WO2015034987A1 - Heat engine system having a selectively configurable working fluid circuit - Google Patents
Heat engine system having a selectively configurable working fluid circuit Download PDFInfo
- Publication number
- WO2015034987A1 WO2015034987A1 PCT/US2014/053994 US2014053994W WO2015034987A1 WO 2015034987 A1 WO2015034987 A1 WO 2015034987A1 US 2014053994 W US2014053994 W US 2014053994W WO 2015034987 A1 WO2015034987 A1 WO 2015034987A1
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- WIPO (PCT)
- Prior art keywords
- working fluid
- pressure side
- high pressure
- expander
- fluid circuit
- Prior art date
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
- F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
- F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
- F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
- F01K23/10—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle with exhaust fluid of one cycle heating the fluid in another cycle
Definitions
- Waste heat is often created as a byproduct of industrial processes where flowing streams of high-temperature liquids, gases, or fluids must be exhausted into the environment or removed in some way in an effort to maintain the operating temperatures of the industrial process equipment.
- Some industrial processes utilize heat exchanger devices to capture and recycle waste heat back into the process via other process streams.
- the capturing and recycling of waste heat is generally infeasible by industrial processes that utilize high temperatures or have insufficient mass flow or other unfavorable conditions.
- waste heat may be converted into useful energy by a variety of turbine generator or heat engine systems that employ thermodynamic methods, such as Rankine cycles or other power cycles.
- thermodynamic methods such as Rankine cycles or other power cycles.
- Rankine and similar thermodynamic cycles are typically steam-based processes that recover and utilize waste heat to generate steam for driving a turbine, turbo, or other expander connected to an electric generator, a pump, or other device.
- An organic Rankine cycle utilizes a lower boiling-point working fluid, instead of water, during a traditional Rankine cycle.
- exemplary lower boiling-point working fluids include hydrocarbons, such as light hydrocarbons (e.g. , propane or butane) and halogenated hydrocarbons, such as hydrochlorofluorocarbons (HCFCs) or hydrofluorocarbons (HFCs) (e.g., R245fa).
- hydrocarbons such as light hydrocarbons (e.g. , propane or butane)
- halogenated hydrocarbons such as hydrochlorofluorocarbons (HCFCs) or hydrofluorocarbons (HFCs) (e.g., R245fa).
- HCFCs hydrochlorofluorocarbons
- HFCs hydrofluorocarbons
- a heat engine system includes a working fluid circuit having a high pressure side and a low pressure side and being configured to flow a working fluid therethrough.
- Each of a plurality of waste heat exchangers is configured to be fluidly coupled to and in thermal communication with the high pressure side of the working fluid circuit, to be fluidly coupled to and in thermal communication with a heat source stream, and to transfer thermal energy from the heat source stream to the working fluid within the high pressure side.
- Each of a plurality of recuperators is fluidly coupled to the working fluid circuit and configured to transfer thermal energy between the high pressure side and the low pressure side of the working fluid circuit.
- a first expander is fluidly coupled to the working fluid circuit and disposed between the high pressure side and the low pressure side and configured to convert a pressure drop in the working fluid to mechanical energy.
- a second expander is fluidly coupled to the working fluid circuit, disposed between the high pressure side and the low pressure side, and configured to convert a pressure drop in the working fluid to mechanical energy.
- a first pump is fluidly coupled to the working fluid circuit between the low pressure side and the high pressure side of the working fluid circuit and configured to circulate or pressurize the working fluid within the working fluid circuit.
- a first condenser is in thermal communication with the working fluid on the low pressure side of the working fluid circuit and configured to remove thermal energy from the working fluid on the low pressure side of the working fluid circuit.
- a heat engine system includes a pump configured to pressurize and circulate a working fluid through a working fluid circuit having a high pressure side and a low pressure side.
- a first expander is configured to receive the working fluid from the high pressure side and to convert a pressure drop in the working fluid to mechanical energy.
- a plurality of waste heat exchangers are disposed in series along a flow path of a heat source stream and configured to transfer thermal energy from the heat source stream to the working fluid and to be selectively positioned in or isolated from the high pressure side.
- Each of a plurality of recuperators is configured to transfer thermal energy from the working fluid flowing through the low pressure side to the working fluid flowing through the high pressure side and to be selectively positioned in or isolated from the high pressure side and the low pressure side.
- a plurality of valves is configured to be actuated to enable selective control over which of the plurality of waste heat exchangers is positioned in the high pressure side, which of the plurality of recuperators is positioned in the high pressure side, and which of the plurality of recuperators is positioned in the low pressure side
- a heat engine system in another embodiment, includes a working fluid circuit having a high pressure side and a low pressure side and being configured to flow a working fluid therethrough.
- a first expander is configured to receive the working fluid from the high pressure side and to convert a pressure drop in the working fluid to mechanical energy.
- a second expander is configured to receive the working fluid from the high pressure side and to convert the pressure drop in the working fluid to mechanical energy.
