In general, embodiments of the present invention relate to silica aerogel materials and methods of fabrication, solar thermal aerogel receivers, and solar energy systems.
Currently available solar energy systems, such as parabolic trough collectors (PTCs), suffer from high cost per unit of exergy. Moreover, commercially available aerogels do not have the material properties necessary for use in a high-efficiency solar thermal receiver for use with e.g., flat reflectors. For example, currently available aerogels are typically not suitable for use at the high operating temperatures that facilitate efficiency.
In accordance with embodiments of the invention, a high-performance air-stable solar thermal receiver includes a hot thermal absorber insulated by an optically transparent thermal insulator, referred to herein as the solar thermal aerogel receiver (STAR). The innovative stack includes a monolithic aerogel layer that is optically transparent and thermally insulating (OTTI) and a black absorber in which the working fluid may be heated. The receiver may have the ability to achieve maximum solar-to-exergy conversion efficiencies of >37% at an optical concentration of 40 suns, providing thermal energy from the thermal absorber, at a reduced total system cost per unit exergy of <$1/Wx, and an estimated lifetime of >25 years.
The technology described herein, including the optically transparent and thermally insulating aerogels, may be useful for concentrating solar power (CSP), as well as solar heating and cooling applications. CSP is an especially promising technology for solar thermal conversion. (Weinstein, L. A., et al., Chem. Rev. 2015, 115, 12797-12838).
In an aspect, embodiments of the invention relate to an aerogel material including silica aerogel defining a porous material with pores having a mean radius of less than 5 nm with a standard deviation of 3 nm.
One or more of the following features may be included. The aerogel material may include percent solids of less than 10%. The aerogel material may include a mean particle size of 1.3 nm. The silica aerogel may have a solar absorptance of >0.9 and IR emittance of <0.3 when in thermal contact with a black absorber at a temperature of 400° C.
The description of elements of the embodiments of other aspects of the invention may be applied to this aspect of the invention as well.
In another aspect, embodiments of the invention relate to an aerogel material including silica aerogel having (i) greater than 95% solar-weighted transmittance at a thickness of 8 mm for wavelengths selected from the range of 250 nm to 2500 nm; and (ii) a 400° C. black-body weighted specific extinction coefficient of greater than 8 m2/kg for wavelengths selected from the range of 1.5 μm to 15 μm.
One or more of the following features may be included. The silica aerogel may have a thermal conductivity of less than 0.025 W/mK at room temperature and less than 0.1 W/mK at 400° C.
The description of elements of the embodiments of other aspects of the invention may be applied to this aspect of the invention as well.
In another aspect, embodiments of the invention relate to a method for forming a silica aerogel. The method may include the steps of diluting tetramethyl orthosilicate (TMOS) by methanol to create a TMOS solution; and adding an ammonia solution comprising ammonia and water to the TMOS solution to form a silica aerogel precursor. The molar ratio of ammonia to TMOS may be less than 0.0025.
One or more of the following features may be included. The method may further include allowing the silica aerogel precursor to gel, thereby forming the silica aerogel. The method may further include annealing the silica aerogel to reduce the size of pores in the silica aerogel. The pores may have a mean radius of less than 5 nm with a standard deviation of 3 nm. This pore size may be attained either before or after annealing.
The method may further include increasing the spectral selectivity of the aerogel insulation layer may by doping the silica aerogel with nanoparticles, such as tin oxide, indium tin oxide, carbon etc., that have strong absorption in the mid-infrared range.
The description of elements of the embodiments of other aspects of the invention may be applied to this aspect of the invention as well.
In another aspect, embodiments of the invention relate to a solar thermal aerogel receiver which may include (i) an opaque frame defining an opening; (ii) an aerogel layer disposed in the opaque frame, with at least a portion of the aerogel layer being disposed proximate the opening; and (iii) a heat transfer fluid pipe in thermal contact with and proximate the aerogel layer.
