Patent Application
20230381735
This invention relates to solar thermochemical reactions. More specifically, this invention relates to systems and methods that use high-temperature heat, available from solar concentrators, to increase the chemical energy content and/or change the chemical composition of a reacting stream.
The Department of Energy's goals for concentrated solar power (CSP) systems include increasing the use of CSP in the United States, making CSP competitive in the intermediate power market by 2015 and developing advanced technologies that will enable CSP to be competitive in the baseload market by 2020. CSP traditionally uses concentrated solar energy to drive heat engines, such as the Rankine Cycle, Brayton Cycle and the Stirling Cycle, producing electricity. Traditional CSP systems have a limited capacity factor in the range of 20-25% since they generate electricity only when direct sunlight is available. This limits the ability of CSP to be used for baseload power generation. The capacity factor for CSP systems can be increased by storing energy received at the collector in a form that can be converted to electricity at later times. Storing solar energy as sensible or latent heat is one option.
Another promising option is converting solar energy to chemical energy in a thermochemical reaction. In this case the energy is stored in the chemical product and this chemical energy can be released as heat for power generation at a later time in an exothermic chemical reaction. An advantage of this closed cycle approach is that the chemical products can be stored at ambient temperatures simplifying transport and storage requirements, and enabling longer term storage without energy degradation. An open cycle approach to solar-thermal to chemical energy conversion is also possible. For instance, solar reforming can be used to upgrade the chemical energy content of a fuel stream such as methane from natural gas or biomass when the sun is available, and this upgraded fuel stream can be used to generate electricity using a heat engine or fuel cell. When direct sunlight is not available, the fossil fuel or biomass energy source can still be used to generate electricity using the same infrastructure. Such a system can be used for baseload power generation and can take advantage of solar energy at high conversion efficiencies when available. Thermochemical energy conversions may also enable CSP systems to co-generate electricity and fuels for other markets (e.g., transportation). Methanol and long-chain hydrocarbons are examples of products that can be produced from syngas, which is a product of a reforming reactor.
A solar thermochemical processing system is disclosed, in accordance with one embodiment of the present invention. The system includes a first unit operation for receiving concentrated solar energy, using heat from the solar energy to drive the first unit operation, wherein the first unit operation also receives a first set of reactants and produces a first set of products. The system further includes a second unit operation for receiving the first set of products from the first unit operation and for producing a second set of products. The system also includes a third unit operation for receiving heat from the second unit operation to produce a portion of the first set of reactants.
In one embodiment, the first unit operation is an endothermic reactor, the second unit operation is an exothermic reactor, and the third unit operation is a vaporizer.
In one embodiment, the endothermic reactor is a solar thermochemical reactor or a reverse-water gas shift reactor. The exothermic reactor is a methanol synthesis reactor, a Fischer-Tropsch reactor, a water-gas shift reactor, or a methanation reactor. The water-gas-shift reaction is used to increase the hydrogen content of a syngas stream, such as might be desirable for a PEM fuel cell or a chemical process where the desired product is hydrogen.
The channels inside the solar thermochemical reactor contain an active catalyst. The first set of reactants are reacted in the presence of the catalyst.
In one embodiment, the methanol synthesis reactor provides heat to the vaporizer and produces syngas and methanol. The syngas and methanol are passed to a separator where the methanol is recovered. Components of the syngas can be used to provide heat for a heat engine through a combustion process and/or to power a fuel cell.
In some embodiments, the system includes a heat pump for taking in heat from the methanol synthesis reactor and providing additional heat to the vaporizer. The system also includes a heat exchanger for preheating the reactants before entering at least one of the reactors and for cooling the products exiting at least one of the reactors.
The heat exchanger can be a micro-channel or meso-channel heat exchanger, and can have a minimum exergetic efficiency of about 85% and a minimum heat transfer power density of about 10 watts/cm3.
In another embodiment of the present invention, a method of producing a fuel is disclosed. The method includes sending a first set of reactants into a first unit operation to produce a first set of products, and sending the first set of products to a second unit operation to produce a second set of products. The method further includes heating a third unit operation using heat from the second unit operation to produce a portion of the first set of reactants. The second set of products is further reacted to produce a fuel. The method also includes achieving carbon utilization in fuel production above approximately 85%.