- a plurality of waste heat exchangers is disposed in series along a flow path of a heat source stream and configured to transfer thermal energy from the heat source stream to the working fluid and to be selectively positioned in or isolated from the high pressure side.
- Each of a plurality of recuperators is configured to transfer thermal energy from the working fluid flowing through the low pressure side to the working fluid flowing through the high pressure side and to be selectively positioned in or isolated from the high pressure side and the low pressure side.
- Each of a plurality of valves is configured to be actuated to enable selective control over which of the plurality of waste heat exchangers is positioned in the high pressure side, which of the plurality of recuperators is positioned in the high pressure side, which of the plurality of recuperators is positioned in the low pressure side, and which of the first expander and the second expander is to receive the working fluid from the high pressure side.
- Figure 1 illustrates a heat engine system having a selectively configurable working fluid circuit, according to one or more embodiments disclosed herein.
- Figure 2 illustrates another heat engine system having a selectively configurable working fluid circuit, according to one or more embodiments disclosed herein.
- Figure 3 illustrates a heat engine system having a process heating system, according to one or more embodiments disclosed herein.
- Figure 4A is a pressure versus enthalpy chart for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4B is a pressure versus temperature chart for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4C is a mass flowrate bar chart for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4D is a temperature trace chart for a recuperator for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4E is a temperature trace chart for a recuperator for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4F is a temperature trace chart for a recuperator for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4G is a temperature trace chart for a waste heat exchanger for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4H is a temperature trace chart for a waste heat exchanger for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4I is a temperature trace chart for a waste heat exchanger for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 4J is a temperature trace chart for a waste heat exchanger for a thermodynamic cycle produced by an embodiment of a heat engine system.
- Figure 5 is an enlarged view of a portion of the pressure versus enthalpy chart shown in Figure 4A.
- Presently disclosed embodiments generally provide heat engine systems and methods for transforming energy, such as generating mechanical energy and/or electrical energy from thermal energy. More particularly, the disclosed embodiments provide heat engine systems that are enabled for selective configuring of a working fluid circuit in one of several different configurations, depending on implementation-specific considerations. For example, in certain embodiments, the configuration of the working fluid circuit may be determined based on the heat source providing the thermal energy to the working fluid circuit. More particularly, in one embodiment, the heat engine system may include a plurality of valves that enable the working fluid to be selectively routed through one or more waste heat exchangers and one or more recuperators to tune the heat engine system to the available heat source, thus increasing the efficiency of the heat engine system in the conversion of the thermal energy into a useful power output.
- the heat engine systems including the selectively configurable working fluid circuits, as described herein, are configured to efficiently convert thermal energy of a heated stream (e.g., a waste heat stream) into useful mechanical energy and/or electrical energy.
- the heat engine systems may utilize the working fluid (e.g., carbon dioxide (CO2)) in a supercritical state (e.g., SC-CO2) and/or a subcritical state (e.g., sub-CCh) within the working fluid circuit for capturing or otherwise absorbing thermal energy of the waste heat stream with one or more waste heat exchangers.
- the thermal energy may be transformed to mechanical energy by a power turbine and subsequently transformed to electrical energy by a power generator coupled to the power turbine.
- the heat engine systems may include several integrated sub-systems managed by a process control system for maximizing the efficiency of the heat engine system while generating mechanical energy and/or electrical energy.
- Figure 1 illustrates an embodiment of a heat engine system 1 00 having a working fluid circuit 102 that may be selectively configured by a control system 101 such that a flow path of a working fluid is established through any desired combination of a plurality of waste heat exchangers 1 20a, 120b, and 120c, a plurality of recuperators 1 30a, and 1 30b, turbines or expanders 160a and 1 60b, a pump 1 50a, and a condenser 1 40a.
- a plurality of bypass valves 1 1 6a, 1 1 6b, and 1 16c are provided that each may be selectively positioned in an opened position or a closed position to enable the routing of the working fluid through the desired components.
- the working fluid circuit 102 generally has a high pressure side and a low pressure side and is configured to flow the working fluid through the high pressure side and the low pressure side.
- the high pressure side extends along the flow path of the working fluid from the pump 1 50a to the expander 1 60a and/or the expander 160b, depending on which of the expanders 1 60a and 1 60b are included in the working fluid circuit 102
- the low pressure side extends along the flow path of the working fluid from the expander 1 60a and/or the expander 1 60b to the pump 1 50a.
- working fluid may be transferred from the low pressure side to the high pressure side via a pump bypass valve 1 41 .
- the working fluid circuit 1 02 may be configured such that the available components (e.g., the waste heat exchangers 120a, 120b, and 1 20c and the recuperators 130a and 130b) are each selectively positioned in (e.g. , fluidly coupled to) or isolated from (e.g., not fluidly coupled to) the high pressure side and the low pressure side of the working fluid circuit.