One or more of the following features may be included. The aerogel layer may include silica aerogel. The silica aerogel may define a porous material with pores having a mean radius of less than 5 nm with a standard deviation of 3 nm. The aerogel layer may include an absorber layer. The aerogel layer may include silica aerogel having (i) greater than 95% solar-weighted transmittance at a thickness of 8 mm for wavelengths selected from the range of 250 nm to 2500 nm; and (ii) a 400° C. black-body weighted specific extinction coefficient of greater than 8 m2/kg for wavelengths selected from the range of 1.5 μm to 15 μm.
The heat transfer fluid pipe may include a black absorber layer.
The solar thermal aerogel receiver may further include a transparent outer layer disposed in the opening in the opaque frame. The transparent outer layer may include at least one of glass and a transparent polymer. The transparent outer layer may form at least a portion of a flat bottom surface of the opaque frame. The aerogel layer may be in direct contact with the transparent outer layer. The transparent outer layer and the aerogel layer may define an air gap therebetween. The opaque frame may further include an insulating layer.
The receiver may have a maximum solar-to-exergy conversion efficiency of greater than 35% at an optical concentration of 40 suns.
The description of elements of the embodiments of other aspects of the invention may be applied to this aspect of the invention as well.
In another aspect, embodiments of the invention relate to a concentrating solar energy system including a solar thermal aerogel receiver and at least one reflector configured to direct sunlight to the opening. The solar thermal aerogel receiver may include an opaque frame defining an opening, an aerogel layer disposed in the opaque frame, with at least a portion of the aerogel layer being disposed proximate the opening, and a heat transfer fluid pipe in thermal contact with and proximate to the aerogel layer.
One or more of the following features may be included. The aerogel layer may include an absorber layer. The aerogel layer may include silica aerogel. The silica aerogel may define a porous material with pores having a mean radius of less than 5 nm with a standard deviation of 3 nm. The aerogel layer may include silica aerogel having (i) greater than 95% solar-weighted transmittance at a thickness of 8 mm for wavelengths selected from the range of 250 nm to 2500 nm; and (ii) a 400° C. black-body weighted specific extinction coefficient of greater than 8 m2/kg for wavelengths selected from the range of 1.5 μm to 15 μm.
The heat transfer fluid pipe may include a black absorber layer. The opaque frame may further include an insulating layer. The solar thermal aerogel receiver may have a maximum solar-to-exergy conversion efficiency of greater than 35% at an optical concentration of 40 suns.
The concentrating solar energy system may further include a transparent outer layer disposed in the opening. The transparent outer layer may include at least one of glass and a transparent polymer. The aerogel layer is in direct contact with the transparent outer layer. The transparent outer layer and the aerogel layer may define an air gap therebetween.
The transparent outer layer may form at least a portion of a flat bottom surface of the opaque frame. The description of elements of the embodiments of other aspects of the invention may be applied to this aspect of the invention as well.
In the drawings, like reference characters generally refer to the same parts throughout different views. Also, the drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention. In the following description, various embodiments of the invention are described with reference to the following drawings, in which:
The STAR configuration provides high receiver efficiency at low cost. The performance enhancement may be achieved through the reduction of thermal losses due to aerogel properties and receiver design. Cost reduction may be at least partially attributed to the STAR being well suited for use with linear Fresnel reflector (LFR) concentrating optics, which may be significantly cheaper than the commonly used parabolic trough concentrators (PTC). The STAR receiver may include air stable absorber coatings/aerogels that further eliminate the cost and complexity of a vacuum-evacuated receiver, which is the industry standard. The inclusion of air-stable absorber coatings/aerogels also enables operation at higher temperatures (up to 600° C.), which further increases receiver efficiency.
Silica Aerogel Properties
In some embodiments of the invention, a silica aerogel is synthesized with improved material properties, allowing the silica aerogel to, e.g., enhance the performance of the STAR. Silica aerogels have a spectral selectivity that allows solar radiation to pass through the bulk yet trap infrared (IR) radiation. In this way, silica aerogels may be both optically transparent and thermally insulating.