In another embodiment of the present invention, a method of providing temperature control to a solar thermochemical reactor is disclosed. The method includes providing a solar thermochemical reactor including a first material, the first material having an inlet and an outlet. The method also includes providing a plurality of flow mechanisms for coupling the inlet to the at least one outlet separately. The method further comprises adjusting the flow mechanisms to control the proportion of fluid flowing through the inlet and the at least one outlet in response to conditions within the reactor. The flow mechanisms can have a different coefficient of thermal expansion than the first material.
In another embodiment of the present invention, a method of storing solar energy is disclosed. The method includes preheating reactants and then directing the reactants into a first endothermic reactor to produce a first set of products. The method further includes cooling the first set of products and then further reacting the first set of products in a first exothermic reactor to produce a second set of products. The heat of reaction from the exothermic reactor is used to produce a portion of the first set of reactants. The method also includes separating the second set of products to enable fuel to be stored. The separating allows methanol or long-chain hydrocarbons to be recovered with unreacted syngas components being sent on to provide either heat for a heat engine through a combustion process or to power a fuel cell.
In another embodiment of the present invention, a method of power generation is disclosed. The method includes preheating reactants and then directing the reactants into a first endothermic reactor to produce a first set of products. The method further includes cooling the first set of products and then further reacting the first set of products in a first exothermic reactor to produce a second set of products. The heat of reaction from the exothermic reactor is used to produce a portion of the first set of reactants. The method also includes separating the second set of products to provide heat for at least one of a heat engine and a fuel cell.
In another embodiment, a method of providing a solar energy augment to the chemical energy content of a reactant stream is disclosed. The method includes heating a solar reforming reactor from a solar concentrator; preheating reactants in a heat exchanger before entering the reactor; and reacting the reactants in the presence of a catalyst in the reactor to generate a product stream at a solar-to-chemical conversion efficiency greater than about 60%. The product stream includes syngas and the syngas is reacted in a chemical reactor to produce fuel. The method can also include cooling the product stream in the heat exchanger and sending the cooled product stream to an exothermic reactor, thereby producing higher energy products.
In another embodiment of the present invention, a solar thermochemical reactor for receiving heat and performing reactions is disclosed. The reactor includes a solar receiving front plate; a back plate with support ribs and an entrance port; a manifold; and a flow channel. A reactant flow enters near the center of the back plate and splits into multiple flow paths. The reactant flows toward the periphery of the reactor through a catalyst and exits as a product through the manifold. The manifold recollects the product to exit away from where the reactants entered the reactor. The reactor has a solar-to-chemical energy conversion efficiency of at least 60%.
The flow channels can comprise narrow size flow channels such as microchannels or mesochannels. Because of their narrow dimensions in the direction of heat or mass transfer, micro- and meso-channels can provide substantial improvements in heat exchangers and chemical reactors, including rapid heat transfer and reduced heat transfer resistance, therefore enabling process intensification and exergetically-efficient unit operations. This is especially useful for unit operations that must be closely associated with solar receivers, such that it might be desirable to place them at or near the focal point of a parabolic dish concentrator and within a compact housing.
The reactor comprises a solar thermochemical augment of at least 20%. In one embodiment, the reactor includes a passive structure to provide adaptive flow control within the reactor.
In another embodiment of the present invention, a tiled receiver reactor for receiving heat and performing reactions is disclosed. The reactor includes a solar receiving front plate and a back plate having individual tile sections. The tile sections include an inlet, at least one outlet, and catalyst channels. The length of at least one flow channel is decreased, making the inlet in closer proximity to the outlets.
In one embodiment, the reactor has a solar-to-chemical energy conversion efficiency of at least 60%, and a passive structure to provide adaptive flow control within the reactor.
In another embodiment of the present invention, a counter radial flow reactor for receiving heat and performing reactions is disclosed. The reactor includes outward flowing channels that enter the center of the reactor and flow in a radial direction toward outlets at the periphery of the reactor. The reactor also includes inward flowing channels, adjacent to the outward flowing channels, which enter at the periphery and exit toward the center of the reactor. The reactor can further include a passive structure to provide adaptive flow control within the reactor.