- the control system 1 01 may utilize the processor 103 to determine which of the waste heat exchangers 1 20a, 1 20b, and 1 20c and which of the recuperators 130a and 130b to position on (e.g. , incorporate in) the high pressure side of the working fluid circuit 1 02. Such a determination may be made by the processor 103, for example, by referencing memory 105 to determine how to tune the heat engine system 1 00 to operate most efficiently with a given heat source.
- a turbopump may be formed by a driveshaft 162 coupling the second expander 1 60b and the pump 150a, such that the second expander 1 60b may drive the pump 1 50a with the mechanical energy generated by the second expander 1 60b.
- the working fluid flow path from the pump 150a to the second expander 1 60b may be established by selectively fluidly coupling the recuperator 130b and the waste heat exchanger 1 20b to the high pressure side by positioning valves the bypass 1 16a and 1 16b in an opened position.
- the working fluid flow path in this embodiment extends from the pump 1 50a, through the recuperator 130b, through the bypass valve 1 16b, through the waste heat exchanger 1 20b, through the bypass valve 1 1 6a, and to the second expander 1 60b.
- the working fluid flow path through the low pressure side in this embodiment extends from the second expander 1 60b through turbine discharge line 1 70b, through the recuperator 1 30b, through the condenser 1 40a, and to the pump 1 50a.
- the working fluid flow path may be established from the pump 150a to the first expander 1 60a by fluidly coupling the waste heat exchanger 120c, the recuperator 1 30a, and the waste heat exchanger 1 20a to the high pressure side.
- the working fluid flow path through the high pressure side extends from the pump 150a, through the waste heat exchanger 120c, through the bypass valve 1 1 6b, through the recuperator 1 30a, through the bypass valve 1 16a, through the waste heat exchanger 120a, through the stop or throttle valve 1 58a, and to the first expander 160a.
- the working fluid flow path through the low pressure side in this embodiment extends from the first expander 160a, through turbine discharge line 1 70a, through the recuperator 1 30a, through the recuperator 130b, through the condenser 140a, and to the pump 150a.
- the tunability of the working fluid circuit 102 may be further increased by providing an additional waste heat exchanger 130c, an additional bypass valve 1 1 6d, a plurality of condensers 140a, 140b, and 140c, and a plurality of pumps 150a, 150b, and 150c.
- each of the first and second expanders 160a, 160b may be fluidly coupled to or isolated from the working fluid circuit 102 via the stop or throttle valves 158a and 158b, disposed between the high pressure side and the low pressure side, and configured to convert a pressure drop in the working fluid to mechanical energy.
- presently contemplated embodiments may include any number of waste heat exchangers, any number of recuperators, any number of valves, any number of pumps, any number of condensers, and any number of expanders, not limited to those shown in Figures 1 -3. Indeed, the quantity of such components in the illustrated embodiments is merely an example, and any suitable quantity of these components may be provided in other embodiments.
- the plurality of waste heat exchangers 120a-120d may contain four or more waste heat exchangers, such as the first waste heat exchanger 1 20a, the second waste heat exchanger 120b, the third waste heat exchanger 120c, and a fourth waste heat exchanger 120d.
- Each of the waste heat exchangers 120a- 1 20d may be selectively fluidly coupled to and placed in thermal communication with the high pressure side of the working fluid circuit 102, as determined by the control system 1 01 , to tune the working fluid circuit 1 02 to the needs of a given application.
- Each of the waste heat exchangers 120a-1 20d may be configured to be fluidly coupled to and in thermal communication with a heat source stream 1 10 and configured to transfer thermal energy from the heat source stream 1 1 0 to the working fluid within the high pressure side.
- the waste heat exchangers 1 20a-120d may be disposed in series along the direction of flow of the heat source stream 1 1 0.
- the second waste heat exchanger 1 20b may be disposed upstream of the first waste heat exchanger 1 20a
- the third waste heat exchanger 1 20c may be disposed upstream of the second waste heat exchanger 120b
- the fourth waste heat exchanger 120d may be disposed upstream of the third waste heat exchanger 1 20c.
- the plurality of recuperators 130a-130c may include three or more recuperators, such as the first recuperator 130a, the second recuperator 1 30b, and a third recuperator 130c.
- Each of the recuperators 130a-130c may be selectively fluidly coupled to the working fluid circuit 1 02 and configured to transfer thermal energy between the high pressure side and the low pressure side of the working fluid circuit 1 02 when fluidly coupled to the working fluid circuit 102.
- the recuperators 1 30a-130c may be disposed in series on the high pressure side of the working fluid circuit 1 02 upstream of the second expander 1 60b.
- the second recuperator 1 30b may be disposed upstream of the first recuperator 1 30a
- the third recuperator 1 30c may be disposed upstream of the second recuperator 130b on the high pressure side.
- the first recuperator 1 30a, the second recuperator 1 30b, and the third recuperator 1 30c may be disposed in series on the low pressure side of the working fluid circuit 1 02, such that the second recuperator 130b may be disposed downstream of the first recuperator 1 30a, and the third recuperator 130c may be disposed downstream of the second recuperator 130b on the low pressure side.