Generally, the thermal insulation characteristics of aerogels effectively reduce the outer surface temperature, reducing the overall heat loss in the STAR compared to the overall heat loss in vacuum-gap receivers. Silica aerogels may increase receiver efficiency and reduced concentration requirements. Aerogels are transmissive at most solar wavelengths because there are no absorption modes for silica at these wavelengths. However, Rayleigh scattering, which is a function of aerogel pore size, reduces the transmission for short wavelengths. By varying the pH during the aerogel synthesis process, and/or varying the drying time during the drying process, the pore size and Rayleigh scattering may be controlled. Although silica aerogels are naturally strongly absorbing from 5-30 μm, absorption from 3-5 μm may be increased through the addition of water or other dopants into the aerogel as further described below.
The thermal conductivity of an aerogel also depends strongly on the aerogel microstructure, which is improved in conjunction with tailoring of optical properties. The thickness of the aerogel also affects the properties of the aerogel, whereby thicker aerogels reduce the surface temperature and corresponding radiative and conductive losses. However, a thicker aerogel may also result in a decrease of the optical transmission. The optimal thickness is therefore that which maximizes the exergetic efficiency of the system. In some embodiments, an 8 mm aerogel sample has a thermal conductivity of less than 0.025 W/mK at room temperature and less than 0.1 W/mK at 400° C. By reducing the thermal losses from the system, aerogels also reduce the amount of optical concentration required for a desired thermal efficiency.
Silica Aerogel Fabrication Process
The synthesis of a silica aerogel is described herein. The synthesized silica aerogel may have properties suitable for use in an embodiment of the STAR. In general, several synthesis variables (e.g., chemical ratio, aging period, aging temperature and drying conditions) affect the spectral selectivity, thermal, and structural properties of aerogels. The absorption of radiation in an aerogel is proportional to its density. The scattering of radiation is a function of the particle size and pore size within the aerogel, which is not only a function of density, but also of the aerogel synthesis technique. By adjusting the pH of the sol-gel solution, the particle and mesoporous structure of aerogels can be tuned, thus changing the scattering coefficient. A further increase in spectral selectivity of the aerogel insulation layer may be achieved by doping aerogels with nanoparticles, such as tin oxide, indium tin oxide, carbon etc., that have strong absorption in the mid-infrared range.
The synthetic method for creating an embodiment of the silica aerogel described herein is based on Tamon et al.'s (hereafter referred to as Tamon) recipe for silica aerogel using tetramethyl orthosilicate (TMOS) as silica precursor and ammonia (NH3) as catalyst. See H. Tamon, T. Sone, and M. Okazaki, Journal of Colloid and Interface Science 188 (1), 162-167 (1997), the entire contents of which are incorporated by reference herein. Unlike Tamon's method where NH3 is mixed with TMOS solution before adding H2O, methods disclosed herein combine NH3 with H2O first, and then add the NH3 solution to the TMOS solution.
To synthesize silica aerogel, sol-gel polymerization may be used as depicted in
In some embodiments, the aerogel may be made water-repellant by treating with a hydrophobic reagent. As before, the aged gel may be removed from the mold and transferred into a glass container with pure EtOH. The hydrophobic reagent (e.g., hexamethyldisilazane ((CH3)3Si)2NH) may be added in the ethanol, at a ratio to the ethanol of, e.g., 1:9. The aged gel may be then kept in the solution at room temperature and dried in CPD as described before.
In some embodiments, the high-temperature stability of the aerogel is improved by providing coating having a thickness of a few nanometers (e.g., <5 nm) to the aerogel. This coating may be formed by atomic layer deposition of Al2O3 or HfO2. This allows the aerogel to maintain structural robustness even at temperatures>600° C., without sacrificing the optical transparency and thermal insulating properties.
This method, in which NH3 is combined with H2O first and then added to the TMOS solution, promotes the protonation of NH3 in H2O resulting in sufficient hydroxide ion (—OH) in the solution. The amount of —OH significantly affects the rate of hydrolysis and condensation reactions (
The synthesis chemistry, pH and drying dynamics may be tuned to obtain OTTI layers with properties that allow for both low thermal conductivity (<0.025 W/mK at room temperature) and high transmissivity in the 250-1100 nm wavelength range for solar radiation.
