Patent Application
20150020993
This invention generally relates to mechanical-chemical energy storage. In particular, the invention relates to a mechanical-chemical energy storage system that stores energy by simultaneously compressing a gas to a higher enthalpy state and recovering the heat of compression by driving a somewhat reversible chemical reaction. The heat energy in the chemical reaction is then recovered while the gas is expanding to a lower enthalpy state.
Energy storage is vitally important for the stability of the electric grid as it relies more on “non-dispatchable” sources of power such as solar and wind. Additionally, there are many applications where long term power may be needed apart from any grid such as in military or emergency situations. Currently, the most common solutions are lead-acid batteries and diesel generators. The shortcomings of these systems are well known. Most electrochemical batteries show a significant degradation in performance as they are discharged. This is evidenced by reduced voltage output and reduced maximum currents observed during the discharge of the battery. Batteries also tend to be less efficient and have reduced service lives when run at greater depths of discharge.
There is increased interest in using stored mechanical energy to ultimately serve as electrical energy storage for grid type applications. This interest is based in part on the robust nature and highly developed state of the art of mechanical power generation equipment, which is economical and scalable. In general, most energy storage schemes compress a working fluid to high pressures or liquefy the working fluid by compression and/or temperature reduction. Alternately, a series of heat pumps (often coupled to generators and/or other heat sources) indirectly accomplish this same goal where working fluid(s) is/are cycled with the combination of heat pumps. This alternative has higher cost associated with extra machinery. In general, to get higher recoveries (efficiencies that we will refer to as “round trip efficiency” or “RTE”) requires more “stages” to recover energy, and each additional stage is met with reduced energy recovery. Thus, these systems require increased capital to achieve high RTE after more than two stages.
Other conventional energy storage systems store energy by compressing a gas to high pressure. Depending on the physical properties (critical temperature) of the gas, it may liquefy. During this compression process, heat is generated and much of this heat is generally lost, which results in reduced RTEs. This is a common problem in compressed air energy storage (CAES). The RTE of conventional systems is around 50%. RTEs of these systems are limited due to the use of assisting gas turbines during operation to increase the overall efficiency of that device. Assisting gas turbines are not a true energy storage systems, but act as a hybrid, wherein stored energy is only recovered if it is also desired to burn natural gas to run the gas turbine to create energy.
Traditional efforts to recover this heat from compression involve storing the heat of compression in a medium (such as water), as sensible heat, which simply raises the temperature of the water. This warm water is stored in an insulated tank until the energy is required to heat the working fluid while expanding it to recover that energy. However, warm water has reduced energy dense medium. Furthermore, the low temperature gradients present engineering challenges to achieve high power output that requires high rates of heat transfer over a low temperature gradient. Problems also exist due to heat from the stored water escaping from the insulated tank giving the system an apparent “self-discharge”, analogous to electrochemical batteries.
The present invention solves one or more of the problems described above by combining the high energy density of a liquefied gas, the high RTE of operating near ambient temperatures, and the ability to achieve high power densities by generating the heat required for expansion when it is needed rather than storing heat for use at some other time.
In one aspect, the present invention provides a method for storing energy comprising: providing an absorbent reservoir containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; and condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; wherein at least some of the heat generated during the condensing step is recycled to drive the desorbing step.
Another aspect of the present invention provides a method for storing energy comprising providing an absorbent reservoir containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; and condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; wherein at least some of the heat generated during the condensing step is recycled to drive the desorbing step.
In some implementations, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water. For example, the working fluid comprises carbon dioxide or ammonia. In some instances, the working fluid comprises ammonia. In other instances, the working fluid comprises nitrous oxide.
In some implementations, the absorbent comprises an organic amine, an inorganic base, an activated carbon, silica gel, a zeolite, a metal organic framework, or any combination thereof. For example, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, diethylenetriamine, or any combination thereof. In other examples, the absorbent comprises a metal halide salt, a mild acid, water, activated carbon, silica gel, a zeolite, or metal organic framework. And, in some examples, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.
In some implementations, the heat generated from the condensing step is recycled to drive the desorbing step using a heat exchanger.
Some implementations further comprise compressing the working fluid using a reversible turbine.
Some implementations further comprise compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.
In some implementations, the working fluid is compressed to and stored at a pressure of from about 1 bar to about 100 bar.
Some implementations further comprise a second compression step after the first compression.
In some implementations, the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar.
In some implementations, the working fluid is stored at ambient temperature.
Some implementations further comprise heating the working fluid prior to expansion using an external heat source.
Another aspect of the present invention provides a method of charging and discharging an energy storage system comprising charging the system comprising providing an absorbent storage tank containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; recycling heat generated during the condensing step to drive the desorbing step; and storing the working fluid in a working fluid reservoir under pressure; and discharging the system comprising expanding the working fluid; chemically absorbing the working fluid with the absorbent in the absorbent reservoir in an exothermic process; recycling heat generated during the absorption reaction to drive the expanding step; and storing the absorbent and the absorbed working fluid in the absorbent reservoir.
In some implementations, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water. For example, the working fluid comprises carbon dioxide. In another example, the working fluid comprises ammonia. And, in some examples, the working fluid comprises nitrous oxide.
In some implementations, the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework. For example, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine. In some examples, the absorbent comprises a metal halide salt, mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework. And, in some examples, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.
In some implementations, the heat generated during the condensing step is recycled drive the desorbing step using a heat exchanger.
In other implementations, the working fluid is compressed by a reversible turbine.
Some implementations further comprise compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.
In some implementations, the working fluid is compressed to and stored at a pressure of from about 1 bar to about 100 bar.
In other implementations, the compressing step comprises a two-stage compression process.
In some implementations, the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar.
In other implementations, the working fluid is stored at ambient temperature.
