method for producing heat, method for increasing the operating temperature and heat pump device

专利摘要:
METHOD FOR HEAT PRODUCTION, METHOD FOR INCREASING OPERATING TEMPERATURE, COMPOSITION AND HEAT PUMP DEVICE. The present invention relates to a method for the production of heat in a high temperature heat pump which comprises the condensation of a gaseous working fluid comprising Z-1,1,1,4,4,4-hexafluoro-2 -butene, in a condenser, producing a liquid working fluid. Also described herein is a method for increasing the maximum viable operating temperature of the condenser in a high temperature heat pump device, which comprises loading the high temperature heat pump with a working fluid comprising Z-1 , 1,1,4,4,4-hexafluoro-2-butene. Also described herein, a composition comprising (a) Z-1,1,1,4,4,4-hexafluoro-2-butene, (b) 2-chloropropane, and (c) at least one lubricant suitable for use at a temperature of at least about 150 ° C, where 2-chloro-propane is present in an amount effective to form an azeotropic or azeotropic combination with Z-1,1,1,4 , 4,4-hexafluoro-2-butene. Also described is a high temperature heat pump device that contains a working fluid comprising Z-1,1,1,4,4,4-hexafluoro-2-butene.
公开号:BR112013018849B1
申请号:R112013018849-9
申请日:2012-01-31
公开日:2021-01-12
发明作者:Konstantinos Kontomaris
申请人:E.I. Du Pont De Nemours And Company；
IPC主号:

专利说明:

[0001] [001] The present invention relates to compositions, as well as methods and devices of high temperature for the production of heating, using working fluids comprising Z-1,1,1,4,4,4-hexafluoro-2 -butene. BACKGROUND OF THE INVENTION
[0002] [002] Conventional methods for the production of heating, including the burning of fossil fuels and the generation of heat from electrical resistance, have the disadvantages of higher operating costs and low energy efficiency. Heat pumps provide an improvement over these methods.
[0003] [003] Heat pumps remove low temperature heat from some available source by evaporating a working fluid in an evaporator, compressing the gaseous working fluid at higher pressures and temperatures, and supplying the high temperature heat through condensation of the gaseous working fluid in a condenser. Residential heat pumps use working fluids, such as the R410A to provide air conditioning and heating for homes. High temperature heat pumps using positive displacement compressors or centrifugal compressors use different working fluids, such as HFC-134a, HFC-245fa and CFC-114, among others.
[0004] [004] The selection of the working fluid for a high temperature heat pump is limited by the higher condenser operating temperature required for the intended application and the resulting condenser pressure. The working fluid must be chemically stable at the upper system temperature. The pressure of the gaseous working fluid at the maximum condenser temperature must not exceed the viable operating pressure of the available compressors and heat exchangers. For subcritical operation, the critical temperature of the working fluid must exceed the maximum operating temperature of the condenser.
[0005] [005] Rising energy costs, global warming and other environmental impacts, in combination with the relatively low energy efficiency of heating systems that operate through the combustion of fossil fuels and electrical resistance heating make heat pumps a attractive alternative technology. HFC-134a, HFC-245fa and CFC-114 have a high potential for global warming and CFC-114 also has an impact in relation to ozone depletion. There is a need for a low global warming potential, low ozone depleting potential working fluids for use in high temperature heat pumps. The fluids that allow the operation of existing heat pump equipment designed for the CFC-114 or HFC-245fa at higher condenser temperatures while still maintaining adequate heating capacity would be particularly advantageous. BRIEF DESCRIPTION OF THE INVENTION
[0006] [006] The use of Z-HFO-1336mzz in high temperature heat pumps increases the capacity of these heat pumps, since it allows the operation at higher temperatures of the condenser obtained with the working fluid used in similar current systems. The condenser temperatures obtained with HFC-245fa and CFC-114 are the highest possible obtained with current systems.
[0007] [007] A method for the production of heat in a high temperature heat pump is described herein comprising the condensation of a gaseous working fluid comprising 1,1,1,4,4,4-hexafluoro-2 -butene, in a condenser, producing a liquid working fluid.
[0008] [008] Also described herein is a method for increasing the maximum viable operating temperature of the condenser in a high temperature heat pump device suitable for use with a first working fluid selected from the group consisting of CFC -114, HFC-134a, HFC-236fa, HFC-245fa, CFC-11 and HCFC-123 in relation to the maximum viable operating temperature of the condenser when the first working fluid is used as the working fluid of the heat pump , which comprises loading the high temperature heat pump with a second working fluid comprising Z-1,1,1,4,4,4-hexafluoro-2-butene.
[0009] [009] Also described herein is a method for replacing a working fluid selected from the group consisting of CFC-114, HFC-134a, HFC-236fa, HFC-245fa, CFC-11 and HCFC-123 in a high temperature heat pump designed for said working fluid which comprises supplying a replacement working fluid comprising Z-1,1,1,4,4,4-hexafluoro-2-butene.
[0010] [010] Compositions comprising (a) Z-1,1,1,4,4,4-hexafluoro-2-butene, (b) 2-chloropropane, and (c) at least one lubricant suitable for use at a temperature of at least about 150 ° C, where 2-chloro-propane is present in an amount effective to form an azeotropic or azeotropic combination with Z-1,1,1 , 4,4,4-hexafluoro-2-butene.
[0011] [011] Also described is a high temperature heat pump device that contains a working fluid comprising Z-1,1,1,4,4,4-hexafluoro-2-butene. BRIEF DESCRIPTION OF THE FIGURES
[0012] [012] Figure 1 is a schematic diagram of an embodiment of a flooded evaporator heat pump device that uses Z-1,1,1,4,4,4-hexafluoro-2-butene as the working fluid.
[0013] [013] Figure 2 is a schematic diagram of an embodiment of a direct expansion heat pump device that uses Z-1,1,1,4,4,4-hexafluoro-2-butene as the working fluid.
[0014] [014] Figure 3 is a schematic diagram of a cascade heat pump system that uses Z-1,1,1,4,4,4-hexafluoro-2-butene as the working fluid. DETAILED DESCRIPTION OF THE INVENTION
[0015] [015] Some terms are defined or clarified before addressing the details of the achievements described below.
[0016] [016] The term "global warming potential" (GWP) is an index to estimate the relative global warming contribution due to atmospheric emissions of one kilogram of a given greenhouse gas (such as a refrigerant or working fluid) in compared to the emission of one kilogram of carbon dioxide. GWP can be calculated for different time horizons, showing the effect of atmospheric useful time for a given gas. GWP over 100 years of the time horizon is usually the referenced value. Any GWP values reported at present are based on 100 years of the time horizon.
[0017] [017] The term "ozone depletion potential" (ODP) is defined in "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project ', section 1.4.4, pages 1.28 to 1.31 (see the first paragraph of this section). The ODP represents the extent of ozone depletion in the stratosphere expected from a compound (such as a refrigerant or a working fluid), on a mass-to-mass basis compared to fluorotrichloromethane (CFC-11).
[0018] [018] The cooling capacity (sometimes referred to as the cooling capacity) is the variation in the enthalpy of a working fluid in an evaporator per unit of mass of the working fluid circulated through the evaporator. The volumetric capacity of the cooling is a term to define the heat removed through the working fluid in the evaporator per unit volume of the gaseous working fluid that leaves the evaporator and enters the compressor. Cooling capacity is a measure of the working fluid's ability to produce cooling. Therefore, the greater the volumetric cooling capacity of the working fluid, the greater the cooling rate that can be produced in the evaporator with the maximum volumetric flow rate attainable with a given compressor.
[0019] [019] In the same way, the volumetric capacity of the heating is a term to define the amount of heat delivered through the working fluid in the condenser per unit volume of the gaseous working fluid in the compressor. The greater the volumetric heating capacity of the working fluid, the higher the heating rate that is produced in the condenser, with the maximum volumetric flow rate attainable with a given compressor.
[0020] [020] The term "performance coefficient" (COP) for cooling is the amount of heat removed in the evaporator from a cycle divided by the energy input required to operate the cycle (for example, to operate the compressor), the greater the COP, the greater the energy efficiency of the cycle.The COP is directly related to the energy efficiency rate (EER), that is, the efficiency index for refrigeration, air conditioning or heat pump equipment in a specific set of internal and external temperatures In the same way, the performance coefficient for heating is the amount of heat supplied to the condenser of a cycle divided by the energy input needed to operate the cycle (for example, to operate the compressor).
[0021] [021] The term "transition temperature" (sometimes simply called "transition") is the absolute value of the difference between the initial and final temperatures of a phase change process of a working fluid within a component of a equipment of a cooling or heating cycle system, exclusive of any subcooling or overheating. This term can be used to describe the condensation or evaporation of an almost azeotropic or non-azeotropic composition. When referring to the transition temperature of a refrigeration, air conditioning or heat pump system, it is common to provide the average transition temperature with the average transition temperature in the evaporator and the transition temperature in the condenser.
[0022] [022] The term "subcooling" is the reduction of the temperature of a liquid below the saturation temperature of the liquid to a certain pressure. By cooling the liquid working fluid that leaves the condenser below its saturation point, the capacity of the fluid working time to absorb heat, during the evaporation step can be increased. Subcooling therefore improves the heating and cooling capacity and energy efficiency of a heating or cooling system based on the conventional steam compression cycle .
[0023] [023] The term "superheat" is the increase in the temperature of the steam leaving the evaporator above the saturation temperature of the vapor, at the evaporator pressure. By heating the steam above the saturation point, the probability of condensation in compression is minimized Overheating can also contribute to the cooling of the cycle and the heating capacity.
[0024] [024] As used herein, the term "a working fluid" is a composition that comprises a compound or mixture of compounds that work primarily for the transfer of heat from a location at a lower temperature (for example, an evaporator ), to another location, at a higher temperature (for example, a condenser) in a cycle in which the working fluid is subjected to a phase change from a liquid to a vapor, is compressed and returns to liquid through the cooling of compressed steam in a repetition cycle. Cooling of compressed steam above its critical point can return the working fluid to a liquid state, without condensation. The repetitive cycle can occur in systems such as heat pumps, refrigeration systems, refrigerators, freezers, air conditioning systems, air conditioning devices, chillers and the like. Working fluids can be a portion of form lations used in the systems. The formulations can also contain other chemical compounds (for example, additives), such as those described below.
