HEAT RECOVERY PROCESS, ORGANIC RANKINE CYCLE SYSTEM AND HFC-245FA REPLACEMENT METHOD

专利摘要:
heat recovery process, organic rankine cycle system and hfc-245fa replacement method. the present invention, in general, relates to innovative working fluid compositions exclusively designed for higher cycle efficiencies, leading to greater overall system efficiencies. in particular, these working fluids are useful in organic rankine cycle (orc) systems for the efficient conversion of heat from various heat sources into mechanical energy. the present invention also relates to innovative processes for recovering heat from a heat source using orc systems with an innovative working fluid comprising at least about 20% by weight of cis-1,1 , 1,4,4,4-hexafluoro-2-butene (hfo-1336mzz-z), trans-1,1,1,4,4,4-hexafluoro-2-butene (hfo-1336mzz-e), or their mixtures.
公开号:BR112014003778B1
申请号:R112014003778-7
申请日:2012-08-16
公开日:2021-04-06
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, in general, refers to innovative working fluids exclusively designed to reduce the impact in relation to climate change and higher cycle efficiencies, leading to greater overall system efficiencies. In particular, these working fluids are useful in the Organic Rankine Cycle (ORC) systems for efficiently converting heat from various heat sources into mechanical energy. The present invention also relates to innovative processes for recovering heat from a heat source using ORC systems with an innovative working fluid comprising at least about 20% by weight of c / s-1 , 1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E) , or their mixtures. BACKGROUND OF THE INVENTION
[0002] [002] Previous Rankine Cycle systems used several working fluids, which include flammable or combustible working fluids - fluids with relatively high toxicity, fluids with relatively high global warming potentials (GWPs) and fluids with depletion potentials. ozone layer (ODPs) other than zero. The industry is working to replace chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that deplete the ozone layer. Environmentally sustainable, non-flammable, low-toxic, working fluids are highly desirable for Rankine Cycle applications.
[0003] [003] Surprisingly, it has been found that the innovative working fluids of the present invention exclusively provide the higher cycle efficiencies in ORC systems which in turn result in greater overall system efficiencies in the power cycle, while offering low toxicity, flammability, zero ODP, and very low GWP. BRIEF DESCRIPTION OF THE INVENTION
[0004] (a) passagem de um primeiro fluido de trabalho na fase líquida através de um trocador de calor ou um evaporador, em que dito trocador de calor ou dito evaporador está em comunicação com dita fonte de calor que fornece dito calor; (b) remoção de, pelo menos, uma porção de dito primeiro fluido de trabalho em uma fase de vapor de dito trocador de calor ou dito evaporador; (c) passagem de dita, pelo menos, uma porção de dito primeiro fluido de trabalho na fase de vapor para um expansor, em que, pelo menos, uma porção de dito calor é convertida em energia mecânica; (d) passagem de dita, pelo menos, uma porção de dito primeiro fluido de trabalho na fase de vapor a partir de dito expansor para um condensador, em que dita, pelo menos, uma porção de dito primeiro fluido de trabalho na fase de vapor é condensada para um segundo fluido de trabalho na fase líquida; (e) opcionalmente, compressão e mistura de dito segundo fluido de trabalho na fase líquida com dito primeiro fluido de trabalho na fase líquida na etapa (a); e (f) opcionalmente, repetição das etapas de (a) a (e), pelo menos, uma vez; em que, pelo menos, cerca de 20% em peso de dito primeiro fluido de trabalho compreende o HFO-1336mzz-Z, HFO-1336mzz-E, ou suas misturas.[004] In one embodiment, the present invention relates to a process for the recovery of heat from a heat source and for the generation of mechanical energy, which comprises the steps of: (a) passing a first working fluid in the liquid phase through a heat exchanger or an evaporator, wherein said heat exchanger or said evaporator is in communication with said heat source which provides said heat; (b) removing at least a portion of said first working fluid in a vapor phase of said heat exchanger or said evaporator; (c) passing said at least a portion of said first working fluid in the vapor phase to an expander, wherein at least a portion of said heat is converted to mechanical energy; (d) passage of said at least a portion of said first working fluid in the vapor phase from said expander to a condenser, wherein said at least a portion of said first working fluid in the vapor phase it is condensed to a second working fluid in the liquid phase; (e) optionally, compressing and mixing said second working fluid in the liquid phase with said first working fluid in the liquid phase in step (a); and (f) optionally, repeating steps (a) to (e) at least once; wherein at least about 20% by weight of said first working fluid comprises HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0005] [005] The present invention also relates to a process for the recovery of heat from a heat source and the generation of mechanical energy, which comprises the steps of: (a) compression of a first working fluid in the liquid phase above the critical pressure of said first working fluid; (b) passing said first working fluid from step (a) through a heat exchanger or fluid heater and heating said first working fluid to a temperature that is higher or lower than the critical said temperature first working fluid, wherein said heat exchanger or said fluid heater is in communication with said heat source which supplies said heat; (c) removing at least a portion of said first heated working fluid from said heat exchanger fluid heater; (d) passing said at least a portion of said first heated working fluid to an expander; wherein at least a portion of said heat is converted to mechanical energy, and; wherein the pressure on said first at least a portion of said first heated working fluid is reduced to below the critical pressure of said first working fluid, thereby making said at least a portion of said first working fluid heated work on a first vapor of working fluid or a first mixture of vapor and liquid working fluid; (e) passing said first working fluid vapor or said first mixture of the working liquid and vapor fluid from said expander to a condenser, wherein said at least a portion of said working fluid vapor work or said mixture of steam and liquid working fluid is completely condensed to a second working fluid in the liquid phase; (f) optionally, compressing and mixing said second working fluid in the liquid phase with said first working fluid in the liquid phase in step (a); (g) optionally, repeating steps (a) to (f) at least once; wherein at least about 20% by weight of said first working fluid comprises HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0006] [006] In one embodiment, the present invention also relates to a composition comprising HFO-1336mzz-Z, at a temperature in the range of about 250 ° C to about 300 ° C, in which said HFO- 1336mzz-Z is in the range from about 50% by weight to about 99.5% by weight.
[0007] [007] In yet another embodiment, the present invention relates to an Organic Rankine Cycle System that extracts heat at an operating pressure in the range of about 3 MPa to about 10 MPa, in which about 20% in The weight of said working fluid comprises HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0008] [008] In another embodiment, the present invention relates to a composition as a working fluid for power cycles, wherein the temperature of said composition is in the range of about 50 ° C to about 400 ° C, and wherein about 20% by weight of said composition comprises HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0009] [009] In another embodiment, the present invention relates to a method for replacing HFC-245fa in a power cycle system. The method comprises removing said HFC-245fa from said power cycle system and loading said system with a working fluid comprising HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. BRIEF DESCRIPTION OF THE FIGURES
[0010] [010] Figure 1 is a block diagram of a heat source and a system of the Organic Rankine Cycle in direct heat exchange, according to the present invention.
[0011] [011] Figure 2 is a block diagram of a heat source and an Organic Rankine Cycle system that uses a secondary circuit configuration to supply heat from a heat source to a heat exchanger for conversion. mechanical energy according to the present invention.
[0012] [012] Figure 3 shows the energy efficiency of Rankine transcritical organic cycles that operate with HFO-1336mzz-Z as the working fluid as a function of the fluid heater pressure for the selected working fluid temperatures at the inlet. expander (Tcond = 54.44 ° C, Tsubrilling = 7.78 ° C; Expander efficiency = 0.85, and Pump efficiency = 0.85).
[0013] [013] Figure 4 shows the energy efficiency of the transcriptic organic Rankine Cycles that operate with the HFO-1336mzz-Z as the working fluid as a function of the fluid heater pressure for the selected working fluid temperatures at the inlet. expander (Tcond = 40 ° C, Tsubrilling = 0 ° C; Expander Efficiency = 0.85; and Pump Efficiency = 0.85).
[0014] [014] Figure 5 shows a transcritical ORC with a completely dry expansion.
[0015] [015] Figure 6 shows a transcritical ORC with partial condensation during expansion, but with dry steam at the exit of the expander.
[0016] [016] Figure 7 shows a transcritical ORC with a wet expansion and with the temperature at the inlet of the expander higher than the critical temperature of the working fluid.
[0017] [017] Figure 8 shows a transcritical ORC with a wet expansion, but with the temperature at the inlet of the expander below the critical temperature of the working fluid. DETAILED DESCRIPTION OF THE INVENTION
[0018] [018] 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 compared to the emission of one kilogram of carbon dioxide. The GWP can be calculated for different time horizons, showing the effect of the atmospheric useful time for a given gas The GWP over a 100-year time horizon is usually the referenced value.
[0019] [019] The term "output of the net power of the cycle" is the rate of generation of mechanical work in the expander (for example, a turbine) below the rate of mechanical work consumed by the compressor (for example, a liquid pump).
[0020] [020] The term "volumetric capacity" for power generation is the output of the net power of the cycle per unit volume of working fluid (as measured in the conditions at the outlet of the expander) circulated through the cycle.
[0021] [021] The term "cycle efficiency" (also referred to as thermal efficiency) is the net output of the cycle's power divided by the rate at which heat is received by the working fluid during the heating phase.
[0022] [022] The term "subcooling" is the reduction in the temperature of a liquid below the liquid's saturation point at a given pressure. The saturation point is the temperature at which a vapor composition is completely condensed into a liquid (also referred to as like the bubble point). But subcooling continues to cool the liquid to a lower temperature at a certain pressure.
[0023] [023] The term "amount of subcooling" is the amount of cooling below the saturation temperature (in degrees) or the lower the saturation temperature of the liquid composition is cooled.
[0024] [024] The term "superheat" defines how much above the saturation vapor temperature (the temperature at which, if the composition is cooled, the first liquid drop is formed, also referred to as a "dew point") a vapor composition is heated.
[0025] [025] The term "temperature glide" (sometimes simply referred to as "phase change") is the absolute value of the difference between the initial and final temperatures of a phase change process by a refrigerant inside a component of a refrigerant 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. The term "average phase change" refers to the average phase change in the evaporator and the phase change in the condenser of a specific refrigeration system operating under a given set of conditions.
[0026] [026] The term "dry", as used in connection with "a dry expansion", for example, is intended to mean an expansion that occurs entirely in the vapor phase, without the liquid working fluid present. Therefore, the term "dry", as used herein, is not related to the presence or absence of water.
[0027] [027] An azeotropic composition is a mixture of two or more different components, which, when in liquid form, at a certain pressure will boil at a substantially constant temperature, the temperature of which may be higher or lower than the boiling temperatures of the components 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 Distillation Systems, McGraw-Hill (New York), 2001, 185-186 , 351-359).
[0028] [028] 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.
[0029] [029] 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.
[0030] [030] As used herein, the terms "comprise", "which comprise", "includes", "which includes", "has", "having" or any other variation thereof, are intended to include a non-exclusive inclusion. For example, a composition, 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 inherent in that composition, 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: 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).