Some implementations further comprise heating the working fluid prior to expansion using an external heat source.
Some implementations further comprise directing the flow of the working fluid a first direction during charging, and reversing the flow of the direction of the working fluid during discharging.
Another aspect of the present invention provides an energy storage system comprising a working fluid reservoir containing compressed working fluid; an expander that fluidly communicates with the working fluid reservoir and is configured to expand the working fluid; an absorbent storage reservoir containing an absorbent, wherein the absorbent reservoir fluidly communicates with the expander and is configured to receive and absorb the expanded working fluid; a first heat exchanger that thermally communicates with the absorbent reservoir and is configured to transfer heat generated by the absorption of the working fluid by the absorbent to the working fluid during the discharge of the system; a pressure release mechanism configured to reduce pressure in the absorbent reservoir; and a compressor that fluidly communicates with the absorbent reservoir and fluidly communicates with the working fluid reservoir and is configured to compress the working fluid that desorbs from the absorbent; and a second heat exchanger in thermal communication with the working fluid in the compressor, in thermal communication with the absorbent and working fluid in the absorbent storage tank, and configured to transfer heat that is generated by the compression of the working fluid, to the absorbent and working fluid in the absorbent storage tank.
In some embodiments, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water.
In some embodiments, the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework. For example, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine. In other examples, the absorbent comprises a metal halide salt, mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework. And, in some examples, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.
In some embodiments, the compressor and expander comprise a reversible turbine.
In other embodiments, the compressor comprises a turbine, piston, radial reaction turbine.
In some embodiments, the expander comprises a turbine, piston, or turbo-expander.
Some embodiments further comprise an electrical generator connected to the expander.
Some embodiments further comprise a motor connected to the compressor.
Some embodiments further comprise an external heat source, in thermal communication with the expanded working fluid.
Some embodiments further comprising a controller connected to the compressor, expander, pressure release mechanism, absorbent storage tank, and working fluid storage tank.
In some embodiments, the first heat exchanger and second heat exchanger each comprise high surface area fin-shaped structures within the absorbent storage tank.
Some embodiments further comprise one or more additional compressors, fluidly connected to and positioned between the first compressor and the working fluid storage tank.
Some embodiments further comprise one or more additional expanders, fluidly connected to and positioned between the first expander and the absorbent storage tank.
In some embodiments, the pressure release mechanism is a valve.
Some embodiments further comprise a pump and a sprayer that each fluidly communicates with each other and with the absorbent storage tank, wherein the pump pumps the absorbent and absorbed working fluid to the sprayer and the sprayer sprays the fluid back into the absorbent storage tank. For example, the sprayer sprays the absorbent over a heat exchanger with high surface area fin-shaped structures within the absorbent storage tank.
Some embodiments further comprise a separator that fluidly communicates with the absorbent storage tank and the compressor.
In some embodiments, the separator is a centrifugal or cyclonic separator.
In some embodiments, the separator is a demister or a filter.
Another aspect of the invention provides a method of charging and discharging an energy storage system comprising: (i) charging the system comprising: providing an absorbent tank containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; recycling heat generated during the condensing step to drive the desorbing step; and storing the working fluid in a working fluid reservoir under pressure; and (ii) discharging the system comprising: expanding the working fluid; chemically absorbing the working fluid with the absorbent in the absorbent reservoir in an exothermic process; recycling heat generated during the absorption reaction to drive the expanding step; and storing the absorbent and the absorbed working fluid in the absorbent reservoir.
Another aspect of the invention provides an energy storage system comprising: a working fluid reservoir containing compressed working fluid; an expander that fluidly communicates with the working fluid reservoir and is configured to expand the working fluid; an absorbent storage reservoir containing an absorbent, wherein the absorbent reservoir fluidly communicates with the expander and is configured to receive and absorb the expanded working fluid; a first heat exchanger that thermally communicates with the absorbent reservoir and is configured to transfer heat generated by the absorption of the working fluid by the absorbent to the working fluid during the discharge of the system; a pressure release mechanism configured to reduce pressure in the absorbent reservoir; a compressor that fluidly communicates with the absorbent reservoir and fluidly communicates with the working fluid reservoir and is configured to compress the working fluid that desorbs from the absorbent; and a second heat exchanger in thermal communication with the working fluid in the compressor, in thermal communication with the absorbent and working fluid in the absorbent storage tank, and configured to transfer heat that is generated by the compression of the working fluid, to the absorbent and working fluid in the absorbent storage tank.
These figures are provided by way of example and are not intended to limit the scope of the invention.
In one aspect, the invention relates to the storage and delivery of energy as mechanical energy. In as much as mechanical and electrical energy are easily interchanged at high efficiencies by motors and generators, the system may also function as a “battery” even though there are no electrochemical reactions involved in the storage of energy by this invention notwithstanding the incidental use of conventional batteries for some system functions.
In another aspect, the invention relates to a chemical and thermodynamic system for energy storage. Energy is stored and released using distinct charge and discharge processes. This system simultaneously compresses a working fluid to a higher enthalpy state and recovers the heat of compression by driving a reversible chemical reaction. The compressed fluid is then expanded to a lower enthalpy state and chemically absorbed, driving the reverse exothermic reaction, from which heat can be supplied to increase the expansion efficiency.
During the discharge process, compressed working fluid (e.g., liquefied or supercritical gas) from a storage tank is expanded through an expansion device such as a turbine, piston, or nozzle, thereby generating power. The expansion results in cooling of the working fluid. The expanded working fluid (gas) exiting the expansion device undergoes a reversible chemical reaction with an absorbent that releases heat (exothermic). The heat is captured, for example by a heat exchanger, and the heat is transferred to the compressed working fluid that has yet to undergo expansion. This transferred heat beneficially increases the enthalpy of the working fluid prior to expansion, thus allowing for greater energy production. The process can continue until the compressed working fluid storage tank is empty.