[0025] [025] As recognized in the prior art, an azeotropic composition is a mixture of two or more different components, which, when in liquid form, at a given pressure will boil at a substantially constant temperature, the temperature of which may be higher or lower than the boiling temperatures of the individual components, and which will provide a gas composition essentially identical to the global liquid composition submitted to boiling, (see, for example, MF Doherty and MF Malone, Conceptual Design of Destination Systems, McGraw-Hill (New York) ), 2001, 185-186, 351-359).
[0026] [026] Consequently, the essential characteristics of an azeotropic composition are those in which, at a given pressure, the boiling point of the liquid composition is fixed, and those in which the gas composition above the boiling composition is essentially that of the composition global boiling liquid (that is, there is no fractionation of the components of the liquid composition). It is also recognized in the prior art that both the boiling point and the weight percentages of each component of the azeotropic composition can change when the azeotropic composition is boiled at different pressures. Therefore, an azeotropic composition can be defined in terms of the unique relationship that exists between the components or in terms of the composition intervals of the components or in terms of percentages in exact weight of each component of the composition characterized by a boiling point fixed at a specified pressure.
[0027] [027] For the purposes of the present invention, a composition of the azeotropic type means a composition that essentially behaves like an azeotropic composition (that is, it has the characteristics of constant boiling or a tendency not to fractionate in boiling or evaporation). Therefore, during boiling or evaporation, the gaseous and liquid compositions, if there is any change, change only minimally or insignificantly. This must be contrasted with non-azeotropic compositions, where during boiling or evaporation, the gaseous and liquid compositions change to a substantial degree.
[0028] [028] In addition, azeotropic compositions exhibit a dew point pressure and a bubble point pressure with virtually no differential pressure. This means that the difference in dew point pressure and bubble point pressure at a given temperature will be small. In the present invention, compositions with a difference in dew point pressure and bubble point pressure less than or equal to 5% (based on bubble point pressure) are considered to be of the azeotropic type.
[0029] [029] It is recognized in this field that, when the relative volatility of a system approaches 1.0, the system is defined as forming an azeotropic or azeotropic composition. Relative Volatility is the relationship between the volatility of component 1 and the volatility of component 2. The relationship between the molar fraction of a component in the vapor to that in the liquid is the volatility of the component.
[0030] [030] To determine the relative volatility of any two compounds, a method known as the PTx method can be used. The vapor-liquid balance (ELV) and, therefore, the relative volatility, can be determined in an isothermal or isobaric manner. The isothermal method requires a measurement of the total pressure of the mixtures of the known composition at constant temperature. In this procedure, the total absolute pressure in a cell of known volume is measured at a constant temperature for different compositions of the two compounds. The isobaric method requires a temperature measurement of mixtures of the known composition at constant pressure. In this procedure, the temperature of a cell of known volume is measured at constant pressure for various compositions of the two compounds. The use of the PTx method is described in detail in “Phase Equilibrium in Process Design”, publisher Wiley-lnterscience, 1970, written by Harold R. Null, on pages 124 to 126, incorporated herein as a reference.
[0031] [031] These measures can be converted into vapor and liquid equilibrium compositions in the PTx cell using an activity coefficient equation model, such as the Non-Random Two Liquids (NRTL) equation, to represent non-idealities of the liquid phase. The use of an activity coefficient equation, such as the NRTL equation, is described in detail in “The Properties of Gases and Liquids”, 4th edition, published by McGraw Hill, written by Reid, Prausnitz and Poling, on pages 241 to 387, and in 'Phase Equilibria in Chemical Engineering', published by Butterworth Publishers, 1985, written by Stanley M. Walas, pages 165 to 244. Both references mentioned are incorporated by reference. Without wishing to be restricted to any theory or explanation, it is believed that the NRTL equation, together with the PTx cell data, can sufficiently predict the relative volatilities of the Z-1,1,1,4,4,4 -hexafluoro-2-butene which contains the compositions of the present invention and can therefore predict the behavior of these mixtures in the multi-stage separation equipment, such as the distillation columns.
[0032] [032] The term "flammability" is used to denote the ability of an ignition and / or flame propagation composition. For working fluids, the lowest flammability limit ("LFL") is the minimum fluid concentration working in the air that is capable of propagating a flame through a homogeneous mixture of the working fluid and the air under the test conditions specified in the ASTM (American Society of Testing and Materials) standard E681-2001. The upper flammability limit ("UFL") is the maximum concentration of the working fluid in the air that is capable of propagating a flame through a homogeneous mixture of the composition and the air, as determined by the ASTM E-681 standard. refrigeration, air conditioning, or heat pumps, refrigerant or working fluid is desired (if not necessary) as it is non-flammable.
[0033] [033] As used herein, the terms "comprise", "understand", "include", "including", "own", "owning" or any other variation thereof, are intended to include non-exclusive inclusion. For example, a process, method, article or equipment that comprises a list of elements is not necessarily limited to just those elements, but may include other elements that are not expressly listed or are inherent in that process, method, article or equipment. In addition, unless expressly stated otherwise, "or" refers to an inclusion and not an exclusion. For example, a condition A or B is satisfied by any of the following options: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
[0034] [034] The transition phrase "consisting of" excludes any unspecified element, step or ingredient. If it is in the claim this will restrict the claim to the inclusion of materials other than those cited, except for the normally associated impurities. When the phrase " consists of ”appearing in a clause in the body of a claim, rather than immediately after the preamble, it limits only the element presented in that clause; the other elements are not excluded from the claim as a whole.
[0035] [035] The transition phrase "consisting essentially of" is used to define the composition, method or device that includes the materials, steps, characteristics, components or elements, in addition to those described literally, provided that these materials, steps, resources, additional components or elements included materially affect the basic and innovative feature (s) of the claimed invention. The term "consisting essentially of" occupies a middle ground between "comprises" and "consists".
[0036] [036] If Depositors have defined a present invention or part of it with an open term, such as "understands", it should be easily understood that (unless otherwise stated) the description should be interpreted as also describing that invention using the terms "which essentially consists of" or "which consists of".
[0037] [037] In addition, the use of "one" or "one" is used to describe the elements and components described herein. This is done for convenience only and to provide a general sense to the scope of the present invention. The present specification should be read including one or at least one and the singular also includes the plural, unless it is obvious that it is understood otherwise.
[0038] [038] Unless otherwise indicated, all technical and scientific terms used in the present have the same meaning as those generally understood by a technician in the subject to which the present invention belongs. Although methods and materials similar or equivalent to those described in this specification can be used in the practice or testing of the embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety, unless a specific passage is cited. In case of conflict, this specification, including definitions, will control it. In addition, the materials, methods and examples are illustrative only and are not intended to be a limitation. COMPOSITIONS
[0039] [039] The compositions as described for use in the present methods and devices include the working fluid comprising Z-1,1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) .
[0040] [040] Z-HFO-1336mzz is a known compound, and its method of preparation has been described, for example, in the publication of US patent application 2,008-0,269,532, incorporated herein by reference in its entirety.
[0041] [041] Compositions that may also be useful in certain embodiments of current methods and devices may include compounds selected from the group consisting of difluoromethane (HFC-32), 2,3,3,3-tetrafluoropropene (HFO- 1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze, E and / or Z isomer), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2-tetrafluoroethane ( HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).
[0042] [042] HFO-1234ze is commercially available from certain fluorocarbon manufacturers (for example, Honeywell International Inc., Morristown, NJ), or can be prepared using methods known in the art. In particular, E-HFO-1234ze, can be prepared by dehydrofluorination of a 1,1,1,2,3-pentafluoropropane (HFC-245eb, CF3CHFCH2F) or 1,1,1,3,3-pentafluoropropane (HFC -245fa, CF3CH2CHF2). The dehydrofluorination reaction can occur in the vapor phase in the presence or absence of a catalyst, and also in the liquid phase, through the reaction with caustic soda, such as NaOH or KOH. These reactions are described in more detail in US patent publication 2006 / 0.106.263, incorporated herein by reference.
[0043] [043] HFO-1234yf can be prepared using methods known in the art. In particular, HFO-1234yf can be prepared by dehydrofluorination of a 1,1,1,2,3-pentafluoropropane (HFC-245eb, CF3CHFCH2F) or 1,1,1,2,2-pentafluoropropane (HFC-245cb, CF3CF2CH3). The dehydrofluorination reaction can occur in the vapor phase in the presence or absence of a catalyst, and also in the liquid phase, through the reaction with caustic soda, such as NaOH or KOH. These reactions are described in more detail in US patent publication 2006 / 0.106.263, incorporated herein by reference.
[0044] [044] HFC-32 is either commercially available or can be prepared by fluorodeclorination of methylene chloride, by reaction with hydrogen fluoride in the presence of a suitable catalyst, as described in US patent 6,274,781.
[0045] [045] HFC-134a and HFC-134 may be commercially available or may be prepared using methods known in the art, for example, using the method described in United Kingdom patent 1,578,933 (incorporated herein by reference) through the hydrogenation of tetrafluoroethylene. The latter reaction can conveniently be carried out at normal or elevated temperatures, for example, up to 250 ° C, in the presence of a hydrogenation catalyst, for example, palladium on alumina. In addition, HFC-134 can be prepared by hydrogenating 1,2-dichloro-1,1,2,2-tetrafluoroethane (ie CCIF2CCIF2 or CFC-114) to 1,1,2,2-tetrafluoroethane as reported by JL Bitner et al., in the US Dep. Comm. Off. Tech. Serv / Rep. 136,732, (1958), pages. 25-27, incorporated herein as a reference. HFC-134a can be prepared by hydrogenating 1,1-dichloro-1,2,2,2-tetrafluoroethane (i.e., CCI2FCF3 or CFC-114a) to 1,1,1,2-tetrafluoroethane.