[0031] [031] 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 in addition to 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.
[0032] [032] 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".
[0033] [033] If Depositors have defined the present invention or a part of it with an open term, such as "understands", it should be readily 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".
[0034] [034] In addition, the use of "one" or "one" is employed to describe the elements and components described herein. This is done only for convenience and to provide a general sense to the scope of the present invention. This specification should be read that includes one or at least one and the singular also includes the plural, unless it is obvious that it is understood otherwise.
[0035] [035] Unless otherwise indicated, all technical and scientific terms used in the present have the same meaning as those normally 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, which includes the definitions, will control it. In addition, the materials, methods and examples are illustrative only and are not intended to be a limitation.
[0036] [036] E-1,1,1,4,4,4-hexafluoro-2-butene (also known as HFO-1336mzz-E or trans-HFO-1336mzz and having the structure E-CF3CH = CHCF3) and Z -1,1,1,4,4,4-hexafluoro-2-butene (also known as HFO-1336mzz-Z or c / s-HFO-1336mzz and having the structure Z-CF3CH = CHCF3), can be produced through of methods known in the art, such as through the hydrochlorination of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene, as described in US patent application publication 2009/0012335 A1, incorporated herein as a reference. PROCESSES FOR HEAT RECOVERY OR HEAT CONVERSION IN MECHANICAL ENERGY
[0037] [037] For the purposes of the present invention, the transcriptic Organic Rankine Cycle is defined as an Organic Rankine Cycle, which extracts heat at a pressure greater than the critical pressure of the working fluid used in the cycle.
[0038] [038] In one embodiment, the present invention relates to innovative processes for the recovery of heat from a heat source and the generation of mechanical energy using the Organic Rankine Cycle ("ORC") systems that use a fluid innovative work environment.
[0039] (a) a passagem de um primeiro fluido de trabalho na fase líquida através de um trocador de calor ou um evaporador, em que dito trocador de calor ou dito evaporador está em comunicação com dita fonte de calor que fornece dito calor; (b) a remoção de, pelo menos, uma porção de dito primeiro fluido de trabalho em uma fase de vapor de dito trocador de calor ou dito evaporador; (c) a passagem de dita, pelo menos, uma porção de dito primeiro fluido de trabalho na fase de vapor para um expansor, em que, pelo menos, uma porção de dito calor é convertida em energia mecânica; (d) a passagem de dita, pelo menos, uma porção de dito primeiro fluido de trabalho na fase de vapor a partir de dito expansor para um condensador, em que dita, pelo menos, uma porção de dito primeiro fluido de trabalho na fase de vapor é condensado com um segundo fluido de trabalho na fase líquida; (e) opcionalmente, a compressão e a mistura de dito segundo fluido de trabalho na fase líquida com dito primeiro fluido de trabalho na fase líquida na etapa (a); (f) opcionalmente, a repetição das etapas de (a) a (e), pelo menos, uma vez; em que, pelo menos, cerca de 20% em peso de dito primeiro fluido de trabalho compreende o HFO-1336mzz-Z, HFO-1336mzz-E, ou suas misturas. Em uma outra realização, o primeiro fluido de trabalho compreende, pelo menos, 30% em peso de HFO-1336mzz-Z, HFO-1336mzz-E, ou suas misturas. Em uma outra realização, o primeiro fluido de trabalho compreende, pelo menos, 40% em peso de HFO-1336mzz-Z, HFO-1336mzz-E, ou suas misturas. Em uma outra realização, o primeiro fluido de trabalho compreende, pelo menos, 50% em peso de HFO-1336mzz-Z, HFO-1336mzz-E, ou suas misturas.[039] In one embodiment, the process described above for recovering heat from a heat source and generating mechanical energy, comprises the following steps: (a) the passage of a first working fluid in the liquid phase through a heat exchanger or an evaporator, wherein said heat exchanger or said evaporator is in communication with said heat source which supplies said heat; (b) removing at least a portion of said first working fluid in a vapor phase of said heat exchanger or said evaporator; (c) passing said at least a portion of said first working fluid in the vapor phase to an expander, wherein at least a portion of said heat is converted to mechanical energy; (d) the passage of said at least a portion of said first working fluid in the vapor phase from said expander to a condenser, wherein said at least a portion of said first working fluid in the vapor phase steam is condensed with a second working fluid in the liquid phase; (e) optionally, compressing and mixing said second working fluid in the liquid phase with said first working fluid in the liquid phase in step (a); (f) optionally, repeating steps (a) to (e) at least once; wherein at least about 20% by weight of said first working fluid comprises HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the first working fluid comprises at least 30% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the first working fluid comprises at least 40% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the first working fluid comprises at least 50% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0040] [040] The working fluid described above comprises at least about 20% by weight of c / s-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or at least about 20% by weight a mixture of them. In another embodiment, the working fluid comprises at least 30% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the working fluid comprises at least 40% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the working fluid comprises at least 50% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In a suitable embodiment, said at least about 20% by weight of c / s-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or said, at least at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or said at least about 20% by weight of a mixture of these is selected from the following percentage content of the working fluid: about 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31,32, 33, 34,35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 50.5, 51, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61, 5, 62, 62.5, 63, 63.5, 64, 64.5, 65, 65.5, 66, 66.5, 67, 67.5, 68, 68.5, 69, 69.5, 70, 70.5, 71.71.5, 72, 72.5, 73, 73, 5, 74, 74.5, 75, 55.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, 80, 80.5, 81, 81, 5, 82, 82.5, 83, 83.5, 84, 84.5, 85, 85.5, 86, 86.5, 87, 87.5, 88, 88.5, 89, 89.5, 90, 90.5, 91.91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98, 5, 99, 99.5, and about 100%.
[0041] [041] In another suitable embodiment, said at least about 20% by weight of c / s-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or said at least about 20% by weight of irans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or said at least about 20% in The weight of a mixture of these is selected from a range defined by two percentage numbers above (which includes the end points).
[0042] [042] In one embodiment of the above process, in which the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 10% by weight of HFO- 1336mzz-E and 90% or greater by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 15% by weight of HFO-1336mzz-E and 85 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 20% by weight of HFO-1336mzz-E and 80 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 25% by weight of HFO-1336mzz-E and 75 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises from about 25% by weight to about 75% by weight of HFO -1336mzz-E and from about 75% by weight to about 25% by weight HFO-1336mzz-Z.
[0043] [043] The working fluid can also comprise less than about 80% by weight of one or more of the other components selected from the following: cis-HFO-1234ze; trans-HFO-1234ze; HFO-1234yf; HFO-1234ye-E or Z; HFO 1225ye (Z); HFO-1225ye (E); HFO-1225yc; HFO-1243zf (3,3,3-trifluoropropene); HFO-1233zd-E or Z; HFO-1233xf; CF3CH = CHCF3 (E); (CF3) 2CFCH = CHF (E & Z) (CF3) 2CFCH = CF2; CF3CHFC = CHF (E &Z); (C2F5) (CF3) C = CH2; HFC-245fa; HFC-245eb; HFC-245ca; HFC-245cb; HFC-227ea; HFC-236cb; HFC-236ea; HFC-236fa; HFC-365mfc; HFC-43-10mee; CHF2-O - CHF2; CHF2-O-CH2F; CH2F-O-CH2F; CH2F-O-CH3; cyclo-CF2-CH2-CF2-O; cyclo-CF2-CF2-CH2-O; CHF2-O - CF2-CHF2; CF3-CF2-O-CH2F; CHF2-O-CHF-CF3, CHF2-O-CF2-CHF2; CH2F-O-CF2-CHF2; CF3-O-CF2-CH3; CHF2-CHF-O-CHF2; CF3-O-CHF-CH2F; CF3-CHF-O-CH2F; CF3-O-CH2-CHF2; CHF2-O-CH2-CF3; CH2F-CF2-O-CH2F; CHF2-O-CF2-CH3; CHF2-CF2-O-CH3; CH2F-O-CHF - CH2F; CHF2-CHF-O-CH2F; CF3-O-CHF-CH3; CF3-CHF-O-CH3; CHF2-O-CH2-CHF2; CF3-O-CH2-CH2F; CF3-CH2-O-CH2F; CF2H-CF2-CF2-O-CH3; propane; cyclopropane; butane; isobutane; n-pentane; isopentane; neopentane; cyclopentane n-hexane; isohexane, heptane, trans-1,2-dichlorethylene, and mixtures with c / s-HFO-1234ze and HFC-245fa.
[0044] [044] In one embodiment, the working fluid comprises 80% by weight or less of at least one of the preceding compounds. In another embodiment, the working fluid comprises 70% by weight or less of at least one of the foregoing compounds. In another embodiment, the working fluid comprises 60% by weight or less of at least one of the foregoing compounds. In another embodiment, the working fluid comprises 50% by weight or less of at least one of the foregoing compounds.
[0045] [045] In one embodiment, the working fluid for heat extraction may consist of HFO-1336mzz-Z. In another embodiment, the working fluid for heat extraction may consist of HFO-1336mzz-E. In another embodiment, the working fluid for heat extraction may consist of a mixture of HFO-1336mzz-Z and HFO-1336mzz-E.
[0046] [046] Note that while the working fluid in the process description above is identified as a "first" working fluid and, as a "second" working fluid, it must be understood that the difference between the two working fluids is only that the first working fluid is the fluid that enters the ORC system, while the second working fluid is the fluid that enters the ORC system after being subjected to at least one step in the process described above.
[0047] [047] In one embodiment of the above process, the efficiency of converting heat to mechanical energy (cycle efficiency) is at least about 7%. In a proper realization, efficiency can be selected from the following: about 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, and about 25%.
[0048] [048] In another embodiment, efficiency is selected from a range that has endpoints (inclusive), according to any two numbers above efficiency. It should be understood that the instant efficiency of the ORC system can vary at any given time, depending on the various variables in the ORC system, such as the temperature of the source and the pressure of the working fluid and its temperature.
[0049] [049] In one embodiment of the above process, the working fluid is HFO-1336mzz-Z, with minimal amounts of other components, and the operating temperature of the evaporator (maximum temperature at which heat is extracted by the working fluid) is less than or equal to about 171 ° C. In a suitable embodiment, the operating temperature can be any of the following temperatures or within the range (inclusive) defined by two numbers below: about 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91.92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, and about 163, 164, 165, 166, 167, 168, 169, 170, and about 171 ° C.
[0050] [050] In another embodiment of the above process, the working fluid is mainly HFO-1336mzz-E, and the operating temperature of the evaporator (maximum temperature at which heat is extracted by the working fluid) is less than or equal to about 137 ° C. In a suitable embodiment, the operating temperature can be any of the following temperatures or within the range (inclusive) defined by two numbers below: about 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95.96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 11 0, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133 , 134, 135, 136, and about 137 ° C.
[0051] [051] In another embodiment, the working fluid is a mixture of HFO-1336mzz-Z and HFO-1336mzz-E and the operating temperature of the evaporator (maximum temperature at which heat is extracted by the working fluid) is at range from about 137 ° C to about 171 ° C.
[0052] [052] In one embodiment of the above process, the operating pressure of the evaporator is less than about 2.5 MPa. In a proper embodiment, the operating pressure can be any of the following pressures or within the range (inclusive) defined by two numbers below: about 1.00, 1.05, 1.10, 1.15, 1.20, 1.25, 1.30, 1.35, 1.40, 1.45, 1.50, 1.55, 1.60, 1.65, 1.70, 1.75, 1.80, 1.85, 1.90, 1.95, 2.00, 2.05, 2.10, 2.15, 2, 20, 2.25, 2.30, 2.35, 2.40, 2.45, and about 2.50 MPa.
[0053] [053] In one embodiment of the above process, said working fluid has a GWP of less than 35. In an appropriate embodiment, the GWP can be any of the following numbers or within the range (inclusive) defined by two numbers below: 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21.21, 5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, and about 35.