- the first recuperator 1 30a may be disposed downstream of the first expander 1 60a on the low pressure side
- the second recuperator 130b may be disposed downstream of the second expander 160b on the low pressure side.
- the heat source stream 1 1 0 may be a waste heat stream such as, but not limited to, a gas turbine exhaust stream, an industrial process exhaust stream, or other types of combustion product exhaust streams, such as furnace or boiler exhaust streams, coming from or derived from a heat source 1 08.
- the heat source 1 08 may be a gas turbine, such as a gas turbine power/electricity generator or a gas turbine jet engine, and the heat source stream 1 10 may be the exhaust stream from the gas turbine.
- the heat source stream 1 1 0 may be at a temperature within a range from about 100°C to about 1 ,000°C, or greater than 1 ,000°C, and in some examples, within a range from about 200°C to about 800°C, more narrowly within a range from about 300°C to about 600°C.
- the heat source stream 1 10 may contain air, carbon dioxide, carbon monoxide, water or steam, nitrogen, oxygen, argon, derivatives thereof, or mixtures thereof.
- the heat source stream 1 1 0 may derive thermal energy from renewable sources of thermal energy, such as solar or geothermal sources.
- the heat engine system 100 also includes at least one condenser 140a and at least one pump 150a, but in some embodiments includes a plurality of condensers 1 40a-140c and a plurality of pumps 1 50a-150c.
- a first condenser 140a may be in thermal communication with the working fluid on the low pressure side of the working fluid circuit 102 and configured to remove thermal energy from the working fluid on the low pressure side.
- a first pump 150a may be fluidly coupled to the working fluid circuit 1 02 between the low pressure side and the high pressure side of the working fluid circuit 1 02 and configured to circulate or pressurize the working fluid within the working fluid circuit 102.
- the first pump 1 50a may be configured to control mass flowrate, pressure, or temperature of the working fluid within the working fluid circuit 102.
- the second condenser 140b and the third condenser 140c may each independently be fluidly coupled to and in thermal communication with the working fluid on the low pressure side of the working fluid circuit 102 and configured to remove thermal energy from the working fluid on the low pressure side of the working fluid circuit 1 02.
- a second pump 150b and a third pump 150c may each independently be fluidly coupled to the low pressure side of the working fluid circuit 102 and configured to circulate or pressurize the working fluid within the working fluid circuit 1 02.
- the second pump 150b may be disposed upstream of the first pump 150a and downstream of the third pump 150c along the flow direction of working fluid through the working fluid circuit 102.
- the first pump 150a is a circulation pump
- the second pump 150b is replaced with a compressor
- the third pump 150c is replaced with a compressor.
- the third pump 150c is replaced with a first stage compressor
- the second pump 150b is replaced with a second stage compressor
- the first pump 1 50a is a third stage pump.
- the second condenser 140b may be disposed upstream of the first condenser 140a and downstream of the third condenser 1 40c along the flow direction of working fluid through the working fluid circuit 102.
- the heat engine system 1 00 includes three stages of pumps and condensers, such as first, second, and third pump/condenser stages.
- the first pump/condenser stage may include the third condenser 140c fluidly coupled to the working fluid circuit 1 02 upstream of the third pump 150c
- the second pump/condenser stage may include the second condenser 140b fluidly coupled to the working fluid circuit 102 upstream of the second pump 1 50b
- the third pump/condenser stage may include the first condenser 1 40a fluidly coupled to the working fluid circuit 1 02 upstream of the first pump 150a.
- the heat engine system 1 00 may include a variable frequency drive coupled to the first pump 150a, the second pump 150b, and/or the third pump 1 50c.
- the variable frequency drive may be configured to control mass flowrate, pressure, or temperature of the working fluid within the working fluid circuit 102.
- the heat engine system 1 00 may include a drive turbine coupled to the first pump 150a, the second pump 150b, or the third pump 150c.
- the drive turbine may be configured to control mass flowrate, pressure, or temperature of the working fluid within the working fluid circuit 1 02.
- the drive turbine may be the first expander 1 60a, the second expander 160b, another expander or turbine, or combinations thereof.
- the driveshaft 1 62 may be coupled to the first expander 1 60a and the second expander 1 60b such that the driveshaft 162 may be configured to drive a device with the mechanical energy produced or otherwise generated by the combination of the first expander 160a and the second expander 1 60b.
- the device may be the pumps 1 50a-1 50c, a compressor, a generator 1 64, an alternator, or combinations thereof.
- the heat engine system 1 00 may include the generator 164 or an alternator coupled to the first expander 1 60a by the driveshaft 1 62.
- the generator 1 64 or the alternator may be configured to convert the mechanical energy produced by the first expander 1 60a into electrical energy.
- the driveshaft 1 62 may be coupled to the second expander 1 60b and the first pump 150a, such that the second expander 1 60b may be configured to drive the first pump 150a with the mechanical energy produced by the second expander 160b.