[0046] [046] In one embodiment, the compositions described in the present can be used in combination with a desiccant in a refrigeration or air conditioning equipment (including chillers), to assist in the removal of moisture. Desiccants can be composed of activated alumina, silica gel, molecular sieves or zeolite-based. Representative molecular sieves include MOLSIV XH-7, XH-6, XH-9 and XH-11 (UOP LLC, Des Plaines, IL).
[0047] [047] In one embodiment, the compositions described herein can be used in combination with at least one lubricant selected from the group consisting of polyalkylene glycols, polyol esters, polyvinyl esters, mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes , and poly (alpha) olefins.
[0048] [048] In some embodiments, lubricants useful in combination with the compositions as described herein may comprise those that are suitable for use with cooling or air conditioning devices. Among these lubricants are those conventionally used in vapor compression refrigeration devices that use chlorofluorocarbon refrigerants. In one embodiment, lubricants comprise those commonly known as "mineral oils" in the field of refrigeration compression lubrication. Mineral oils comprise paraffins (for example, saturated straight chain and branched carbon hydrocarbons), naphthenes ( that is, cyclic paraffins) and aromatics (for example, saturated cyclic hydrocarbons, which contain one or more rings characterized by alternating double bonds). In one embodiment, lubricants comprise those commonly known as "synthetic oils" in the field of refrigeration compression lubrication. Synthetic oils comprise alkyl and alkyl (i.e., linear and branched alkyl alkyl benzenes) paraffins and naphthenes, and poly (synthetic alpha-olefins). Representative conventional lubricants are commercially available from BVM 100 N (paraffinic mineral oil marketed by BVA Óleos), naphthenic mineral oil commercially available from Crompton Co. under the trademarks of Suniso® 3GS and Suniso® 5GS, naphthenic mineral oil commercially available from Pennzoil under the registered trademark of Sontex® 372LT, naphthenic mineral oil commercially available from Calumet Lubricants under the registered trademark of Calumet® RO-30, linear alkylbenzenes commercially available from Shrieve Chemicals under the registered trademarks of Zerol® 75, Zerol® 150 and Zerol® 500 and HAB 22 (branched alkylbenzene sold by Nippon Oil).
[0049] [049] In other embodiments, lubricants may also comprise those that are designed for use with hydrofluorocarbon refrigerants and are miscible with the refrigerants of the present invention, under operating conditions of compression and air conditioning refrigeration devices. Such lubricants include, but are not limited to polyol esters (POEs), such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs), such as Dow's RL-488A (Dow Chemical, Midland, Michigan) , polyvinyl ethers (PVEs) and polycarbonates (PCs).
[0050] [050] Lubricants are selected, considering the requirements of a particular compressor and the environment in which the lubricant will be exposed.
[0051] [051] Of interest are high temperature lubricants with high temperature stability. The maximum temperature that the heat pump will reach will determine which lubricants are needed. In one embodiment, the lubricant must be stable at temperatures of at least 150 ° C. In an additional embodiment, the lubricant must be stable at temperatures of at least 155 ° C. In an additional embodiment, the lubricant must be stable at temperatures of at least 165 ° C. Of particular interest are polyolefin lubricants (POA) with stability greater than about 200 ° C and polyol ester lubricants (POE) with stability at temperatures up to about 200 to 220 ° C. Also of particular interest are perfluoropolyether lubricants that exhibit stability at temperatures from about 220 to about 350 ° C. PFPE lubricants include those available from DuPont (Wilmington, DE) under the trademark Krytox®, such as the XHT series with thermal stability up to about 300 to 350 ° C. Other PFPE lubricants include those marketed under the trademark Demnum ™ from Daikin Industries (Japan), with thermal stability up to about 280 to 330 ° C, and are available from Ausimont (Milan, Italy), under the registered Fomblin® trademarks and Galden® such as the one available under the trademark Fomblin®-Y Fomblin®-Z with thermal stability up to about 220 to 260 ° C.
[0052] [052] For the operation of the high temperature condenser (associated with high temperature elevators and high compressor discharge temperatures), working fluid formulations (for example, Z-HFO-1336mzz or mixtures containing the Z-HFO-1336mzz) and lubricants with high thermal stability (possibly in combination with oil cooling or other reduction approaches) will be advantageous.
[0053] [053] In one embodiment, the present invention includes a composition comprising: (a) Z-1,1,1,4,4,4-hexafluoro-2-butene, (b) 2-chloropropane, and (c) at least one lubricant suitable for use at a temperature of at least about 150 ° C, where 2-chloro-propane is present in an amount effective to form an azeotropic or azeotropic combination with Z-1, 1,1,4,4,4-hexafluoro-2-butene. Of interest are those embodiments in which the lubricant is suitable for use at a temperature of at least about 155 ° C. Also of interest are those embodiments in which the lubricant is suitable for use at a temperature of at least about 165 ° C.
[0054] [054] It was previously described in PCT patent application publication WO2009 / 155490 (incorporated herein as a reference in its entirety), that Z-HFO-1336mzz and 2-chloropropane form azeotropic compositions ranging from about 51 , 05% by weight (33.3% by mol) to about 99.37% by weight (98.7% by mol) of Z-HFO-1336mzz and from about 0.63% by weight (1 , 3 mol%) to about 48.95% by weight (66.7 mol%) of 2-chloropropane (which forms the boiling azeotropic compositions at a temperature from about -50 ° C to about 160 ° C and pressure from about 0.2 psia (1.4 kPa) to about 342 psi (2,358 kPa)). For example, at 29.8 ° C and atmospheric pressure (14.7 psi, 101 kPa), the azeotropic composition is 69.1% by weight (51.7% by mol) of Z-1.1.1, 4,4,4-hexafluoro-2-butene and 30.9% by weight (48.3% by mol) of 2-chloro-propane. In addition, azeotropic compositions formed between Z-HFO-1336mzz and 2-chloro-propane have been described. In the case of temperatures of 20 ° C and above, azeotropic compositions contain from about 1% by weight to about 99% by weight of Z-HFO-1336mzz and from about 99% by weight at about 1% by weight of 2-chloropropane.
[0055] [055] Particularly useful will be non-flammable compositions comprising Z-HFO-1336mzz and 2-chloropropane. Compositions comprising Z-HFO-1336mzz and 2-chloropropane with less than 5% by weight of 2-chloropropane are expected to be non-flammable, while compositions containing 4% by weight or less of 2-chloropropane are non-flammable.
[0056] [056] In one embodiment, the compositions can be used with about 0.01% by weight to about 5% by weight of a stabilizer, free radical scavenger or antioxidant. Such other additives include but are not limited to nitromethane, hindered phenols, hydroxylamines, thiols, phosphites or lactones. Simple additives or combinations thereof can be used.
[0057] [057] Optionally, in an additional embodiment, certain additives from the cooling or air conditioning or heat pump system can be added, if desired, to the working fluids, as described in the present, in order to improve performance and system stability. These additives are known in the field of refrigeration and air conditioning, and include, but are not limited to, anti-wear agents, extreme pressure lubricants, oxidation and corrosion inhibitors, metal surface deactivators, free radical scavengers and control agents. foam. In general, these additives can be present in the working fluids of the present invention in small amounts in relation to the total composition. Usually concentrations from less than about 0.1% by weight to up to about 3% by weight of each of the additives are used. These additives are selected based on the requirements of the individual system. These additives include members of the triaryl phosphate family of EP (extreme pressure) lubricity additives, such as butylated triphenyl phosphates (BTPP), or other alkylated triaryl phosphate esters, for example, related compounds and Syn-0 tricyclic phosphates -Ad 8478 from Akzo Chemicals. In addition, metal dialkyl dithiophosphates (for example, zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1375 and other members of this chemical family can be used in the compositions of the present invention. Other anti-wear additives include product oils natural and asymmetric polyhydroxyl lubrication additives, such as Synergol TMS (International Lubricants) .In the same way, stabilizers, such as antioxidants, free radical scavengers, and water scavengers can be employed. , but are not limited to, butylated hydroxy toluene (BHT), epoxides and mixtures thereof. Corrosion inhibitors include dodecyl succinic acid (DDSA), amine phosphate (AP), oleoyl sarcosine, imidazone derivatives and substituted sulfonates. metal surface deactivators include areoxalyl bis (benzylidene) hydrazide (CAS reg No. 6629-10-3), N, N'-bis (3,5-di-tert-butyl-4-hydroxyhyd rocinamoil hydrazine (CAS reg. at the. 32687-78-8), 2,2'-oxamidobis-ethyl- (3,5-di-tert-butyl-4-hydroxyhydrocinamate (CAS reg. 70331-94-1), N, N'- (disalicyclidene) -1,2-diaminopropane (CAS reg. 94-91-7) and ethylenediaminetetraacetic acid (CAS reg. 60-00-4) and their salts and mixtures.
