TITLE

[0001] High Efficiency Absorption Heat Pump and Methods of Use

FIELD OF THE INVENTION [0002] The invention is directed generally to heat pumps, and more specifically to a high pressure absorption heat pump using carbon dioxide and a low vapor pressure absorber as the circulating fluid.

BACKGROUND [0003] Heat pumps are well known in the art. A heat pump is simply a device for delivering heat or cooling to a system, whereas a refrigerator is a device for removing heat from a system. Thus, a refrigerator may be considered a type of heat pump. Throughout the application, the invention will be referred to as a heat pump with the understanding that the designation of refrigerator, air conditioner, water heater, cogeneration system (also referred to as combined heat and power or CHP system, which is the use of a heat engine or a power station to simultaneously generate both electricity and useful heat), and tri generation system (a cogeneration system that additionally produces cooling) could be substituted without changing the operation of the device. The inherent feature of a heat pump is to transport / move thermal energy from a heat source to a heat sink. The use of the term heat pump, thus is broadly applied as the transport of thermal energy from one enthalpy / entropy state to another. Thus, the utilization of heat pumps is not restricted to the generation of heating or cooling, but also for the intrinsic movement of thermal energy in virtually any thermodynamic cycle including means to convert such thermal energy into power generation (e.g., electrical or mechanical energy). [0004] In absorption heat pumps, an absorbent such as water absorbs the refrigerant, typically ammonia, thus generating heat. When the combined solution, also referred to as binary solutions, is pressurized and heated further, the refrigerant is expelled. When the refrigerant is pre-cooled and expanded to a low pressure, it provides cooling. The low pressure refrigerant is then combined with the low pressure depleted solution to complete the cycle.

[0005] Many current absorption heat pump/refrigerators make use of either a water-ammonia couple, or a water-lithium bromide couple. These two absorption couples suffer from certain drawbacks. The water-ammonia couple raises security problems in view of the toxicity and flammability of ammonia, and LiBr is corrosive and very failure

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prone due to low pressure operation, i.e., small leaks create contamination. Moreover, the tendency to crystallize can be a clogging problem. Operating at very low pressures is often impossible due to the freezing of water. Other absorption processes have been proposed, but generally involve working fluids that are toxic, flammable, ozone- depleting, or have high atmospheric green house effects.

[0006] United States Patent No. 6,374,630 for "Carbon dioxide absorption heat pump" to Jones discloses a traditional absorption cycle utilizing supercritical carbon dioxide. The '630 patent does not anticipate an absorber having either a very low vapor pressure, a boiling point less than 50 ⁰ C, or any means to achieve a coefficient of performance better than 0.70. The '630 patent further does not anticipate any nonthermal means to reduce desorption temperature, nor the extraction of expansion energy. It is understood that the term carbon dioxide and the abbreviations for carbon dioxide used are interchangeable that include CO.sub.2 and CO2. Likewise, the term water and the abbreviations for water used are interchangeable that include H.sub.2 O and H2O. [0007] United States Patent Application No. US 2003/0182946 for "Method and apparatus for using magnetic fields for enhancing heat pump and refrigeration equipment performance" to Sami et al. utilizes a magnetic field that is operable to disrupt intermolecular forces and weaken intermolecular attraction to enhance expansion of the working fluid to the vapor phase. Magnetic field energy has been found to alter the polarity of refrigerant molecules and disrupt intermolecular Van der Waals dispersion forces between refrigerant molecules, though Sami et al. does not anticipate the utilization of a magnetic field to reduce desorption energy.

[0008] United States Patent No. 6,434,955 for "Electro-adsorption chiller: a miniaturized cooling cycle with applications from microelectronics to conventional air- conditioning" to Ng et al. presents the combination of absorption and thermoelectric cooling devices. The governing physical processes are primarily surface rather than bulk effects, or involve electron rather than fluid flow. The '955 patent does not anticipate a continuous absorption process, but rather the transfer of thermal energy from a batch desorption process into the sequentially processed batch for subsequent desorption. [0009] United States Patent Application No. US 2003/0221438 for "Energy efficient sorption processes and systems" to Rane, et al. devises adsorption modules with heat transfer passages in thermal contact with the adsorption module wall and switchable heat pipes. Adsorption module of this invention leads to lower cycle times as low as 5 minutes that yields an efficient multi-stage regeneration processes for regenerating liquid

desiccant using rotating contacting disks. The '438 patent does not anticipate either a continuous process or an absorption process.

[0010] United States Patent Application No. US 2002/0078696 for "Hybrid heat pump" and United States Patent No. 6,539,728 for "Hybrid heat pump", both to Korin, disclose a hybrid heat pump system that includes (i) a membrane permeator having a permselective membrane capable of selectively removing vapor from a vapor-containing gas to yield a dry gas, and (ii) a heat pump having (a) an internal side for exchanging thermal energy with a process fluid, (b) an external side for exchanging thermal energy with an external environment, and (c) a thermodynamic mechanism for pumping thermal energy between the internal side and the external side in either direction. Korin uses membranes to pre-condition air in conjunction with a refrigeration air conditioning system, and does not perform or anticipate any phase separation within the refrigerant itself. Furthermore, although membranes have been used in various separation applications, their use for heat pump systems has been limited. U.S. Patent Nos. 4,152,901 and 5,873,260 propose to improve an absorption heat pump by using of a semipermeable membrane and pervaporation membrane, respectively. U.S. Patent No. 4,467,621 proposes to improve vacuum refrigeration by using sintered metal porous membrane, and U.S. Patent No. 5,946,931 describes a cooling evaporative apparatus using a microporous PTFE membrane. These patents do not anticipate the use of membranes for phase separation within an absorption system, but rather within adsorption systems.

[0011] United States Patent No. 4,152,901 to Munters discloses a method and apparatus for transferring energy in an absorption heating and cooling system where the absorbent is separated from the working medium by diffusing the mixture under pressure through a semi-permeable membrane defining a zone of relatively high pressure and a zone of relatively low pressure, higher than the ambient pressure. The '901 patent does not anticipate supercritical operation, as it explicitly states that the "dilute solution of working medium is passed to the evaporator upon being depressurized, while the concentrated absorbent solution, upon being reduced to the ambient pressure, is passed into the sorption station".

[0012] United States Patent No. 5,873,260 for "Refrigeration apparatus and method" to Linhardt, et al. utilizes the increased pressure of the absorbent/refrigerant solution that is then supplied to a pervaporation membrane separator to provide as one output stream a vapor-rich refrigerant, and as another output stream a concentrated liquid

absorbent. The '260 patent does not anticipate supercritical fluids as explicitly stated "the pressure of the substantially vaporized refrigerant input to the absorber is less than 50 psia" and "the pressure of the absorbent/refrigerant solution entering the membrane separator is within the range of about 250 to 400 psia." The '260 patent further notes that "Osmotic-membrane-absorption refrigeration cycles are also capable of reaching low temperatures and may have a COP higher than conventional ammonia/water heat- separation systems, but require very high pressures, of the order of 2,000 psia or more to force the refrigerant through the pores of the osmotic membrane." It is to be noted that a pervaporation membrane operates in a totally different fashion from the prior art membrane separation processes used in refrigeration and heat pump systems. Such prior art membrane systems rely on osmotic pressure to force the refrigerant through the membrane thereby separating the refrigerant from other constituents. For the ammonia- water pair, this conventionally requires pressures of the order of magnitude of 2,000 to 4,000 PSI and higher. Osmotic membranes are porous which allows the ammonia to pass through the membrane. Pervaporation membranes are not porous, but pass constituents through the membrane by dissolving the selected material into the membrane. This allows a much lower driving force, significantly less than 400 PSI ₅ to act as the driver. In the case of an ammonia- water mixture, the pervaporation membrane, selectively passes ammonia and water vapor and rejects liquid water. [0013] United States Patent No. 6,739,142 for "Membrane desiccation heat pump" to Korin discloses a system that includes a membrane permeator for removing vapor from a process gas and for providing a vapor-depleted process. This patent does not disclose the use of any supercritical fluids.

