinc, copper, chromium(II), iron(II), manganese, nickel or cobalt ions, alone or in mixtures.

[0096] According to another aspect, it is understood that the treatment aimed at achieving the cation exchange or modification defined above can be carried out on the zeolite crystals (powder), or on already formed zeolites (agglomerated, impregnated, etc.), or either before or after forming the zeolite adsorbent.

[0097] According to a preferred embodiment of the present invention, the zeolite adsorbent is based on type A zeolite or faujasite zeolite, even more preferably the zeolite adsorbent is based on type A zeolite (3A, 4A or 5A) and / or zeolite 13X, more preferably either zeolite 3A powder or agglomerates based on potassium-exchanged type A zeolite powder, the potassium exchange possibly being carried out on the initial powder and / or on the final agglomerates.

[0098] According to certain embodiments, two or more zeolite adsorbents can be used. These embodiments are preferred given the different properties of zeolites with respect to air and water adsorption. More precisely, some zeolites, such as zeolite 3A, are particularly efficient at adsorbing water, while other zeolites, such as zeolite 5A or zeolite 13X, are particularly efficient at adsorbing air. Therefore, by using them in combination, more efficient protection against air and water can be obtained. For example, the two or more zeolite adsorbents can be zeolite 13X and zeolite 3A, or zeolite 3A and zeolite 5A, or zeolite 13X, zeolite 3A, and zeolite 5A.

[0099] According to certain preferred embodiments, two or more zeolite adsorbents can be arranged in layers within the cartridge. For example, zeolite 3A can form a first layer, followed by a second layer comprising zeolite 5A and / or zeolite 13X. The term "first layer" refers to the layer that first comes into contact with the heat transfer fluid stream in the fluid direction.

[0100] According to another preferred embodiment, the zeolitic adsorbent that can be used in the context of the present invention is based on potassium-exchanged A-type zeolite, the exchange rate being between 20% and 70%, preferably between 30% and 70%, more preferably between 40% and 70%, and most particularly preferably between 50% and 70% of the total amount of exchangeable cation sites (as molar equivalents).

[0101] When the zeolite adsorbent is a zeolite aggregate, the agglomerating binder is preferably attapulgite, colloidal attapulgite, sepiolite, bentonite, kaolin, halloysite, possibly used alone or in mixture(s) with other clays or naturally occurring zeolites (clinoptilolite, mordenite or chabazite). Preferably, the agglomerating binder comprises mainly attapulgite or kaolin, and even more preferably contains attapulgite.

[0102] Non-limiting examples of zeolite adsorbents that may be used in the context of the present invention include adsorbents sold by CECA under the names Siliporite® H3Ri, Siliporite® NK10, Siliporite® NK30, Siliporite® SA 1720, Siliporite® NK20, Siliporite® G5 XP, adsorbents sold by ZEOCHEM under the names Purmol® 3ST (3A), Purmol® 4ST (A), Zeochem® Z4-01, Zeochem® 4A-8BL, or adsorbents sold by GRACE under the names Sylosiv®, Cryosiv®, or adsorbents sold by Molsiv® 3A, Molsiv® 4A, Molsiv® Examples include adsorbents sold by UOP under the names 5A, XH-7™, XH-9™ and XH-11™.

[0103] According to certain embodiments, one or more compounds capable of removing traces of acidity present in the heat transfer fluid can also be used in combination with molecular sieves, particularly zeolite adsorbents. This or these compounds can be selected from metal oxides such as aluminum oxide, alkaline earth metal oxides, alkali metal oxides, metal hydroxides such as aluminum hydroxide, alkaline earth metal hydroxides, alkali metal hydroxides, aluminosilicate minerals such as andalusite, kyanite (disthene), sillimanite, calcium aluminosilicate, sodium aluminosilicate, and silicon oxide. Preferably, this compound is aluminum oxide, and more preferably, this compound is activated aluminum oxide. Activated aluminum oxide is a granular and porous material that can be used to produce highly porous materials from aluminum hydroxide through its dehydroxylation. Activated alumina is a 200m 2 / g.

[0104] Molecular sieves, such as zeolite adsorbents, can adsorb air and water, thereby reducing the reactivity and therefore acidity of the medium, however, it is also preferred to use one or more of the above compounds to remove any traces of acidity.

[0105] If one or more compounds capable of removing traces of acidity are used, this or these compounds may also be in the form of at least one layer in the cartridge containing the zeolite adsorbent(s). The layer containing the compound capable of removing traces of acidity is preferably arranged upstream of the layer(s) containing molecular sieve (especially zeolite adsorbent), in particular the layer upstream of the first layer containing zeolite adsorbent (relative to the circulation direction of the heat transfer fluid stream).

