Patent Application
20200354840
The invention generally concerns generation of hydrogen (H2) and oxygen (O2) from an aqueous solution. This can performed by using a reactor that includes a H2 generation chamber and an O2 generation chamber. The reactor does not have to include a H2 and O2 permeable material such as an H2 and O2 permeable membrane or an ionic bridge.
Hydrogen (H2) is a clean alternative to fuel. Conventional technology produces hydrogen on a commercial scale from steam reforming of methane. Due to the depletion of fossil fuels, there is a necessity to find an alternative feedstock to meet the growing demand for hydrogen production globally.
One alternative to methane steam reforming to produce hydrogen is through water-splitting. The reduction and oxidation half reactions for water-splitting are as follows:
2H++2e−H2 (1)
H2O+2h+O2+4H+ (2)
2H2O2H2+O2 (3)
Water-splitting can be achieved through electrolysis of water, photocatalytic splitting of water, or electrophotocatalytic splitting of water. These approaches are performed in acidic or basic media in conjunction with ion exchange membranes. The selection of the membrane can depend on the pH of the medium. For instance, a proton exchange membrane (PEM) can be used in an acidic environment, while an alkaline anion exchange membrane can used in a basic environment. Although membrane-based systems have high-energy efficiency and separate H2/O2 spontaneously, their application remains challenging by high cost and long-term stability. These cost and stability issues severely limit the commercial scalability of membrane-based systems. Hence, researchers have been investigating alternative methods. By way of example, Hashemi et al. (Energy Environ. Sci., 2015, 8, 2003) describes a membrane-less electrolyzer for hydrogen production across the pH scale. In this system, two parallel plates are coated with hydrogen and oxygen evolution catalysts, respectively, and are separated by less than a few hundreds of micrometers. The electrolyte flows between the catalyst plates and the evolved gases move close to the corresponding catalyst surface due to the Segre'-Silberberg effect. Each of the product gas streams can be collected in dedicated outlets. Stacks of these planes in horizontal can be used for higher throughput. Holmes-Gentle (Sustainable Energy Fuels, 2017, 1, 1184) describes a membrane-less photoelectrochemical cell similar to the Hashemi membrane-less electrolyzer. Both of these systems suffer in that the H2/O2 separation is only possible under supersaturating conditions right before the bubble formation. Further, the fact that there is only one reactor chamber where H2 and O2 are being produced can increase the possibility of creating an explosive H2 and O2 gas mixture exiting the reactor. In yet another example, U.S. Pat. No. 4,105,517 to Frosch describes a cyclic process for solar photolysis of water that includes production of H2 from water in the presence of Eu+2 photo-oxidizable reagent, pumping the resulting acidic solution to a second tank, where oxygen is generated in the dark during regeneration of the photocatalyst. This process suffers in that H2 and O2 are not produced simultaneously and requires regeneration of the process to be done in the absence of light. Further, the commercial scalability of these systems may not be economically feasible.
While various attempts to produce water-splitting systems have been made, they do not appear to meet the demands for commercial-scale production of H2 and O2 from water.
A discovery has been made that addresses at least some of the problems associated with currently available water-splitting processes. In one instance, the invention can address the problem associated with cross-contamination of H2 and O2 during the water-splitting process, and in particular, during the separation of H2 and O2 gases from the electrolyte solution. During this separation process, H2 and O2 combination can occur due to the continuous mixing of the aqueous solution with dissolved gasses. According to Henry's law, at a constant temperature, the amount of a given gas that dissolves in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid; this is expressed by the following equation: C=k×P(gas), where C is the solubility of a gas at a fixed temperature in a particular solvent (in units of M or mL gas/L), k is Henry's law constant (often in units of M/atm), and Pgas is the partial pressure of the gas (often in units of Atm). In the context of the present invention, a reactor design has been discovered that can generate H2 and O2 under electrolysis and/or photoelectrical conditions in separate chambers and allows for the electrolyte solution to be purged and recycled to the reactor. In some embodiments, the H2 and O2 is generated simultaneously. This provides for an elegant flow through design with minimal cross-contamination of O2 in the H2 generating chamber and H2 in the O2 generating chamber. Notably, cross-contamination of H2 in the O2 generating chamber and O2 in the H2 generating chamber can be limited to less than 0.2 mol. %. Limiting cross-contamination can result in a H2/O2 oxygen mixture having H2 and O2 ratios under the explosion limit (5%). Still further, the reactor design can be operated in a cost efficient and safe manner that lends itself to commercial scale production of H2 and/or O2.