[0014] United States Patent No. 6,918,254 for "Superheater capillary two-phase thermodynamic power conversion cycle system" to Baker discloses a two-phase thermodynamic power system including a capillary device, vapor accumulator, superheater, an inline turbine, a condenser, a liquid pump and a liquid preheater for generating output power as a generator through the generation of a staggered or pulsed release of vapor flow. The capillary device, such as a loop heat pipe or a capillary pumped loop, is coupled to a vapor accumulator, superheater, the inline turbine for generating output power for power generation, liquid pump and liquid preheater. The capillary device receives input heat that is used to change phase of liquid received from the liquid preheater, liquid pump and condenser into vapor for extra heating in the superheater used to then drive the turbine. A superheater in combination with a liquid

pump and preheater are implemented for use with the evaporator for improved thermal efficiency while operating at maximum cycle temperatures well below other available power conversion cycles. The '254 patent requires a capillary device including loop heat pipes and pumped loop in order to increase the single working fluid (i.e., to achieve the pressure differential resulting from the gain in thermal energy) pressure in lieu of the traditional utilization of a compressor to increase pressure within a thermodynamic power conversion cycle. Furthermore, the '254patent utilizes the superheater stage to eliminate any liquid drops in order to avoid liquid impingement within turbine blades. The '254 patent is also a low pressure device having low pressure differentials between the high pressure and low pressure stage as specifically noted by its reference to capillary wicks with pores sizes of about one micron (commercially available) that can sustain a pressure differential of approximately ten psi. In conclusion, '254the patent does not enable the utilization of working fluids including fluids characterized as supercritical, binary composition, and / or non-toxic fluids. The patent '254 is dependent on the utilization of a capillary device as a means to achieve a pressure differential.

[0015] United States Patent No. 5,899,067 for "Hydraulic engine powered by introduction and removal of heat from a working fluid" to Hageman discloses a thermal source as a means to increase a working fluid's pressure which in turn drives a piston for pumping, or alternatively refers to the piston being connected to a generator to result in electricity. The '067 patent is dependent in its operation of sequentially heating and cooling a fluid to enable the pressure on the piston to be increased by heating and then decreased by cooling to enable recovery from the fully expanded to fully compressed positions. The '067 patent is both a low pressure device, utilizes a single working fluid, and being comprised of a moving piston, has relatively very little surface, area all resulting in slow power conversion rates and large physical size.

[0016] "Poly(ionic liquid)s as New Materials for CO2 Absorption" by Youqing Shen et al., Department of Chemical and Petroleum Engineering, University of Wyoming, Laramie, Wyoming 82071, USA, received for publication on February 9, 2005, identifies that simply making ionic liquids into polymeric forms significantly increases CO.sub.2 sorption capacity as compared with ionic liquids. Shen et al., further notes that especially the polymers of tetraalkylammonium-based ionic liquids have CO.sub.2 sorption capacities 6.0—7.6 times of those of room temperature ionic liquids. The CO.sub.2 sorption and desorption of the polymer solids are very fast, and the desorption is

completely reversible. Shen et a!., then specifically note the utilization of said polymers as being "very prospective as sorbent and membrane materials for CO.sub.2 separation".

[0017] Exemplary poly(ionic liquid)s, as noted by Shen et al., are comprised of ionic liquids PF.sub.6 anions having the highest CO.sub.2 -sorption capacity. More specifically, poly(ionic liquids) include l-[2-(Methylacryloyloxy)ethyl]-3-butyl- imidazolium tetrafluoroborate ([MABI] [BF.sub.4]) and l-(p-vinylbenzyl)-3-butyl- imidazolium tetrafluoroborate ([VBBI] [BF.sub.4], poly[l-(4-vinylbenzyl)-3- butylimidazolium tetrafluoroborate] (PVBIT), poly[(l-(4-vinylbenzyl)-3- butylimidazolium hexafluorophosphate] (PVBIH), and poly[2-(l-butylimidazolium-3- yl)ethyl methacrylate tetrafluoroborate] (PBIMT). Specific results testing particle size yielded the conclusion that CO.sub.2 absorption capacity is mainly dependent on chemical structure of poly(ionic liquid)s, while the rate of CO.sub.2 absorption is dependent on particle size.

[0018] Shen et al., clearly by the polymer being stationary as either a sorbent or membrane materials, does not anticipate the utilization of poly(ionic liquid)s as being heat transfer fluid or working fluid within a thermodynamic cycle.

[0019] The prior art lacks a high efficiency, a system with a coefficient of performance greater than 0.7, environmentally friendly and efficient absorption cycle that uses a non-toxic, non-corrosive working fluid with a positive working pressure.

SUMMARY

[0020] A safe, environmentally friendly absorptive cooling, heating, and energy generation process is provided. The process uses a carbon dioxide absorption cycle that utilizes a liquid, non-toxic absorbent such as ionic liquids, from which the carbon dioxide gas is absorbed. Only the carbon dioxide refrigerant is circulated to the evaporator and condenser heat exchangers, the components directly in contact with breathable air, thus avoiding a series of drawbacks associated with the absorber. The further incorporation of a thermodynamic hydraulic pump increases the energy efficiency, especially in combustion power generation cycles, as it eliminates a substantial portion of energy utilized for compression prior to combustion.

[0021] One aspect of the invention is to integrate an absorption heat pump with integral power extraction capabilities to a standard vapor compression heat pump as a means of increasing total power conversion and cooling coefficient of performance.

[0022] The figures depicted within the specification of the invention provide exemplary configurations of the most important components of the energy conversion system. A detailed description of the figures is provided in the following paragraphs.

BRIEF DESCRIPTION OF DRAWINGS

[0023] Fig. 1 is a flowchart view of the absorption heat pump depicted with an expansion turbine configuration as the mechanical energy extraction device.

[0024] Fig. 2 is a flowchart view of the absorption heat pump depicted with an expansion turbine configuration as the mechanical energy extraction device driving a vapor compression pump (i.e., compressor).

[0025] Fig. 3 is a flowchart view of the absorption heat pump depicted with a magnetic refrigeration heat pump configuration as non-thermal means of increasing strong solution temperature.

[0026] Fig. 4 is a flowchart view of the absorption heat pump depicted with a sealed containment of an expansion turbine configuration

[0027] Fig. 5 is a flowchart view of the absorption heat pump depicted with a multiple stage heat pump system's condenser pre-heating strong solution.

[0028] Fig. 6 is a three dimensional view of the absorption heat pump depicted with a pre-heating of strong solution through the containment of combustor and recuperator.

[0029] Fig. 7 is a cross-sectional view of the absorption heat pump depicted with the strong solution desorption thermal energy obtained by an integral microchannel heat exchanger within solar collector.

[0030] Fig. 8 is a flowchart view of an absorption heat pump depicted in a Goswami cycle.

[0031] Fig. 9A and Fig. 9B are flowchart views of a thermodynamic hydraulic pump.

[0032] Fig. 10 is a flowchart view of non-thermal nanofiltration membrane to desorb refrigerant from strong solution. [0033] Fig. 1 IA, 1 IB, 11C, and 1 ID are flowchart views of multiple configurations of two stage absorption heat pump systems.

[0034] Fig. 12 is a flowchart view of multiple use refrigerant desorbed from an absorption heat pump system.

[0035] Fig. 13 is a flowchart view of multiple use weak solution and/or refrigerant to clean combustion byproducts.

[0036] Fig. 14 is a flowchart view of an absorption heat pump system as an integral component of a biomass to biofuel conversion process. [0037] Fig. 15 is a flowchart view of an integrated liquid desiccant and combustion sytem.

[0038] Fig. 16 is a flowchart view of a membrane filtration system with pressure equilibrium across the membrane.

[0039] Fig. 17 is a flowchart view of an integrated combustion system having independent control of a compressor and energy extraction device.

[0040] Fig. 18 is a flowchart view of a cavitation enhanced absorption heat pump and enhanced biomass to biofuel conversion process.

[0041] Fig. 19 is a flowchart view of a absorption heat pump utilizing bottom cycle waste heat to power the compressor. [0042] Fig. 20 is a flowchart view of a thermal bus switching circuit.

[0043] Fig. 21 is a flowchart view of a thermal bus and a range of thermal sources.

[0044] Fig. 22 is a flowchart view of a thermal bus and a range of thermal sinks.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] The inventive high efficiency absorption heat pump device, hereinafter also referred to as "ScHPX", is now set forth as a device principally comprised of a supercritical absorption heat pump, low vapor pressure absorbers and a series of integral components to achieve desorption using non-thermal means. [0046] The term "thermodynamic cycle" is defined as a process in which a working fluid undergoes a series of state changes and finally returns to its initial state.

[0047] The term "solar energy" is defined as energy derived from the sun, which most often refers to the direct conversion of radiated photons into electrons or phonons through a wide range of means. Solar energy is also indirectly converted into additional energy forms such as the heating of ground water (a.k.a. geothermal water).

[0048] The term "geothermal" is defined as relating to the internal heat of the earth, which is impacted by absorbed solar energy.