[0058] [058] In other embodiments, additional additives include stabilizers, which comprise at least one compound selected from the group consisting of hindered phenols, thiophosphates, butylated triphenylphosphorothionates, organo phosphates, or phosphites, aryl alkyl ethers, terpenes, terpenoids, epoxides, fluorinated epoxides, oxethanes, ascorbic acid, thiols, lactones, thioethers, amines, nitromethane, alkylsilanes, benzophenone derivatives, aryl sulfides, divinyl terephthalic acid, diphenyl terephthalic acid, ionic liquids and mixtures thereof. Representative stabilizer compounds include, but are not limited to, tocopherol; hydroquinone; t-butylhydroquinone; monothiophosphates; and dithiophosphates, commercially available from Ciba Specialty Chemicals, Basel, Switzerland, hereinafter "Ciba", under the brand name Irgalube® 63, dialkylthiophosphate esters, commercially available from Ciba under the brand names Irgalube® 353 and Irgalube® 350, respectively; butylated triphenylphosphorthionates, respectively; commercially available from Ciba under the brand name Irgalube® 232; amine phosphates, commercially available from Ciba under the brand name Irgalube® 349 (Ciba); hindered phosphites, commercially available from Ciba as Irgafos® 168 and Tris- (di-tert-butylphenyl) phosphite, commercially available from Ciba under the trademark of Irgafos® OPH; (di-n-octyl phosphite), and diphenyl iso-decyl phosphite, commercially available from Ciba under the trademark of Irgafos® DDPP; anisole; 1, 4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene; d-limonene; retinal; pinene; menthol, vitamin A; terpinene; dipentene; lycopene, beta carotene, bornane; 1,2-propylene oxide; 1,2-butylene oxide, n-buti l glycidyl ether; trifluoromethyloxirane; 1,1-bis (trifluoromethyl) oxirane; 3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd), 3-ethyl-3 - ((phenoxy) methyl) -oxetane, such as OXT-211 (Toagosei Co., Ltd), 3-ethyl-3 - ((2-ethylhexyloxy) methyl) -oxetane, such as OXT-212 (Toagosei Co., Ltd); Ascorbic acid; methanethiol (methylmercaptan); ethanethiol (ethyl mercaptan); Coenzyme A, dimercaptosuccinic acid (DMSA); grapefruit mercaptan ((R) -2- (4-methyl-cyclohex-3-enyl) propane-2-thiol)); cysteine ((R) -2-amino-3-sulfanyl-propanoic acid); lipoamide (1,2-dithiolane-3-pentanamide); 5,7-bis (1,1-dimethylethyl) -3- [2,3 (or 3,4) -dimethylphenyl] -2 (3H) -benzofuranone, commercially available from Ciba under the brand name Irganox® HP-136; benzyl sulfyl phenyl; diphenyl sulfide; diisopropylamine; 3,3'-thiodipropionate dioctadecyl, commercially available from Ciba under the brand name Irganox® PS 802 (Ciba); didodecyl 3,3'-thiopropionate, commercially available from Ciba under the brand name Irganox® PS 800; di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, commercially available from Ciba under the brand name Tinuvin® 770; poly- (N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate, commercially available from Ciba under the brand name Tinuvin® 622LD (Ciba); methyl amine bis-sebacate; amine bis-sebacate ; phenol-alpha-naphthylamine, bis (dimethylamino) methylsilane (DMAMS); tris (trimethylsilyl) silane (TTMSS); vinyltriethoxysilane; vinyltrimethoxysilane; 2,5-difluorobenzophenone; 2 ', 5'-dihydroxyacetophenone; 2-aminobenzophenone; benzyl sulfide phenyl; diphenyl sulfide; dibenzyl sulfide; ionic liquids and others.
[0059] [059] In one embodiment, ionic liquid stabilizers comprise at least one ionic liquid. Ionic liquids are organic salts that have melting points below 100 ° C.
[0060] [060] In an additional embodiment, ionic liquid stabilizers comprise the salts containing cations selected from the group consisting of pyridinium, pyridazinium, pyrimidiniums, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium and triazolium and mixtures thereof; and anions selected from the group consisting of [BF4] -, [PF6] -, [SbF6] -, [CF3SO3] -, [HCF2CF2SO3] -, [CF3HFCCF2SO3] -, [HCCIFCF2SO3] -, [(CF3SO2) 2N ] -, [(CF3CF2SO2) 2N] -, [(CF3SO2) 3C] -, [CF3CO2] - and F-. Representative ionic liquid stabilizers include emim BF4 (1-ethyl-3-methylimidazolium tetrafluoroborate); bmim BF4 (1-butyl-3-methylimidazolium tetraborate); emim PF6 (1-ethyl-3-methylimidazolium hexafluorophosphate) and bmim PF6 (1-butyl-3-methylimidazolium hexafluorophosphate), which are available from Fluka (Sigma-Aldrich). HEAT PUMPS
[0061] [061] In one embodiment of the present invention, a heat pump device is provided which contains a working fluid comprising Z-1,1,1,4,4,4-hexafluoro-2-butene.
[0062] [062] A heat pump is a type of device for producing heating and / or cooling. A heat pump includes an evaporator, a compressor, a condenser, and an expansion device. A working fluid circulates through these components in a repetitive cycle. Heating is produced in the condenser, in which energy (in the form of heat) is extracted from the working fluid, since the steam is condensed to form the liquid working fluid. Cooling is produced in the evaporator, where the energy is absorbed to evaporate the working fluid to form the gaseous working fluid.
[0063] [063] Heat pumps can include the flooded evaporators from one embodiment that are shown in Figure 1, or the direct expansion evaporators from one embodiment that are shown in Figure 2.
[0064] [064] Heat pumps use positive displacement compressors or dynamic compressors. Positive displacement compressors include screw, reciprocating, or scroll (scroll) compressors. Of interest, it is the heat pumps that use screw compressors. Dynamic compressors include centrifugal and axial compressors. Also of interest are the heat pumps that use centrifugal compressors.
[0065] [065] Residential heat pumps are used for the production of hot air to heat a residence or home (including a single family or attached houses of several units) and produce maximum condenser operating temperatures of around 30 ° C and 50 ° C.
[0066] [066] Of interest, are high temperature heat pumps that can be used for heated air, water, another means of heat transfer or a part of an industrial process, such as a piece of equipment, area of storage or process flow. These heat pumps can produce maximum condenser operating temperatures above 55 ° C. The maximum operating temperature of the condenser that can be achieved in a high temperature heat pump will depend on the working fluid used. This maximum operating temperature of the condenser is limited by the normal boiling characteristics of the working fluid (for example, the saturation pressure and critical temperature) and also by the pressure to which the heat pump compressor can raise the working fluid pressure. gaseous. This maximum pressure to which the working fluid can be exposed is limited by the thermal stability of the working fluid.
[0067] [067] Of particular value are high temperature heat pumps, which operate at condenser temperatures of at least about 100 ° C. The Z-HFO-1336mzz allows the creation and operation of centrifugal heat pumps, operated at condenser temperatures higher than those accessible with many working fluids available today. Of interest are the realizations that use the working fluids comprising the Z-HFO-1336mzz operated at condenser temperatures around 150 ° C. Also of interest are the realizations using the working fluids comprising the Z-HFO-1336mzz operated at condenser temperatures at around 155 ° C. Also of interest are the realizations that use the working fluids comprising the Z-HFO-1336mzz operated at condenser temperatures around 165 ° C. Of particular interest are the embodiments using the working fluids comprising the Z-HFO-1336mzz operated at condenser temperatures at least about 150 ° C. Examples include embodiments using working fluids comprising Z-HFO-1336mzz operated at condenser temperatures of at least about 155 ° C, and embodiments using working fluids comprising Z-HFO- 1336mzz operated at condenser temperatures at least about 165 ° C.
[0068] [068] Also of interest, are the heat pumps that are used for the production of simultaneous heating and cooling. For example, a single heat pump unit can produce hot water for domestic use and can also produce refrigeration for summer air conditioning comfort.
[0069] [069] Heat pumps, including the flooded evaporator and direct expansion, can be coupled with an air treatment and distribution system to provide the comfort of air conditioning (air cooling and dehumidification) and / or heating for the residence (single family or attached homes) and large commercial buildings, including hotels, office buildings, hospitals, universities and others. In another embodiment, heat pumps can be used to heat water.
[0070] [070] To illustrate the way in which heat pumps operate, reference is made to the Figures. A flooded evaporator heat pump is shown in Figure 1. In this heat pump a first heat transfer medium, which is a hot liquid, comprising water, and, in some embodiments, additives, or other transfer medium of heat such as, for example, a glycol (for example, ethylene glycol or propylene glycol), enters the heat transport pump from a low temperature heat source, such as a building air treatment system or heated water from the condensers of a cooling location that flows to the cooling tower, as shown by entering the arrow (3), through a bundle of tubes or coil (9), in an evaporator (6), which has an inlet and an outlet. The first means of transferring hot heat is supplied to the evaporator, where it is cooled through the liquid working fluid, which is shown at the bottom of the evaporator. Note that in FIGURE 1, the bundle of tubes or coil (9) is shown in the evaporator (6) to be partially located in the gaseous working fluid and, partially, in the liquid working fluid. In most cases, the bundle of tubes or coil (9) will be fully immersed in the liquid working fluid contained in the evaporator (6). The liquid working fluid evaporates as it has an evaporation temperature (at the operating pressure of the evaporator) below the temperature of the first hot heat transfer medium that flows through the bundle of tubes or coil (9). The first cooled heat transfer medium recirculates back to the low temperature heat source, as shown by the arrow (4), via a portion of the tube or coil bundle return (9). The liquid working fluid, shown at the bottom of the evaporator (6) in Figure 1, vaporizes and is sucked into a compressor (7), which increases the pressure and temperature of the gaseous working fluid. The compressor compresses this vapor so that it can be condensed in a condenser (5) at a pressure and temperature higher than the pressure and temperature of the gaseous working fluid when it leaves the evaporator. A second heat transfer medium enters the condenser at the arrow (1) in the Figure by means of a bundle of tubes or coils (10) in the condenser (5) from a location where the high temperature heat is supplied (" heatsink ”), such as a water heater for domestic or service use, or a hydronic heating system. The second heat transfer medium is heated in the process and returns via a return beam circuit tubes or coil (10) and the arrow (2) for the heat sink This second heat transfer medium cools the gaseous working fluid in the condenser and causes the vapor to condense to the liquid working fluid in a way that there is liquid working fluid in the lower portion of the condenser, as shown in Figure 1. The liquid working fluid condensed in the condenser flows back to the evaporator through an expansion device (8), which can be an orifice, tube capillary or expansion valve. The expansion device (8) reduces the pressure of the liquid working fluid, and partially converts the liquid working fluid to steam, which means that the liquid working fluid expands when the pressure drops between the condenser and the evaporator. The expansion cools the working fluid, that is, the liquid working fluid and the gaseous working fluid to the saturated temperature under pressure of the evaporator, so that the liquid working fluid and the gaseous working fluid are present in the evaporator.
[0071] [071] In some embodiments, the gaseous working fluid is compressed to a supercritical state and the container (5) in Figure 1 represents a supercritical liquid cooler in which the gaseous working fluid is cooled to a liquid state, without condensation .
[0072] [072] In some embodiments, the first heat transfer medium used in the device shown in Figure 1 is the cooled water returned from a building in which air conditioning is provided or from some other body to be cooled. Heat is extracted from the chilled water returning to the evaporator (6) and the chilled chilled water is supplied back to the building or another body to be cooled. In this embodiment, the device shown in Figure 1 works to simultaneously cool the first heat transfer medium that provides cooling to the body to be cooled (for example, building air) and heat the second heat transfer medium that provides heating for a body to be heated (for example, water for domestic or service use, or process flow).