In another embodiment of the present invention, a solar gas-to-liquids process is disclosed. The process includes preheating a fluid stream including methane and water in a heat exchanger. The process further includes reacting the fluid stream in a solar thermochemical reactor to generate a product stream at a solar-to-chemical energy conversion efficiency of at least 60%, wherein the product stream includes syngas. The process also includes cooling the product stream in the heat exchanger; and reacting the syngas in a chemical reactor that produces fuel. In one embodiment, the carbon utilization is above about 85%.
In another embodiment of the present invention, a solar gas-to-liquids-and-electricity process is disclosed. The process includes preheating reactants and then directing the reactants into a first endothermic reactor to produce a first set of products. The process further includes cooling the first set of products and then further reacting the first set of products in a first exothermic reactor to produce a second set of products. The heat of reaction from the exothermic reactor is used to produce a portion of the first set of reactants. The process also includes separating the second set of products to provide heat for at least one of a heat engine and a fuel cell. In one embodiment, the carbon utilization is above 85%. In another embodiment, the carbon utilization is above 90%.
In another embodiment of the present invention, a receiver is disclosed. The receiver includes channel walls defining a flow channel; and a flow control device. The device includes an orifice cover partially blocking an outlet orifice, and wherein the device is coupled to the channel walls. Fluid in the flow channel may exit through the outlet orifice.
In one embodiment, the receiver is a heat exchanger or a reactor. The flow control device is made from a material with lower or higher thermal expansion compared to the flow channel. The material is, but not limited to, tungsten. The device can be coupled to the channel walls via two different length legs of the device.
In another embodiment of the present invention, a receiver is disclosed. The receiver includes a flow channel having an inlet and an outlet. The receiver also includes an insert coupled to the outlet. The insert has a lower or higher thermal expansion coefficient compared to the receiver. The receiver further includes a pin to constrain movement of the insert.
In one embodiment, the insert is constructed from a refractory material. The refractory material is, but not limited to, tungsten. In one embodiment, the receiver further comprises a plurality of flow channels. Each flow channel includes an inlet, an outlet, and an insert. Movement of the insert is constrained by a pin, and the receiver may be a heat exchanger or a reactor.
The present invention is directed to the use of high-temperature heat that is available from solar concentrators to change the chemical composition or increase the chemical energy content of a reacting stream. Embodiments of the invention include, but are not limited to, open and closed-cycle chemical loops that efficiently convert concentrated solar energy into chemical energy through the use of chemical conversion reactions, and advanced process-intensive micro- and meso-channel process technology, which enables unit chemical operations to be made compact enough to be mounted at the focal point of a dish-concentrator, a central receiver, or another solar concentrator installation.
A microchannel may be of any length in the general direction of bulk flow and has one dimension, e.g., the width, that is greater than or equal to 1 micron and less than or equal to 5 millimeters.
A mesochannel may be of any length in the general direction of bulk flow and has one dimension, e.g., the width, that is greater than 5 millimeters and less than or equal to 5 centimeters.
It is especially useful to couple microchannel and mesochannel reactors and heat exchangers with solar concentrators, such as parabolic dish and central receiver concentrators, which by virtue of being able to concentrate direct normal solar energy by factors of 100 or 1000, or greater, provide sufficiently high fluxes and temperatures (e.g., greater than 500° C.) to enable high temperature endothermic reactions.
In certain embodiments, concentrated solar energy is used to drive an efficient, high temperature endothermic chemical reaction to produce higher energy products and to enable chemical energy storage. This fuel upgrading and chemical energy storage can be coupled with a heat engine or fuel cell to produce electricity at higher capacity factors and reduced costs compared to other solar energy systems.
In other embodiments, concentrated solar energy can be used to produce transportation fuels and other chemical products. For example, methane can be converted to synthesis gas (or ‘syngas’), followed by a Fischer-Tropsch reaction to produce long-chain hydrocarbons, with subsequent additional processing steps to produce gasoline, diesel fuel, jet fuel, or other fuel products in what is known as a “gas-to-liquids” process. Conventional gas-to-liquids processes would consume a portion of the chemical content and energy in the feedstock reactants in order to drive endothermic gas-to-liquids operations, with one result being that a significant portion of the carbon in the methane feedstock is emitted from the plant as CO2. Typically only about 60% of the feedstock carbon finds its way into the liquid hydrocarbon product. However, with the concentrated solar energy providing moderate- and high-temperature heat to drive endothermic unit operations, such as reforming and distillation, more effective utilization of the feedstock is realized, carbon dioxide emissions are substantially reduced, the plant produces a greater quantity of product fuel and reduced quantities of carbon dioxide, a greenhouse gas.