[0106] Alternatively, this or these compounds can be used in admixture with molecular sieve(s).

[0107] The present invention is preferably practiced in heat transfer equipment including vapor compression systems.

[0108] Heat transfer equipment is used in heat transfer processes, which can be processes for heating or cooling a fluid or an object.

[0109] The heat transfer equipment can also be used in a process for producing mechanical work or electricity according to the Rankine cycle.

[0110] For heating and cooling applications, a vapor compression system includes at least one evaporator, one compressor, one condenser, and one pressure regulator, as well as lines for transporting a heat transfer fluid between these elements. The evaporator and condenser contain heat exchangers for exchanging heat between the heat transfer fluid and other fluids or objects.

[0111] The compressor particularly includes the use of single-stage or multi-stage centrifugal or mini-centrifugal compressors. Rotary, scroll, reciprocating, or screw compressors can also be used. The compressor may be driven by an electric motor or a gas turbine (e.g., powered by the vehicle's exhaust gases in mobile applications) or a set of gears.

[0112] Vapor compression systems operate according to a standard vapor compression cycle, which involves changing the state of a heat transfer fluid from a liquid phase (or two-phase liquid / vapor) to a vapor phase at a relatively low pressure, then compressing the fluid in the vapor phase to a relatively high pressure, changing the state of the heat transfer fluid from the vapor phase to the liquid phase (condensation) at the relatively high pressure, and reducing the pressure to start the cycle again.

[0113] Preferably, the molecular sieve is disposed in a cartridge as described above, which is disposed in a vapor compression system or an organic Rankine cycle type system. The fluid passing through the cartridge can be in vapor form, liquid form, or two-phase form (liquid and vapor). The cartridge can be disposed upstream or downstream of a pressure regulator, compressor, turbine, or series of exchangers. Preferably, the cartridge may be disposed in the lowest temperature zone, i.e., between the turbine and the liquid pump in the organic Rankine cycle. Preferably, the fluid passing through the cartridge is in liquid form.

[0114] The heat transfer facility may also optionally include at least one coolant fluid circuit used to transfer heat (with or without a change of state) between the heat transfer fluid circuit and a fluid or object to be heated or cooled.

[0115] The heat transfer facility may also optionally include two (or more) vapor compression systems containing the same or different heat transfer fluids, for example, the vapor compression systems may be coupled to one another.

[0116] Refrigeration processes and installations according to the invention include methods and installations for air conditioning (with mobile installations, e.g. in vehicles or in stationary installations), for refrigeration (with mobile installations, e.g. in containers or in stationary installations), and for freezing and cryogenics.

[0117] The heating installation according to the invention comprises a heat pump.

[0118] For applications to generate mechanical work or electricity, the heat transfer system is a heat engine that includes at least one evaporator, an expansion element, a condenser, and a pump, as well as lines for transporting a heat transfer fluid between these elements. The heat transfer system can then be implemented as a Rankine cycle.

[0119] Preferably, the molecular sieve is disposed within a cartridge as described above, which is disposed in the thermodynamic system, preferably after the expansion member, such that the heat transfer fluid exiting the expansion member passes through the cartridge containing the molecular sieve.

[0120] The expansion element can be either a turbine with one or more stages, or a pressure regulator, for example, a rotary, helical, reciprocating or screw type pressure regulator.

[0121] Any type of heat exchanger can be used to implement the heat transfer fluid according to the invention, in particular a parallel current heat exchanger or, preferably, a counter current heat exchanger.

[0122] In particular, the evaporator used in the context of the present invention may be a dry expansion evaporator or a flooded evaporator. In a dry expansion evaporator, all of the heat transfer fluid is evaporated at the outlet of the evaporator and the vapor phase is superheated.

[0123] In a flooded evaporator, the heat transfer fluid in liquid form does not completely vaporize. The flooded evaporator includes a separator between the liquid and vapor phases.

[0124] The present invention is particularly useful when such evaporators are used, particularly when prior art stabilizers with high boiling points are inefficient because the stabilizer thickens in the evaporator and does not travel with the heat transfer fluid toward the condenser.

[0125] The alkene stabilizer compounds are not trapped, or substantially not trapped, by the molecular sieve, and therefore the combined action of the alkene compounds and the molecular sieve allows the heat transfer fluid to be used at high temperatures while limiting isomerization and decomposition of the fluid.