[0073] [073] It is understood that the device shown in Figure 1 can remove heat in the evaporator (6) from a wide variety of heat sources, including solar, geothermal and waste heat and heat supplies to from the condenser (5) to a wide variety of heat sinks.
[0074] [074] It should be noted that for a single component working fluid composition, the composition of the gaseous working fluid in the evaporator and condenser is the same as the composition of the liquid working fluid in the evaporator and condenser. In this case, evaporation and condensation occur at a constant temperature. However, if a working fluid mixture (or mixture) is used, as in the present invention, the liquid working fluid and the gaseous working fluid in the evaporator or condenser can have different compositions. This can lead to inefficient systems and difficulties in maintaining the equipment, therefore, a single component working fluid is more desirable. An azeotropic or azeotropic composition will essentially function as a single component working fluid in a heat pump, such that the liquid composition and the gaseous composition are essentially the same reduction of any deficiencies that may arise from use non-azeotropic or non-azeotropic composition.
[0075] [075] An embodiment of a direct expansion heat pump is illustrated in Figure 2. In the heat pump, as illustrated in Figure 2, the first liquid heat transfer medium, which is a hot liquid, such as hot water , enters an evaporator (6 ') at the entrance (14). Most of the liquid working fluid (with a small amount of gaseous working fluid) enters a coil (9 ') in the evaporator on the arrow (3) and evaporates. As a result, the first liquid heat transfer medium is cooled in the evaporator, and a first cooled liquid heat transfer medium exits the evaporator at the outlet (16), and is sent to a low temperature heat source (for example, hot water flows to a cooling tower). The gaseous working fluid leaves the evaporator on the arrow (4 ') and is sent to a compressor (7'), where it is compressed and exits as a high temperature and high pressure gaseous working fluid. This gaseous working fluid enters a condenser (5 ') through a condenser coil (10') on the arrow (1 '). The gaseous working fluid is cooled by a second liquid heat transfer medium, such as water, in the condenser and becomes a liquid. The second liquid heat transfer medium enters the condenser through the entrance of a condenser heat transfer medium (20). The second liquid heat transfer medium removes heat from the condensed gaseous working fluid, which becomes the liquid working fluid, and this heats the second liquid heat transfer medium in the condenser. The second liquid heat transfer medium leaves the condenser through the outlet of the condenser heat transfer medium (18). The condensed working fluid exits the condenser via a lower coil (10 ') on the arrow (2'), as shown in Figure 2 and flows through an expansion device (12), which can be, for example, a orifice or expansion valve. The expansion device (12) reduces the pressure of the liquid working fluid. A small amount of steam, produced as a result of the expansion, enters the evaporator with the liquid working fluid, through the coil (9 ') and the cycle is repeated.
[0076] [076] In some embodiments, the gaseous working fluid is compressed to a supercritical state and the container (5 ') in Figure 1 represents a supercritical liquid cooler, often referred to as a gas cooler, in which the working fluid gas is cooled to a liquid state, without condensation.
[0077] [077] In some embodiments, the first heat transfer medium used in the device illustrated in Figure 2 is cooled from the return water from a building where air conditioning is provided or from some other body to be cooled. Heat is extracted from the chilled water returning to the evaporator (6 ') and the chilled chilled water is supplied back to the building or another body to be cooled. In this embodiment, the device illustrated in Figure 2 works to simultaneously cool the first heat transfer medium that provides the cooling for a body to be cooled (for example, building air) and heat the second heat transfer medium that provides the heating for a body to be heated (for example, water for domestic or service use, or process flow).
[0078] [078] It is understood that the device shown in Figure 2 can remove heat in the evaporator (6 ') from a wide variety of heat sources, including solar, geothermal and waste heat and heat supply waste. condenser (5 ') for a wide variety of heat sinks.
[0079] [079] Compressors useful in the present invention include dynamic compressors. Of interest, as examples of dynamic compressors are centrifugal compressors. A centrifugal compressor uses the rotating elements to accelerate the working fluid radially, and in general, it comprises a rotor and diffuser housed in a housing. Centrifugal compressors, in general, take the working fluid to the rotor inlet, or central inlet of a rotating rotor, and radially accelerate it outward. Some pressure increases occur in the rotor, but most of the pressure increase occurs in the diffuser where the kinetic energy is converted into potential energy (or weakly, the moment is converted into pressure). Each rotor-diffuser assembly is a compressor stage. Centrifugal compressors are built with from 1 to 12 or more steps, depending on the desired final pressure and the volume of refrigerant to be treated.
[0080] [080] The pressure ratio, or compression ratio, of a compressor is the ratio of the absolute discharge pressure to the absolute inlet pressure. The pressure delivered by a centrifugal compressor is virtually constant over a relatively wide range of capacities. The pressure that a centrifugal compressor can develop depends on the peripheral speed of the rotor. Peripheral speed is the speed of the rotor measured at the peripherals of its blades and is related to the diameter of the rotor and its speed of rotation, often expressed in revolutions per minute. The peripheral speed required in a specific application depends on the work of the compressor that is necessary to raise the thermodynamic state of the working fluid from the conditions of the evaporator to those of the condenser. The volumetric capacity of the centrifugal compressor flow is determined by the size of the passages through the rotor. This makes the size of the compressor more dependent on the pressure required than the volumetric flow capacity required.
[0081] [081] Also of interest, as examples of dynamic compressors are axial compressors. A compressor in which the liquid enters and leaves in the axial direction, is called an axial flow compressor. Axial compressors are blade-based, rotary, airfoil compressors, or in which the working fluid essentially flows parallel to the axis of rotation. This is in contrast to the other rotary compressors, such as centrifugal or mixed flow compressors where the working fluid can enter axially, but will have a significant radial component at the outlet. Axial compressors produce a continuous flow of compressed gas, and have the benefits of high efficiency and great mass flow capacity, particularly in relation to their cross section. They do, however, need several rows of airfoils to achieve high pressure increases making them complex and costly compared to other projects.
[0082] [082] Positive displacement compressors draw steam from a chamber and the volume of the chamber is reduced to compress the steam. After being compressed, steam is forced from the chamber, further decreasing the chamber volume to zero or close to zero.
[0083] [083] Of interest, as examples of positive displacement compressors are reciprocating compressors. Reciprocating compressors use pistons driven by a crankshaft. They can be fixed or portable, they can be single or multistage, and they can be driven by electric motors or internal combustion engines. Small reciprocating compressors from 5 to 30 hp are seen in automotive applications and are usually for intermittent service. Larger reciprocating compressors up to 100 hp are found in large industrial applications. Discharge pressures can vary from low pressure to very high pressure (above 5,000 psi or 35 MPa).
[0084] [084] Also of interest, as examples of positive displacement compressors are screw compressors. Screw compressors use two positive displacement, rotating mesh helical screws to force the gas into a smaller space.
[0085] [085] Screw compressors, in general, are for continuous operation in commercial and industrial applications and can be fixed or portable. Its application can be from 5 hp (3.7 kW) to more than 500 hp (375 kW) and from low pressure to very high pressure (above 1200 psi or 8.3 MPa).
[0086] [086] Also worthy of interest, as examples of positive displacement compressors are spiral compressors (scroll). Scroll compressors are similar to screw compressors and include two spirals interspersed in a spiral shape to compress the gas. The output is more pulsating than that of a rotary screw compressor.
[0087] [087] In one embodiment, the high temperature heat pump device may comprise more than one heating circuit (or cycle). The performance (performance coefficient for heating and volumetric heating capacity) of high temperature heat pumps, operated with the Z-HFO-1336mzz as the working fluid is significantly improved when the evaporator is operated at temperatures close to temperature of the condenser required for the application, that is, when the required temperature rise is reduced. When the heat supply to the evaporator is only available at low temperatures, therefore requiring high temperature elevators leading to poor performance, a dual-fluid / double-loop cascade cycle configuration can be advantageous. The low-stage or low-temperature circuit of the cascade cycle would be operated with a liquid with a lower boiling point than that of Z-HFO-1336mzz and, preferably, with relatively low GWP, such as HFC-32, HFO -1234yf, E-HFO-1234ze, HFC-134a, HFC-134, HFC-227ea and mixtures thereof, such as HFO-1234yf / HFC-32, HFO-1234yf / HFC-134a, HFO-1234yf / HFC-134, HFO -1234yf / HFC-134a / HFC-134, E-HFO-1234ze / HFC-134a, E-HFO-1234ze / HFC-134, E-HFO-1234ze / HFC-134a / HFC-134, E-HFO-1234ze / HFC-227ea, HFO-1234ze-E / HFC-134 / HFC-227ea, E-HFO-1234ze / HFC-134 / HFC-134a / HFC-227ea, HFO-1234yf / E-HFO-1234ze / HFC-134 / HFC-134a / HFC 227ea, etc. The evaporator of the low temperature circuit (or low temperature cycle) of the cascade cycle receives the available low temperature heat, increases the heat to an intermediate temperature between the available low temperature heating temperature and the required heating working temperature and transfers heat to the high stage or high temperature circuit (or high temperature cycle) of the cascade system to a cascade heat exchanger. Then, the high temperature circuit, operated with a working fluid comprising Z-HFO-1336mzz (for example, a mixture of Z-HFO-1336mzz and 2-chloropropane), further elevates the heat received in the heat exchanger. cascading heat to the condenser temperature needed to satisfy the desired heating job. The cascade concept can be extended to configurations with three or more heating lift circuits over wider temperature ranges and using different fluids at different temperature sub-intervals to optimize performance.
[0088] [088] According to the present invention, a cascade heat pump system is provided which contains at least two heating cycles to circulate a working fluid through each cycle. One embodiment of such a cascade system is generally shown (110) in Figure 3. The cascade heat pump system of the present invention has at least two heating cycles, including a first cycle, or cycle lower (112), as shown in Figure 3, which is a low temperature cycle, and a second, or higher (114) cycle, as shown in Figure 3, which is an average temperature cycle (114). Each circulates through the same working fluid.