[0049] The term "ionic liquids" "ILs" is defined as liquids that are highly solvating, non-coordinating medium in which a variety of organic and inorganic solutes

are able to dissolve. They are effective solvents for a variety of compounds, and their lack of a measurable vapour pressure makes them a desirable substitute for Volatile Organic Compounds (VOCs). Ionic liquids are attractive solvents as they are nonvolatile, non-flammable, have a high thermal stability, and are relatively inexpensive to manufacture. The key point about ionic liquids is that they are liquid salts, which means they consist of a salt that exists in the liquid phase and have to be manufactured; they are not simply salts dissolved in liquid. Usually one or both of the ions is particularly large and the cation has a low degree of symmetry. These factors result in ionic liquids having a reduced lattice energy and hence lower melting points. [0050] The term "electride" is defined as being like alkalides except that the anion is presumed to be simply an electron which is localized to a region of the crystal between the complexed cations.

[0051] The term "alkalide" is defined as a class of ionic compounds where the Anions are of the Type I group (Alkali) elements Na, K, Rb, Cs (no known 'Lithide' exists). The cation is an alkali cation complexed by a large organic complexant. The resulting chemical form is A+ [Complexant] B-, where the complexant is either a Cryptand, Crown Ether, or Aza-Crown.

[0052] The term "nanofluid" is defined as a fluid that contains nanoscale powders, which are powders having a diameter of less than about 1 micron and preferably less than about 100 nanometers.

[0053] The term "supercritical" is defined as the point at which fluids have been exploited above their critical temperatures and pressures.

[0054] The term "heat pump" is defined as the transport of thermal energy extracted from a heat source to a heat sink by means including vapor compression, absorption, and adsorption.

[0055] The term "cyclic compound" is one in which a series of carbon atoms are connected together to form a loop or ring. Benzene is a well known example.

[0056] The term "polycyclic" is used when more than one ring is combined in a single molecule, and the term "macrocycle" is used for a ring containing more than a dozen atoms.

[0057] The term "electron acceptor" is a compound that receives or accepts an electron during cellular respiration. The process starts with the transfer of an electron from an electron donor. During this process (electron transport chain) the electron acceptor is reduced and the electron donor is oxidized. Examples of acceptors include

oxygen, nitrate, iron (III), manganese (TV) ₅ sulfate, carbon dioxide, or in some cases the chlorinated solvents such as tetrachloroethene (PCE), trichloroethene (TCE), dichloroethene (DCE), and vinyl chloride (VC).

[0058] The term "absorption" is widely accepted in the application of heat pumps for cooling. Absorption, in chemistry, is a physical or chemical phenomenon or a process in which atoms, molecules, or ions enter some bulk phase - gas, liquid or solid material. This is a different process from adsorption, since the molecules are taken up by the volume, not by surface. A more general term is sorption which covers adsorption, absorption, and ion exchange. [0059] The term "stoichiometric combustion" is the ideal combustion process during which a fuel is burned completely. A complete combustion is a process which burns all the carbon (C) to (CO.sub.2), all hydrogen (H) to (H.sub.2 O) and all sulfur (S) to (SO.sub.2). If there are unburned components in the exhaust gas such as C, H.sub.2, CO the combustion process is incomplete. [0060] The term "excess gas" is defined as the amount of gas in excess of the stoichiometric amount.

[0061] The term "process intensification reactor" is defined as the miniaturization of chambers in which chemical reactions take place. The utilization of micromixing, particularly with supercritical fluids, achieves high mass transfer and fast reaction times. Supercritical fluids include gases such as carbon dioxide, methane, methanol, ammonia, ethanol, butanol, and hydrogen. The supercritical fluids can be prepared into emulsions, which preferably are nanoemulsions as a means of increasing surface area significantly. Devices include hydrodynamic cavitation devices, microchannel reactors, spinning disk, spinning tube in tube, oscillating flow reactors, and reactive distillation reactors. [0062] The ScHPX, an extension of the Champagne Heat Pump as developed by

Jones, establishes novel methods to decrease the desorption temperature and total energy requirements to achieve desorption. The refrigerant, which is the circulating working fluid, is comprised of any environmentally friendly fluid (a.k.a. greenhouse friendly) whereby the fluid expands into a gas within the evaporator. A wide range of refrigerants, specifically those known in the art for absorption heat pumps are compatible with

ScHPX. The preferred refrigerant is selected from the group of ammonia and carbon dioxide. The more preferred refrigerant is carbon dioxide, which has reduced toxicity and perceived safety. The specifically preferred refrigerant operates within the supercritical or transcritical range, as determined by the specific refrigerant.

[0063] The inventive heat pump also achieves superior desorption through a modified spinning disc reactor "SDR". SDR's have extremely high heat and mass transfer coefficients. The strong solution is simultaneously pumped into the center of the disc and forms a thin film as the liquid moves outwards. The centrifugal force creates intense interfering waves, which generate high heat transfer between the strong solution and the spinning disc. The SDR can also be used through the intense local mixing to accelerate the absorption of the supercritical CO.sub.2. into the weak solution.

[0064] The ScHPX is further comprised of an absorber in which the refrigerant is absorbed as a method to either increase temperature lift (i.e., transform a relatively low temperature fluid to a higher temperature (a.k.a. higher quality) of a thermal source, or provide cooling. The energy requirements of an absorption system is limited to traditionally a thermal source for desorption, and mechanical or electrical energy to pump / pressurize the strong solution. The term "energy efficiency" is the energy output divided by the energy input required to produce the desired output. A high efficiency absorption system, which is characterized in terms of coefficient of performance "COP", requires methods to reduce principally the desorption energy requirements. Desorption is effectively the process in which the refrigerant separates from the absorber.

[0065] The inventive ScHPX utilizes a range of absorbers which includes at least one absorber selected from the group consisting of ionic liquids, ionic solids, electride solutions, and alkalide solutions. Ionic liquids and solids are recognized in the art of environmentally friendly solvents. Electride and alkalide solutions are recognized in the art of chemical reduction methods and oxidation methods respectively. ScHPX uniquely features ionic liquids "IL", which have very low if not negligible vapor pressure, preferably ionic liquids compatible with supercritical carbon dioxide "scCO2". The inventive combination of scCO2 and ILs have excellent carbon dioxide solubility and simple phase separation due to their classification as partially miscible fluid combinations. Partially miscible fluids are both miscible and immiscible as a direct function of both pressure and temperature. A partially miscible fluid in its immiscible state can be simply decanted for phase separation, which is inherently a low energy separation method. The phase behavior of CO.sub.2 with ionic liquids and how the solubility of the gas in the liquid is influenced by the choice and structure of the cation and the anion.

[0066] The preferred embodiment of the working fluid is an ionic liquid and poly(ionic liquid) "emulsion" having the combined benefits of fluid flow of the ionic

liquid monomers and the enhanced absorption/ desorption properties of the poly(ionic liquid) polymers, also referred to as ionic polymers. The standard categorization of the ionic liquid "emulsions" is the characterization as one phase of the emulsion as being an "ionic liquid monomer" or abbreviated as "ILM" phase and the other phase as being an "ionic liquid polymer" or abbreviated as "ILP" phase. The ILM and ILP phases are described also as an ionic liquid slurry, hereinafter referred to as "ILS". A preferred ILS is comprised of at least one ionic liquid monomer and at least one ionic liquid polymer. The preferred ILS is comprised of an ILP having particle size approximately between about 0.1 nanometers and about 500 microns. The particularly preferred ILS is comprised of an ILP having particle size approximately between about 10 nanometers and about 5 microns. And the specifically preferred ILS is comprised of an ILP having particle size approximately between about 0.1 nanometers and about 500 nanometers. Prior work utilizing nanoscale powders has identified 100 nanometers, without being bound by theory, as a significant size threshold having a quantum effect on heat transfer. Nanoscale powder size is a highly non-linear process in which particles of 50 nanometers have superior results as compared to 100 nanometers. And likewise, 30, 20, and 10 nanometers are each superior to the respective larger size. Another significant threshold is 10 nanometers, again without being bound by theory, as a size threshold wherein powder sizes of less than 10 nanometers have heat transfer performance benefits that are not realized for powder sizes above 10 nanometers. The mean free path of phonons is accepted as being less than 10 nanometers.

[0067] Most noted are the inclusion of binary working fluids having at least one fluid selected from at least one from the group of ionic liquid, poly(ionic liquid) polymer, electride, alkalide, and nanofluid solutions. The particularly preferred working fluids have at least one fluid selected from the group consisting of ionic liquids, combination of ionic liquids and poly(ionic liquid) polymers. The specifically preferred working fluid is comprised of a heat transfer fluid comprised of at least one ionic liquid and at least one poly(ionic liquid) polymer. The further inclusion of nanoscale powders including conductive powders, semiconductive powders, or combinations thereof increase the thermal conductivity of the working fluid.