- the heat engine system 1 00 may include a process heating system 230 fluidly coupled to and in thermal communication with the low pressure side of the working fluid circuit 102.
- the process heating system 230 may include a process heat exchanger 236 and a control valve 234 operatively disposed on a fluid line 232 coupled to the low pressure side and under control of the control system 101 .
- the process heat exchanger 236 may be configured to transfer thermal energy from the working fluid on the low pressure side of the working fluid circuit 1 02 to a heat-transfer fluid flowing through the process heat exchanger 236.
- the process heat exchanger 236 may be configured to transfer thermal energy from the working fluid on the low pressure side of the working fluid circuit 102 to methane during a preheating step to form a heated methane fluid.
- the thermal energy may be directly transferred or indirectly transferred (e.g. , via a heat-transfer fluid) to the methane fluid.
- the heat source stream 1 10 may be derived from the heat source 108 configured to combust the heated methane fluid, such as a gas turbine electricity generator.
- the heat engine system 1 00 may include a recuperator bus system 220 fluidly coupled to and in thermal communication with the low pressure side of the working fluid circuit 1 02.
- the recuperator bus system 220 may include turbine discharge lines 170a, 170b, control valves 1 68a, 168b, bypass line 210 and bypass valve 21 2, fluid lines 222, 224, and other lines and valves fluidly coupled to the working fluid circuit 102 downstream of the first expander 1 60a and/or the second expander 1 60b and upstream of the condenser 140a.
- the recuperator bus system 220 extends from the first expander 1 60a and/or the second expander 1 60b to the plurality of recuperators 130a-130c, and further downstream on the low pressure side.
- one end of a fluid line 222 may be fluidly coupled to the turbine discharge line 1 70b, and the other end of the fluid line 222 may be fluidly coupled to a point on the working fluid circuit 1 02 disposed downstream of the recuperator 1 30c and upstream of the condenser 140c.
- one end of a fluid line 224 may be fluidly coupled to the turbine discharge line 170b, the fluid line 222, or the process heating line 232, and the other end of the fluid line 224 may be fluidly coupled to a point on the working fluid circuit 102 disposed downstream of the recuperator 130b and upstream of the recuperator 1 30c on the low pressure side.
- the types of working fluid that may be circulated, flowed, or otherwise utilized in the working fluid circuit 1 02 of the heat engine system 100 include carbon oxides, hydrocarbons, alcohols, ketones, halogenated hydrocarbons, ammonia, amines, aqueous, or combinations thereof.
- Exemplary working fluids that may be utilized in the heat engine system 1 00 include carbon dioxide, ammonia, methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, methanol, ethanol, acetone, methyl ethyl ketone, water, derivatives thereof, or mixtures thereof.
- Halogenated hydrocarbons may include hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) (e.g., 1 ,1 ,1 ,3,3-pentafluoropropane (R245fa)), fluorocarbons, derivatives thereof, or mixtures thereof.
- HCFCs hydrochlorofluorocarbons
- HFCs hydrofluorocarbons
- R245fa 1-pentafluoropropane
- the working fluid circulated, flowed, or otherwise utilized in the working fluid circuit 102 of the heat engine system 100, and the other exemplary circuits disclosed herein may be or may contain carbon dioxide (CO2) and mixtures containing carbon dioxide.
- CO2 carbon dioxide
- the working fluid circuit 102 contains the working fluid in a supercritical state (e.g., SC-CO2).
- Carbon dioxide utilized as the working fluid or contained in the working fluid for power generation cycles has many advantages over other compounds typically used as working fluids, since carbon dioxide has the properties of being non-toxic and nonflammable and is also easily available and relatively inexpensive. Due in part to a relatively high working pressure of carbon dioxide, a carbon dioxide system may be much more compact than systems using other working fluids.
- carbon dioxide CO2
- SC-CO2 supercritical carbon dioxide
- SUV-CO2 subcritical carbon dioxide
- the working fluid in the working fluid circuit 1 02 may be a binary, ternary, or other working fluid blend.
- the working fluid blend or combination can be selected for the unique attributes possessed by the fluid combination within a heat recovery system, as described herein.
- one such fluid combination includes a liquid absorbent and carbon dioxide mixture enabling the combined fluid to be pumped in a liquid state to high pressure with less energy input than required to compress carbon dioxide.
- the working fluid may be a combination of carbon dioxide (e.g., sub-C02 or SC-CO2) and one or more other miscible fluids or chemical compounds.
- the working fluid may be a combination of carbon dioxide and propane, or carbon dioxide and ammonia, without departing from the scope of the disclosure.
- the working fluid circuit 102 generally has a high pressure side and a low pressure side and contains a working fluid circulated within the working fluid circuit 1 02.
- the use of the term "working fluid" is not intended to limit the state or phase of matter of the working fluid.
- the working fluid or portions of the working fluid may be in a liquid phase, a gas phase, a fluid phase, a subcritical state, a supercritical state, or any other phase or state at any one or more points within the heat engine system 100 or thermodynamic cycle.