During the charge process, the absorbed working fluid is desorbed through an endothermic reaction that is driven by a reduction in the pressure of the working fluid and absorbent. Energy is provided to a compression device that compresses the working fluid to a liquid or supercritical state and is stored in a storage tank. Heat from the compression process is captured and transferred to drive the endothermic desorption reaction. The process can continue until all of the working fluid has been desorbed and stored in the storage tank.
The systems and methods of the present invention have some or all of the following properties:
For brevity, from here on we will refer to the “grid” as being any application or solution for which the invention is suitable. We shall also refer to the operation of any of these systems in which energy is put into the device to charge it, as “charging” or “recharging”. Consistent with this definition, when energy is taken out of the device it is referred to as “discharging”. Any cycle of charge (partial or full) and discharge (partial or full) will simply be referred to as a “cycle”.
As used herein, “chemical absorption” refers to absorption using a chemical bond of a covalent pair to form either a solution or compound.
As used herein, the term “tank” and “reservoir” are used interchangeably to refer to a storage chamber.
As used herein, “desorption” is a process that is the inverse of absorption whereby some, or all, of an absorbed substance is released. Specifically, desorption is the process by which the molecules of a covalent pair are separated from each other in order to form, or reconstitute the original, prior to absorption, covalent pair.
For brevity, embodiments of the invention may be described as involving either an “absorption” or “adsorption” process. It will be understood to the reader that either process may be used in the embodiments of the invention depending on the choice of materials. Similarly, the terms “absorption agent”, “absorbent”, or “sorbent” are used interchangeably and may each refer to either a liquid or a solid agent that can absorb or adsorb a fluid, respectively.
As used herein, “round trip efficiency” or “RTE” is calculated as the power produced during expansion divided by the power required for compression.
As used herein, “activated carbon” is a form of carbon processed to be riddled with small, low-volume pores that increase the surface area available for adsorption or chemical reactions.
As used herein, the term “metal organic framework” refers to crystalline compounds consisting of metal ions or clusters coordinated to organic molecules to form one-, two-, or three-dimensional structures. In some cases, the structures are porous and the pores are stable during elimination of the guest molecules (often solvents) and can be used for the storage of gases.
As used herein, the term “food oil” refers to oils commonly used in cooking and food preparation including olive oil, palm oil, soybean oil, canola oil (rapeseed oil), pumpkin seed oil, corn oil, sunflower oil, safflower oil, peanut oil, grape seed oil, sesame oil, argan oil, rice bran oil and other vegetable oils.
As used herein, the term “silicone oil” refers to any liquid polymerized siloxane with organic side chains. Examples of silicone include are hexamethyldisiloxane and simethicone.
As used herein, the terms “first” and/or “second” do not refer to order or denote relative positions in space or time, but these terms are used to distinguish between two different elements or components. For example, a first component does not necessarily proceed a second component in time or space; however, the first component is not the second component and vice versa. Although it is possible for a first component to precede a second component in space or time, it is equally possible that a second component precedes a first component in space or time.
Referring to
In this embodiment, the system undergoes charging or recharging when desorbed working fluid (e.g., working fluid in a liquid physical state) is channeled from the absorbent tank or reservoir to the compressor (e.g., a piston cylinder) along flow pathway 1 where the working fluid is compressed. From the compressor, the compressed working fluid is channeled along flow pathway 2 to a heat exchanger that cools and/or condenses the compressed working fluid. The cooled and/or condensed working fluid is channeled along flow pathway 3 to the working fluid tank where it is stored until the system discharges energy. During the charging process, heat may be transferred in a closed loop, along flow pathways 4 and 5, from the compressor to the absorbent tank to enhance the efficiency of the system.
In this embodiment, the system undergoes discharging when desorbed working fluid is channeled from the working fluid tank, along flow pathways 6 and 7, to one or more heat exchangers that transfer heat to the working fluid. From the one or more heat exchangers, the heated working fluid is channeled, along flow pathway 8, to the expander wherein the working fluid undergoes volumetric expansion. Energy is discharged from system from the expander that may be coupled with a generator for producing electrical energy. The expanded working fluid, i.e., working fluid in a gaseous physical state, is channeled, along flow pathways 9 and 10, to the absorbent tank, wherein the working fluid is mixed or dissolved in the absorbent. In some embodiments, heat flows, along flow pathway 11, from one or more heat exchangers to the condensed working fluid before the fluid is expanded. After the working fluid is expanded, the one or more heat exchangers can transfer heat, along flow pathway 12, away from absorbent tank where heat is generated during the dissolution of the working fluid in the absorbent.
Alternatively, the system of the present invention may undergo discharging when desorbed working fluid having a liquid physical state is channeled, along flow pathway 13, to an expander wherein the liquid working fluid is transformed into an expanded vapor. The expanded vapor is channeled, along flow pathways 14 and 15, to one or more heat exchangers that transfer heat to or from the expanded vapor. The working fluid is then channeled, along flow pathway 16, to the working fluid tank, where it is stored until the system undergoes charging or recharging.
The system may undergo charging when desorbed working fluid is channeled, along flow pathways 17 and 18, from the working fluid tank to one or more heat exchangers and, along flow pathway 19, to the compressor, wherein the working fluid is compressed. From the compressor, compressed working fluid is channeled to one or more heat exchangers, along flow pathways 20-22, to the absorbent tank wherein the working fluid is mixed or dissolved in the absorbent.