[0068] The utilization of a poly(ionic liquid) polymer and at least one additional working fluid selected from the group consisting of ionic liquids, non-polymeric solid adsorbents, and combinations thereof maintains the ability of the working fluid to be

pumped and circulated through heat exchangers for increased heat transfer while demonstrating superior absorption and desorption of refrigerant rates.

[0069] A specifically preferred ionic liquid or ionic polymer is itself magnetic having distinct advantages including higher rates of absorption and desorption when subjected/removed from magnetic fields, and the ability to isolate said materials from the refrigerant more readily by non-thermal means.

[0070] The further addition of at least one non-ionic compound selected from the group consisting of cyclic, polycyclic, and macrocycle compounds, and combinations thereof including antioxidants, polyphenols, lignans, and vitamins, provides the working fluid with enhanced thermal stability and operating life, and without being bound by theory enhanced heat transfer and electron transfer.

[0071] Electron transfer mediators include polycationic protein, thialoto-bridged complexes, thiolated complexes, metalloproteins, protein complexes having an iron-sulfur cluster, trehalose complexes, iron-sulfur cluster, sodium-ammonia, sulfur-ammonia, a chitosan complex including chitosan lactate, chitosan alpha lipoic acid, or thiolated chitosan, or combinations thereof. Additional additives impacting electron transfer include iron salts, derivatives of iron salts, potassium salts, lactic acid salts, derivatives of potassium salts, derivatives of lactic acid salts, phytic acid, gallic acid and combinations thereof. [0072] Energy conversion including absorption heat pumps are particularly preferred when further comprised of at least one additive selected from the group consisting of electron transfer mediator, electron donor, electron acceptor, ultraviolet absorber, infrared absorber, quantum dot, nanoscale powder, and combinations thereof. The utilization of nanoscale powders enhances heat transfer and electrical conductivity by quantum means, without being bound by theory. The addition of additives, preferably in the nanoscale range, has an impact on the conversion of photons to phonons, photons to electrons, electrons to phonons, phonons to electrons, etc.

[0073] The particularly preferred application of the heat transfer fluid is operable within thermal energy conversion devices including devices selected from the group consisting of solar thermal flat panels, solar thermal concentrator receivers, thermionics emission cell, thermovoltaic cell, electricity generator, compressor, and heat pump. And the specifically preferred application is whereby the fluid and at least one absorbed gas (preferably CO.sub.2) operable with the transcritical or supercritical region in solution whereby the subsequently desorbed gas is utilized within a thermodynamic cycle

including cycles selected from the group consisting of Goswami, Uehara, Kalina, Rankine, Carnot, Joule-Brayton, Ericsson, and Stirling.

[0074] Additional combinations of refrigerants and absorbers are recognized in the art as having partial miscibility. A further aspect of the inventions is the achievement of phase separation as a function of at least one function selected from the group consisting of temperature, pressure, and pH. The preferred solution further includes the utilization of small amounts of pH to vary solubility of the refrigerant within the absorber. The more preferred solution varies temperature and pressure, in combination with pH control using methods including electrodialysis. An additional method to enable phase separation is the application of electrostatic fields, as electrostatic fields increase solubility of ionic fluids.

[0075] The inventive ScHPX further leverages electride and alkalide solutions. The preferred electride solution is comprised of ammonia. The principal benefit of electrides is centered around the transfer of free electrons (i.e., energy state) between the cathode and anode. An additional benefit, which is important to the later incorporation of nanoscale powders, is the electride' s strong reducing characteristics. This is important as nanoscale powders, specifically metals, readily oxidize due in part to the powder's high surface area.

[0076] Yet another embodiment of the invention is the further inclusion of at least one nanoscale powder selected from of the group consisting of conductive, semi- conductive, ferroelectric, and ferromagnetic powders. Nanoscale powders, as recognized in the art, maintain colloidal dispersions while enhancing or varying a range of properties including magnetism, thermophysical properties (e.g., thermal conductivity), electrical conductivity, and absorption characteristics. The more preferred nanoscale powders are further comprised of nanoscale powders having nanoscale surface modifications, including surface modifications selected from the group of monolayer, and nanoscale multi-layers (i.e., surface coatings of less than 100 nanometers). The specifically preferred nanoscale powders enhance more than one parameter selected from the group consisting of thermophysical properties, electrical conductivity, and solar light spectrum absorption.

[0077] A yet further feature of the inventive ScHPX is the integration of mechanical energy extraction devices. The mechanical energy extraction devices enhance efficiency (i.e., COP) by extracting energy during the expansion stage of the refrigerant following the desorption step. Referring to Fig. I ₅ the mechanical energy can be

transformed by utilizing the refrigerant desorbed from the desorber 50 through a valve or flow regulator 20 into a wide range of useful forms of energy as known in the art, including an expansion turbine 65. The ScHPX ₅ depending on the operating conditions, has further cooling capacity through a heat exchanger 25 prior to refrigerant being absorbed in the absorber 30. These forms include transforming mechanical energy to electrical energy (e.g., alternating or direct current electricity generation), or driving pumps, compressors, or motors. These include energy extraction devices selected from the group consisting of gerotor, Quasiturbine, piston, spherical engine, expansion turbine, expansion pump, Stirling cycle engine, Ericsson cycle engine, and ramjet turbine. The preferred mechanical extraction device leverages the refrigerants supercritical state, which features relatively high mass flow "density" and operations within the supersonic range. Referring to Fig. 2, the more preferred mechanical extraction device is an integral supersonic device selected from the group consisting of compressor 15 and turbine 65. The specifically preferred device operates on either the ramjet or pulsejet principle. The result is a relatively compact high efficiency compressor or turbine for respectively inputting mechanical energy by pressurizing the strong solution or extracting mechanical energy by reducing the pressure during the expansion of the refrigerant.

[0078] Referring to Fig. 2, the ScHPX has the ability to be in fluid communication with a traditional vapor compression system, such as compressor 15. The refrigerant desorbed from the desorber 50 is further compressed with the vapor compressor 15 that elevates both the temperature and pressure as a method to increase the coefficient of performance when cooling is desired, as compressor energy is required only to incrementally increase the pressure gain beyond the desorber 50 pressure, which is significantly less electrically/mechanically energy intensive. The refrigerant is in fluid communication with a heat exchanger 25 that acts effectively as a condenser, which thermal energy can be transferred for many purposes including a second stage absorption heat pump desorber, preheating combustion air, preheating combustion fuel, heating a secondary heat transfer fluid, or combinations thereof.

[0079] As noted earlier, the most critical aspect to the efficiency in an absorption heat pump is the desorption energy. The ScHPX achieves desorption by the inventive combination of both non-thermal methods and traditional thermal methods. Traditional thermal methods, as known in the art, are achieved by simple heat transfer through air-to- liquid or liquid-to-liquid heat exchangers whereby a relatively hotter fluid transfers thermal energy to the relatively cooler strong solution. The preferred non-thermal

methods are selected from the group consisting of magnetic refrigeration, vapor compression heat pump, solar activated direct spectrum light absorption, electrostatic field, electrodialysis, membrane separation, electrodesorption, pervaporation, gas centrifuge, vortex tube CO.sub.2-liquid absorber, and decanting. Membranes used for CO.sub.2 removal do not operate as filters, where small molecules are separated from larger ones through a medium with pores. Instead, they operate on the principle of solution-diffusion through a nonporous membrane. The CO.sub.2 first dissolves into the membrane and then diffuses through it. Because the membrane does not have pores, it does not separate on the basis of molecular size. Rather, it separates based on how well different compounds dissolve into the membrane and then diffuse through it. An array of polyvinylchloride vinylacetate membranes, for example, allows for quicker permeation of CO.sub.2. Very small molecules and highly soluble molecules, small molecules (e.g., CO.sub.2) permeate faster than large molecules.

[0080] Referring to Fig. 10, an additional non-thermal means of desorption includes microwave and/or radio frequency energy. The preferred working fluid containing ionic liquids and ionic polymers are unique in their ability to absorb microwave energy. A preferred embodiment is the utilization of a nanofiltration device 400 that is void of materials that absorb microwave energy, absorb radio frequency energy, disrupt electrostatic field, disrupt magnetic field, or combinations thereof. The localized exposure of the strong solution to the aforementioned fields yields rapid and energy efficient desorption.

[0081] Membrane separation includes traditional ultra-filtration and nanofiltration as a method to separate components by means including molecular weight and particle size separation. [0082] Referring to Fig. 3, the more preferred non-thermal method utilizes the combination of ferroelectric / ferromagnetic nanoscale powders in combination with magnetic refrigeration 105 that utilizes the magnetocaloric effect to raise the strong solution 100 to higher than the desorption temperature, and the subsequent removal of the working fluid from the magnetic field enables the refrigerant 120 to desorb yielding weak solution 115 transforming the strong solution into weak solution by either utilizing less thermal energy from a heat exchanger 25 or even no thermal energy (i.e., without any heat exchangers). The specifically preferred implementation continuously and sequentially pulses the strong solution into at least two desorption zones. Sequentially

pulsing the strong solution into the desorption zone enables a reduction of the pumping energy required to pressurize the strong solution into the desorption zone.