[0054] [054] Figure 1 shows a schematic diagram of an ORC system realization for using heat from a heat source. A heat supply heat exchanger (40) transfers the heat supplied from a heat source (46) to the working fluid that enters the heat supply heat exchanger (40) in the liquid phase. The heat supply heat exchanger (40) is in thermal communication with the heat source (communication can be by direct contact or other means). In other words, the heat supply heat exchanger (40) receives heat energy from the heat source (46) through any known means of heat transfer. The working fluid of the ORC system circulates through the heat supply heat exchanger (40), in which it gains heat. At least a portion of the liquid working fluid is converted to steam in the heat supply heat exchanger (an evaporator in some cases) (40).
[0055] [055] The working fluid, at the moment, in the form of steam is directed to the expander (32) in which the expansion process results in the conversion of at least a portion of the thermal energy provided by the heat source into mechanical energy , in general, the energy of the axis. The shaft power can be used to perform any mechanical work, using conventional arrangements of belts, pulleys, gears, transmissions or similar devices, depending on the desired speed and required torque. In one embodiment, the shaft can also be connected to an electrical energy generating device (30), such as an induction generator. The electricity produced can be used locally or delivered to a grid.
[0056] [056] The working fluid still in the form of steam leaving the expander (32) continues to the condenser (34), in which the proper heat rejection causes the fluid to condense into the liquid.
[0057] [057] It is also desirable to have a liquid equalization tank (36) located between the condenser (34) and the pump (38) to ensure that there is always an adequate supply of working fluid in the liquid state for the suction of the pump. The liquid working fluid flows to a pump (38) that raises the fluid pressure, so that it can be introduced back into the heat supply heat exchanger (40), thereby completing the cycle circuit of Rankine.
[0058] [058] In an alternative embodiment, a secondary heat exchange circuit that operates between the heat source and the ORC system can also be used. In Figure 2, an Organic Rankine Cycle system is shown using a secondary heat exchange circuit. The main Organic Rankine Cycle operates as described above for Figure 1. The secondary heat exchange circuit shown in Figure 2 operates as follows: heat from the heat source (46 ') is transported to the heat exchanger of heat supply (40 '), using a heat transfer medium (i.e., the secondary fluid of the heat exchange circuit). The heat transfer medium moves from the heat supply heat exchanger (40 ') to a pump (42') which pumps the heat transfer medium back to the heat source (46 '). This arrangement offers another means of removing heat from the heat source and sends that source to the ORC system. This arrangement provides flexibility by facilitating the use of a variety of sensitive heat transfer fluids. In fact, the working fluids of the present invention can be used as secondary heat exchange circuit fluids as long as the pressure in the circuit is maintained at or above the fluid saturation pressure at the fluid temperature in the circuit. Alternatively, the working fluids of the present invention can be used as secondary heat exchange circuit fluids or heat transport fluids to extract heat from heat sources in a mode of operation in which the working fluids can evaporate during the heat exchange process, generating large differences in fluid density sufficient to sustain the fluid flow (thermosyphon effect). In addition, high boiling point fluids, such as glycols, brine, silicones, or other essentially non-volatile fluids can be used for the transfer of sensitive heat in the described secondary circuit arrangement. High-boiling liquids can be fluids with boiling points of 150 ° C or higher. A secondary heat exchange cycle can make maintenance of any heat source or ORC system easier, as the two systems can be more easily isolated or separated. This approach can simplify the design of the heat exchanger compared to having a heat exchanger with a portion of the high mass flow / low heat flow followed by a portion of the high heat flow / mass flow low.
[0059] [059] Organic compounds, in general, have an upper temperature limit above which thermal decomposition will occur. The onset of thermal decomposition refers to a particular chemical structure and, therefore, varies for different compounds. To access a high temperature source using direct heat exchange with the working fluid, design considerations for heat flow and mass flow, as mentioned above, can be employed to facilitate heat exchange while maintaining the fluid working temperature below its initial thermal decomposition temperature. Direct heat exchange in such a situation usually requires additional mechanical and handling characteristics that increase costs. In such situations, a secondary circuit design can facilitate access to the high temperature heat source by managing the temperatures, while circumventing the concerns listed in the case of direct heat exchange.
[0060] [060] Other components of the ORC system for carrying out the secondary heat exchange circuit are essentially the same as those described for Figure 1. As shown in Figure 2, a liquid pump (42 ') circulates the secondary fluid ( for example, heat transfer medium), through the secondary circuit, so that it enters the portion of the heat source (46 ') where it gains heat. The fluid then passes to the heat exchanger (40 ’), where the secondary fluid releases heat to the ORC working fluid.
[0061] [061] In yet another embodiment, the present invention relates to the innovative working fluid exclusively designed for greater cycle efficiencies in power cycles, thus leading to greater overall system efficiencies. In particular, these working fluids are useful in the Organic Rankine Cycle ("ORC") systems for efficiently converting heat from various heat sources into mechanical energy. This working fluid is described above. ORGANIC TRANSCRIPTIC RANKINE CYCLES
[0062] [062] In one embodiment, organic Rankine cycles are transcritical cycles. Accordingly, the present invention relates to a process for recovering heat from a heat source, which comprises the following steps: (a) the compression of a first working fluid in the liquid phase above the critical pressure of said first working fluid; (b) passing said first working fluid from step (a) through a heat exchanger or fluid heater and heating said first working fluid to a temperature that is higher or lower than the critical temperature of said first working fluid, wherein said heat exchanger or said fluid heater is in communication with said heat source which provides said heat; (c) removing at least a portion of said first heated working fluid from said heat exchanger or fluid heater; (d) the passage of said at least a portion of said first heated working fluid to an expander, in which at least a portion of said heat is converted into mechanical energy, and wherein the pressure on said at least a portion of said first heated working fluid is reduced to below the critical pressure of said first working fluid, thereby making said at least a portion of said first working fluid heated in a first vapor of working fluid or a first mixture of vapor and liquid working fluid; (e) the passage of said first vapor of working fluid or said first mixture of the working fluid of vapor and liquid from said expander to a condenser, wherein said at least a portion of said fluid vapor of work or said mixture of working fluids of vapor and liquid is completely condensed to a second working fluid in the liquid phase; (f) optionally, compressing and mixing said second working fluid in the liquid phase with said first working fluid in the liquid phase in step (a); (g) optionally, repeating steps (a) to (f) at least once; wherein at least about 20% by weight of said first working fluid comprises HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the first working fluid comprises at least 30% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the first working fluid comprises at least 40% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the first working fluid comprises at least 50% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0063] [063] In one embodiment of the above process, in which the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 10% by weight of HFO- 1336mzz-E and 90% or greater by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 15% by weight of HFO-1336mzz-E and 85 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 20% by weight of HFO-1336mzz-E and 80 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 25% by weight of HFO-1336mzz-E and 75 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises from about 25% by weight to about 75% by weight of HFO-1336mzz -E and from about 75% by weight to about 25% by weight of HFO-1336mzz-Z.
[0064] [064] In one embodiment of the above process, the efficiency of converting heat to mechanical energy (cycle efficiency) is at least about 7%. In a proper realization, efficiency can be selected from the following: about 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, and about 25%.
[0065] [065] In another embodiment, efficiency is selected from a range that has endpoints (inclusive), according to any two efficiency numbers above.
[0066] [066] The working fluid described above comprises at least about 20% by weight of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or, at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or at least about 20% by weight of a mixture of them. In a suitable embodiment, said at least about 20% by weight of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or said at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or said at least about 20% by weight of a mixture of these is selected from the following percentage content of the work fluid: about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 50.5, 51, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 62, 62.5, 63, 63.5, 64, 64.5, 65, 65.5, 66, 66.5, 67, 67.5, 68, 68.5, 69, 69.5, 70, 70.5, 71, 71.5, 72, 72.5, 73, 73, 5, 74, 74.5, 75, 55.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, 80, 80.5, 81.81.5, 82, 82.5, 83, 83.5, 84, 84.5, 85, 85.5, 86, 86.5, 87, 87.5, 88, 88.5, 89, 89.5, 90, 90.5, 91, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98, 5, 99, 99.5, and about 100% by weight.
[0067] [067] In another suitable embodiment, said at least about 20% by weight of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or said, at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or said at least about 20% by weight of a mixture of these is selected from an interval defined by two percentage numbers above (which includes the end points).
[0068] [068] In one embodiment, the working fluid for heat extraction may consist of HFO-1336mzz-Z. In another embodiment, the working fluid for heat extraction may consist of HFO-1336mzz-E. In another embodiment, the working fluid for heat extraction may consist of a mixture of HFO-1336mzz-Z and HFO-1336mzz-E.
[0069] [069] It should be noted that, at higher operating temperatures, cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z) in the working fluid can be subjected to a isomerization to its trans isomer, i.e., trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E). Surprisingly it has been found that such isomerization can be minimal, even at higher temperatures, such as 250 ° C.
[0070] [070] The working fluid may also comprise less than about 80% by weight of one or more of the other components selected from the following: cis-HFO-1234ze; trans-HFO-1234ze; HFO-1234yf; HFO-1234ye-E or Z; HFO-1225ye (Z); HFO-1225ye (E); HFO-1243zf - (3,3,3-trifluoropropene); HFO1225yc; HFO-1233zd-E or Z; HFC-1233xf; CF3CH = CHCF3 (E) (CF3) 2CFCH = CHF (E & Z) (CF3) 2CFCH = CF2; CF3CHFC = CHF (E &Z); (C2F5) (CF3) C = CH2, HFC-245fa; HFC-245eb; HFC-245ca; HFC-245cb; HFC-227ea; HFC-236cb; HFC-236ea; HFC-236fa; HFC-365mfc; HFC-43-10mee; CHF2-O - CHF2, CHF2-O-CH2F; CH2F-O-CH2F; CH2F-O-CH3; cyclo-CF2-CH2-CF2-O; cyclo-CF2-CF2-CH2-O; CHF2-O - CF2-CHF2; CF3-CF2-O-CH2F; CHF2-O-CHF-CF3, CHF2-O-CF2-CHF2; CH2F-O-CF2-CHF2; CF3-O-CF2-CH3; CHF2-CHF-O-CHF2; CF3-O-CHF-CH2F; CF3-CHF-O-CH2F; CF3-O-CH2-CHF2; CHF2-O-CH2-CF3; CH2F-CF2-O-CH2F; CHF2-O-CF2-CH3; CHF2-CF2-O-CH3; CH2F-O-CHF - CH2F; CHF2-CHF-O-CH2F; CF3-O-CHF-CH3; CF3-CHF-O-CH3; CHF2-O-CH2-CHF2; CF3-O-CH2-CH2F; CF3-CH2-O-CH2F; CF2H-CF2-CF2-O-CH3; propane; cyclopropane; butane; isobutane; n-pentane; isopentane; neopentane; cyclopentane n-hexane; isohexane, heptane, trans-1,2-dichlorethylene, and mixtures with cis-HFO-1234ze and HFC-245fa.
[0071] [071] In one embodiment of the above process, the working fluid comprises 80% by weight or less of at least one of the above compounds. In another embodiment, the working fluid comprises 70% by weight or less of at least one of the foregoing compounds. In another embodiment, the working fluid comprises 60% by weight or less of at least one of the above compounds. In another embodiment, the working fluid comprises 50% by weight or less of at least one of the above compounds.
[0072] [072] Note that while the working fluid in the process description above is identified as a "first" working fluid and, as a "second" working fluid, it must be understood that the difference between the two working fluids is only that the first working fluid is the fluid that enters the ORC system, while the second working fluid is the fluid that enters the ORC system after being subjected to at least one step in the process described above.