Another aspect of the present invention relates to an energy storage system comprising: a working fluid reservoir containing compressed working fluid; an expander that fluidly communicates with the working fluid reservoir and is configured to expand the working fluid; an absorbent storage reservoir containing an absorbent, wherein the absorbent reservoir fluidly communicates with the expander and is configured to receive and absorb the expanded working fluid; a first heat exchanger that thermally communicates with the absorbent reservoir and is configured to transfer heat generated by the absorption of the working fluid by the absorbent to the working fluid during the discharge of the system; a pressure release mechanism configured to reduce pressure in the absorbent reservoir; a compressor that fluidly communicates with the absorbent reservoir and fluidly communicates with the working fluid reservoir and is configured to compress the working fluid that desorbs from the absorbent; and a second heat exchanger in thermal communication with the working fluid in the compressor, in thermal communication with the absorbent and working fluid in the absorbent storage tank, and configured to transfer heat that is generated by the compression of the working fluid, to the absorbent and working fluid in the absorbent storage tank.
In some embodiments, the working fluid comprises carbon dioxide, freon, methane, ammonia, nitrous oxide, air, or water.
In some embodiments, the working fluid comprises carbon dioxide.
In some embodiments, the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework.
In some embodiments, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine. For example, the absorbent comprises monoethanolamine (MEA). In some embodiments the absorbent comprises a mixture of MEA and water.
In some embodiments, the working fluid comprises ammonia.
In some embodiments, the absorbent comprises a metal halide salt (e.g. MgCl2 or CaCl2), mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework.
In some embodiments, the working fluid comprises nitrous oxide.
In some embodiments, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.
In some embodiments, the compressor and expander comprise a reversible turbine.
In some embodiments, the compressor comprises a turbine, piston, radial reaction turbine.
In some embodiments, the expander comprises a turbine, piston, or turbo-expander.
In some embodiments, the system further comprises an electrical generator connected to the expander.
In some embodiments, the system further comprises a motor connected to the compressor.
In some embodiments, the system further comprises an external heat source, in thermal communication with the expanded working fluid.
In some embodiments, the system further comprises a controller connected to the compressor (motor), expander (generator), pressure release mechanism, absorbent storage tank, working fluid storage tank, or any combination thereof.
In some embodiments, the first heat exchanger and second heat exchanger each comprise high surface area fin-shaped structures within the absorbent storage tank.
In some embodiments, the system further comprises one or more additional compressors, fluidly connected to and positioned between the first compressor and the working fluid storage tank.
In some embodiments, the system further comprises one or more additional expanders, fluidly connected to and positioned between the first expander and the absorbent storage tank.
In some embodiments, the pressure release mechanism is a valve.
In some embodiments, the system further comprises a pump that fluidly communicates with the absorbent storage tank and a sprayer in fluid communication with the pump and the absorbent storage tank. For example, the pump pumps the absorbent and absorbed working fluid to the sprayer and the sprayer sprays the fluid back into the absorbent storage tank. In some embodiments, the sprayer atomizes the fluid to small droplets. In some embodiments the sprayer sprays the absorbent over the heat exchanger with high surface area fin-shaped structures within the absorbent storage tank.
In some embodiments, the system further comprises a separator that fluidly communicates with the absorbent storage tank and the compressor. In some embodiments the separator is a centrifugal or cyclonic separator. In other embodiments the separator is a demister or a filter.
Another embodiment of the present invention, illustrated in
In
There are several suitable expansion type devices available to recover the energy from expanding gases. These can be of any design and include both turbines and piston type motors. In general, the turbines, when used in this application, are commonly called “turbo-expanders”. In some embodiments, the expander or turbo-expander obtains conversion efficiency in excess of about 80% of the energy in the expanding gas. In other embodiments, the turbo-expander obtains about 90% efficiency. In some embodiments, the expander is a radial reaction turbine (RRT). And, in some embodiments, the RRT is configured to run with supercritical working fluids, such as CO2, to achieve high efficiencies. To use an RRT, the absorbent(s) are selected that match the pressure range of the output of the RRT in the system.
The critical temperature of CO2 is 31° C. At this temperature, the pressure of the CO2 is 56 bar. In some instances, the pressures in the RRT vary between about 50 bar and about 120 bar. If a solid absorbent is paired with a supercritical working fluid (e.g., CO2), the heat transfer associated with the solid absorbent will be improved because supercritical fluids are efficient heat transfer agents.
As illustrated in
In systems of the present invention, heat exchangers can possess any suitable configuration.
Referring to
The working fluid travels along flow paths 44, 130, and 138 to a compressor. Electrical energy runs motor 106 that compresses or increases the pressure of the working fluid. The motor may operate compressor 108 or the motor may reverse the operation of turbo-expander so that the turbo-expander functions to compress the working fluid. Any suitable compressor can be used to complete this step. The pressurized work fluid is channeled along flow path 128, 134, and 136 to the working fluid storage tank, where it is stored until a discharge cycle begins.
As illustrated in
Depending on how much pressure change is desired in the cycle, the compressor may be one or more (e.g., 1, 2, 3, 4, or more) stages. The choice of pressure range is governed by design choices based on absorbent properties and the desired energy density. Energy density is related to the operating pressure since, as can be seen by
As shown in
In some embodiments, the vacuum action of the intake side of the compressor will be sufficient to allow working fluid (e.g., CO2) to be released from the absorbent. In these embodiments, this is an endothermic reaction and the absorbent will cool. However, the action of compressing the working fluid will generate heat. In some embodiments, this heat is removed to maintain efficiencies. Further, the absorbent cannot cool indefinitely, so as the absorbent cools, heat generated in the compressor heats the absorbent. The heat going to the absorbent may drive the endothermic reaction and facilitate the release of additional working fluid (e.g., CO2) for compression. This continues until the working fluid (e.g., CO2) tank is full or until it is desired to stop the recharging process.