- the working fluid is in a supercritical state over certain portions of the working fluid circuit 1 02 of the heat engine system 100 (e.g.
- thermodynamic cycle may be operated such that the working fluid is maintained in a supercritical state throughout the entire working fluid circuit 1 02 of the heat engine system 100.
- the high pressure side of the working fluid circuit 1 02 may be disposed downstream of any of the pumps 1 50a, 150b, or 1 50c and upstream of any of the expanders 1 60a or 1 60b
- the low pressure side of the working fluid circuit 1 02 may be disposed downstream of any of the expanders 160a or 1 60b and upstream of any of the pumps 1 50a, 150b, or 150c, depending on implementation-specific considerations, such as the type of heat source available, process conditions, including temperature, pressure, flowrate, and whether or not each individual pump 150a, 150b, or 1 50c is a pump or a compressor, and so forth.
- the pumps 1 50b and 1 50c are replaced with compressors and the pump 1 50a is a pump
- the high pressure side of the working fluid circuit 1 02 may start downstream of the pump 1 50a, such as at the discharge outlet of the pump 1 50a, and end at any of the expanders 160a or 160b
- the low pressure side of the working fluid circuit 1 02 may start downstream of any of the expanders 1 60a or 1 60b and end upstream of the pump 1 50a, such as at the inlet of the pump 1 50a.
- the high pressure side of the working fluid circuit 1 02 contains the working fluid (e.g., SC-CO2) at a pressure of about 15 MPa or greater, such as about 1 7 MPa or greater or about 20 MPa or greater, or about 25 MPa or greater, or about 27 MPa or greater.
- the high pressure side of the working fluid circuit 1 02 may have a pressure within a range from about 1 5 MPa to about 40 MPa, more narrowly within a range from about 20 MPa to about 35 MPa, and more narrowly within a range from about 25 MPa to about 30 MPa, such as about 27 MPa.
- the low pressure side of the working fluid circuit 102 includes the working fluid (e.g., CO2 or sub-CCb) at a pressure of less than 15 MPa, such as about 12 MPa or less, or about 10 MPa or less.
- the low pressure side of the working fluid circuit 1 02 may have a pressure within a range from about 1 MPa to about 10 MPa, more narrowly within a range from about 2 MPa to about 8 MPa, and more narrowly within a range from about 4 MPa to about 6 MPa, such as about 5 MPa.
- the heat engine system 1 00 further includes the expander 1 60a, the expander 1 60b, and the driveshaft 1 62.
- Each of the expanders 1 60a, 160b may be fluidly coupled to the working fluid circuit 1 02 and disposed between the high and low pressure sides and configured to convert a pressure drop in the working fluid to mechanical energy.
- the driveshaft 162 may be coupled to the expander 160a, the expander 160b, or both of the expanders 160a, 160b.
- the driveshaft 162 may be configured to drive one or more devices, such as a generator or alternator (e.g. , the generator 164), a motor, a generator/motor unit, a pump or compressor (e.g., the pumps 1 50a-1 50c), and/or other devices, with the generated mechanical energy.
- the generator 1 64 may be a generator, an alternator (e.g., permanent magnet alternator), or another device for generating electrical energy, such as by transforming mechanical energy from the driveshaft 1 62 and one or more of the expanders 1 60a, 1 60b to electrical energy.
- a power outlet (not shown) may be electrically coupled to the generator 164 and configured to transfer the generated electrical energy from the generator 1 64 to an electrical grid 1 66.
- the electrical grid 1 66 may be or include an electrical grid, an electrical bus (e.g. , plant bus), power electronics, other electric circuits, or combinations thereof.
- the electrical grid 166 generally contains at least one alternating current bus, alternating current grid, alternating current circuit, or combinations thereof.
- the generator 164 is a generator and is electrically and operably connected to the electrical grid 166 via the power outlet.
- the generator 1 64 is an alternator and is electrically and operably connected to power electronics (not shown) via the power outlet.
- the generator 1 64 is electrically connected to power electronics that are electrically connected to the power outlet.
- the heat engine system 1 00 further includes at least one pump/compressor and at least one condenser/cooler, but certain embodiments generally include a plurality of condensers 1 40a-1 40c (e.g., condenser or cooler) and pumps 150a-150c (e.g., pump or compressor).
- Each of the condensers 140a-1 40c may independently be a condenser or a cooler and may independently be gas-cooled (e.g., air, nitrogen, or carbon dioxide) or liquid-cooled (e.g., water, solvent, or a mixture thereof).
- Each of the pumps 150a-150c may independently be a pump or may be replaced with a compressor and may independently be fluidly coupled to the working fluid circuit 1 02 between the low pressure side and the high pressure side of the working fluid circuit 102. Also, each of the pumps 150a-150c may be configured to circulate and/or pressurize the working fluid within the working fluid circuit 102.