[0073] [073] In one embodiment of the above process, the temperature at which the first working fluid is heated in step (b) is in the range of about 50 ° C to about 400 ° C, preferably from about 150 ° C to about 300 ° C, more preferably from about 175 ° C to 275 ° C, most preferably from about 200 ° C to 250 ° C.
[0074] [074] In a suitable embodiment, the operating temperature at the expander inlet can be any of the following temperatures or within the range (inclusive) defined by two numbers below: about 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 160, 161, 162 and about 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 201,202, 203, 204, 205, 206, 207, 208, 209, 210, 211,212, 213, 214, 215, 216, 217, 218, 219, 220, 221,222, 223, 224, 225, 226, 227, 228, 229, 230, 231,232, 233, 234, 235, 236, 237, 238, 239, 240, 241,242, 243, 244, 245, 246, 247, 248, 249, 250, 251,252, 253, 254, 255, 256, 257, 258, 259, 260, 261,262, 263, 264, 265, 266 , 267, 268, 269, 270, 271,272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 288, 289, 290, 291,292, 293 , 294, 295, 296, 297, 298, 299, 300, 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 311, 312, 313, 314, 315, 316, 317, 318 , 319, 320, 321, 322, 323, 324, 325, 326, 327, 228, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343 , 344, 345, 346, 347, 348, 349, 350, 351, 352, 353, 354, 355, 356, 357, 358, 359, 360, 361, 362, 363, 364, 365, 366, 367, 368 , 369, 370, 371, 372, 373, 374, 375, 376, 377, 378, 379, 380, 381, 382, 383, 384, 385, 386, 387, 388, 389, 390, 391,392, 393, 394 , 395, 396, 397, 398, 399, 400 ° C.
[0075] [075] In one embodiment of the above process, the working fluid in step (a) is pressurized in the range of about 3 MPa to about 10 MPa. In a proper embodiment, the operating pressure can be any of the following pressures within the range (inclusive) defined by two numbers below: about 3.0, 3.1.3.2, 3.3, 3.4, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, and 10.0 MPa.
[0076] [076] In one embodiment of the above process, said working fluid has a GWP of less than 35. In an appropriate embodiment, the GWP can be any of the following numbers or within the range (inclusive) defined by two numbers below: 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21.21, 5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30,30,5, 31, 31,5, 32, 32,5, 33, 33,5, 34, 34,5 and about 35.
[0077] [077] In the first stage of the Transcritical Organic Rankine Cycle (ORC) system, described above, the working fluid in the liquid phase comprising at least about 20% by weight of cis-1,1,1,4 , 4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene ( HFO-1336mzz-E), or at least about 20% by weight of its mixture, is compressed to above its critical pressure. The critical pressure of HFO-1336mzz-Z is 2.903 MPa, the critical pressure of HFO-1336mzz-E is 3.149 MPa. In a second stage, said working fluid is passed through a heat exchanger to be heated to a higher temperature before the fluid enters the expander in which said heat exchanger is in thermal communication with said heat source. In other words, the heat exchanger receives heat energy from the heat source by any known means of heat transfer. The ORC system's working fluid circulates through the heat recovery heat exchanger, in which it gains heat.
[0078] [078] In the next step, at least a portion of said first heated working fluid is removed from said heat exchanger. The working fluid is routed to the expander where the expansion process results in the conversion of at least part of the energy content of the working fluid into mechanical energy, often the energy of the shaft. The shaft power can be used to perform any mechanical work, using the conventional arrangements of belts, pulleys, gears, transmissions or similar devices, depending on the desired speed and required torque. In one embodiment, the shaft can also be connected to an electrical power generating device, such as an induction generator. The electricity produced can be used locally or delivered to the grid. The pressure on the working fluid is reduced to below the critical pressure of said working fluid, therefore, making the working fluid a first working fluid in the vapor phase.
[0079] [079] In the next step, the working fluid currently in the vapor phase is passed from the expander to a condenser, where the working fluid in the vapor phase is condensed to the working fluid in the liquid phase. The steps above form a closed-loop system and can be repeated many times. EXAMPLE 1 - TRANSCRITICAL ORC; TOTALLY DRY EXPANSION
[0080] [080] Figure 5 shows an embodiment of the present invention, in which a transcriptic ORC is used. Figure 5 is a pressure-enthalpy diagram for the cycle of this realization. The substantially vertical lines in the graph are isentropic lines. The lines that are vertical in the left half of the curve, but start showing the deviation and the curvature in the right half of the graph are the isothermal lines. The dashed line on the left side of the dome shape is the saturated liquid line. The dashed line on the right side of the dome shape is the saturated vapor line. In the first stage, the working fluid is compressed (pressurized) above the critical pressure of the working fluid, which is generally substantially isentropic. It is then heated, under a condition of substantially constant pressure (isobaric) to a temperature above its critical temperature. In the next step, the expanded working fluid, in general, is substantially isentropic. The temperature of the fluid is reduced during the expansion step below its critical temperature. The fluid at the end of the expansion step is in the superheated vapor state. In the next step, the working fluid is cooled and condensed and the heat is rejected and its temperature is reduced. The working fluid passes through two phase change limits, the saturated vapor curve, shown on the right side, and then the saturated liquid curve on the left. The working fluid is in a slightly subcooled liquid state at the end of this step. EXAMPLE 2 - TRANSCRITICAL ORC; PARTIAL CONDENSATION DURING EXPANSION / DRY STEAM AT EXPANDER OUTPUT
[0081] [081] Figure 6 shows an embodiment of the present invention, in which a transcriptic ORC is used. Figure 6 is a pressure-enthalpy diagram for the cycle of this realization. The substantially vertical lines in the graph are isentropic lines. The lines that are vertical in the left half of the curve, but start showing the deviation and the curvature in the right half of the graph are the isothermal lines. The dashed line on the left side of the dome shape is the saturated liquid line. The dashed line on the right side of the dome shape is the saturated vapor line. In the first stage, the working fluid is compressed (pressurized) above the critical pressure of the working fluid, which is generally substantially isentropic. It is then heated, under a condition of substantially constant pressure to a temperature above its critical temperature.
[0082] [082] The working fluid temperature is higher than its critical temperature only to such an extent that, in the next step, when the expanded working fluid is, in general, substantially isentropic, and its temperature is reduced, the isentropic expansion it approximately controls the saturated vapor curve, in such a way that expansion results in partial condensation or nebulization of the working fluid. At the end of this expansion step, however, the working fluid is in the state of superheated steam, that is, its locus is on the right side of the saturated vapor curve.
[0083] [083] In the next step, the working fluid is cooled and condensed and the heat is rejected and its temperature is reduced. The working fluid passes through two phase change limits, the saturated vapor curve, shown on the right side, and then the saturated liquid curve on the left. The working fluid is in a slightly subcooled liquid state at the end of this step. EXAMPLE 3 - TRANSCRITICAL ORC; WET EXPANSION; EXPANDER TENTRADA> TCRITICA
[0084] [084] Figure 7 shows an embodiment of the present invention, in which a transcriptic ORC is used. Figure 7 is a pressure-enthalpy diagram for the cycle of this realization. The substantially vertical lines in the graph are isentropic lines. The lines that are vertical in the left half of the curve, but start showing the deviation and the curvature in the right half of the graph are the isothermal lines. The dashed line on the left side of the dome shape is the saturated liquid line. The dashed line on the right side of the dome shape is the saturated vapor line.
[0085] [085] In the first stage, the working fluid is compressed (pressurized) above the critical pressure of the working fluid, in general, substantially isentropic. It is then heated under a condition of substantially constant pressure to a temperature just slightly above its critical temperature.
[0086] [086] The working fluid temperature is higher than its critical temperature only to such an extent that, in the next step, when the expanded working fluid is, in general, substantially isentropic, its temperature is reduced, and the isentropic expansion it is a wet expansion. Specifically, the working fluid at the end of the expansion step is a vapor-liquid mixture.
[0087] [087] In the next step, the working fluid is cooled, the vapor portion of the working fluid is condensed and the heat is rejected and its temperature is reduced. The working fluid in a vapor-liquid mixture passes through a phase change limit on the saturated liquid curve. The working fluid is in a slightly subcooled liquid state at the end of this step. EXAMPLE 4 - TRANSCRITICAL ORC; WET EXPANSION; EXPANDER TENTRADA <TCRITICA
[0088] [088] Figure 8 shows an embodiment of the present invention, in which a transcriptic ORC is used. Figure 8 is a pressure-enthalpy diagram for the cycle of this realization. The substantially vertical lines in the graph are isentropic lines. The lines that are vertical in the left half of the curve, but start showing the deviation and the curvature in the right half of the graph are the isothermal lines. The dashed line on the left side of the dome shape is the saturated liquid line. The dashed line on the right side of the dome shape is the saturated vapor line.
[0089] [089] In the first stage, the working fluid is compressed (pressurized) above the critical pressure of the working fluid, in general, substantially isentropic. It is then heated under a condition of substantially constant pressure to a temperature below its critical temperature.
[0090] [090] In the next step, the working fluid is expanded, in general, substantially isentropic, to a state of low pressure and temperature in which a vapor-liquid mixture (wet expansion) is formed.
[0091] [091] In the next step, the working fluid is cooled, the vapor portion of the working fluid is condensed and the heat is rejected. The working fluid is in a slightly subcooled liquid state at the end of this step.
[0092] [092] While the above examples show substantially isentropic, isentalpical, or isothermal expansions and pressurizations and isobaric heating or cooling, the other cycles, in which such isentropic, isentalpical, isothermal, or isobaric conditions are not maintained, but the cycle, however , is achieved, are within the scope of the present invention.
[0093] [093] An embodiment of the present invention relates to the Variable Phase Cycle or Trilateral Cycle (Phil Welch and Patrick Boyle: “New Turbines to Enable Efficient Geothermal Power Plants” GRC Transactions, Vol. 33, 2009). The liquid working fluid is pressurized and then heated in a heat exchanger without vaporization. The pressurized, heated liquid that exits the heat exchanger is directly expanded in a two-stage expander. The low pressure fluid is condensed, closing the cycle.
[0094] [094] In one embodiment, the present invention relates to a working fluid composition used in ORC systems to recover heat from heat sources, in which the working fluid composition is maintained at a temperature in the range from about 175 ° C to about 300 ° C, preferably from about 200 ° C to 250 ° C and wherein the composition comprises at least about 20% by weight of cis-1.1 , 1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro- 2-butene (HFO-1336mzz-E), or at least about 20% by weight of a mixture thereof. ORC SYSTEMS
[0095] [095] In yet another embodiment, the present invention relates to ORC systems using the innovative working fluid comprising at least about 20% by weight of cis-1,1,1,4,4,4- hexafluoro-2-butene (HFO-1336mzz-Z), or at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E ), or at least about 20% by weight of a mixture thereof. In another embodiment of the system, the working fluid comprises at least 30% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment of the system, the working fluid comprises at least 40% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment of the system, the working fluid comprises at least 50% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0096] [096] In an embodiment of the above system, in which the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 10% by weight of HFO- 1336mzz-E and 90% or greater by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 15% by weight of HFO-1336mzz-E and 85 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 20% by weight of HFO-1336mzz-E and 80 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 25% by weight of HFO-1336mzz-E and 75 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises from about 25% by weight to about 75% by weight of HFO-1336mzz -E and from about 75% by weight to about 25% by weight HFO-1336mzz-Z.