Table 1 shows the properties of an un-annealed OTTI silica aerogel in accordance with an embodiment of the invention, compared with the properties of a commercially available aerogel as measured using Small Angle X-ray Scattering (SAXS).
These measurements indicate smaller particle size and pore size of the synthesized OTTI silica aerogel than the commercially available aerogel. The smaller particle and pore size are advantageous in giving the OTTI silica aerogel the properties that enable it to be used in the STAR receiver.
Aerogel Property Enhancement Using Annealing
High temperature annealing of the above described silica aerogel may eliminate hydrophilic groups (—OH) on the surface of aerogel resulting in enhancement of transmission in the absorption region (>1100 nm) by minimizing molecular absorption. Some embodiments of OTTI silica aerogels demonstrate suitable thermal stability at 400° C., which corresponds to the 391° C. maximum outlet temperature of the STAR receiver. Annealing may take place in an oven at a temperature of 400° C., reached by increasing the oven temperature by 10° C./min. For example, a 1200° C. dual split tube furnace, OTF-1200X, available from MTI Corporation may be used. In some embodiments, the aerogel is annealed for 336 hours. After annealing, the aerogel sample may be cooled in a ceramic dish.
For one embodiment, a durability test was conducted where the aerogel sample was annealed in an oven at high temperature for a long duration and allowed to rest at ambient conditions. For example,
The optically transparent thermally insulating OTTI silica aerogel layers provide the desired optical transparency and thermal insulation for use in solar thermal receivers. The OTTI layer serves to reduce the radiation, conduction, and convection heat losses from the hot absorber to the ambient.
Table 2 summarizes monolithic silica aerogel SAXS characterization before and after annealing at 600° C. for 4 hours;
The data in Table 2 demonstrates the increase in solar-weighted transmittance and decrease in pore size that may be achieved through annealing of the silica aerogel.
In some embodiments, the mean pore radius of the silica aerogel is less than 5 nm with a standard deviation of 3 nm. In some embodiments the silica aerogel has a mean particle size of 1.3 nm and includes solids of less than 10%. In some embodiments, an 8 mm thick silica aerogel in thermal contact with a blackbody absorber has a solar absorptance of greater than 0.9 and an IR emittance of less than 0.3 at high temperatures, such as ˜400° C.
Aerogel Optical Properties
In a preferred embodiment, total transmission of the OTTI aerogel is increased while still maintaining good physical stability. Commercially available monolithic OTTI aerogels (e.g., Aerogel Technologies™) demonstrate transmission of ˜85%. In some embodiments, the STAR receiver requires higher transmission (e.g., >95% transmission) than the transmission achieved with commercially available aerogels. High transmission may be achieved in the silica aerogel by controlling the pore size and silica particle size of the aerogel, i.e., small pore and particle sizes with narrow distributions increase transmission, through the above described synthesis method and annealing process.
OTTI aerogels demonstrate suitable spectral properties for use with embodiments of the STAR. OTTI aerogels demonstrate 96% solar-weighted transmittance over a 250-2500 nm wavelength through an 8 mm thick sample, as indicated in
Aerogel Thermal Properties
Generally, two properties determine how effective an aerogel is as an insulator: the spectral extinction coefficient and the thermal conductivity including solid conduction and gaseous conduction. The spectral extinction coefficient may be measured using Fourier transform infrared spectroscopy (FTIR). While it is difficult to measure the solid thermal conductivity directly because radiation cannot be eliminated, if the radiative properties of the aerogel are known, the thermal conductivity can be deduced from aerogel conductance measurements.
A detailed numerical model of the radiative transfer within an aerogel may be used to tune an OTTI layer for a given incident spectrum, operating temperature, and ambient conditions. A model may be used to solve the spectral equation of radiative transfer and couple it to the heat equation. The radiative transfer equation (Equation 1) and the heat equation (Equation 2) are shown below:
where Keλ is the spectral extinction coefficient, Ksλ is the scattering coefficient, Kaλ is the absorption coefficient, Iλ is the spectral intensity, Ibλ is the spectral blackbody intensity, pλ is the scattering phase function, Ω is the solid angle, x is the position in the sample, T is the temperature, k is the thermal conductivity, and qR is the radiative heat flux. The radiative heat flux is given below:
The model may use the spectral extinction coefficient (Keλ), which is the sum of the scattering (Ksλ) and absorption coefficients (Kaλ), as an input to solve the radiative transfer equation.