Accordingly, systems of the present invention may be charged or discharged and reversed at any part of the cycle. These systems may also be run at any power level even its maximum power right to the very end of the cycle. It may be discharged to 100% depth of discharge as often as desired and at full power as well with no detrimental effects to the system.
In some embodiments, during the recharge cycle, as the working fluid (e.g., CO2) is being released from the absorbent, some absorbent may become entrained in the working fluid. Should this be the case, an optional separator 24 may be placed between the absorbent reservoir and the intake to the expander (e.g., turbo-expander). In some embodiments, such as the embodiment illustrated in
Another embodiment of the mechanical-chemical energy storage system is described in the schematic diagram shown in
In one loop, the expanded working fluid (e.g., CO2) or exhaust from the expansion device travels through heat exchanger (Hx3). Later, this low-pressure working fluid (e.g., CO2 gas) labeled “low pressure CO2” is compressed by one or more compressors C1-C5 returning to higher pressure carbon dioxide phase. During the compression of the carbon dioxide gas, which is an exothermic process, heat is captured by one or more heat exchangers Hx4-Hx7.
In another loop, the expanded working fluid or exhaust from the expansion device reacts with an absorber (e.g., aqueous ammonia (˜36% solution)) in an exothermic reaction that generates heat while absorbing the working fluid (e.g., CO2). Thus, this additional energy increases the enthalpy of the working fluid allowing for a greater energy production from this part of the cycle. Since the temperature of the absorbent is higher than the temperature of the cooling working fluid, energy will naturally flow in the desired direction shown by the arrow in the discharge portion of
In another loop, the low concentration liquid working fluid and absorbent solution (e.g., CO2 and ammonia solution) exiting the reboiler is circulated into the chamber containing Hx1 and Hx2 heat exchangers. Working fluid gas (e.g., CO2 gas) is further separated from absorbent (e.g., ammonia) in this chamber and circulated via heat exchanger Hx3 into compressors C1-C5. Thus, the working fluid (e.g., CO2) gas enters into the next cycle.
Another embodiment of the mechanical-chemical energy storage system is described in the schematic diagrams shown in
Working Fluids
All suitable working fluids are within the scope of the invention. Suitable working fluids can be expanded and compressed and can be absorbed by an absorbent. Exemplary working fluids include fluids that can be compressed to a liquid, critical, or trans-critical state at the desired operating pressures and temperatures. For example, the desired temperature may be ambient temperature (about 20 to 25° C.) and the desired pressure range may be from about 40 to 60 bar, thus, exemplary working fluids would be in a liquid, critical, or trans-critical state at those conditions. Some exemplary working fluids will be absorbed by the absorbent in a reversible and/or exothermic process. Some specific exemplary working fluids include carbon dioxide (CO2), ammonia (NH3), nitrous oxide (N2O), air, and water.
Examples of suitable working fluids are described in Table 1.
1Possible solvents for freons, hydrocarbons and Nitrous oxide include butanediammine, 2-diethylamino ethanol, aqueous Na glycinate solution, diethanolamine, olive oil, aqueous hydroxide solution, dodecane, ammonia water, amine based solvent (e.g., Stonvent), vegetable oil, paraffins, or any combination thereof.
Absorbents
All suitable absorbents are within the scope of the invention. Suitable absorbents agents are capable of chemically absorbing a working fluid. Exemplary absorbents will absorb the working fluid in a reversible and/or endothermic process. Some specific exemplary absorbents include: absorbents of carbon dioxide, such as organic amines (e.g., monoethanolamine (MEA), piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine), inorganic bases (e.g., potassium carbonate, ammonium carbonate), activated carbon, silica gel, zeolites, and metal organic frameworks; absorbents of ammonia, such as salts that form ammonates, halide salts (e.g., magnesium chloride (MgCl2), calcium chloride (CaCl2)), mild acids, water, activated carbon, silica gel, zeolites, and metal organic frameworks; absorbents of nitrous oxide, such as oils that dissolve nitrous oxide (e.g., food oils, silicone oils), activated carbon, silica gel, zeolites, and metal organic frameworks; and absorbents of air such as activated carbon and zeolites. The terms “absorption agent”, “absorbent”, and “sorbent” are used interchangeably and may each refer to either a liquid or a solid agent that can absorb or adsorb a fluid, respectively.
Examples of pairs of absorbents and working fluids suitable for use in the present invention are described in Table 2.
One aspect of the invention relates to a method for storing energy comprising: providing an absorbent reservoir containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; and condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; wherein at least some of the heat generated during the condensing step is recycled to drive the desorbing step.
In some implementations, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water.
In some implementations, the working fluid comprises carbon dioxide or ammonia.
In some implementations, the absorbent comprises an organic amine, an inorganic base, an activated carbon, silica gel, a zeolite, a metal organic framework, or any combination thereof.
In some implementations, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, diethylenetriamine, or any combination thereof. For example, the absorbent comprises monoethanolamine (MEA). In some implementations the absorbent comprises a mixture of MEA and water.
In some implementations, the working fluid comprises ammonia.
In some implementations, the absorbent comprises a metal halide salt, a mild acid, water, activated carbon, silica gel, a zeolite, or metal organic framework.
In some implementations, the working fluid comprises nitrous oxide.
In some implementations, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.
In some implementations, the heat generated from the condensing step is recycled to drive the desorbing step using a heat exchanger.
In some implementations, the method further comprises compressing the working fluid using a reversible turbine.
In some implementations, the method further comprises compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.
In some implementations, the working fluid is compressed to and stored at a pressure of from about 1 bar to about 200 bar (e.g. 10 bar to 100 bar, or about 50 bar).
In some implementations, the method further comprises a second compression stage after the first compression.
In some implementations, the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar (e.g., about 0.5 bar to about 5 bar, or about 1 bar).
In some implementations, the working fluid is stored at ambient temperature.