Additional heat exchangers are shown in
CH4+H2O→CO+3H2 (1)
CO+H2O↔CO2+H2 (2)
Because the combined reaction is highly endothermic, solar energy is effectively converted to chemical energy within the reformer. The hot syngas exiting the reactor immediately flows into the high-temperature recuperator where it preheats the combined methane/steam stream before feeding the low-temperature recuperator(s) mentioned above. Upon leaving the recuperator(s), the syngas stream flows through other heat exchangers and an air-cooled radiator where it is further cooled before flowing through a vapor-liquid separator (VLS) where condensed water is removed. The relatively dry syngas exiting the VLS is characterized in terms of flow-rate and composition, after which it is ready for use, either in a combustion-driven system or in a chemical process such as methanol synthesis.
The heat engines in
System startup began with the use of the screen, allowing the reactor to be started with less than the full heat available from the solar concentrator. Circle tracking was used after the screen was removed, again to limit the solar flux on the reactor, with testing eventually progressing to full solar energy (“full sun”). The results of this day of testing are illustrated in
The initial test condition, as shown in
Due to significant mid-day cloud cover, the system was shut down in order to remove the screen and perform some system diagnostics. By about 2 p.m., the cloud cover had passed and the system was restarted.
The next few steady state values were obtained using circle tracking mode at increasing methane feed rates. Unfortunately, water pump issues caused the steam-to-carbon ratio to drift during this time. Nonetheless, the data obtained during this circle-tracking period yielded some useful results. Methane conversion increased during this time period as the reactor temperature (and product outlet temperature) continued to rise. Methane conversion relative to equilibrium conversion (at reactor outlet temperature), referred to as “conversion approach” also continued to rise, reaching as high as 75%.
The day's experiments concluded by operating the system with direct sun. By this time, the direct normal incidence (DNI) was beginning to wane, but the results are quite encouraging relative to our stated goals. For instance, our approach to equilibrium conversion continued to rise and reached a level of about 99% and overall methane conversion exceeded 90%. In addition, the overall solar-to-chemical energy conversion, calculated as the ratio of the increase in the Higher Heating Value of the reacting stream to the direct normal sunlight that was incident upon the dish concentrator, was calculated to be 63±4%, which represents the highest values of which we are aware. These exceptional results were enabled by the highly effective thermal recuperation provided by the microchannel heat exchangers, resulting in significant preheat of the reactant stream entering the reactor and allowing the majority of the concentrated solar energy to be used to drive the endothermic steam reforming reaction.
Use of a highly active catalyst is an enabling factor in the deployment of compact reactors, in which heat and mass transfer resistance has been minimized. Under such conditions, the reforming catalyst used here greatly outperforms standard base-metal reforming catalysts in terms of activity and coking. The combination of device architecture and catalyst selection enables process intensification, a key to capturing concentrated solar energy in a chemical process.
Also in
Reaction channel geometries were developed that were more suited to the circular receiver geometry used on circular parabolic dish solar concentrators.
Radial flow is a natural choice for incorporating reaction channels into circular solar receiver geometry.
Another approach for incorporating reaction channels into a circular geometry is to divide the geometry up into smaller sections containing inlets, outlets and catalyst channels. These reactor “tiles” can be combined to fill the circular receiver area. An advantage of the tiled geometry is that the length of a given flow channel can be decreased making the cool inlets in closer proximity to hot outlets, and better enabling thermal conduction in the top plate to decrease the temperature gradients seen at the surface and in the top plate of the receiver-reactor. This advantage creates the ability to compensate for hot spots on the receiver surface due to aberrations or imperfections of the parabolic solar concentrator. With individual control of the flow through each tile section, areas receiving a higher solar flux could be fed more methane and steam.