[0126] Thus, the present invention is particularly useful when elevated temperatures exist at at least one point in the fluid circuit, more specifically temperatures of 100° C. or higher, or 110° C. or higher, or 120° C. or higher, or 130° C. or higher, or 140° C. or higher, or 150° C. or higher, or 160° C. or higher, or 170° C. or higher, or 180° C. or higher, or 190° C. or higher, or 200° C. or higher, or 210° C. or higher, or 220° C. or higher, or 230° C. or higher, or 240° C. or higher, or 250° C. or higher, or 260° C. or higher, or 270° C. These are specifically the conditions under which HCFO-1233zdE is most likely to be converted to HCFO-1233zdZ or decomposed.

[0127] In particular, in air conditioners, although typical operating temperatures are below 100°C, hot spots at the compressor outlet can reach temperatures above 100°C, affecting the heat transfer fluid for a short period of time (e.g., less than 1%) of the total duration of circulation.

[0128] In heat pumps, condensation temperatures can reach approximately 160°C. In this case, the heat transfer fluid may be at a temperature of approximately 160°C for a significant proportion (e.g., approximately 50%) of its total circulation duration. Furthermore, hot spots of 150-200°C may also be observed at the compressor outlet. Due to the effects of long residence times at temperatures above 100°C and the presence of spots at temperatures approaching or even exceeding 200°C, stabilizers are required.

[0129] In organic Rankine cycle engine cycles for power generation, temperatures can reach 165°C. In this case, the heat transfer fluid may be at or above about 165°C for a significant portion (e.g., about 50%) of its total circulation time. Furthermore, hot spots of 180-250°C or even above 250°C may also be observed at the turbine inlet. The effects of long residence times at temperatures above 100°C and the presence of spots at temperatures approaching or potentially exceeding 250°C necessitate the use of stabilizers.

[0130] Also, in heat transfer equipment, the temperature of the composition used as the heat transfer fluid remains above the freezing temperature of the alkene compound to avoid the deposition of solids in the circuit.

[0131] Because of its ability to operate at higher temperatures, the present invention also allows for increased superheat of the heat transfer fluid, which results in increased yield and therefore improved system performance.

[0132] Therefore, the heating can be from 1 to 90° C., preferably from 10 to 80° C. For example, the heating can be increased from 1 to 5° C., or from 5 to 10° C., or from 10 to 15° C., or from 15 to 20° C., or from 20 to 25° C., or from 25 to 30° C., or from 30 to 35° C., or from 35 to 40° C., or from 40 to 45° C., or from 45 to 50° C., or from 50 to 55° C., or from 55 to 60° C., or from 60 to 65° C., or from 65 to 70° C., or from 70 to 75° C., or from 75 to 80° C., or from 80 to 85° C., or from 85 to 90° C.

[0133] The term "superheat" (equivalent to "evaporator superheat" herein) means the temperature difference between the maximum temperature reached by the heat transfer fluid before the compressor or turbine (i.e., the maximum temperature reached by the heat transfer fluid at the end of the superheating step following evaporation) and the temperature at the end of evaporation. [Example]

[0134] The following examples illustrate the invention without limiting it.

[0135] Example 1 - Study on the thermal stability of HCFO-1233zdE Consider an organic Rankine cycle operating between a room temperature of 30°C and a heat source temperature of 300-600°C, using HCFO-1233zdE as the heat transfer fluid. The temperature of the HCFO-1233zdE can reach temperatures in excess of 200°C at the evaporator outlet.

[0136] As the alkene compound, 2-methyl-2-butene is used.

[0137] The thermal stability results at 220°C in a sealed tube are shown in the table below. TIFF0007792248000001.tif109170

[0138] Therefore, the results show that 2-methyl-2-butene can be made less acidic by the action of the sieve on water and air. Without the sieve, the results show that the presence of water and air alters the stability of this composition at very high temperatures (>200°C), despite the presence of 2-methyl-2-butene.

[0139] Example 2 - Use of Cartridges Containing Zeolite Adsorbent Cartridges containing 3A molecular sieves as adsorbents are placed under conditions representative of the turbine outlet of an organic Rankine cycle.

[0140] A mixture of heat transfer fluid (HCFO-1233zdE) with a total mass of 1400 g was prepared by adding 0.5 wt % 2-methyl-2-butene and 250 ppm water to the mixture.

[0141] The cartridge contains 200 g of 3A molecular sieves.