In some implementations, the method further comprises heating the working fluid prior to expansion using an outside heat source.
Another aspect of the invention relates to a method of charging and discharging an energy storage system comprising: (1) charging the system comprising: providing an absorbent storage tank containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; and recycling heat generated during the condensing step to drive the desorbing step; and storing the working fluid in a working fluid reservoir under pressure; and (2) discharging the system comprising: expanding the working fluid; chemically absorbing the working fluid with the absorbent in the absorbent reservoir in an exothermic process; recycling heat generated during the absorption reaction to drive the expanding step; and storing the absorbent and the absorbed working fluid in the absorbent reservoir.
In some implementations, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water.
In some implementations, the working fluid comprises carbon dioxide.
In some implementations, the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework.
In some implementations, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine. For example, the absorbent comprises monoethanolamine (MEA). In some implementations the absorbent comprises a mixture of MEA and water.
In some implementations, the working fluid comprises ammonia.
In some implementations, the absorbent comprises a metal halide salt (e.g., MgCl2, CaCl2), mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework.
In some implementations, the working fluid comprises nitrous oxide.
In some implementations, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.
In some implementations, the heat generated during the condensing step is recycled drive the desorbing step using a heat exchanger.
In some implementations, the working fluid is compressed by a reversible turbine.
In some implementations, the method further comprises compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.
In some implementations, the working fluid is compressed to and stored at a pressure of from about 1 bar to about 100 bar, (e.g. from about 10 bar to about 100 bar, from about 20 bar to about 80 bar, or about 50 bar).
In some implementations, the compressing step comprises a two-stage compression process.
In some implementations, the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar (e.g. about 1 bar).
In some implementations, the working fluid is stored at ambient temperature.
In some implementations, the method further comprises heating the working fluid prior to expansion using an external heat source.
In some implementations, the method further comprises directing the flow of the working fluid a first direction during charging, and reversing the flow of the direction of the working fluid during discharging.
Another aspect of the mechanical-chemical energy storage systems of the present invention are illustrated in
When it is desired to recharge the system, the reverse process is shown in the charge portion of
Another aspect of the present invention provides a method of storing energy using mechanical-chemical energy storage system is described in
Some implementations further include discharging energy from the mechanical-chemical energy storage system. Discharging energy from this system comprises expanding the working fluid through expanders (e.g., turbines, turbo-expanders, pistons, or any combination thereof) E10-E30. One or more heat exchangers Hx80, Hx10, and Hx20 transfer heat to the working fluid. The one or more heat exchangers are arranged to input heat to the working fluid between successive expansions. In some instances, the heat exchangers are arranged along the working fluid flow path between expanders. Alternatively, a single heat exchanger can input heat to the working fluid between successive expansions.
Magnesium chloride can form ammonates. MgCl2 can absorb up to 6 molecules of ammonia to form MgCl2*6NH3.
The pressure of the ammonia over the MgCl2 varies as more or less ammonia is incorporated into the molecular structure. Since the salt and its ammonate are solid, the heat generated from the reaction needs to be allowed to move to the cooling ammonia by either packing the salt on one side of a heat exchanger and having the ammonia on the other side of the same heat exchanger or by having an intermediate heat transfer fluid carry the heat away from the salt and deliver it to the ammonia.
Simplified chemical equations representing these reactions include:
MgCl2+NH3==>MgCl2*NH3 (1)
MgCl2*NH3+NH3==>MgCl2*2NH3 (2)
MgCl2*2NH3+NH3==>MgCl2*3NH3 (3)
MgCl2*3NH3+NH3==>MgCl2*4NH3 (4)
MgCl2*4NH3+NH3==>MgCl2*5NH3 (5)
MgCl2*5NH3+NH3==>MgCl2*6NH3 (6)
As NH3 pressure is increased all of the above reactions will go to completion (to the right). This is the case as the system is discharging.
These are also all exothermic reactions. Thus, the heat that is released can be used to expand the ammonia to get addition energy from the system. Note that this heat energy is generated when and as the system discharges. It is not stored as heat but used right away to create more energy and increase the efficiency of the system.
Further, removing ammonia during the recharge step will drive the reactions to the left and create a source of cold to help with the liquefaction of ammonia. Again this cold is not stored as a cold material but is generated as the recharging process takes place.
In this case, the vacuum at the intake of the compression device could be sufficient to start removing ammonia from the MgCl2*NH3 and drive the recharge reaction. The additional heat from the compression of the ammonia can also drive the release of the ammonia until the recharging is complete.
Monoethanolamine (MEA), usually as a 30% solution in water, has been used for many years for removal of CO2 from natural gas.
The simplified chemical equations representing these reactions include:
CO2+H2O==>HCO3−+H+ (7)
MEA+HCO3−==>MEAHCO2−+H2O (8)
These reactions are exothermic and give off heat as CO2 is absorbed. These are essentially simple acid-base reactions that are easily reversible since they are not too exothermic.
The fact that a gas is part of the equilibrium helps the reaction be driven in either direction by change of gas pressure. This allows for the storage of energy as chemical potential and allows for the control of this reaction by pressure and temperature.
Thus, as CO2 exits the turbo-expander, the equilibrium in reaction 7 is pushed to the right, which also pushes reaction 8 to the right, releasing heat energy as needed to expand the CO2 further.
These relationships, shown in
As an example, a system may have a vacuum side of the compressor that will operate at 100 pascals and will charge the MEA up to 100,000 pascals. The amount of CO2 can then be calculated by finding those two points on the graph where the line crosses and reading down to how much CO2 is absorbed by the MEA at those pressures. In this case, when charging at 100,000 pascals, the mole ratio is about 0.6 moles of CO2 per mole of MEA. Down at the lower pressure the ratio is about 0.2 to 1. These two ratios are subtracted and it is determined that the capacity of the MEA operation between these pressures will cycle at about 0.4 moles of CO2 per mole of amine. It should be noted that these curves are at a single temperature.