[0089] [089] As shown in Figure 3, the cascade heat pump system of the present invention includes a first expansion device (116). The first expansion device has an inlet (116a) and an outlet (116b). The first expansion device reduces the pressure and temperature of a first liquid working fluid that circulates through the first low temperature cycle.
[0090] [090] The cascade heat pump system of the present invention also includes an evaporator (118), as shown in Figure 3. The evaporator has an inlet (118a) and an outlet (18b). The first liquid working fluid from the first expansion device enters the evaporator through the evaporator inlet and is evaporated in the evaporator to form a first gaseous working fluid. The first gaseous working fluid then circulates to the evaporator outlet.
[0091] [091] The cascade heat pump system of the present invention also includes a first compressor (120). The first compressor has an inlet (120a) and an outlet (120b). The first gaseous working fluid from the evaporator circulates to the inlet of the first compressor and is compressed, thereby increasing the pressure and temperature of the first gaseous working fluid. The first compressed gaseous working fluid then circulates to the outlet of the first compressor.
[0092] [092] The cascade heat pump system shown in Figure 3 also includes a cascade heat exchanger system (122). The cascade heat exchanger has a first inlet (122a) and a first outlet (122b). The first gaseous working fluid of the first compressor enters the first inlet of the heat exchanger and is condensed in the heat exchanger to form a first liquid working fluid, thereby rejecting heat. The first liquid working fluid then circulates at the first outlet of the heat exchanger. The heat exchanger also includes a second inlet (122c) and a second outlet (122d). A second liquid working fluid circulates from the second inlet to the second outlet of the heat exchanger and is evaporated to form a second gaseous working fluid, thereby absorbing the heat rejected by the first working fluid (as it is condensed). This heat is rejected to the environment. The second gaseous working fluid then circulates to the second outlet of the heat exchanger. Thus, in the realization of Figure 3, the heat rejected by the first working fluid is directly absorbed by the second working fluid.
[0093] [093] The cascade heat pump system shown in Figure 3, also includes a second compressor (124). The second compressor has an inlet (124a) and an outlet (124b). The second gaseous working fluid from the cascade heat exchanger is drawn into the compressor through the inlet and is compressed, thereby increasing the pressure and temperature of the second gaseous working fluid. The second gaseous working fluid then circulates to the outlet of the second compressor.
[0094] [094] The cascade heat pump system shown in Figure 3 also includes a condenser (126) containing an inlet (126a) and an outlet (126b). The second working fluid of the second compressor circulates from the inlet and is condensed in the condenser to form a second liquid working fluid, producing heat. The second liquid working fluid exits the condenser through the outlet.
[0095] [095] The cascade heat pump system shown in Figure 3 also includes a second expansion device (128) containing an inlet (128a) and an outlet (128b). The second liquid working fluid passes through the second expansion device, which reduces the pressure and temperature of the second liquid working fluid exiting the condenser. This liquid can be partially vaporized during this expansion. The pressure and reduced temperature of the second liquid working fluid circulates to the second inlet of the cascade heat exchanger system from the expansion device.
[0096] [096] In addition, the stability of Z-HFO-1336mzz at temperatures higher than its critical temperature allows the creation of heat pumps operated according to a transcritical or supercritical cycle in which heat is rejected by the working fluid in the state supercritical and made available for use in a temperature range (including temperatures higher than the critical temperature of Z-HFO-1336mzz) (see the thesis by Angelino and Invernizzi, Int. J. Refrig., 1994, vol. 17, n ° 8, pages 543554, hereby incorporated by reference). The supercritical fluid is cooled to a liquid state, without going through an isothermal condensation transition. Several cycle configurations are described by Angelino and Invernizzi.
[0097] [097] For the operation of the high temperature condenser (associated with the high temperature elevators and the high discharge temperature of the compressor), the working fluid formulations (for example, the Z-HFO-1336mzz or mixtures containing the Z-HFO-1336mzz) and lubricants with high thermal stability (possibly in combination with oil cooling or other reduction approaches) can be advantageous.
[0098] [098] For the operation of the high temperature condenser (associated with the high temperature elevators and the high discharge temperature of the compressor), the use of magnetic centrifugal compressors (for example, Danfoss-Turbocor type) that do not require the use of lubricants, it will be advantageous.
[0099] [099] For the operation of the high temperature condenser (associated with the high temperature elevators and the high discharge temperature of the compressor), the use of compressor materials (for example, shaft sealants and others), with high stability thermal may also be required. METHODS
[0100] [0100] In one embodiment, a method is provided for the production of the high temperature heat pump which comprises the condensation of a gaseous working fluid comprising 1,1,1,4,4,4-hexafluoro-2- butene, in a condenser, producing a liquid working fluid.
[0101] [0101] In one embodiment, the heating is produced in a heat pump comprising said condenser, which further comprises passing a heat transfer medium through the condenser, in which said condensation of the working fluid heats the heat transfer medium ; and passing the heated heat transfer medium from the condenser to a body to be heated.
[0102] [0102] A body to be heated can be any space, object or liquid that can be heated. In one embodiment, a body to be heated can be a room, building, or passenger compartment in an automobile. Alternatively, in another embodiment, a body to be heated can be a second or the heat transfer medium or fluid.
[0103] [0103] In one embodiment, the heat transfer medium is water and the body to be heated is water. In a further embodiment, the heat transfer medium is water and the body to be heated is air for heating the space. In a further embodiment, the heat transfer medium is an industrial heat transfer liquid and the body to be heated is a chemical process flow.
[0104] [0104] In an additional embodiment, the heating production method further comprises compressing the gaseous working fluid in a centrifugal compressor.
[0105] [0105] In one embodiment, the heating is produced in a heat pump comprising said condenser, which further comprises passing a fluid to be heated through said condenser, thereby heating the fluid. In one embodiment, the liquid is air, and the air heated from the condenser passes into a space to be heated. In an additional embodiment, the liquid is a portion of a process flow, and the heated portion is returned to the process.
[0106] [0106] In some embodiments, the heat transfer medium can be selected from water, glycol (such as ethylene glycol or propylene glycol). Of particular interest, it is an embodiment in which the first means of heat transfer is water and the body to be cooled is air for cooling the space.
[0107] [0107] In an additional embodiment, the heat transfer medium can be an industrial heat transfer liquid, in which the body to be heated is a chemical process flow, which includes the process lines and process equipment, such as like distillation columns. Of interest are industrial heat transfer liquids, including ionic liquids, various brines, such as aqueous calcium or sodium chloride, glycols, such as propylene glycol or ethylene glycol, methanol and other heat transfer media, such as those listed in section 4 of the 2006 ASHRAE Manual on refrigeration.
[0108] [0108] In one embodiment, the method for producing heat comprises extracting heat in a high temperature heat pump from the flooded evaporator as described above in relation to Figure 1. In this method, the liquid working fluid is evaporated to form a gaseous working fluid in the vicinity of a first heat transfer medium. The first heat transfer medium is a hot liquid, such as water, which is transported to the evaporator via a pipe from a low temperature heat source. The hot liquid is cooled and either returned to the low temperature heat source or passed to a body to be cooled, such as a building. The gaseous working fluid is then condensed in the vicinity of a second heat transfer medium, which is a refrigerated liquid, which is brought in from the proximity of a body to be heated (heat sink). The second heat transfer medium cools the working fluid in such a way that it is condensed to form a liquid working fluid. In this method, a flooded evaporator heat pump can also be used to heat water for domestic or service use, or a process flow.
[0109] [0109] In an additional embodiment, the method for the production of heat comprises the production of heat in a high temperature heat pump of direct expansion, as described above in relation to Figure 2. In this method, the liquid working fluid is passed through an evaporator and evaporates to produce a gaseous working fluid. A first liquid heat transfer medium is cooled through the evaporating working fluid. The first means of transferring liquid heat is passed out of the evaporator to a low temperature heat source or a body to be cooled. The gaseous working fluid is then condensed in the vicinity of a second heat transfer medium, which is a refrigerated liquid, which is brought in from the proximity of a body to be heated (heat sink). The second heat transfer medium cools the working fluid in such a way that it is condensed to form a liquid working fluid. In this method, a direct expansion heat pump can also be used to heat water for domestic or service use, or a process flow.
[0110] [0110] In some embodiments of the method for producing heat in a high temperature heat pump, heat is exchanged between at least two heating stages, which is referred to earlier in the present as a cascade heat pump. In these embodiments, the method comprises the absorption of heat in a working fluid in a heating stage operated at a selected condensing temperature; and transferring that heat to the working fluid of another heating stage operated at a higher condensing temperature, wherein the working fluid of the heating stage operating at a higher condensing temperature comprises Z-1,1,1,4, 4,4-hexafluoro-2-butene. The working fluid of the heating stage operated at a higher condensing temperature can still comprise 2-chloropropane. The method for producing heat can be carried out in a cascade heat pump system with two heating stages or with a cascade heat pump system with more than two heating stages.
[0111] [0111] In one embodiment of the method for producing heating, the high temperature heat pump includes a compressor that is a centrifugal compressor.
[0112] [0112] In a further embodiment of the present invention there is described a method of increasing the maximum viable operating temperature of the condenser in a high temperature heat pump device which comprises loading the high temperature heat pump with a cooling fluid. work comprising Z-1,1,1,4,4,4-hexafluoro-2-butene.
[0113] [0113] The use of Z-HFO-1336mzz in high temperature heat pumps increases the capacity of these heat pumps, as it allows operation at higher condenser temperatures than those obtained with the working fluid used in similar current systems . The condenser temperatures obtained with the HFC-245fa and CFC-114 are the highest possible with current systems.
[0114] [0114] When the CFC-114 is used as the working fluid in a high temperature heat pump, the maximum viable operating temperature of the condenser with normally available centrifugal heat pumps is about 122 ° C. In one embodiment of the method for increasing the maximum viable operating temperature of the condenser, when a composition comprising Z-1,1,1,4,4,4-hexafluoro-2-butene, is used as the working fluid of the pump of heat, the maximum viable operating temperature of the condenser is increased to a temperature above about 122 ° C.