[0083] Yet another aspect of the invention is the absence of a compressor in the standard absorption design. The only moving part is limited to a very small pump where small is in terms of energy consumed as compared to total system energy. The utilization of a free-piston pump offers the opportunity for high efficiency, quiet, low cost and oil free vapor compression. The absence of oil is important in achieving benefits including avoidance of oil solubilizing in the preferred supercritical carbon dioxide, which presents significant complexities, and eliminating the oil boundary layer created on the heat transfer surfaces, which presents a deterioration of heat transfer. An ultra high COP ScHPX does incorporate a vapor compression stage as a method to achieve COPs comparable and beyond the highest vapor compression heat pumps. The preferred compressors are also oil-free, which is achieved by incorporating many techniques as known in the art for reducing friction, including diamond coatings, diamond like coatings, ultrafine diamond coatings, air bearings, magnetically levitation and solid lubricants.

[0084] Another aspect of the invention further avoids the complexities associated with leak-free pumps or compressors. Referring to Fig. 4, the ScHPX thus further includes a sealed container 35, whereby the sealed container captures refrigerant leaked by the pumping system that is periodically evacuated into the weak solution. The sealed container captures low pressure strong solution which is leaked into the sealed container. A controller monitors the pressure within the sealed container to determine when a control valve is switched whereby the pump 460 between the absorber 30 and desorber 50, which normally pressurizes the strong solution into the desorber, now pressurizes the losses into the sealed container into the absorber. [0085] The physical size and the rate of absorption are additional important components of any absorption system. The inventive ScHPX further includes a cavitation device, whereby the cavitation device enhances the absorption rate by creating micro- bubbles with significantly greater surface area. The more preferred cavitation device is selected from the category of devices that create hydrodynamic cavitation. [0086] Physical size of the ScHPX is further reduced by the utilization of microchannel heat exchangers, whereby the supercritical fluids have reduced surface tension that counteract the fluid friction associated with high surface area heat exchangers.

[0087] ScHPX System Configuration

[0088] The inventive ScHPX is unique not only due to specific components but also in terms of operational configuration. A multistage absorption heat pump system, also known as a cascading system, whereby one distinct refrigerant A is used in at least one distinct stage and at least one other distinct refrigerant B is used in at least one other distinct stage. Each stage is in effect a distinct thermodynamic cycle, though each stage is coupled to the other as one's output is the other's input. The preferred ScHPX leverages the differences in desorption temperature of a refrigerant A and absorption temperature of refrigerant B. Referring to Fig. 5, in other words, the condensing thermal source (i.e. condenser 259) of one stage is the desorption thermal source of the other stage (i.e. condenser 258).

[0089] Yet another configuration is the ScHPX having direct infusion of a parallel energy generation system or combustor such that its exhaust is infused into the absorber. One key advantage is the capture of latent energy from the exhaust stream. A more preferred implementation utilizes techniques as known in the art to selectively enable the refrigerant to enter the absorber, thus the exhaust air is treated to remove byproducts, whereby byproducts include NO.sub.x and sulfur. This implementation achieves concurrent carbon dioxide sequestration. The cooling available from the ScHPX is then utilized to precool the combustion air to increase turbine capacity and energy efficiency.

[0090] Referring to Fig. 6, a further gain in efficiency is obtained by capturing thermal energy directly recovered from thermal conduction losses of a combustion chamber 230 and combustion recuperator 220. Recuperators are often utilized to capture waste heat, though thermal conduction through the external walls of the recuperator limit total energy recovered, especially for space constrained implementations such as mobile vehicle applications.

[0091] Thermal energy of the inventive ScHPX uniquely utilizes low quality thermal sources. One such source is a non-concentrated solar collector. The more preferred solution has an integral heat exchanger within the solar collector. Referring to Fig. 7, a more preferred implementation is a solar collector 300 that achieves at least one benefit selected from the group consisting of concentrating solar energy 310 as a means of reducing thermal losses and cooling photovoltaic cells 320. A specifically preferred implementation is an integral microchannel heat exchanger 340 to further reduce thermal losses and heat exchanger size. And the particularly preferred implementation has a

translucent film 330 separating the solar collector and heat exchanger, whereby photons from the solar spectrum enable photon stimulated desorption, thus reducing the desorption temperature. Stimulated desorption is also achieved by external electrical and electromagnetic fields. The further inclusion of nanoscale powders, including quantum dots and ultraviolet absorbers, enhance efficiency whereby the colloidal dispersion of powders within the absorber enhances direct conversion of photons to electrons, and subsequent electron transmission between cathode and electrode. The optimal solution has at least one solar collector stage followed by at least one solar concentrator stage where each stage creates an independent pressure zone (i.e., a superheated vapor state). [0092] The utilization of the inventive ScHPX as noted earlier yields higher power generating efficiency when the working fluid is further elevated to higher vapor states. The elevation of the working fluid to a first vapor state through the utilization of a relatively lower temperature heat source, such as waste heat or non-concentrated solar energy, is subsequently elevated to a higher vapor state through means including traditional vapor compressor, concentrated solar energy, a combustion source, a relatively higher temperature heat source, or combinations thereof. This elevation from one lower vapor state to subsequent higher vapor states can be repeated. The optimal energy efficiency replaces the utilization of the traditional vapor compressor with staggered increases in vapor states as a means of elevating vapor state through a series of thermodynamic stages via a thermal-hydraulic compressor / pump. The utilization of a high surface area heat exchanger as an integral component of the thermal-hydraulic pressure increasing zone enables rapid increases in pressure. The ability to rapidly increase the pressure within each zone enables the expansion device to receive a working fluid with a constant pressure. [0093] Numerous methods and devices exist to isolate one zone from the other.

One such means is a valve-less hydraulic pump comprised of a rotating cylinder having microchannels on the exterior portion of the rotating cylinder. The internal part of the rotating cylinder is exposed to the thermal source. The rotating cylinder is within a further external cylinder that seals each microchannel thus isolating each zone within the microchannel from the other zones. During the period of rotation, the working fluid within the microchannel increases in both temperature and thus pressure. The fluid enters an individual microchannel, preferentially from an inlet duct that is perpendicular to the microchannel along the entire length of the microchannel. Likewise, the exit duct has the

same orientation with respect to the microchannel, but offset rotationally along the cylinder.

[0094] Alternatively, the thermal-hydraulic compressor / pump incorporates a high surface area "solid" / slurry heated up to a specified temperature, that is subsequently placed into a "sealed container". The working fluid is then infused into the sealed container leading to a rapid increase hi pressure. The further incorporation of a spring piston to create a counter-force, preferentially such that the spring creates a constant force at least equivalent to the desired entry pressure of the expansion device. The spring further enables all of the superheated vapor to be ejected from the pressure zone and to maintain a constant pressure. The further utilization of a flexible bladder or springs enhances the constant pressure output from one pressure zone into the next or to the expansion device. A further advantage is that each pressure zone is essentially emptied for full occupancy by the prior pressure zone.

[0095] Referring to Fig. 9B, independent pressure zones are alternatively produced by the utilization of input diode 200, also referred to as input flow control devices. One such device utilized to regulate the output is an output diode 240, also referred to as a pressure relief valve. The utilization of a series of pressure relief valves, such that the cracking pressure is set incrementally to increase from the first pressure relief valve to the last with incremental increases for each pressure relief valve, is an effective way to prevent backflow and to provide inherently controllable means to increase working fluid vapor state. The aggregate of the series of pressure relief valves within a heat exchanger, heater 250, or displacement pump heater 220 is hereinafter referred to as a "pressure train" heat exchanger. Thus the pressure relief valve creates effectively independent zones within the pressure train. There are numerous methods known in the art to achieve precise and / or relative pressure control.

[0096] It is anticipated that the optimal scenario is such the last independent zone enables output flow to occur at a precise pressure, whether the pressure be controlled by an electronic pressure control in conjunction with a pressure sensor or a mechanical pressure relief valve. Such a relief valve can also be activated at a differential pressure between the prior output zone and the subsequent input zone.

[0097] Multiple parallel pressure train heat exchangers enable a constant pressure output to the power extraction device, such that an increase in either or both the number of pressure relief valves within the pressure train and / or the number of multiple parallel pressure trains leads to a most constant pressure output.