The typical aerogel 400° C. black-body weighted specific extinction coefficient may be measured to be around 10±0.5 m2/kg, based on IR transmittance measurements (shown in
The radiative transfer equation (RTE) model, described previously, predicts heat transfer coefficients of <7 W/m2K at the operating temperatures of the STAR receiver (e.g., THigh=400° C. and TLow=100° C.). Low values of heat transfer coefficients represent an insulator at the high operating temperatures of the STAR receiver.
Receiver Design and Performance
Referring to
The layer of aerogel 938 is in thermal contact with and proximate to one or more heat transfer fluid pipes 940 housed in the frame 932. The absence of a gap or vacuum between the aerogel layer and the heat transfer fluid pipes, as is present in currently available receivers, reduces heat loss due to conduction and convection and reduces the receiver height. A reduction in receiver height may increase the amount of incident light that travels through the aerogel layer and reaches the heat transfer fluid pipes. The number of heat transfer fluid pipes depends on the desired capacity of the receiver. In some embodiments, as illustrated, the receiver 928 contains six heat transfer fluid pipes. One or more of the heat transfer fluid pipes 940 may include a black absorber layer, e.g., black paint, to increase absorption.
A black absorber layer 942 may be disposed on the aerogel layer 938 and/or on the one or more heat transfer fluid pipes 940. The black absorber layer 942 may be formed from a black material, e.g., stainless steel coated with black paint.
In some instances, the aerogel 938 defines an air gap between the aerogel 938 and the transparent outer layer 936 to prevent condensation on the interior of the transparent outer layer that may accumulate from water in the aerogel at high temperatures. In other embodiments, the aerogel layer 938 is disposed in the frame 932 in direct contact with the transparent outer layer 936. In this embodiment, the transparent outer layer 936 provides mechanical stability to the aerogel layer 938. An additional advantage may be increased heat transfer between the transparent outer layer 936 and the aerogel layer 938.
An insulating layer 944 may be disposed in the frame 932, e.g., above the pipes 940 and/or adjacent to the aerogel 938 in the portion of the frame 932 that is not optically active. The insulating layer 944 increases the efficiency of the receiver 928 by preventing heat loss.
In some instances, the pipe or pipes 940 may be configured to relay a heat transfer fluid to a heat storage unit 946 from which heat may be dispatched.
In one embodiment, the STAR 928 is coupled with at least one reflector, e.g., a reflector array 930, such as an LFR to form the concentrated solar energy system. The one or more reflectors may be configured to direct sunlight to the opening 934. The flat geometry, i.e., flat bottom surface 936, of the receiver 928 makes it compatible with an LFR and helps reduce IR losses.
The receiver 928 may be sized according to the width of the absorber layer or number of heat transfer fluid pipes, such that at least 90% of the incident light from the reflector hits the absorber or heat transfer fluid pipes. The height of the receiver may vary with the amount of insulation and the length may vary depending on the receiver's intended use, e.g., from 100 cm to 1000 m. For example, the frame 932 may be 10 cm×30 cm×500 cm.
A thickness of the aerogel may be selected from a range of 5 mm to 15 mm, depending on the aerogel properties and solar concentration. Referring also to
Referring also to
In some embodiments, the STAR receiver receives solar radiation from the reflector array at a concentration of about 40 suns. In some embodiments of the STAR the transparent outer layer 936 defines a relatively wide aperture (e.g., 10-40 cm, compared to 7-9 cm for industry standard vacuum tubes). Additionally, in some embodiments, the receiver may be fixed and supported more effectively to allow for a greater range of optimization in design geometry. The use of the previously described silica aerogel in the design allows for operating temperatures comparable to conventional linear CSP receivers with less concentration area, meaning the footprint and supporting structures may be reduced without sacrificing efficiency.