- the condensers 1 40a-140c may be in thermal communication with the working fluid in the working fluid circuit 102 and configured to remove thermal energy from the working fluid on the low pressure side of the working fluid circuit 102.
- the working fluid may flow through the waste heat exchangers 120a-1 20d and/or the recuperators 130a-1 30c before entering the expander 160a and/or the expander 1 60b.
- a series of valves and lines e.g., conduits or pipes
- the bypass valves 1 16a-1 1 6d, the stop or control valves 1 1 8a- 1 18d, the stop or control valves 1 28a-1 28c, and the stop or throttle valves 158a, 158b may be utilized in varying opened positions and closed positions to control the flow of the working fluid through the waste heat exchangers 120a-1 20d and/or the recuperators 1 30a-1 30c.
- valves may provide control and adjustability to the temperature of the working fluid entering the expander 1 60a and/or the expander 1 60b.
- the valves may be controllable, fixed (orifice), diverter valve, 3-way valve, or even eliminated in some embodiments.
- each of the additional components e.g., additional waste heat exchangers and recuperators may be used or eliminated in certain embodiments).
- recuperator 1 30b may not be utilized in certain applications.
- the common shaft or driveshaft 162 may be employed or, in other embodiments, two or more shafts may be used together or independently with the pumps 1 50a-1 50c, the expanders 160a, 1 60b, the generator 164, and/or other components.
- the expander 1 60b and the pump 150a share a common shaft
- the expander 160a and the generator 1 64 share another common shaft.
- the expanders 160a, 1 60b, the pump 150a, and the generator 1 64 share a common shaft, such as driveshaft 1 62.
- the other pumps may be integrated with the shaft as well.
- the process heating system 230 may be a loop to provide thermal energy to heat source fuel, for example, a gas turbine with preheat fuel (e.g. , methane), process steam, or other fluids.
- Figures 4A-4J and 5 illustrate pressure versus enthalpy charts, temperature trace charts, and recuperator temperature trace charts for thermodynamic cycles produced by the heat engine system 100 depicted in Figures 1 -3, according to one or more embodiments disclosed herein. More specifically, Figure 4A is a pressure versus enthalpy chart 300 for a thermodynamic cycle produced by the heat engine system 1 00, Figure 4B is a pressure versus temperature chart 302 for the thermodynamic cycle, and Figure 4C is a mass flowrate bar chart 304 for the thermodynamic cycle.
- Figure 4D, Figure 4E, and Figure 4F are temperature trace charts 306, 308, and 310 for the recuperator 130a, the recuperator 1 30b, and the recuperator 1 30c, respectively, for the thermodynamic cycle produced by the heat engine system 1 00.
- Figure 4G, Figure 4H, Figure 4I, and Figure 4J are temperature trace charts 312, 31 4, 31 6, and 318 for the waste heat exchanger 120a, the waste heat exchanger 1 20b, the waste heat exchanger 1 20c, and the waste heat exchanger 120d, respectively, for the thermodynamic cycle.
- FIG 5 is an enlarged view of a portion 320 of the pressure versus enthalpy chart 300 shown in Figure 4A.
- the pressure versus enthalpy chart illustrates labeled state points for the thermodynamic cycle of the heat engine system 1 00.
- the described thermodynamic power cycles may include greater use of recuperation as ambient temperature increases, minimizing the use of costly waste heat exchangers and increasing the net system output power for some ambient conditions.
- first and second features are formed in direct contact
- additional features may be formed interposing the first and second features, such that the first and second features may not be in direct contact.
- exemplary embodiments described herein may be combined in any combination of ways, i.e., any element from one exemplary embodiment may be used in any other exemplary embodiment without departing from the scope of the disclosure.