In order to simulate an exemplary process, a CHEMCAD simulation software package was used. The process was simulated in sections rather than in a single simulation to allow for the use of different models for the fluid properties in certain segments of the process. Initial simulations were performed assuming a constant CO2 mass flow rate (1 lb/sec) and assuming negligible carryover of any impurities or sorbents through the expansion/contraction steps. It is also assumed that the heat of solution of the CO2 and sorbent is capable of heating the solution to the fixed set point temperature for the calculation. Therefore, it must be noted that the highest temperatures in the simulations below may not be achievable without additional heat input (this will be discussed further).
Using a single stage expander,
Referring to
In order to improve the performance of compressors and expanders, multiple stages are often employed. For example, in the calculations used in
For the two-stage process, the first stage pressurized the 80° F. working fluid from 200-425 psia; the compression caused the fluid to warm, so a heat exchanger is used to reduce the temperature to 80° F. Then the second stage is run to pressurize from 425-900 psia.
For the three-stage process, the first stage pressurized the 80° F. working fluid from 200-330 psia; the compression caused the fluid to warm, so a heat exchanger is used to reduce the temperature to 80° F. Then the second stage is run to pressurize from 330-550 psia. Again, the compression heated working fluid is cooled to 80° F. and then enters the third stage where it achieves a final pressure of 900 psia.
As can be seen in
Of particular interest in evaluating the process will be the percentage of the recharge power that can be delivered in discharge mode; this will be referred to as the Round Trip Efficiency (RTE). The minimum acceptable value for this process is 0.6 (60%).
One method to improve power output is to pressurize the liquid CO2 with a standard pump when it leaves the storage tank, and then add heat to move the working fluid into a supercritical state. This approach works because the power required to pressurize a liquid is significantly lower than the power output that can be gained from the expander (assuming a heat source is available, of course).
Up to this point, the sorbent has not been considered in the analysis. All of the above calculations look at CO2, and the power generated or consumed during discharge or recharge steps. The choice of sorbent is important for the system design. Of particular interest for the preceding analysis is the heat of solution. It has been assumed that the energy needed to heat the working fluid is available. One sorbent of interest is monoethanolamine (MEA). It has a high heat of solution with CO2. Using the CHEMCAD AMINE model, it is possible to calculate the temperature of CO2/MEA mixed solutions. One simulation looked at mixing 100% pure MEA with CO2, and it was found that ˜17 wt % CO2 was dissolved and the final solution temperature achieved 330° F. Using this heated sorbent as the heat supply for the CO2 heat exchanger prior to the expander, we found that it was possible to heat the CO2 to 280° F. in two expansion stages. The outgoing sorbent stream still retained a significant amount of heat, as the outlet temperature was ˜290° F. after heating the CO2.
In order to achieve a high sorbent temperature, the MEA sorbent must dissolve a significant amount of CO2.
Another exemplary process was simulated using the software package described above. The following assumptions were made: 1) All streams can be heated or cooled to 80° F. from the atmosphere, whether heating or cooling. All phase change energy is supplied from the atmosphere. Energy to run the air blowers is neglected. 2) Working fluid liquid inlet condition is set at 70° F., where the fluid is a liquid at its vapor pressure. 3) Pressure is set between 100-856 psia and 200-856 psia. 4) Piston work is calculated as PdV. A simple curve fit of Pressure to Volume information was used for the integration. 5) Piston heat is calculated as TdS. 6) Assumed inefficiencies remained the same as with isentropic process—85% for expansion, 75% for compression. Lost energy is not accounted for in the simulation. 7) RTE is calculated as the power produced during piston expansion divided by the power required by the piston compression.
A schematic of the process used for the simulation is shown in
To balance a system, such as the system described in this example or the other embodiments described herein, calculation of the minimum heat and maximum temperature of the absorber may be useful. Two criteria should be met. The first is the minimum heat of reaction required for the absorber. This is calculated by dividing the amount of energy required to reverse the chemical reaction of the working fluid with the absorber (the ‘B’ unit op column Q in the recharge cycle above) by the number of moles of working fluid needed to create a given amount of energy, which in this model is set at 1#/sec. Thus, for CO2 in this case is 10.32 moles.
So in the example above Q=56.2 kJ this divided by 10.32 moles=5.45 kJ/mole as a minimum reaction energy (delta G) for each mole of working fluid that reacts with each mole of absorber. The order of magnitude of this energy is actually very low compared to most chemical reactions. While it is good to have a delta G larger than the minimum it also needs to be reversible at a temperature that is available from the heat of compression. In general the higher the delta G the higher the temperature (and or pressure differential) that will be required to reverse the reaction. There is no exact formula that relates delta G to the temperature so each system has to be considered to make sure that it is reversible. Zeolites and activated carbons have delta G values of about 5 to about 20 kJ/mole for CO2 and NH3 working fluids. Another example is water and CO2 going to HCO3−, which has a delta G of about 12 kJ/mole. Many of these compounds can easily be desorbed by allowing the pressure to decrease on them.
In the case of a solid absorbent, a secondary heat transfer loop using an inert heat transfer liquid may also be used. Heat exchange could also be accomplished by injecting an inert heat exchange fluid (such as silicone oil) into the expander and/or compressor as opposed to the external heat exchangers discussed herein.