There can also be a dead spot in the flow field. The catalyst in this area contributes little to the reaction. Although maximum temperatures are similar to the radial flow simulations, the smaller tile dimensions decrease temperature gradients and produce a more uniform temperature at the receiver surface.
The metal 850 in the center of the tile dramatically improves heat conduction to the back side of the catalyst channels 860. Compared to the previous tile geometry, this geometry with discrete flow channels and heat conduction paths to the back plate 820 requires significantly less catalyst material to achieve the same amount of methane conversion. These metal conduction paths also function as structural supports and greatly increase the strength of the reactor.
One of the issues with accomplishing a reforming reaction in a solar receiver-reactor is the uniformity or nonuniformity of the heat flux provided by a solar concentrator. It would be expected that the reforming reaction is most active at the inlet where methane concentrations are highest and lowest where the methane is depleted. However, if a constant heat flux per area on the receiver-reactor surface is accomplished, the reaction rate will be limited by the heat supplied and the temperatures achieved, and a more constant reaction rate in the channel may be realized. This happens as areas with a high methane concentration are cooler and areas with low methane concentration are hotter such that the higher catalyst activity (at higher temperatures) compensates for the low methane concentration. As a result, uniform heat flux on the receiver-reactor contributes to the temperature gradients and the maximum temperatures seen in the reactor structure. Lower maximum temperatures are desirable in that the strength and creep rupture resistance of the metal used to construct the reactor are higher, and catalyst deactivation lower at lower temperatures. In short, while higher temperatures may contribute to higher solar-to-chemical energy conversion efficiencies, running a portion of the receiver-reactor at excessively high temperatures will decrease the lifetime of the unit. A possible solution to this problem that can reduce excessive reactor temperatures is a geometry with counter flowing channels. In a counter-flow geometry the methane rich portion of one channel (the inlet portion) is placed adjacent to the methane depleted portion (outlet) of other channels, as shown in
In one embodiment, half of the reactants enter at the center of the reactor 900 and flow through the catalyst sections 920 to the periphery of the reactor 900; the other half of the reactants enter at the periphery and flow toward the center.
A counter-flow radial geometry, similar to
In the simulation, the maximum temperature at the receiver surface was approximately 60 to 80° C. cooler compared to the tiled or radial flow reactor geometries. The lower temperatures achievable with counter-flow geometry will have a significant beneficial impact on reactor strength and lifetime. However, the flow channels are more complex when compared to designs with radial flow in one direction, and this could increase the difficulty or cost of fabricating or assembling the reactor.
The present invention describes embodiments of several reactors with smaller catalyst channel thickness and geometries that incorporate metal ribs or other structures improve heat conduction which benefits reactor performance. Counter-flow geometry is beneficial in reducing the maximum temperature and temperature gradients. Excessively high reactor temperatures can decrease lifetime and the strength and creep rupture resistance of the reactor housing, and degrade catalyst performance.
Excessively cold temperatures are also to be avoided, as reaction kinetics and conversions are directly proportional for endothermic reactions. Thus there is a need to control localized reaction temperatures within a preferred temperature range.
The solar flux on a receiver surface is not uniform. The flux can vary with position, and maximum solar flux on a portion of the receiver can be 2 or 3 times the average flux. The receivers of the present invention are designed to cope with this nonuniform flux. Flow instabilities can also occur in receivers with multiple flow paths when large changes in the working fluids density and/or viscosity accompany the heat transfer process. Importantly, to maximize receiver efficiency it is desirable to have each portion of the receiver operating at close to an optimum flow rate that minimizes the temperature differences between the receiver's surface and working fluid and that maintains acceptable operating temperatures. Adaptive flow control may be used to accomplish this.
Passive flow control features can be used that exploit differences in thermal expansion to increase the flow to hotter sections of the receiver, minimizing hot spots and providing more uniform heating of the working fluid. In one embodiment, such flow control features consist of inserts of a refractory metal, such as tungsten, with a different thermal expansion coefficient than the receiver's body. The difference in thermal expansion is used to open up a flow feature, such as an orifice, increasing working fluid flow in hotter sections of the receiver and reducing fluid flow in colder sections. These adaptive flow features are designed to adjust the flow within an appropriate range based on working fluid properties and solar fluxes expected at the receiver's surface.