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Abstract
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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AU2014315252A AU2014315252B2 (en) | 2013-09-05 | 2014-09-04 | Heat engine system having a selectively configurable working fluid circuit |
BR112016004873-3A BR112016004873B1 (en) | 2013-09-05 | 2014-09-04 | THERMAL ENGINE SYSTEM HAVING A SELECTIVELY CONFIGURABLE OPERATING FLUID CIRCUIT |
EP14841858.5A EP3042048B1 (en) | 2013-09-05 | 2014-09-04 | Heat engine system having a selectively configurable working fluid circuit |
KR1020167008749A KR102304249B1 (en) | 2013-09-05 | 2014-09-04 | Heat engine system having a selectively configurable working fluid circuit |
JP2016540367A JP2016534281A (en) | 2013-09-05 | 2014-09-04 | Heat engine system with selectively changeable working fluid circuit |
MX2016002907A MX2016002907A (en) | 2013-09-05 | 2014-09-04 | Heat engine system having a selectively configurable working fluid circuit. |
CN201480057131.1A CN105765178B (en) | 2013-09-05 | 2014-09-04 | Heat engine system with selectively configurable operating fluid loop |
CA2923403A CA2923403C (en) | 2013-09-05 | 2014-09-04 | Heat engine system having a selectively configurable working fluid circuit |
Applications Claiming Priority (10)
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US201361874321P | 2013-09-05 | 2013-09-05 | |
US61/874,321 | 2013-09-05 | ||
US201462010731P | 2014-06-11 | 2014-06-11 | |
US201462010706P | 2014-06-11 | 2014-06-11 | |
US62/010,706 | 2014-06-11 | ||
US62/010,731 | 2014-06-11 | ||
US14/475,678 US9926811B2 (en) | 2013-09-05 | 2014-09-03 | Control methods for heat engine systems having a selectively configurable working fluid circuit |
US14/475,640 | 2014-09-03 | ||
US14/475,640 US9874112B2 (en) | 2013-09-05 | 2014-09-03 | Heat engine system having a selectively configurable working fluid circuit |
US14/475,678 | 2014-09-03 |
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PCT/US2014/053994 WO2015034987A1 (en) | 2013-09-05 | 2014-09-04 | Heat engine system having a selectively configurable working fluid circuit |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITUB20160955A1 (en) * | 2016-02-22 | 2017-08-22 | Nuovo Pignone Tecnologie Srl | CYCLE IN CASCAME OF RECOVERY OF CASCAME THERMAL AND METHOD |
KR101797435B1 (en) | 2017-05-08 | 2017-11-13 | 두산중공업 주식회사 | Supercritical CO2 generation system applying recuperator per each heat source |
US11480074B1 (en) | 2021-04-02 | 2022-10-25 | Ice Thermal Harvesting, Llc | Systems and methods utilizing gas temperature as a power source |
US11486370B2 (en) | 2021-04-02 | 2022-11-01 | Ice Thermal Harvesting, Llc | Modular mobile heat generation unit for generation of geothermal power in organic Rankine cycle operations |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080282702A1 (en) * | 2007-05-15 | 2008-11-20 | Ingersoll-Rand Company | Integrated absorption refrigeration and dehumidification system |
US20100287934A1 (en) * | 2006-08-25 | 2010-11-18 | Patrick Joseph Glynn | Heat Engine System |
US20100319346A1 (en) * | 2009-06-23 | 2010-12-23 | General Electric Company | System for recovering waste heat |
US20120047892A1 (en) * | 2009-09-17 | 2012-03-01 | Echogen Power Systems, Llc | Heat Engine and Heat to Electricity Systems and Methods with Working Fluid Mass Management Control |
US20120319410A1 (en) * | 2011-06-17 | 2012-12-20 | Woodward Governor Company | System and method for thermal energy storage and power generation |
US20130036736A1 (en) | 2009-09-17 | 2013-02-14 | Echogen Power System, LLC | Automated mass management control |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002090747A2 (en) * | 2001-05-07 | 2002-11-14 | Battelle Memorial Institute | Heat energy utilization system |
GB0111301D0 (en) * | 2001-05-09 | 2001-06-27 | Bowman Power Systems Ltd | Power generation apparatus |
US8752381B2 (en) * | 2010-04-22 | 2014-06-17 | Ormat Technologies Inc. | Organic motive fluid based waste heat recovery system |
-
2014
- 2014-09-04 WO PCT/US2014/053995 patent/WO2015034988A1/en active Application Filing
- 2014-09-04 WO PCT/US2014/053994 patent/WO2015034987A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100287934A1 (en) * | 2006-08-25 | 2010-11-18 | Patrick Joseph Glynn | Heat Engine System |
US20080282702A1 (en) * | 2007-05-15 | 2008-11-20 | Ingersoll-Rand Company | Integrated absorption refrigeration and dehumidification system |
US20100319346A1 (en) * | 2009-06-23 | 2010-12-23 | General Electric Company | System for recovering waste heat |
US20120047892A1 (en) * | 2009-09-17 | 2012-03-01 | Echogen Power Systems, Llc | Heat Engine and Heat to Electricity Systems and Methods with Working Fluid Mass Management Control |
US20130036736A1 (en) | 2009-09-17 | 2013-02-14 | Echogen Power System, LLC | Automated mass management control |
US20120319410A1 (en) * | 2011-06-17 | 2012-12-20 | Woodward Governor Company | System and method for thermal energy storage and power generation |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITUB20160955A1 (en) * | 2016-02-22 | 2017-08-22 | Nuovo Pignone Tecnologie Srl | CYCLE IN CASCAME OF RECOVERY OF CASCAME THERMAL AND METHOD |
WO2017144422A1 (en) * | 2016-02-22 | 2017-08-31 | Nuovo Pignone Tecnologie Srl | Waste heat recovery cascade cycle and method |
US11143102B2 (en) | 2016-02-22 | 2021-10-12 | Nuovo Pignone Tecnologie Srl | Waste heat recovery cascade cycle and method |
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US11624355B2 (en) | 2021-04-02 | 2023-04-11 | Ice Thermal Harvesting, Llc | Modular mobile heat generation unit for generation of geothermal power in organic Rankine cycle operations |
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