The performance of an ideal blackbody absorber coupled with the previously described OTTI silica aerogel depends on several factors including the operating temperature, aerogel thickness, and optical concentration. For example, for an 8 mm thick aerogel sample paired with an ideal blackbody absorber having an absorptance of 1 at 400° C., the solar absorptance is 0.96 and the emittance in the IR is around 0.2. This expected performance relates to operation in air and is comparable to state-of-art high-temperature spectrally selective surfaces that operate in vacuum. In some embodiments, an 8 mm thick aerogel in thermal contact with a blackbody absorber has a solar absorptance of greater than 0.9 and an IR emittance of less than 0.3 at high temperature such as ˜400° C.
For a CSP system including the STAR, with properties of the synthesized OTTI silica aerogel previously described, the model predicts a peak exergetic efficiency of 37.2% and an annual average exergetic efficiency of 26.3%. Modeling may be used to identify the aerogel properties that are required for improved system performance targets. For example, for a 39.5% peak efficiency, the aerogel will need to be 98% transmitting and have a heat transfer coefficient of 4 W/m2K through an 8 mm thickness. The estimated annual average exergetic efficiencies in this example are above 31% with peak efficiencies exceeding 42% if the receiver is operated at 500° C. Modeling of the heat transfer fluid (HTF) performance uses well established heat transfer correlations and fluid properties known to one of skill in the art. Heat transfer within the solid, non-aerogel portions of the receiver (i.e., pipe walls, absorber plates, insulation, etc.) may be modeled with Fourier's law.
Receiver Design and Fabrication
To decrease the total cost of the receiver, the assembly process may be simplified to use cost-effective components and processes. Referring to
An exemplary process for fabricating an embodiment of a single module section of the STAR receiver is shown in
A utility scale plant may include several 5 m long STAR modules joined together. Two modules may meet at a fixed support where each module has exposed HTF pipes. Bellows connectors may be welded to the pipes, allowing the modules to couple thermally. A custom made insulation piece may be added around the bellows to prevent heat loss from the length of receiver that is not optically active (i.e., connection area between the two modules). Above the insulation piece an aluminum capping element may be fixed to each module through a set of linear fasteners.
An alternative embodiment of the STAR receiver is shown in
Referring to
Receiver Geometries
Different receiver configurations are illustrated in
A “vacuum tube” configuration is shown in
Solar Thermal Receiver Assembly
An outdoor test system 1560 may be used to measure the performance of various embodiments of the STAR receiver 1528.
Standard piping and connections are used throughout to minimize set up time. Since the physical system is symmetric about the receiver, for ease of setup and wiring, the controls mimic the physical layout. A primary control cabinet (not shown) houses data acquisition (DAQ) components that are shared throughout the prototype (such as pump and cooler controllers and thermocouple board); while the auxiliary control cabinets are used for motor controllers for the linear Fresnel reflector elements.
Outdoor Prototype
Thus, particular embodiments of the subject matter have been described. Other embodiments are within the scope of the following claims. In some cases, the actions recited in the claims can be performed in a different order and still achieve desirable results. In addition, the processes depicted in the accompanying figures do not necessarily require the particular order shown, or sequential order, to achieve desirable results. In certain implementations, multitasking and parallel processing may be advantageous.
This application is the national stage of International (PCT) Patent Application No. PCT/US2017/019415, entitled “Low Cost Parabolic Cylindrical Trough for Concentrated Solar Power” and filed on Feb. 24, 2017, which claims priority to and the benefit of U.S. Provisional Patent Application No. 62/299,090, entitled “Solar Thermal Aerogel Receiver (Star)” and filed on Feb. 24, 2016, each of which is hereby incorporated by reference herein in its entirety.
This invention was made with Government support under Grant No. DE-AR0000471 awarded by the Department of Energy. The Government has certain rights in the invention.
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Number | Date | Country | |
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20190100439 A1 | Apr 2019 | US |
Number | Date | Country | |
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62299090 | Feb 2016 | US |