[0142] The heat transfer fluid, in the liquid phase, passes through the cartridge at a temperature of 80° C. and a pressure of 7 bar.

[0143] The heat transfer fluid was collected and analyzed after passing through a molecular sieve cartridge.

[0144] It was found that the water content of the heat transfer fluid was reduced to 15 ppm and all of the alkene compound 2-methyl-2-butene in the heat transfer fluid was recovered.

[0145] Example 3 - Organic Rankine Cycle Performance

[0146] An analysis of the performance of an organic Rankine cycle operating on HCFO-1233zdE with an evaporating temperature of 150°C and a condensing temperature of 40°C was carried out in an installation according to the invention.

[0147] The results are shown in the following table. TIFF0007792248000002.tif128170

[0148] Volumetric capacity and yield results are given as a percentage of the results obtained at 0°C superheat.

[0149] The above results show that, despite a reduction in volumetric capacity, increasing the superheat of the heat transfer fluid from 0 to 68°C, which is made possible by the present invention, allows for a 30% increase in yield.

Claims

1. 1. Use of a combination of a C3-C6 alkene compound containing only one double bond and at least one molecular sieve for limiting or preventing the isomerization of trans-1-chloro-3,3,3-trifluoropropene to cis-1-chloro-3,3,3-trifluoropropene and / or limiting or preventing the decomposition of trans-1-chloro-3,3,3-trifluoropropene, wherein the molecular sieve is disposed in a cartridge and has a Si / Al molar ratio of at least 1.

2. 2. The use according to claim 1, wherein the alkene compound is butene or pentene.

3. The alkene compound is a boiling point below 100°C, and / or - freezing temperature below 0°C, 3. The use according to claim 1 or 2, wherein

4. The use according to any one of claims 1 to 3, wherein the alkene compound is 2-methyl-2-butene.

5. 5. Use according to any one of claims 1 to 4, wherein the at least one molecular sieve is at least one zeolite adsorbent.

6. 6. The use according to claim 5, wherein the at least one zeolite adsorbent is selected from A-type zeolites, faujasite-type zeolites, Y-type zeolites, and mixtures thereof.

7. 6. The use according to claim 5, wherein the at least one zeolite adsorbent is selected from zeolite 3A, zeolite 5A, zeolite 13X, and mixtures thereof.

8. 8. Use according to any one of claims 1 to 7, in which at least one molecular sieve for adsorbing air and at least one molecular sieve for adsorbing water are used.

9. 1. A method for heating or cooling a fluid or object by a vapor compression circuit comprising a heat transfer fluid comprising, in succession, vaporizing a heat transfer fluid, compressing the heat transfer fluid, condensing the heat transfer fluid, and expanding the heat transfer fluid, wherein the heat transfer fluid comprises trans-1-chloro-3,3,3-trifluoropropene and a C3 to C6 alkene compound, and wherein the heat transfer fluid is in contact with a molecular sieve, the molecular sieve being disposed in a cartridge and having a Si / Al molar ratio of at least 1.

10. 1. A method of generating electricity by a heat engine comprising a heat transfer fluid including, in succession, vaporizing a heat transfer fluid, expanding the heat transfer fluid in a power-generating turbine, condensing the heat transfer fluid, and compressing the heat transfer fluid, wherein the heat transfer fluid comprises trans-1-chloro-3,3,3-trifluoropropene and a C3 to C6 alkene compound, and the heat transfer fluid is in contact with a molecular sieve, the molecular sieve being disposed in a cartridge and having a Si / Al molar ratio of at least 1.

11. 11. The method of claim 9 or 10, wherein the heat transfer fluid reaches a temperature of 100°C or higher.

12. A heat transfer system comprising a vapor compression circuit containing a heat transfer fluid comprising trans-1-chloro-3,3,3-trifluoropropene and a C3 to C6 alkene compound and equipped with a molecular sieve, wherein the molecular sieve is disposed in a cartridge and has a Si / Al molar ratio of at least 1.

13. 13. The installation according to claim 12, selected from heat pumps, mobile or stationary installations for heating, air conditioning, refrigeration or freezing, and heat engines.

14. The method according to any one of claims 9 to 11, wherein the alkene compound is 2-methyl-2-butene.

15. The facility according to claim 12 or 13, wherein the alkene compound is 2-methyl-2-butene.

16. 15. The method of any one of claims 9 to 11 and 14, wherein the molecular sieve is a zeolite adsorbent.

17. 16. The system of any one of claims 12, 13, and 15, wherein the molecular sieve is a zeolite adsorbent.

Images