Another exemplary process was simulated using the computer software package described above. The following assumptions were made: 1) All streams can be heated or cooled to 80° F. from the atmosphere, whether heating or cooling. All phase change energy is supplied from the atmosphere. Energy to run the air blowers is neglected. 2) Working fluid (CO2) liquid inlet condition is set at 70° F., where the fluid is a liquid at its vapor pressure. 3) Pressure is set between 200-856 psia. 4) Desorption conditions not accounted for—assumed to happen at any T, P set. No pressure or temperature swing has been included. 5) Work is calculated as isentropic. 6) Assumed inefficiencies based mechanical losses (BNI)—98% for expansion, 96% for compression. Lost energy is not accounted for in the simulation. 7) RTE is calculated as the power produced during piston expansion divided by the power required by the piston compression.
A schematic of the process used for the simulation is shown in
One issue with conventional compressed air energy storage is the low energy density of the compressed gas. However, zeolite type absorbents will absorb air and have acceptable delta G values. If air were to be compressed into an insulated tank of zeolites, and then simply discharged to the atmosphere (no absorption on discharge) this would increase both the RTE of compressed air energy storage as well as the energy density.
This would operate conceptually as a half-system with only a single storage tank and that is not a closed cycle. However, it is an improvement over ordinary CAES. Both the heat of compression and the absorption energy will be stored and available for discharge. Although activated carbon also absorbs air, there should be a warning that high pressure air could ignite certain carbons and this would be a limit on those particular absorbents.
The absorption of carbon dioxide in aqueous ammonia solution leads to a number of products including ammonium carbamate, bicarbonate, and carbonate. The ratio of these reaction products are a function of the carbon dioxide loading, solution pH, and the concentration of ammonia in the aqueous media.
Simplified chemical equations representing these reactions include:
NH2COONH4(q)+H2ONH4HCO3(aq)+NH3(aq)ΔHrx=8.06 kJ/mol (9)
2NH4HCO3(aq)(NH4)2CO3(aq)+CO2(g)+H2O ΔHrx=26.88 kJ/mol (10)
NH4HCO3(aq)NH3(aq)+CO2(g)+H2O ΔHrx=64.26 kJ/mol (11)
NH2COONH4(aq)2NH3(aq)+CO2(g)ΔHrx=72.32 kJ/mol (12)
(NH4)2CO3(aq)2NH3(aq)+CO2(g)+H2O ΔHrx=101.22 kJ/mol (13)
The schematic flow diagram for the process is shown in
The operating parameters for the initial feasibility evaluation are:
1) Absorption vessel conditions are 150° F. and 257 psi (˜66° C. and 1.77 Mpa);
2) Desorption vessel conditions are 180° F. and 257 psi (˜82° C.);
3) Ammonia concentration level of 36% was maintained;
4) Total flow rate of working fluid equal to 142.6 kg/s;
5) Expansion efficiency: 88%;
6) Compressor efficiency: 84%;
7) Heat exchanger efficiency: 2%;
8) The molar ratios of carbon dioxide to ammonia in solution are between 0.35 to 0.60;
9) The reversible heat of reaction: 80 kJ/mol; and
10) Thermodynamic and transport properties estimated with using the National Institute of Standards and Technology (NIST) standard reference program.
All state functions, for each location, as shown in
3Locations are shown in FIG. 13.
All calculations and thermodynamic state function are normalized to 1 kg of carbon dioxide of working fluid. The assumed value for heat capacity (Cp), for the carbon dioxide/ammonia/water solution is equal to 1 cal/g ° C. The assumed density for the carbon dioxide/ammonia/water solution is equal to 1 g/cm3. The sensible heat requirements: 29.9 kJ/kg carbon dioxide and stripping heat is zero.
The value for each expansion and compression work is calculated as follows: E1 is calculated by referring to Table 5 above and
4Expansion stages E1, E2 and E3 are shown in FIG. 13.
3 Compression stages C1, C2, C3, C4 and C5 are shown in FIG. 13.
Estimation of Sensible Heat:
The sensible heat is defined as the amount of energy required to raise the temperature of the solution to the temperature of regeneration, which while not recovered in this flow chart, may allow for partial recovery. Assuming 36% by weight of ammonia concentration in water and maintaining the molar ratio of carbon dioxide to ammonia in the solution between 0.35 to 0.6 during absorption and desorption cycle, the reaction heat is:
(Qabsorption+Qdesorption)/2=(122.95+119.54)/2=121.3 kJ/kg CO2
Since the total ΔQ for desorption and absorption is essentially equal.
Accepting reaction heat 80 kJ/mol, as reported in the literature
80×[(1000×0.36)(0.6−0.35)/17]=424 kJ/kg of solution
The ΔT is the temperature difference between stream 43 and reboiler 180−135° F.=25° C.
Qsensible=(121.3×25×4.18)/424=29.9 kJ/kg CO2
The system Efficiency:
Efficiency (RTE)=[(Work out)/(Work in +Sensible Heat)]×100
RTE=[75.65/(82.55+29.9)]×100=67.2%
The system illustrated in
This simulation calculates the thermodynamic efficiency of CO2 working fluid as it completes a full charge-discharge cycle. Note that this simulation does not show a specific absorption reaction. It assumes that heat is put into a given reaction during charging/compression and withdrawn from the reverse of that reaction during the discharge/expansion thru the heat exchangers. The data generated in this simulation is presented in Tables 8-15, below.
All publications and patents referred to in this disclosure are incorporated herein by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Should the meaning of the terms in any of the patents or publications incorporated by reference conflict with the meaning of the terms used in this disclosure, the meaning of the terms in this disclosure are intended to be controlling. Furthermore, the foregoing discussion discloses and describes merely example embodiments of the present invention. One skilled in the art will readily recognize from such discussion and from the accompanying drawings and claims, that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims.
This U.S. application claims the benefit of U.S. provisional application Nos. 61/844,914, filed on Jul. 11, 2013, and 61/968,450, filed on Mar. 21, 2014. Each of these documents is incorporated herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61844914 | Jul 2013 | US | |
| 61968450 | Mar 2014 | US |