The use of adaptive flow control enhances flow stability and optimizes working fluid flow as a function of the solar flux incident on the receiver's surface. This type of adaptive flow control is desirable in solar receivers where the incident solar flux varies as a function of position. The desire to adaptively control the mass flow rate entering different portions of a heat exchange structure is somewhat unique to solar receivers. The control features of the present invention use differences in thermal expansion to increase the working fluid flow in hotter sections of the receiver, compensating for increased solar flux.
The terms “passive flow control” and “adaptive flow control” are used interchangeably. The term “adaptive” describes how the control device adjusts the flow depending on the temperature. The term “passive” emphasizes that the device self-adjusts without the intervention of an outside user or signal.
The adaptive flow control structure is designed to alter the flow—at the designed pressure drop—through the orifice or control feature changes in a way that compensates for the local heat flux, minimizing the differences in working fluid temperature exiting different portions of the receiver.
For a quantitative calculation, assume the receiver temperature is kept within 100° C. of target-assume it is in the range of 700 to 800° C. with a target of 750° C., and to accomplish this it is necessary to throttle the flow in different portions of the receiver from zero flow to full flow. In this case the adaptive flow control is needed to go from completely shut (zero flow) to fully open with a 100° C. temperature change. Microchannels with height dimensions of a few thousands of an inch may be used. The flow control passage will have similar dimensions and will assume a 0.001″ relative motion between the two dissimilar metals is required to turn off the flow. Tungsten has a thermal expansion coefficient of approximately 4.7×10−6 to 5.0331×10−6 in/(in ° C.), and Hastalloy (refractory metal used to build the microchannel) has a thermal expansion coefficient of approximately 14×10−6 in/(in ° C.). The difference in the thermal expansion between these materials is about 9×10−6 in/(in ° C.). For a 100 C temperature change we can achieve a difference in length of about 9×10−4, so to achieve a relative motion of 0.001″ an adaptive flow control element with a length of 1.11″ is required.
It is also possible to build flow control features that use leverage to amplify the relative motion achieved from the thermal expansion.
To achieve the greatest actuation for a given temperature rise it is desirable to make the passive flow control device out of a material with a thermal expansion significantly different from the thermal expansion of the flow channel. For example, Tungsten with a thermal expansion coefficient of approximately 5×10−6 cm/(cm ° C.) could be used to build a passive control device for use in a flow channel constructed from Hastalloy with a thermal expansion coefficient of approximately 14×10−6 cm/(cm ° C.). One implementation of this concept is shown in
The device of
The present invention also describes systems and methods of efficiently converting solar energy into chemical energy. Applications include thermochemical energy storage for concentrating solar power plants, which otherwise would be unable to produce electricity when sunlight is not available, and the production of synthetic transportation fuels from natural gas and/or biomass. High methane conversion was accomplished as well as relatively high solar-to-chemical energy conversion.
Also, the methanol synthesis reactor only partially converts syngas to methanol, so that the products of the system include both methanol and unconverted synthesis gas. In addition, the methanol synthesis reactor provides a substantial portion of the heat that is needed for water vaporization. It is through this integration of thermal components that high overall solar-to-chemical energy conversion can be obtained.
The present invention has been described in terms of specific embodiments incorporating details to facilitate the understanding of the principles of construction and operation of the invention. As such, references herein to specific embodiments and details thereof are not intended to limit the scope of the claims appended hereto. It will be apparent to those skilled in the art that modifications can be made in the embodiments chosen for illustration without departing from the spirit and scope of the invention.
This application claims priority to U.S. Provisional Application Ser. No. 61/511,788, filed Jul. 26, 2011, titled “SYSTEMS AND METHODS INVOLVING SOLAR THERMOCHEMICAL REACTIONS”, hereby incorporated by reference in its entirety for all of its teachings.
The invention was made with Government support under Contract DE-AC05-76RL01830, awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 61511788 | Jul 2011 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15950068 | Apr 2018 | US |
| Child | 17361213 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17361213 | Jun 2021 | US |
| Child | 18191141 | US | |
| Parent | 13559127 | Jul 2012 | US |
| Child | 15950068 | US |