[0115] [0115] In an additional embodiment of the method to increase the maximum viable operating temperature of the condenser, when a composition comprising Z-1,1,1,4,4,4-hexafluoro-2-butene, is used as the fluid of the heat pump, the maximum viable operating temperature of the condenser is increased to a temperature above about 125 ° C.
[0116] [0116] In an additional embodiment of the method to increase the maximum viable operating temperature of the condenser, when a composition comprising Z-1,1,1,4,4,4-hexafluoro-2-butene, is used as the fluid working temperature of the heat pump, the maximum viable operating temperature of the condenser is increased to a temperature above about 130 ° C.
[0117] [0117] In one embodiment, the maximum viable operating temperature of the condenser, when the working fluid comprises Z-1,1,1,4,4,4-hexafluoro-2-butene, is increased to at least about 150 ° C.
[0118] [0118] In an additional embodiment, the maximum viable operating temperature of the condenser, when the working fluid comprises Z-1,1,1,4,4,4-hexafluoro-2-butene, is increased to at least about 155 ° C.
[0119] [0119] In an additional embodiment, the maximum viable operating temperature of the condenser, when the working fluid comprises Z-1,11,4,4,4-hexafluoro-2-butene, is increased to at least about 165 ° C.
[0120] [0120] It is feasible that temperatures as high as 170 ° C (or higher when transcript operation is permitted) are achieved with a high temperature heat pump using Z-1,1,1,4,4,4-hexafluoro -2-butene. However, at temperatures above 155 ° C, some changes to the compressor, or compressor materials, may be required.
[0121] [0121] In a further embodiment of the present invention, a method is provided for replacing a working fluid selected from the group consisting of CFC-114, HFC-134a, HFC-236fa, HFC-245fa, CFC-11 and HCFC-123 in a high temperature heat pump created for said working fluid which comprises the supply of a replacement working fluid which comprises Z-1,1,1,4,4,4-hexafluoro-2-butene.
[0122] [0122] In a further embodiment of the present invention, a method is provided for using a working fluid composition comprising Z-HFO-1336mzz in a high temperature heat pump suitable for using a working fluid selected from the group consisting of CFC-114, HFC-134a, HFC-236fa, HFC-245fa, CFC-11 and HCFC-123. The method comprises loading the high temperature heat pump with the working fluid comprising the Z-HFO-1336mzz. In a further embodiment, the method comprises loading the high temperature heat pump with the working fluid comprising Z-HFO-1336mzz and 2-chloropropane. In a further embodiment, the method comprises loading the high temperature heat pump with a working fluid that essentially consists of Z-HFO-1336mzz and 2-chloropropane. In a further embodiment, the working fluid still comprises a lubricant.
[0123] [0123] According to the present invention, it is possible to replace a high temperature heat pump fluid (for example, the CFC-114 or HFC-245fa), in a system originally created for said temperature heat pump fluid elevated with a working fluid comprising the Z-HFO-1336mzz, in order to increase the operating temperature of the condenser.
[0124] [0124] According to the present invention, it is also possible to use a working fluid comprising the Z-HFO-1336mzz in a system originally created as a chiller using a conventional cooling working fluid (for example, a chiller using HFC-134a or HCFC-123 or CFC-11 or CFC-12, or HFC-245fa) for the purpose of converting the system to a high temperature heat pump system. For example, a conventional cooling working fluid can be replaced in an existing cooling system with the working fluid comprising the Z-HFO-1336mzz to achieve this goal. According to the present invention, it is also possible to use a working fluid comprising Z-HFO-1336mzz in a system originally created as a comfort (ie low temperature) heat pump system using a heating fluid. work of the conventional comfort heat pump (for example, a heat pump using HFC-134a or HCFC-123 or CFC-11 or CFC-12, or HFC-245fa) for the purpose of converting the system to a system high temperature heat pump. For example, a conventional comfort heat pump working fluid can be replaced in an existing comfort heat pump system, with a working fluid comprising the Z-HFO-1336mzz to achieve this goal. EXAMPLES
[0125] - SUBRRESFRIAMENTO = 10,00 °C - SUPERAQUECIMENTO ADICIONADO NO EVAPORADOR = 15,00 °C - EFICIÊNCIA DO COMPRESSOR = 0,80 (80%) [0125] The concepts described herein will be described in the following examples, which do not limit the scope of the present invention described in the claims. COMMON OPERATING CONDITIONS FOR ALL EXAMPLES - COOLING = 10.00 ° C - OVERHEATING ADDED TO THE EVAPORATOR = 15.00 ° C - COMPRESSOR EFFICIENCY = 0.80 (80%)
[0126] [0126] The performance of Z-HFO-1336mzz in a water heating heat pump is determined and compared to the performance for HFC-245fa and CFC-114. The data are shown in Tables 1 (a) and 1 (b). The data are based on the following conditions: Evaporator temperature 25 ° C Condenser temperature 85 ° C
[0127] [0127] Note that the GWP value for HFC-245fa is taken from: - "Climate Change 2007 - IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report on Climate Change", in the section entitled "Working Group 1 Report: "The Physical Science Basis”, Chapter 2, pages. 212-213, Table 2.14. Specifically, GWP values are used over 100 years of the time horizon.
[0128] [0128] Note the GWP value for CFC-114 from Calm, J.M. and G.C. Hourahan 2007, “Refrigerant data update”, Heating / Piping / Air Conditioning Engineering, vol. 79 (1), pages 50-64.
[0129] [0129] The use of Z-HFO-1336mzz allows this application with a COP for heating 0.62% higher than HFC-245fa and 2.64% higher than CFC-114. In addition, Z-HFO-1336mzz offers lower toxicity than HFC-245fa and substantially better environmental properties (ie, zero ODP and very low GWP) than CFC-14 and HFC-245fa. Z-HFO-1336mzz would not be a substitute for HFC-245fa or CFC-114 in most cases, due to its lower heating capacity. However, the Z-HFO-1336mzz would serve as an excellent low GWP working fluid in new systems that offer improved energy efficiency compared to existing working fluids / systems. EXAMPLE 2 HEATING PERFORMANCE WITH AVAILABLE HEAT SOURCE, AT 50 ° C FOR Z-HFO-1336MZZ VERSUS HFC-245FA AND CFC-114
[0130] [0130] The performance of the Z-HFO-1336mzz in a water heating heat pump is determined and compared with the performance for the HFC-245fa and CFC-114. The data are presented in Tables 2 (a) and 2 (b). The data are based on the following conditions: Evaporator temperature 50 ° C Condenser temperature 85 ° C
[0131] [0131] When the temperature of the available heat source (Tevap = 50 ° C) is higher than Example 1 (Tevap = 25 ° C) for the same required condenser temperature (Tcond = 85 ° C), the coefficient of performance (COP or energy efficiency) for heating and volumetric heating capacity are significantly improved for all working fluids, especially for the Z-HFO-1336mzz. The COP for heating with Z-HFO-1336mzz is 1.4% higher than HFC-245fa and 2.66% higher than CFC-114. In addition, Z-HFO-1336mzz offers lower toxicity than HFC-245fa and substantially better environmental properties (ie, zero ODP and very low GWP) than CFC-114 and HFC-245fa. EXAMPLE 3 SIMULTANEOUS COOLING AND HEATING PERFORMANCE FOR Z-HFO-1336MZZ VERSUS HFC-245FA AND CFC-114
[0132] [0132] A heat pump can be used to simultaneously supply hot water for domestic use and chilled water for air conditioning. The performance of Z-HFO-1336mzz on a machine that provides heating and cooling simultaneously is determined and compared to the performance of HFC-245fa and CFC-114. The data are presented in Tables 3 (a) and 3 (b).
[0133] [0133] The data are based on the following conditions: Evaporator temperature 5 ° C Condenser temperature 85 ° C
[0134] [0134] The Z-HFO-1336mzz allows this application, with a total attractive CPO for simultaneous heating and cooling that is comparable to HFC-245fa and 3.47% higher than CFC-114. In addition, Z-HFO-1336mzz offers lower toxicity than HFC-245fa and substantially better environmental properties (ie, zero ODP and very low GWP) than CFC-14 and HFC-245fa. EXAMPLE 4 HEATING PERFORMANCE WITH THE HEAT SOURCE AVAILABLE AT 75 ° C FOR THE Z-HFO-1336MZZ VERSUS THE HFC-245FA AND CFC-114
[0135] [0135] The performance of Z-HFO-1336mzz in a high temperature heat pump is determined and compared with the performance for HFC-245fa and CFC-114. The data are presented in Tables 4 (a) and 4 (b). The data are based on the following conditions: Evaporator temperature 75 ° C Condenser temperature 120 ° C
[0136] [0136] The performance of Z-HFO-1336mzz over HFC-245fa and CFC-114 significantly improved at elevated operating temperatures. The Z-HFO-1336mzz allows an application that needs a condenser temperature of 120 ° C, using the available heat that allows an evaporator temperature of 75 ° C, with a COP (energy efficiency) for heating of 3.78 % higher than HFC-245fa and 6.82% higher than CFC-114. In addition, Z-HFO-1336mzz offers lower toxicity than HFC-245fa and substantially better environmental properties (ie, zero ODP and very low GWP) than CFC-114 and HFC-245fa. EXAMPLE 5 HEATING PERFORMANCE WITH AVAILABLE HEAT SOURCE, AT 100 ° C AND 120 ° C FOR Z-HFO-1 336MZZ
[0137] [0137] The performance of Z-HFO-1336mzz in a high temperature heat pump is determined and compared with the performance for HFC-245fa and CFC-114. The data are shown in Table 5. The data is based on the following conditions: Condenser temperature 155 ° C
[0138] [0138] The condenser temperature of 155 ° C exceeds the critical temperature of the HFC-245fa and CFC-114, therefore, a heat pump rejects heat through a conventional condensation step cannot operate with any of these fluids working temperature at this condenser temperature. The Z-HFO-1336mzz generates a vapor pressure of about 2.18 MPa at a temperature of 155 ° C.