T/US2007/001120

[0098] Referring to Fig. 9B, additional devices that both create independent pressure zones include a Quasiturbine, quasiturbine used as positive displacement pump, positive displacement pump comprised of an inlet duct 210, an internal heater 220, and an exit duct 230, and hydraulic pump. [0099] Referring to Fig. 8, the final implementation feature of the ScHPX achieves higher efficiency by operating with the Goswami, Kalina, Baker, or Uehara cycle. Under the Goswami cycle, the ScHPX can be optimized to provide maximum levels of heating, cooling or energy, in addition to optimal total energy efficiency.

[00100] An absorption heat pump system is depicted having at least two pressure stages wherein each sequential stage has increasing pressure with first stage Pl less than second stage P2. The utilization of at least one "compression" stage comprised of absorption utilizes significantly less mechanical/electrical energy as compared to traditional vapor compression compressors. An absorption heat pump uniquely transforms thermal energy, which is often waste heat or readily available from supporting processes, into pressure due to lower energy requirements of compressing a

"incompressible" liquid versus a compressible vapor. The benefits are realized under numerous configurations including, referring to Fig. HA where working fluid / absorbent 450, such as ILs, is blended with strong solution from absorber 430, such as solid adsorbent (Al), into a second stage absorber 431. The blended strong solution (A2) is subsequently pumped 460 from a lower pressure (Pl) to an increased pressure (P2) that is in fluid communication with desorber 50. The desorbed refrigerant can optionally be compressed via a traditional vapor compressor 15 for numerous purposes including increasing condenser temperature and elevating pressure for a subsequent extraction process. Referring to Fig. 1 IB ₃ refrigerant desorbed from a first stage absorption heat pump desorber 50 and then regulated with flow valve 20 into a second stage absorption heat pump absorber 30 to be elevated to an increased pressure by pumping 460 the strong solution, which is incompressible. Referring to Fig. 11C, refrigerant desorbed from a first stage absorption heat pump desorber 50 and then regulated with flow valve 20 into a second stage vapor compression compressor 15 to be elevated to an increased pressure. Referring to Fig. 1 ID, alternatively depicts the vapor compression compressor 15 as the first stage, such as instances when the initial pressure PO is not sufficient for the refrigerant to be absorbed into the weak solution of the second stage absorption heat pump absorber 30, which is then subsequently elevated to a yet higher pressure with high mechanical/electrical energy efficiency by high pressure pump 460. All of these

aforementioned configurations utilize less mechanical/electrical energy as compared to a single, or even multiple, stage vapor compression compressor. [00101] Example 1

[00102] The absorption heat pump system wherein the operating mode to increase pressure from the initial pressure PO to the second stage pressure P2 is selected from the group consisting of (1) having a first adsorption or absorption stage having pressure Pl .sub.1 including solid or liquid adsorbents and a second adsorption or absorption stage having pressure P2.sub.l wherein first stage adsorbent Al. sub.1 is combined with a second stage liquid non-compressible adsorbent A2.sub.l and wherein Pl. sub.1 is less than P2.sub.l, or (2) having a first stage non-absorption compression stage including compressors or turbochargers wherein first stage increases pressure from initial pressure P0.sub.2 to operating pressure Pl.sub.2 and a second stage comprised of an absorption stage including solid or liquid adsorbents wherein Pl.sub.2 is less than P2.sub.2. [00103] Example 2

[00104] Example 1 is further comprised of a third stage to further increase the pressure wherein pressure increasing means includes a non-absorption compression stage (i.e., traditional compressors, turbochargers, etc.) or an absorption pumping stage. [00105] Referring to Fig. 12, the desorbed refrigerant, from desorber 50, wherein the refrigerant is subsequently processed in at least one post desorbtion process ^• stage selected from the group consisting of reaction chemistry (includes eixzymatic chemistry, fermentation chemistry), component extraction, supercritical combustion, and combinations thereof, wherein the combined mechanical and electrical energy (E.sub.l) required to increase working fluid pressure to operating pressure (Pl) is at least ten percent lower than the combined mechanical and electrical energy (E.sub.2) required to increase working fluid pressure to operating pressure (Pl) by compressing the compressible portion of working fluid. This configuration is an enabling approach to increase the utilization of benefits recognized in the art of supercritical extraction, supercritical combustion, and process intensification reactors "PIR". A wide range of specific devices as known in the art are recognized for PIR including hydrodynamic cavitation, microchannel, spinning disk, spinning tube in tube, oscillating flow, and reactive distillation reactors. The further incorporation of nanoscale catalysts within the PIR, and more specifically with the utilization of supercritical working fluids increases the reaction rates dramatically due to high mass transfer rates and lower viscosity. An

01120

post desorbtion process stage, most notably within biomass to biofuel conversion applications, is an enzymatic reaction that is further comprised of immobilized enzymes.

[00106] Biomass to biofuel conversion, most notably cellulose to ethanol, is widely known in the art to utilize enzymes. However, the failure to solubilize cellulose demands the use of "free" as compared to immobilized enzymes to obtain acceptable enzymatic conversion rates. The inventive utilization of ionic liquids, and preferably poly(ionic liquid) polymers of which a wide range are known in the art having the ability to solubilize cellulose, uniquely enables immobilized enzymes to be utilized in combination. The further utilization of refrigerants, particularly supercritical fluids including carbon dioxide significantly lowers the viscosity of the solubilized cellulose within the ILs. Poly(ionic liquid) polymer "PILP" are superior to ILs due to the relative ease in recovering the immobilized enzymes, which are incorporated into the PILP by means known in the art of immobilizing enzymes into polymers, especially when utilizing membrane filtration as a means to isolate the enzymatic converted biomass from the ILs and PILP. The combination of ILs and PILP provides the benefit of both immobilized enzymes, while having the relatively easy circulation of ILs in comparison to PILPs thus achieving effective biomass transport to the immobilized enzymes. A preferred embodiment of the inventive application has the unique ability for the immobilized enzymes to be reused to yield a dramatic economic and conversion rate, with the further advantage of having the subsequent ability to remove the spent enzymes from the IL and PILP slurry, which are then subsequently replenished with active enzymes, and again further subsequently immobilized within the PELP.

[00107] The immobilized enzymes, which are specialty proteins that catalyze chemical reactions are removed from ILs by the further addition of different enzymes that effectively transform the immobilized enzymes into byproducts including amino acids, protein hydrolysates, or combinations thereof. Short chain amino acids and protein hydrolysates have increased water solubility, thus can be washed from the IL and PILP slurry easily. Thus, the removal of immobilized enzymes takes advantage of the byproducts being insoluble or partially immiscible into the IL or PILP phase. The determination of when either/both the IP and PILP, and immobilized enzymes are "spent" with the requirement to be removed/regenerated/replaced is by placement of detectors to monitor at least one condition selected from the group consisting of ionic liquid absorption rate, ionic liquid desorption rate, catalytic conversion rate, enzymatic conversion rate, and combinations thereof.

[00108] Referring to Fig. 12, a series of sensors 70 are placed to monitor the strong solution, the weak solution, and the refrigerant within the absorption heat pump, and both prior and post to the subsequent process 470 that utilizes means to accelerate the biomass to biofuel conversion rate including catalysts and enzymes. An alternative subsequent process to the absorption heat pump system is supercritical combustion. The prior noted benefits of achieving supercritical pressures by utilizing waste heat, including from said supercritical combustion process, enables the parasitic process loss reduction of energy generated from the combustion process (i.e., energy coupled with the energy extraction device such as turbine) to be utilized to generate additional mechanical/electrical energy, while the low quality thermal energy is recovered to drive the compression of intake air.

[00109] Referring to Fig. 13, a yet further advantage of the present embodiment of the absorption heat pump, particularly the low energy availability of supercritical fluids, enables at least one component of the combustion waste byproducts to be removed from within the working fluid (e.g., CO.sub.2). The weak solution desorbed from desorber 50, which contains ILs and/or PILP, and/or the desorbed refrigerant into the combustion. process 480. It is widely recognized that supercritical carbon dioxide and ionic liquids, both individually and in combination, are superior solvents, thus operating the supercritical combustion process discontinuously enables the non-combustion portion of the discontinuous operation to clean away the combustion byproducts. The further utilization of a fuel containing excess gas greater than the gas required for stoichiometric combustion enables continuous removal of byproducts, specifically when the excess gas is supercritical CO2. Regardless of whether the weak solution and/or refrigerant are utilized to clean the combustion chamber from the combustion process 480, the "cleaning" fluid must have combustion waste byproducts removed from means known in the art for separation, including nanofiltration 400, prior to being utilized again within the absorption heat pump cycle.