[0097] [097] In one embodiment, the working fluid in the ORC system can consist of HFO-1336mzz-Z. In another embodiment, the working fluid in the ORC system can consist of HFO-1336mzz-E. In another embodiment, the working fluid in the ORC system can consist of a mixture of HFO-1336mzz-Z and HFO-1336mzz-E.
[0098] [098] In another embodiment, the present invention includes an Organic Rankine Cycle System extracting heat at an operating pressure in the range of about 3 MPa to about 10 MPa, wherein said system contains a working fluid, and wherein about 50% by weight of said working fluid comprises HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0099] [099] The innovative working fluid of the present invention can be used in an ORC system to extract thermal energy and convert that energy into mechanical energy from heat sources, such as low pressure steam, thermal energy sources low grade, such as industrial waste heat, solar energy, geothermal hot water, low pressure geothermal steam (primary or secondary provisions) or distributed power generation equipment, using fuel cells or main engines, such as turbines , microturbines or internal combustion engines. Low-pressure steam can also be accessed in a process known as a Rankine binary cycle. Large amounts of low pressure steam can be found in several places, such as fossil fuel powered by electricity generating power plants. The working fluid of the present invention can be adapted to suit the cooling quality of power plants (temperature), maximizing the efficiency of the binary cycle.
[0100] [100] Other heat sources include the residual heat recovered from the exhaust gases from the mobile internal combustion engines (for example, diesel engines from the truck or train or ship), aircraft engines, waste heat from the gases exhaust from stationary internal combustion engines (for example, stationary diesel engine power generators), residual heat from fuel cells, heat available from combined Heating, Cooling and Power or district heating and cooling plants, residual heat from biomass powered engines, heat from methane or natural gas burners or methane boilers or methane fuel cells (for example, in distributed power generation facilities) operated with methane from from several sources including biogas, landfill gas and coal bed methane, heat from the combustion of bark and lignin in paper / cellulose plants, ca from the incinerators, heat from the low pressure flow in conventional steam power plants to conduct "cylindrical" Rankine cycles with a composition that is at least about 20% by weight of cis-1, 1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z) or at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro- 2-butene (HFO-1336mzz-E) or at least about 20% by weight of a mixture thereof, as the working fluid, geothermal heat for Rankine cycles, with a composition that is at least about of 20% by weight of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or at least about 20% by weight of trans-1,1 , 1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or at least about 20% by weight of a mixture thereof, as the above-ground working fluid ( binary cycle geothermal power plants), geothermal heat for Rankine cycles with HFO-1336mzz-Z or-HFO 1336mzz-E or mixtures of HFO-1336m zz-Z and HFO-1336mzz-E as the working fluid of the Rankine cycle and as a geothermal heat carrier in underground circulation in deep wells with the flow largely or exclusively driven by temperature-induced variations in fluid density, known as “The thermosiphon effect” (for example, see Davis, AP and EE Michaelides: “Geothermal power production from abandoned oil wells”, Energy, 34 (2009) 866-872; Matthews, H.B. US patent 4,142,108 - Feb 27, 1979) solar heat from solar panel arrays, which includes parabolic solar panel arrays, solar heat from Concentrated Solar Power Plants, heat removed from photovoltaic solar systems ( PV) to cool the PV system to maintain a high efficiency of the PV system. In other embodiments, the present invention also uses other types of ORC systems, for example, small-scale Rankine cycle systems (for example, from 1 to 500 kW, preferably from 5 to 250 kw), using the micro-turbines or small positive displacement expanders (for example, Tahir, Yamada and Hoshino: “Efficiency of compact organic Rankine cycle system with rotary-vane-type expander for low-temperature waste heat recovery”, Int'l. J. of Civil and Environ Eng 2: 1 2010), cascade, combined, multi-stage Rankine cycles, and Rankine cycle systems with stoves to recover the heat from the steam coming out of the expander.
[0101] [101] Other sources of heat include at least one operation associated with at least one industry selected from the group consisting of: oil refineries, petrochemical plants, oil and gas pipelines, chemical industry, commercial buildings, hotels, shopping malls, supermarkets, bakeries, food processing industries, restaurants, paint curing ovens, furniture manufacturing, plastic molders, cement kilns, wood ovens, calcination operations, steel industry, glass industry, foundries, melting , air conditioning, refrigeration and central heating. METHODS FOR THE REPLACEMENT OF HFC-245FA IN ORC SYSTEMS
[0102] [102] The ORC systems currently in use using HFC-245fa may present the need for an innovative working fluid with less global warming potential (GWP). The GWP of the HFC-245fa is 1,030. The GWP for the working fluids of the present invention are considerably lower. HFO-1336mzz-Z has a GWP of 9.4, while HFO-1336mzz-E has a GWP of around 32. As a result, many working fluids can be formulated that provide the most environmentally sustainable working fluids for ORC systems using HFO-1336mzz-Z, HFO-1336mzz-E or their mixtures.
[0103] [103] In one embodiment, a method is provided for replacing HFC-245fa in a power cycle system which comprises removing said HFC-245fa from said power cycle system and loading said system with a replacement working fluid comprising at least about 20% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the replacement working fluid comprises at least 30% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the replacement working fluid comprises at least 40% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the replacement working fluid comprises at least 50% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0104] [104] In one embodiment of the above process, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 10% by weight of HFO- 1336mzz-E and 90% or greater by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 15% by weight of HFO-1336mzz-E and 85 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 20% by weight of HFO-1336mzz-E and 80 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 25% by weight of HFO-1336mzz-E and 75 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises from about 25% by weight to about 75% by weight of HFO -1336mzz-E and from about 75% by weight to about 25% by weight HFO-1336mzz-Z.
[0105] [105] The working fluid described above comprises at least about 20% by weight of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or, at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or at least about 20% by weight of a mixture of them. In another embodiment, the working fluid comprises at least 30% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the working fluid comprises at least 40% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In another embodiment, the working fluid comprises at least 50% by weight of HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof. In a suitable embodiment said at least about 20% by weight of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z) or said at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), or said, at least about 20% by weight of a mixture of these is selected from the following percentage content of the working fluid: about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34,35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 50.5, 51, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 62, 62.5, 63, 63.5, 64, 64.5, 65, 65.5, 66, 66.5, 67, 67.5, 68, 68.5, 69, 69.5, 70, 70.5, 71, 71.5, 72, 72.5, 73, 73, 5, 74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, 80, 80.5, 81.81.5, 82, 82.5, 83, 83.5, 84, 84.5, 85, 85.5, 86, 86.5, 87, 87.5, 88, 88.5, 89, 89.5, 90, 90.5, 91, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98, 5, 99, 99.5, and about 100%.
[0106] [106] In another suitable embodiment said at least about 20% by weight of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), or said, at at least about 20% by weight of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E) or said at least about 20% by weight of a mixture of these is selected from a range defined by two percentage numbers above (which includes the end points).
[0107] [107] In one embodiment of the above process, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 10% by weight of HFO- 1336mzz-E and 90% or greater by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 15% by weight of HFO-1336mzz-E and 85 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 20% by weight of HFO-1336mzz-E and 80 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises at least about 25% by weight of HFO-1336mzz-E and 75 % or more by weight of HFO-1336mzz-Z. In another embodiment, where the working fluid comprises a mixture of HFO-1336mzz-Z and HFO-1336mzz-E, the working fluid comprises from about 25% by weight to about 75% by weight of HFO -1336mzz-E and from about 75% by weight to about 25% by weight HFO-1336mzz-Z.
[0108] [108] The working fluid may also comprise less than about 80% by weight of one or more of the other components selected from the following: cis-HFO-1234ze; trans-HFO-1234ze; HFO-1234yf; HFO-1234ye-E or Z; HFO 1225ye (Z); HFO-1225ye (E); HFO-1225yc; HFO-1243zf (3,3,3-trifluoropropene); HFO-1233zd-E or Z; HFO-1233xf; CF3CH = CHCF3 (E); (CF3) 2CFCH = CHF (E & Z) (CF3) 2CFCH = CF2; CF3CHFC = CHF (E &Z); (C2F5) (CF3) C = CH2; HFC-245fa; HFC-245eb; HFC-245ca; HFC-245cb; HFC-227ea, HFC-236cb; HFC-236ea, HFC-236fa; HFC-365mfc; HFC-43-10mee; CHF2-O - CHF2; CHF2-O-CH2F; CH2F-O-CH2F; CH2F-O-CH3; cyclo-CF2-CH2-CF2-O; cyclo-CF2-CF2-CH2-O; CHF2-O - CF2-CHF2, CF3-CF2-O-CH2F; CHF2-O-CHF-CF3; CHF2-O-CF2-CHF2; CH2F-O-CF2-CHF2; CF3-O-CF2-CH3; CHF2-CHF-O-CHF2; CF3-O-CHF-CH2F; CF3-CHF-O-CH2F; CF3-O-CH2-CHF2; CHF2-O-CH2-CF3; CH2F-CF2-O-CH2F; CHF2-O-CF2-CH3; CHF2-CF2-O-CH3; CH2F-O-CHF - CH2F; CHF2-CHF-O-CH2F; CF3-O-CHF-CH3; CF3-CHF-O-CH3; CHF2-O-CH2-CHF2; CF3-O-CH2-CH2F; CF3-CH2-O-CH2F; CF2H-CF2-CF2-O-CH3; propane; cyclopropane; butane; isobutane; n-pentane; isopentane; neopentane; cyclopentane n-hexane; isohexane, heptane, trans-1,2-dichlorethylene, and mixtures with cis-HFO-1234ze and HFC-245fa.
[0109] [109] In one embodiment, the working fluid comprises 80% by weight or less of at least one of the above compounds. In another embodiment, the working fluid comprises 70% by weight or less of at least one of the above compounds. In another embodiment, the working fluid comprises 60% by weight or less of at least one of the foregoing compounds. In another embodiment, the working fluid comprises 50% by weight or less of at least one of the above compounds.
[0110] [110] In one embodiment, the working fluid for heat extraction may consist of HFO-1336mzz-Z. In another embodiment, the working fluid for heat extraction may consist of HFO-1336mzz-E. In another embodiment, the working fluid for heat extraction may consist of a mixture of HFO-1336mzz-Z and HFO-1336mzz-E. EXAMPLES
[0111] [111] The concepts described herein will be described in the following examples, which do not limit the scope of application of the present invention described in the claims. EXAMPLE A
[0112] [112] Example A demonstrates the generation of energy from the exhaust heat of the diesel engine using Rankine cycles with HFO-1336mzz-Z under subcritical conditions, where the evaporation of the Tevap temperature is below the critical temperature of HFO-1336mzz-Z (T cr_HFO-1336mzzz-Z = 171.28 ° C).
[0113] [113] The generation of mechanical energy from the heat extracted from the exhaust gases of internal combustion engines (for example, diesel engines), using Rankine cycle systems with HFO-1336mzz-Z as the fluid of work is illustrated in the Examples below. The mechanical energy generated through the Rankine cycle is in addition to the mechanical energy generated by the fuel combustion engine and increases the total amount of mechanical energy generated per unit mass of fuel burned.
[0114] [114] The performance of the working fluid comprising HFO-1336mzz-Z (CF3CH = CHCF3) is compared to the performance of the well-known working fluid of HFC-245fa (CHF2CH2CF3). EXAMPLE A1 LOW TEMPERATURE OPERATION (T EVAPORATOR - 132.22 ° C)
[0115] [115] Table A1 shows that HFO-1336mzz-Z virtually matches the energy efficiency of HFC-245fa, offering a much lower GWP. In addition, HFO-1336mzz-Z generates substantially lower operating pressures than HFC-245fa. (However, the volumetric capacity of HFO-1336mzz-Z to generate energy, CAP, is less than that of HFC-245fa.