[0139] [0139] The components of the large tonnage centrifugal cooler normally available can accommodate maximum operating pressures of up to about 2.18 MPa without major changes. Therefore, the Z-HFO-1336mzz can allow applications to satisfy heating jobs that require condenser temperatures up to about 155 ° C with systems that largely consist of the components normally available in the large tonnage centrifugal chiller. In addition, Z-HFO-1336mzz is non-flammable, has an attractive toxicity profile and attractive environmental properties, including excellent energy efficiency (COP) for these operating conditions. EXAMPLE 6 CHEMICAL AND THERMAL STABILITY OF Z-HFO-1336MZZ
[0140] [0140] The chemical stability of Z-HFO-1336mzz in the presence of metals was analyzed according to the sealed tube test methodology of ANSl / ASHRAE Standard 97-2007. The stock of Z-HFO-1336mzz used in the sealed tube tests was 99.9864 +% pure weight (136 ppmw impurities) and contained virtually no water or air.
[0141] [0141] The sealed glass tubes, each containing three metal coupons made of steel, copper and aluminum immersed in Z-HFO-1336mzz, were aged in a greenhouse heated to various temperatures up to 250 ° C for 14 days. Visual inspection of the tubes after thermal aging indicated clear liquids without discoloration or other visible deterioration of the fluid. In addition, there was no change in the appearance of the metal coupons, indicating degradation by corrosion or others.
[0142] [0142] Table 6 shows the measured fluoride ion concentrations in aged liquid samples. The concentration of the fluoride ion can be interpreted as an indicator of the degree of degradation of Z-HFO-1336mzz. Table 3 shows that the degradation of Z-HFO-1336mzz was surprisingly minimal even with the upper temperature tested (250 ° C).
[0143] [0143] Table 7 shows changes in composition, quantified by GCMS, samples of Z-HFO-1336mzz after aging in the presence of steel, copper and aluminum, at various temperatures for two weeks. Only insignificant proportions of the new unknown compounds appeared as a result of aging to the upper temperature tested (250 ° C).
[0144] [0144] The HFO-1336mzz transisomer, EE-HFO-1336mzz, is expected to be thermodynamically more stable than the c / s-isomer, the Z-HFO-1336mzz, for about 5 kcal / mol. Surprisingly, despite the substantial thermodynamic driving force for the isomerization of Z-HFO-1336mzz to the most stable transisomer, the measurement results in Table 7 indicate that Z-HFO-1336mzz remained largely in the Z (or cis) isomeric form even at the upper temperature tested (250 ° C). The effect of the small proportion (3,022.7 ppm or 0.30227% by weight) of E-HFO-1336mzz that formed after two weeks of aging at 250 ° C on the thermodynamic properties of the working fluid (Z-HFO-1336mzz) and therefore, in the performance of the cycle, it would be insignificant.
[0145] [0145] The non-flammable range for compositions comprising Z-HFO-1336mzz and 2-chloropropane was determined in accordance with ASTM E681 - test procedure 2001, as required in ASHRAE 34-2007 and described in “ Addendum p ”with ASHRAE Standard 34-2007. The test conditions were 60 ° C, with 50% relative humidity.
[0146] [0146] A composition containing 95% by weight of Z-HFO-1336mzz and 5% by weight of 2-chloropropane was tested as described above and found to be flammable, with a lower flammability limit (LFL) of 7, 75% by air volume and an upper flammability limit (UFL) of 8.0% by air volume. Then, a composition containing 96% by weight of HFO-Z-1336mzz and 4% by weight of 2-chloropropane was tested as described above and found to be non-flammable. Therefore, compositions with less than 5% by weight of 2-chloropropane are expected to be non-flammable, while compositions containing 4% by weight or less are non-flammable. EXAMPLE 8 PERFORMANCE OF A HIGH TEMPERATURE HEAT PUMP WITH A Z / HFO-1336MZZ / 2-CHLOROPROPANE MIXTURE OF 80/20% BY WEIGHT AS THE WORKING FLUID
[0147] [0147] Table 8 summarizes the performance of a heat pump with a working fluid consisting of 80% by weight of Z-HFO-1336mzz and 20% by weight of 2-chloropropane, referred to as "Mixture A".
[0148] [0148] Mixture A has substantially greater energy efficiency for heating and volumetric heating capacity than liquid Z-HFO-1336mzz. It is also expected to have greater compatibility with mineral oil lubricants than liquid Z-HFO-1336mzz. Mixture A is also expected to have substantially greater thermal stability and substantially less flammability than liquid 2-chloropropane.

权利要求:
Claims (9)
[0001]
METHOD FOR PRODUCTION OF HEAT in a high temperature heat pump, characterized by comprising the condensation of a gaseous working fluid comprising Z-1,1,1,4,4,4-hexafluoro-2-butene, in a condenser (5.5 ', 126), thereby producing a liquid working fluid, in which the temperature of the condenser (5.5', 126) of said high temperature heat pump is at least 100 ° C, and wherein said high temperature heat pump comprises a compressor (7.7 ', 120.124), which is a centrifugal compressor or a positive displacement compressor.
[0002]
METHOD, according to claim 1, characterized in that it further comprises the passage of a heat transfer medium through the condenser (5), by which said condensation of the working fluid heats the heat transfer medium; and passing the heated heat transfer medium from the condenser (5) to a body to be heated.
[0003]
METHOD, according to claim 1, characterized by the heat being exchanged between at least two heating stages comprising: - the absorption of heat in a first working fluid in a heating stage which is a first cycle (112) operated at a selected condenser temperature (122a, 122b, 122c); and transferring that heat in a cascade heat exchanger (122) to a second working fluid from another heating stage, which is a second cycle (114) operated at a higher temperature of the condenser (126); wherein the second working fluid of the heating stage which is the second cycle (114) operated at the upper temperature of the condenser (126) comprises Z-1,1,1,4,4,4-hexafluoro-2-butene.
[0004]
METHOD FOR INCREASING THE MAXIMUM OPERATING TEMPERATURE OF THE CONDENSER (5.5 ', 126), in a high temperature heat pump device, characterized by understanding the loading of the high temperature heat pump with a working fluid as defined in claim 1, and wherein said high temperature heat pump comprises a compressor (7.7 ', 120.124), which is a centrifugal compressor or a positive displacement compressor.
[0005]
METHOD, according to claim 4, characterized in that the maximum viable operating temperature of the condenser (5.5 ', 126) is increased to a temperature above 122 ° C.
[0006]
High temperature HEAT PUMP DEVICE, characterized in that it contains a working fluid as defined in claim 1, wherein said high temperature heat pump includes an evaporator (6.6 ', 118), a compressor (7.7' , 120,124), a capacitor (5.5 ', 126), and an expansion device (8,12,116,128); and wherein the temperature of the condenser (5.5 ', 126) of said high temperature heat pump is at least 100 ° C, and wherein said compressor (7.7', 120.124) is a centrifugal compressor or a compressor positive displacement.
[0007]
DEVICE, according to claim 6, characterized in that it has at least two heating stages that include a first cycle (112) and a second cycle (114) arranged as a cascade heating system, each cycle circulating a working fluid through of the same, where the heat is transferred from the first cycle (112) to the second cycle (114) and where the heating fluid of the second cycle (114) comprises Z- 1,1,1,4,4,4- hexafluoro-2-butene.
[0008]
DEVICE, according to claim 6, characterized in that it has at least two heating stages that include a first cycle (112) and a second cycle (114) arranged as a cascade heating system, each stage circulating a working fluid through of the same, which comprises: (a) a first expansion device (116) for reducing the pressure and temperature of a first liquid working fluid; (b) an evaporator (118), which has an inlet (118a) and an outlet (118b), in which the first liquid working fluid from the first expansion device (116) enters the evaporator (118) through the inlet from the evaporator (118a) and is evaporated in the evaporator (118) to form a first gaseous working fluid, and circulates to the outlet (118b); (c) a first compressor (120) having an inlet (120a) and an outlet (120b), in which the first gaseous working fluid from the evaporator (118) circulates to the inlet (120a) of the first compressor (120 ) and is compressed, thereby increasing the pressure and temperature of the first gaseous working fluid, and the first compressed gas refrigerant circulates to the outlet (120b) of the first compressor (120); (d) a cascade heat exchanger system (122) which has: (i) a first inlet (122a) and a first outlet (122b), in which the first gaseous working fluid circulates from the first inlet (122a) to the first outlet (122b) and is condensed in the heat exchanger system ( 122) to form a first liquid working fluid, thereby rejecting heat; and (ii) a second inlet (122c) and a second outlet (122d), in which a second liquid working fluid circulates from the second inlet (122c) to the second outlet (122d) and absorbs the heat rejected by the first work and forms a second gaseous working fluid; (e) a second compressor (124) having an inlet (124a) and an outlet (124b), in which the second gaseous working fluid from the cascade heat exchanger system (122) is drawn into the compressor (124 ) and is compressed, thereby increasing the pressure and temperature of the second gaseous working fluid; (f) a condenser (126) having an inlet (126a) and an outlet (126b) for circulating the second gaseous working fluid through it, and for condensing the second gaseous working fluid from the compressor (124 ) to form a second liquid working fluid, thereby producing heat, whereby the second liquid working fluid exits the condenser (126) through the outlet (126b); and (g) a second expansion device (128) for reducing the pressure and temperature of the second liquid working fluid that leaves the condenser (126) and enters the second inlet (122c) of the cascade heat exchanger system (122); - wherein the second working fluid comprises Z-1,1,1,4,4,4-hexafluoro-2-butene; and wherein the temperature of the condenser (126) of said high temperature heat pump is at least 100 ° C.
[0009]
DEVICE, according to claim 8, characterized in that the first working fluid comprises at least one fluoroolefin selected from the group consisting of HFO-1234yf and E-1234ze.

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法律状态:
2019-07-09| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-06-02| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-10-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-03| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|

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2021-01-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/01/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161437964P| true| 2011-01-31|2011-01-31|

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US61/437,964|2011-01-31|

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US201161525296P| true| 2011-08-19|2011-08-19|

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US61/525,296|2011-08-19|

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PCT/US2012/023267|WO2012106305A1|2011-01-31|2012-01-31|Producing heating using working fluids comprising z 1,1,1,4,4,4-hexafluoro-2-butene|

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