[00110] Referring to Fig. 14, is another preferred embodiment wherein the absorption/adsorption/ion exchange of byproducts from biomass to biofuel conversion process, which include carbon dioxide, methane, methanol, or combinations thereof, are utilized to produce additional biofuels. Traditional corn-based starch to ethanol conversion is widely recognized as producing significant quantities of CO2, and additionally both utilizes a significant quantity of thermal energy while producing low quality waste heat. This waste heat recovered from biomass process 490 through heat

exchanger 25 is in fluid communication with desorber 50 through heat exchanger 25. Another benefit of the utilization of supercritical combustion is the ability to add at least one fuel additive 510 including chitosan, glycerine, cellulose, and lignan. The preferred embodiment is such that the chitosan, cellulose, and lignan are precipitated out of IL and PILP slurry by water injection, and specifically preferred within a microchannel as a means of creating particle size less than about 10 microns and more preferably less than about 1 micron and particularly preferred sizes less than about 100 nanometers. The high surface area enables more complete combustion 520, which reduces the production of char, ash, and tar. An excellent carrier for the biomass precipitates include at least one fuel additive selected from the group consisting of biodiesel, natural gas, butanol, ethanol, gasoline, carbon dioxide, ammonia, hydrogen, and water. Yet additional additives include water, wet biomass, glycerine, glycerol, glycol including a glycol, dimethyleglycol, trimethylene glycol, or combinations thereof. A fuel containing colloidal suspensions of biomass precipitates is ideally suited for supercritical combustion within a porous combustion chamber, as recognized in the art to produce effectively zero emissions. Alternatively, the desorbed refrigerant that is at supercritical pressures enables more effective process intensification reactions 530. The reactions include at least one further conversion process selected from the group consisting of catalytic reactions, combustion reactions, enzymatic reactions, and combinations thereof. A particularly preferred embodiment is the conversion of biomass byproducts into additional biofuels that are electrochemical Iy converted 500 into a liquid or gaseous biofuel. The specifically preferred configuration transforms waste heat to produce electricity which, at least in part, powers the electrochemical conversion process. This configuration significantly increases the revenue yield of the biomass to biofuel conversion plant, as the revenue per unit of energy produced is much greater than the wholesale price of electricity. The ability to remain off-grid and produce methanol (e.g., from CO2 + H2O in a reverse fuel cell) or other electrochemical reaction products has numerous benefits including more carbon dioxide neutrality, increased revenue, faster reaction rates due in part to supercritical pressures, higher electrical conductivity due in part to IL, PILP, electron transfer mediators, etc. and process intensification devices 530.

[00111] Referring to Fig. 15, another embodiment is an absorption heat pump system in fluid communication with a liquid desiccant system. A preferred embodiment includes the conversion of combustion processes to be supercritical combustion 520 where exhaust waste heat is recovered. The combination uniquely

enables the waste heat utilized from the liquid desiccant system 540 to be recovered via heat exchanger 25 to desorb 50 the strong solution, which can be subsequently recovered to preheat subsequent combustion cycle 550 including at least one selected from the group consisting of combustion cycle air intake, combustion cycle fuel, and combinations thereof. Continuing the process of waste heat recovery enables the combustion exhaust to be recovered to produce increased cooling, power, or combinations thereof by means including desorbing working fluid, regenerating spent/wet liquid desiccant system, or combinations thereof. Another configuration is an energy conversion system wherein the spent liquid desiccant from the liquid desiccant system 540, either as dry desiccant/wet desiccant and with/without refrigerant desorbed from the absorption system desorber 50 is further utilized as the fuel or one component of the fuel for the combustion cycle 550. The preferred liquid desiccant is comprised of glycerine, glycerol, or glycol including a glycol selected from the group consisting of dimethyleglycol and trimethylene glycol, or combinations thereof. This distinct capability yields fundamental advantages for integrating a variety of biofuel production into one plant, specifically the integration of a biodiesel plant having significant thermal energy and glycerine as byproducts, both being valuable inputs for ethanol production. A yet preferred embodiment recovers latent energy from said combustion cycle 550 exhaust becoming spent liquid absorbent and wherein said spent liquid absorbent is then utilized as the fuel or one component of the fuel for the combustion cycle. The spent liquid desiccant can be further comprised of at least one fuel selected from the group consisting of biodiesel, natural gas, butanol, ethanol, gasoline, carbon dioxide, ammonia, and hydrogen.

[00112] Referring to Fig. 16 is an enabling feature for the utilization of membrane filtration, including micro- and nanofiltration, under conditions of supercritical pressures. A series of detectors/controllers are required to maintain the pressure across the desorption chamber membrane nanofiltration 400 wherein the pressure differential across the membrane is less than maximum membrane operating pressure. A minimum of two detectors/sensors 70 are required to monitor the pressure on each side of the membrane. Flow valves 20 are required to vary the flow of the strong solution into the input side of the membrane while utilizing and controlling the flow of refrigerant to achieve precise pressure control. This occurs by simultaneously controlling the flow through flow valves 20 of refrigerant into the output side of the membrane to maintain the pressure differential into the acceptable operating levels in accordance to the membrane specifications. The isolated refrigerant can be optionally stored in a high pressure storage

tank 560, and can be further pressurized using a traditional vapor compression compressor 15 in order to maintain adequate pressure particularly during startup conditions. Each flow valve 20 of the working fluids is individually controlled for both sides of the chamber membrane. [00113] Referring to Fig. 17 is another feature realized by implementing a preferred embodiment of the absorption heat pump system, which is an energy conversion system comprised of an individually controlled compressor and energy extraction device, and a fuel combustion chamber wherein the compression energy is dynamically controlled or switched to maximize power generation. The compression energy is provided from at least one source selected from the group consisting of (a) thermal storage system 590, (b) high pressure storage tank 560 including air, working fluid, or hydraulic oil, (c) external preheater 580 including thermal energy from said fuel combustion chamber, solar, and geothermal sources, and (d) absorption heat pump utilizing waste heat for desorber 50 from at least one source selected from the group consisting of said fuel combustion chamber, biomass to biofuel conversion process, solar, and geothermal sources where expansion energy extracted from turbine 65 drives a compressor 15 to compressor intake air 570.

[00114] Referring to Fig. 18 is yet another feature wherein the refrigerant desorbed from desorber 50 is comprised of CO2. The CO2 is supercritical has distinct advantages in the preprocessing of biomass 600 wherein the working fluid passes through a separation process including nanofiltration 400 as a means of isolating carbon dioxide from other components within said working fluid including water, minerals, mineral salts, non-combustibles, combustion byproducts, or combinations thereof. The additional separation of cyclic, polycyclic, and macrocycle compounds including polyphenols, aromatic ring containing compounds from the biomass prior to biomass to biofuel conversion process 610 has benefits including increasing the conversion rate to biofuels and extracting high value add components to increase the revenue stream. The isolating of CO2 is an effective means of sequestering CO2, particularly because the CO2 is already at supercritical pressure therefore avoiding the significant energy penalty associated with traditional CO2 sequestration. Yet another preferred embodiment is the further inclusion of cavitation devices that enhance at least one rate selected from the group consisting of absorption 710, desorption 720, or combinations thereof. The relatively high viscosity of ILs and PILPs, especially with high solids biomass gains

significantly from the use of cavitation devices which provides intimate mixing while operating in the absorption mode, and stripping while operating in the desorption mode.

[00115] Referring to Fig. 19, another embodiment is an absorption heat pump system in fluid communication with a combustion process. A preferred embodiment includes the recovery of exhaust air 581 waste heat through recuperator 863 from the combustion process 480 such that the bottom cycle low quality energy is transformed into useful energy by the absorption heat pump system high pressure desorbed from desorber 50 refrigerant through a pressure exchanger 861, such as gerotor or a combination compressor and expander (e.g., turbine) with a common shaft, for "compressing" the intake air 570 to a higher pressure (preferably supercritical pressure). Another preferred embodiment preheats the intake air 570 through a condenser 860 that recovers the heat of absorption from absorber 30 (which has gained thermal energy via evaporator 862 within an air conditioning / refrigeration cycle). Another more preferred embodiment utilizes the exhaust air 581 in fluid communication downstream of recuperator 863 to at least in part provide thermal energy to desorb refrigerant and then to provide thermal energy through a heat exchanger 25 for a wide range of purposes including domestic hot water and preheating of process water. The resulting thermal energy from the aforementioned combustion process 480 can be utilized for a wide range of thermal energy conversion processes including steam cycle, process heat, boiler, and supercritical boiler.