[0116] [116] The thermodynamic efficiency of the Rankine cycle operating with HFO-1336mzz-Z, 11.41%, virtually coincides with that of HFC-245fa under the same operating conditions as the cycle. The evaporator pressure with HFO-1336mzz-Z (1.41 MPa) is substantially lower than with HFC-245fa (2.45 MPa). (The volumetric rate of the upper flow at the expander outlet is required to generate a target mechanical power rate with the HFO-1336mzz-Z than with the HFC-245fa. Equivalently, a lower amount of mechanical work is generated when a volume unit of HFO-1336mzz-Z is circulated through the cycle (311.86 kJ / m3) than HFC-245fa (543.63 kJ / m3). EXAMPLE A2 HIGH TEMPERATURE OPERATION (T EVAPORATOR - 155O C)
[0117] [117] HFO-1336mzz-Z has a higher critical temperature (see Table A2) and generates lower vapor pressures than HFC-245fa. As a result, HFO-1336mzz-Z can allow subcritical operation of the Organic Rankine Cycle at temperatures higher than that of HFC-245f (see Table A3). TABLE A2 CRITICAL POINT OF HFO-1336MZZ-Z COMPARED TO HFC-245FA
[0118] [118] HFO-1336mzz-Z can be used as a working fluid for an organic subcritical cycle of Rankine operating with a heat source that allows the evaporator to reach a temperature of 155 ° C (that is, higher than the critical temperature HFC-245fa). Table A3 shows that an evaporator temperature of 155 ° C leads to a substantially improved efficiency and volumetric capacity for power generation (of 14.90% and 18.53%, respectively) in relation to an evaporation temperature of 132 , 22 ° C. EXAMPLE A3 HIGH TEMPERATURE OPERATION (T EVAPORATOR - 161.60 ° C)
[0119] [119] HFO-1336mzz-Z generates lower vapor pressures than HFC-245fa at a specified temperature. Therefore, for any maximum, permitted, determined working pressure of the evaporator, the HFO-1336mzz-Z can allow organic Rankine Cycles operating at higher evaporator temperatures than the HFC-245fa. Table A4 compares an Organic Rankine Cycle with HFO-1336mzz-Z and an evaporator temperature of 161.6 ° C for an Organic Rankine Cycle with HFC-245fa and an evaporator temperature of 132.22 ° C. Both cycles operate at an evaporator operating pressure of 2.45 MPa. The cycle operating with HFO-1336mzz-Z achieves greater energy efficiency (13.51%) than HFC-245fa (11.42%). TABLE A4 RANKINE CYCLE WITH HFO-1336MZZ-Z VS HFC-245FA IN PEVAP = 2.45 MPA
[0120] [120] Example B demonstrates the generation of energy from the exhaust heat from the diesel engine using Rankine Cycles with HFO-1336mzz-Z under transcript conditions.
[0121] [121] Surprisingly, HFO-1336-mzz-Z remains chemically stable at temperatures substantially higher than its critical temperature (171.28 ° C). Therefore, HFO-1336-mzz-Z can allow Rankine cycles to collect heat sources at temperatures above 171.28 ° C, using HFO-1336-mzz-Z as the working fluid in a state supercritical. The use of heat sources of higher temperature leads to greater energy efficiency of the cycle and volumetric capacities for the generation of energy (in relation to the use of heat sources of lower temperature).
[0122] [122] When a supercritical fluid heater is used instead of the evaporator (or boiler) of the conventional, subcritical Rankine cycle, the heater pressure and the heater outlet temperature (or equivalent, the expander inlet temperature ) should be specified. Figure 3 shows the energy efficiency of a transcritical Rankine cycle operating with HFO-1336mzz-Z as the working fluid as a function of the pressure of the supercritical fluid heater and the temperature of the working fluid at the expander inlet. For example, operating the supercritical fluid heater at a pressure of 5 MPa, and a heater outlet temperature (or expander inlet temperature) of 225 ° C achieves an energy efficiency of the Rankine cycle of 15.5%. At higher inlet temperatures of the expander, maximum efficiency is achieved at significantly higher heater pressures. The higher operating pressures of the supercritical fluid heater would be necessary for the use of more robust sized equipment.
[0123] [123] Often, the temperature of the heat source is reduced during the heat exchange process. In the case of the subcritical operation of the Rankine cycle, the temperature of the working fluid is constant throughout the heat extraction evaporation process. The use of a supercritical fluid to extract the heat allows a better correspondence between the different temperatures of the heat source and the supercritical working fluid in relation to the case of the subcritical operation. As a result, the effectiveness of the heat exchange process for the transcritical cycle may be greater than that of the subcritical cycle (see Chen et al., Energy, 36, (2011), 549-555 and references therein). EXAMPLE B1: ORANGE TRANSCRIPTIC RANKINE CYCLE WITH T EXPANDER IN ~ 200 OR 250 ° C TABLE B1 PERFORMANCE OF RANKINE'S TRANSCRITICAL ORGANIC CYCLES WITH HFO-1336MZZ-Z AS THE WORKING FLUID IN TWO SELECTED SETS OF AEB CONDITIONS
[0124] [124] Table B1 shows that a Rankine cycle that first heats HFO-1336mzz-Z to 3 MPa to 200 ° C, then expands the heated HFO-1336mzz-Z to operating pressure (0.21 MPa ) of the condenser in Tcond = 54.44 ° C reaches a thermal efficiency of 14.2% and a volumetric capacity for energy generation of 412.03 kJ / m3. Even greater efficiency and volumetric capacity for power generation can be achieved when the working fluid, HFO-1336mzz-Z, is heated to 250 ° C at a pressure of 6 MPa. HFO-1336mzz-Z remains sufficiently stable at 250 ° C. The greatest efficiencies and capacities are achieved with the transcriptic cycles vs the subcritical cycles in example A. Table B2 compares the performance of a Rankine transcriptic cycle with HFO-1336mzz-Z as the working fluid for HFC-245fa for the same efficiency of the pressure of the fluid heater, outlet temperature of the heater, condenser temperature, subcooling of the liquid, efficiency of the expander and compressor of the liquid (ie, pump). TABLE B2 PERFORMANCE OF AN ORGANIC TRANSCRIPTIC RANKINE CYCLE WITH HFO-1336MZZ-Z AS THE WORKING FLUID COMPARED TO HFC-245FA
[0125] [125] Table C1 shows that HFO-1336mzz-Z could allow the organic Rankine cycles assembled with HVAC type equipment widely available and relatively low cost operating at moderate evaporator pressures (no more than about 2.18 MPa) and also offers safety, attractive health and attractive environmental properties and energy efficiency. The use of low-cost equipment substantially expands the practical applicability of ORCs (see Joost J. Brasz, Bruce P. Biederman and Gwen Holdmann: “Power Production from a Moderate -Temperature Geothermal Resource”, GRC Annual Meeting, 25-28 September 2005; Reno, NV, USA). Table C1 shows that the energy efficiency enabled by HFO-1336mzz-Z, 15.51%, is 15.06% higher than the energy efficiency, 13.48%, enabled by HFC-245fa. TABLE C1 HEALTH, SAFETY, ENVIRONMENT AND HFO-1336MZZ-Z ORC PERFORMANCE PROPERTIES FOR EVAPORATION PRESSURE EQUAL TO 2.18 MPA COMPARED TO HFC-245F.
[0126] [126] The energy efficiency of the Rankine cycle with an expander inlet temperature of 250 ° C monotonically increases with the heater pressure increasing from above the critical pressure of 9 MPa for HFO-1336mzz- Z and for HFC-245fa. The selected heater pressure (9 MPa) in Table C2 is higher than the maximum working pressure of the most commonly available HVAC type equipment.
[0127] [127] Table C2 shows that HFO-1336mzz-Z can allow Rankine cycle transcriptic systems to convert available heat at relatively high temperatures (250 ° C) into energy with an energy efficiency of 2.7% greater than HFC-245fa (under the same operating conditions), offering safety and more attractive environmental properties.
[0128] [128] Tables C1 and C2 show that Rankine cycle transcript systems with HFO-1336mzz-Z, used to convert the available heat at relatively high temperatures (250 ° C) into energy, can achieve greater energy efficiency than Subcritical ORCs operating with HFO-1336mzz-Z. TABLE C2 PERFORMANCE OF A TRANSCRIPTIC ORC OPERATING WITH THE HFO-1336MZZ-Z, AT A SUPERCRITICAL PRESSURE OF THE 9 MPA FLUID HEATER AND A 250 ° C EXPANDER INPUT TEMPERATURE COMPARED TO THE HFC-245FA.
[0129] [129] Figure 4 shows energy efficiency as a function of heater pressure at different expander inlet temperatures. Surprisingly it was found that the energy efficiency increased with the pressure of the heater at high inlet temperatures of the expander. The efficiency at 10 MPa for an expander temperature of 250 ° C has been found to be over 18%. EXAMPLE C4 CHEMICAL STABILITY OF HFO-1336MZZ-Z
[0130] [130] The chemical stability of HFO-1336mzz-Z in the presence of metals was analyzed according to the sealed tube testing methodology of ANSl / ASHRAE standard 97-2007. The HFO-1336mzz-Z stock used in the sealed tube tests was 99.9864 + in pure percentage weight (136 ppmw of impurities) and contained virtually no water or air.
[0131] [131] The sealed glass tubes, each containing three metal coupons produced from steel, copper, aluminum and immersed in HFO-1336mzz-Z, were aged in an oven heated to various temperatures up to 250 ° C for 14 days. Visual inspection of the tubes after thermal aging indicated clear liquids without any discoloration or other visible deterioration of the fluid. In addition, there was no change in the appearance of the metal coupons indicating corrosion or other degradation.
[0132] [132] Table C3 shows the measured fluoride ion concentrations in aged liquid samples. The fluoride ion concentration can be interpreted as an indicator of the degree of degradation of HFO-1336mzz-Z. Table C3 indicates that the degradation of HFO-1336mzz-Z was surprisingly reduced even at the maximum temperature tested (250 ° C). TABLE C3 CONCENTRATION OF FLUORIDE IONS IN THE SAMPLES OF HFO-1336MZZ-Z AFTER AGING AT VARIOUS TEMPERATURES FOR TWO WEEKS
[0133] [133] Table C4 shows changes in composition, quantified by GCMS, of HFO-1336mzz-Z samples after aging in the presence of steel, copper and aluminum, at different temperatures, for two weeks. Only negligible proportions of the unknown innovative compounds appeared as a result of aging even at the maximum temperature tested (250 ° C).
[0134] [134] The HFO-1336mzz trans isomer, HFO-1336mzz-E, is expected to be thermodynamically more stable than the cis isomer, HFO-1336mzz-Z, by about 5 kcal / mol. Surprisingly, despite the substantial thermodynamic driving force for the isomerization of HFO-1336mzz-Z to the most stable trans isomer, the results measured in Table C4 indicate that the HFO-1336mzz-Z remained largely in the Z (or cis) isomer even at the maximum temperature tested (250 ° C). The effect of the small proportion (3,022.7 ppm or 0.30227% by weight) of HFO-1336mzz-E that formed after two weeks of aging at 250 ° C on the thermodynamic properties of the working fluid (HFO-1336mzz-Z ) and therefore on the performance of the cycle, it would be negligible. TABLE C4 CHANGES IN THE COMPOSITION OF SAMPLES OF HFO-1336MZZ-Z (QUANTIFIED BY GCMS) AFTER AGING IN THE PRESENCE OF STEEL, COPPER AND ALUMINUM COUPONS IN SEVERAL TEMPERATURES FOR TWO WEEKS
[0135] [135] Table D compares the performance of a Rankine subcritical cycle operating with HFO-1336mzz-E as the working fluid for Rankine subcritical cycles operating with HFO-1336mzz-Z or HFC-245fa as the fluids of work. The evaporator pressure for all cycles compared in Table D is 2.18 MPa. The energy efficiency of the cycle with the HFO-1336mzz-E is 8.46% lower than the energy efficiency with the HFC-245fa. The volumetric capacity for power generation with HFO-1336mzz-E is 8.6% higher than the volumetric capacity with HFC-245fa.
[0136] [136] The performance of HFC-245f is supported through the performance of HFO-1336mzz-Z and HFO-1336mzz-E. This suggests that the mixtures of HFO-1336mzz-Z and HFO-1336mzz-E could be formulated to replace HFC-245f in existing applications of the Rankine cycle. TABLE D HEALTH, SAFETY, ENVIRONMENT AND ORC PERFORMANCE PROPERTIES OF HFO-1336MZZ-E FOR EVAPORATION PRESSURE EQUAL TO 2.18 MPA COMPARED TO HFO-1336MZZ-ZE HFC-245F
[0137] [137] Table E compares the performance of a Rankine cycle with HFO-1336mzz-E at an evaporating temperature of 120 ° C for HFO-1336mzz-Z and HFC-145fa. The energy efficiency of the cycle with the HFO-1336mzz-E is 3.8% lower than the energy efficiency with the HFC-245fa. The volumetric capacity for power generation with HFO-1336mzz-E is 16.2% higher than with HFC-245fa.
[0138] [138] The performance of the HFC-245fa is supported through the performance of HFO-1336mzz-Z and HFO-1336mzz-E. This suggests that the mixtures of HFO-1336mzz-Z and HFO-1336mzz-E could be formulated to replace HFC-245fa in existing applications of the Rankine cycle. TABLE E SUBCRITICAL PERFORMANCE OF ORC WITH HFO-1336MZZ-E AT AN EVAPORATION TEMPERATURE OF 120 ° C
[0139] [139] Table F summarizes the performance of Rankine cycles, with HFO-1336mzz-E / HFO-1336mzz-Z mixtures of three different compositions. The composition of the HFO-1336mzz-E / HFO-1336mzz-Z mixtures can be varied to achieve different performance targets. TABLE F SUBCRITICAL PERFORMANCE OF ORCS WITH HFO-1336MZZ-E / HFO-1336MZZ-Z MIXTURES OF DIFFERENT COMPOSITIONS
[0140] [140] Table G compares the transcriptic performance of ORCs with HFO-1336mzz-E, HFO-1336mzz-Z, a 50/50% by weight mixture of HFO-1336mzz-E and HFO-1336mzz-Z, and HFC- 245fa. TABLE G TRANSCRITICAL ORC PERFORMANCE WITH THE HFO-1336MZZ-E
[0141] [141] From the data, it was shown that HFO-1336mzz-Z and its mixtures with HFO-1336mzz-E provide efficiencies close to those of HFC-245fa. In addition, the addition of HFO-1336mzz-E to HFO-1336mzz-Z allows the use of such a mixture, which can provide a volumetric capacity for power generation to approximate the volumetric capacity of the HFC-245fa, while providing a fluid environmentally sustainable working environment for the industry.

权利要求:
Claims (12)
[0001]
PROCESS FOR HEAT RECOVERY from a heat source and mechanical energy generation, characterized by understanding the steps of: (a) compression of a first working fluid in the liquid phase above the critical pressure of said first working fluid; (b) passing said first working fluid from step (a) through a heat exchanger or fluid heater and heating said first working fluid to a temperature that is higher than the critical temperature of said first working fluid, wherein said heat exchanger or said fluid heater is in communication with said heat source which supplies said heat; (c) removing at least a portion of said first heated working fluid from said heat exchanger fluid heater; (d) passing said at least a portion of said first heated working fluid to an expander, in which at least a portion of said heat is converted into mechanical energy, and wherein the pressure on said first at least a portion of said first heated working fluid is reduced to below the critical pressure of said first working fluid, thereby rendering said at least a portion of said first heated working fluid in one first vapor of working fluid or a first mixture of vapor and liquid working fluid; (e) passing said first working fluid vapor or said first vapor and liquid working fluid mixture from said expander to a condenser, wherein said at least a portion of said working fluid vapor or said mixture of steam and liquid working fluid is completely condensed to a second working fluid in the liquid phase; (f) optionally, compressing and mixing said second working fluid in the liquid phase with said first working fluid in the liquid phase in step (a); (g) optionally, repeating steps (a) to (f) at least once; wherein the first working fluid consists of HFO-1336mzz-E, or mixtures of HFO-1336mzz-Z and HFO-1336mzz-E, wherein said mixtures consist of 64% by weight to 94% by weight of HFO-1336mzz -AND.
[0002]
PROCESS, according to claim 1, characterized by the efficiency of converting heat into mechanical energy (cycle efficiency) of at least 7%.
[0003]
PROCESS according to claim 1, characterized by the temperature at which the first working fluid is heated in step (b) is in the range of 50 ° C to 400 ° C.
[0004]
PROCESS, according to claim 1, characterized by the pressure at which the first working fluid is pressurized in step (a) is in the range of 3 MPa to 10 MPa.
[0005]
PROCESS, according to claim 1, characterized in that said first working fluid has a GWPs of less than 35.
[0006]
PROCESS, according to claim 1, characterized in that said heat-producing process is at least one operation associated with at least one industry selected from the group consisting of: oil refineries, petrochemical plants, oil and gas pipelines, chemical industry, commercial buildings, hotels, shopping malls, supermarkets, bakeries, food processing industries, restaurants, paint curing ovens, furniture manufacturing, plastic molders, cement kilns, wood ovens, calcination operations, steel industry, industry glass, foundries, melting, air conditioning, refrigeration and central heating.
[0007]
PROCESS, according to claim 1, characterized in that it further comprises a secondary heat exchanger circuit disposed between said heat exchanger in step (a) and said process that produces said heat.
[0008]
PROCESS, according to claim 3, characterized in that said secondary heat exchanger circuit comprises the passage of a secondary fluid in communication with both said heat exchanger and said process that produces said heat, thus transferring said heat from said process to said fluid secondary, which subsequently transfers said heat from said secondary fluid to said first working fluid in the liquid phase.
[0009]
PROCESS according to claim 4, characterized in that said secondary fluid comprises at least one high boiling fluid.
[0010]
PROCESS, according to claim 5, characterized in that said secondary fluid is at least one selected from the group consisting of: glycols, silicones and other non-volatile fluids.
[0011]
ORGANIC RANKINE CYCLE SYSTEM, characterized by extracting heat at an operating pressure, as defined in any one of claims 1 to 10, in the range of 3 MPa to 10 MPa, in which said system contains a working fluid, and in which 50% by weight of said working fluid comprises HFO-1336mzz-Z, HFO-1336mzz-E, or mixtures thereof.
[0012]
METHOD FOR REPLACING HFC-245FA in a power cycle system, as defined in any one of claims 1 to 10, characterized in that it comprises the removal of said HFC-245fa from said power cycle system and the loading of said system with a working fluid consisting of HFO-1336mzz-E, or mixtures of HFO-1336mzz-Z and HFO-1336mzz-E, wherein said mixtures consist of 64% by weight to 94% by weight of HFO-1336mzz-E .