[00116] Referring to Fig. 20, another embodiment is a dynamic thermal bus for switching a series of thermal sources, depicted here as a general heat exchanger 25 and heat pump 850 (i.e., in this scenario the thermal diode 93 reverses to be in fluid communication with condenser). The preferred embodiment has a switching array 94 comprised of at least an incoming switching circuit 95 and outgoing switches 92

(including normally open as shown with preferably one normally closed 91 as shown), as known in the art, having the capability to switch any thermal source from a series of thermal sources to any thermal bus circuit of a series of thermal bus circuits. A representative example of the varying thermal bus circuits is a series of circuits having a target temperature that deviates from the thermal bus temperature mean 834. This example utilizes three circuits having a temperature target differential often degrees Celsius below the mean respectively 833, 832, and 831, in addition to three circuits having a temperature target differential often degrees Celsius above the mean respectively 835, 836, and 837. Each thermal bus circuit has at least one sensor 70

including temperature sensor to detect the actual circuit temperature. Additional detector/measurements include mass flow rate, thermal energy flow rate, and pressure. Measuring the pressure is critical, especially when the pressures are in the supercritical range in order to maintain the pressure below bursting pressure, to minimize pressure losses. A preferred embodiment of the dynamic thermal bus is to integrate a series of sensors 70 to detect/monitor critical parameters, particularly parameters (hereinafter referred to as "non-linear parameters") to identify the non-linear algorithm for thermal source energy efficiency, thermal sink energy efficiency, thermal source end product coefficient of performance, and thermal sink end product coefficient of performance. (e.g., refrigeration, electrical energy produced, etc. divided by total energy input) as a function of at least one parameter selected from the group consisting of thermal bus heat exchanger inlet temperature, thermal bus heat exchanger outlet temperature, thermal bus mass flow rate, thermal source inlet temperature, thermal source outlet temperature, and thermal source mass flow rate. Numerous methods know in the art are anticipated to control fluid flow including valves, smart materials whose properties change as a function preferably though not limited to temperature, variable speed pumps, flow switches and thermal diodes.

[00117] Referring to Fig.21, an alternative embodiment is depicted showing a series of heat sources wherein a thermal source has insufficient thermal energy being transported away to the thermal bus from the thermal source leading to the switching circuit routing the thermal source thermal energy into thermal contact/communication directly to a thermal sink including heat pump 850 for temperature lift. Yet another embodiment is where a lower temperature circuit, such as supporting a refrigerator evaporator 920 is then directed in fluid communication to a thermal source including heat pump 851 for subcooling. The multiple circuit thermal bus is represented by an example of three circuits 810, 820, and 830 which are in switchable fluid communication by methods known in the art for switching flows and/or thermal transport as represented by switched circuit 840. Yet another embodiment is a configuration where the thermal sources within any one circuit are in series of thermal sources by sequentially increasing thermal source inlet temperature as a method to maximize heat transfer of each thermal source. Alternatively where the thermal sinks within any one circuit are in series of thermal sinks by sequentially decreasing thermal sink inlet temperature as a method to maximize heat transfer of each thermal sink.

[00118] A wide range of thermal sinks or sources are anticipated both within residential/commercial/ϊndustrial environments including refrigerator condenser 910, refrigerator evaporator 920, dish washer waste heat recovery 930 (also optionally with water recovery), oven cooler 940, water faucet sink 950, shower 960, electronics cooler 970, lighting cooler 980 (including LEDs particularly a series of LEDs), a heat pump condenser 990, heat pump evaporator 991, one or more external heat exchangers 992, and/or a window heat exchanger 993. The aforementioned window heat exchanger transforms non- visible light (i.e., ultraviolet and/or infrared spectrum) into thermal energy that is in thermal contact with a thermal bus circuit. The optimal implementation of the window heat exchanger is a visible light transparent composite, preferably comprised of a high thermal conductivity nanocomposite to transport the thermal energy into the thermal bus. The more preferred embodiment includes a visible light transparent nanocomposite film having high thermal conductivity, contained within the multi-pane cavity, in thermal communication with the window heat exchanger (preferably a supercritical pressure fluid heat exchanger, and particularly preferred a fluid having nanoscale additives with low visible light absorption and high infrared and/or high ultraviolet light absorption). The particularly preferred embodiment of the window heat exchanger is further comprised of a nanocomposite film having an exterior film reflecting to the interior infrared and/or ultraviolet spectrum waves. The heat exchanger is further comprised of a nanocomposite film on an interior pane that reflects infrared and/or ultraviolet spectrum waves from the exterior facing to back to the thermally conductive film and reflects infrared and/or ultraviolet spectrum waves from the interior of the building (in which the window heat exchanger is built) back into the occupied building space to minimize thermal losses. The window heat exchanger and/or thermally conductive film is preferably further comprised of aerogels as one such method to minimize thermal losses. The thermally conductive film and window heat exchanger are further thermally isolated from the window structure as known in the art.

[00119] Referring to Fig. 22, the thermal bus fluid flow rate is controlled within the preferred embodiment by a variable speed control of pump 460 utilizing a series of sensors 70 that detect/monitor a range of parameters to determine energy efficiency including incoming and outgoing temperature, fluid flow rate, energy consumption kilowatt hour "kwh", power generation kwh, BTTJ (i.e., thermal energy) meter. Due to non-linearity of thermodynamics, achieving the optimal total system energy efficiency is not simply dependent on maximizing thermal waste heat recovery

from thermal sources but rather precise flow control as the preferred method to impact the temperature change (i.e., delta T ) across thermal sources. The thermal bus is controlled to maximize the temperature gain of the highest thermal bus circuit within the constraints of thermal energy sinks maximum thermal energy demand including maximum flow rate and maximum temperature (i.e., the system will not increase the flow rate beyond the maximum useful level by aggregate of energy sinks or beyond the maximum useful temperature of any energy sink while concurrently sacrificing the energy efficiency of other energy sinks). The determination to maximize temperature of a thermal circuit has many penalty conditions in terms of individual component energy efficiency including (a) the reduction of total amount of recovered waste heat, (b) reducing the subcooling/precooling post condenser within a vapor compression system which may lead to lower energy efficiency to achieve air conditioning / refrigeration, (c) biomass preprocesses 600 and/or biomass fermentation processes have clear maximum process temperatures in which enzymatic reactions will deteriorate and enzymes could even become inactivated, (d) increasing temperature for removal of absorption energy within absorber 30 leads to lower absorption cooling, (e) increasing temperature beyond critical desorption temperature simply increases the amount of energy needing to be removed in the subcooling portion of the absorption cooling cycle, (f) increasing temperature beyond design limits of components such as turbine 65 blades may gain energy efficiency but at the cost of system lifetime where incremental revenue gain of power generation may not exceed incremental increase in maintenance expense, and (g) numerous thermal sinks are not operated in either steady state/equilibrium conditions including liquid desiccant cooling system 540 which in fact is discontinuously regenerated. Another feature of the preferred embodiment utilizes the aforementioned switcher circuit 840 to determine the output from a particular selected thermal bus circuit (e.g., highest temperature circuit 837) being routed in fluid communication to a particular selected thermal sink including devices such as refrigeration condenser 910, or intake air 570 for a subsequent combustion process.

[00120] The thermal bus fluid flow direction/pathway is controlled by a series of algorithms based on non-linear parameters representing the thermal sources and thermal sinks in fluid communication (i.e., connected) to the thermal bus. The thermal source(s) and thermal sink(s) are connected to at least one thermal bus circuit by a thermal interface including thermal diode and/or thermal switch (including thermal diode/switch of the following types as known in the art: liquid metal switches, phase

change materials, smart materials, switches comprised of movable thermal contact including high thermal conductivity nanocomposites such as a carbon nanotube array composite). The particular preferred thermal source/sink is connected via a switch circuit array having the means to vary thermal communication with at least two thermal bus circuits. The specifically preferred dynamic thermal bus switch circuit is controlled in accordance to a thermal bus control system comprised of at least a series of non-linear parameters and at least one thermal diode/switch. The dynamic thermal bus is further comprised of thermal storage devices preferably further comprised of sensors to provide real-time feedback of storage capacity level and temperature. The control system modes of operation include: (a) method to maximize total thermal energy to mechanical/electrical energy conversion, (b) method to maximize mass flow rate at highest achievable temperature, (c) method to maximize mass flow rate at lowest achievable temperature, (d) method to minimize energy consumption from fuel sources having green house gas emissions, (e) method to minimize total energy consumption cost from all sources where cost includes any green house gas emissions penalties, (f) aforementioned method "e" with further comprised of parametric operating constraints that ensure each thermal source and thermal sink (hereinafter also referred to as "equipment") meets minimum operating conditions, and (g) aforementioned method "f" further comprised of quantitative costs for failure to meet minimum operating conditions. The control system is further comprised of data including calendars, equipment operating schedules, predictive equipment operating schedules, predictive weather, and building occupancy schedules, and further comprised of non-linear algorithms including equipment energy consumption algorithms and equipment energy generation algorithms.