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同族专利:

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公开号 | 公开日

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JP2019082176A|2019-05-30|

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US9593599B2|2017-03-14|

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AU2012299148A1|2014-01-30|

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JP6800942B2|2020-12-16|

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JP6791783B2|2020-11-25|

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KR102054779B1|2019-12-11|

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KR20140054252A|2014-05-08|

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CN107327327A|2017-11-07|

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IN2014DN00158A|2015-05-22|

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CN103906821B|2017-05-24|

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US20140174084A1|2014-06-26|

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HK1198590A1|2015-04-30|

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KR102043047B1|2019-11-11|

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JP2014529033A|2014-10-30|

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KR20190003818A|2019-01-09|

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US20170138223A1|2017-05-18|

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US10590808B2|2020-03-17|

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WO2013028476A3|2014-05-01|

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AU2016216632B2|2017-12-21|

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EP2744981A2|2014-06-25|

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AR087596A1|2014-04-03|

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AU2016216632A1|2016-09-01|

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CN107327327B|2020-04-17|

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WO2013028476A2|2013-02-28|

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AU2012299148B2|2016-06-09|

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JP6158182B2|2017-07-05|

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BR112014003778A2|2017-06-20|

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JP2017172579A|2017-09-28|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-12-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-04-06| 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 16/08/2012, 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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US201161525531P| true| 2011-08-19|2011-08-19|

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US61/525,531|2011-08-19|

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PCT/US2012/051239|WO2013028476A2|2011-08-19|2012-08-16|Processes and compositions for organic rankine cycles for generating mechanical energy from heat|

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