In a particular aspect of the invention a water-splitting system for the production hydrogen (H2) gas and oxygen (O2) gas from an aqueous electrolyte solution is described. The water-splitting system can include a reactor having H2 and O2 generating chambers that can be separate chambers but do not have to be separated by a H2 and/or O2 gas permeable material (e.g., a membrane, an ionic bridge, or both). The H2 generating chamber can include a cathode and at least a first fluid inlet. The O2 generating chamber can include an anode in electrical communication with the cathode and at least a first fluid inlet. The first fluid inlets of each of the H2 and O2 generating chambers can be fluidly coupled to a purged electrolyte source, a purge gas source, or a combination thereof. The first fluid inlets can each receive a purged electrolyte solution, a purge gas, or a combination thereof. The system can further include a H2 reservoir fluidly coupled to the H2 generating chamber. The H2 reservoir can produce a H2 containing gas stream and a H2 containing electrolyte solution stream. In some embodiments, the system can further include a H2 purification system that can be fluidly coupled with an H2 outlet of the H2 reservoir, preferably a H2 permeable membrane. In some embodiments, the system can include an O2 reservoir fluidly coupled to the O2 generating chamber. The O2 reservoir can produce an O2 containing gas stream and an O2 containing aqueous electrolyte solution stream. The system can further include an O2 purification system that can be fluidly coupled to an O2 outlet of the O2 reservoir, preferably a O2 permeable membrane. In some embodiments, an electrolyte source (e.g., a reservoir that contains the electrolyte source) can be fluidly coupled to each of the first fluid inlets. The electrolyte source can receive and purge the electrolyte solution from the H2 generating chamber and/or the O2 generating chamber. The purged electrolyte solution can be returned to the first fluid inlets of the H2 generating and O2 generating chambers using a fluid mover (e.g., pumped or pressurized to the chambers). In some embodiments, the first fluid inlets can be purge gas inlets. In another embodiment, the first fluid inlets can receive the purged electrolyte solution, and the H2 generating chamber and the O2 generating chamber each can further include a second fluid inlet. Each second fluid inlet can be fluidly coupled to a purge gas source. In a preferred embodiment, the reactor can be a flow-through reactor. In a preferred embodiment, the anode and the cathode are included in a H2 or O2 impermeable material positioned at least partially between or substantially between the H2 generating chamber and the O2 generating chamber. The anode can include an oxidation catalyst, preferably a H2 generating photocatalyst in fluid communication with the aqueous electrolyte solution in the H2 generating chamber. The H2 generating chamber can receive electromagnetic radiation, which can be used to excite the photocatalyst, which in turn catalyzes the production of H2 and holes. The cathode can include a reduction catalyst, preferably an O2 generating photocatalyst, in fluid communication with the aqueous electrolyte solution in the O2 generating chamber. The O2 generating chamber can receive electromagnetic radiation, which can be used to excite the photocatalyst, which in turn catalyzes the production of O2 and electrons. The produced electrons can be transferred to the anode via an electrical connection between the cathode and anode (e.g., conductive material such as a conductive wire). In some embodiments, the H2 generating chamber can be fluidly coupled to the O2 generating chamber. The H2 generating chamber can be coupled to the O2 generating chamber by one or more apertures. In some embodiments, first and second apertures are comprised in a conduit that connects the H2 generating chamber with the O2 generating chamber. The apertures or conduit can be positioned in the lower portion of the two chambers to allow transport of ions into each chamber with limited or without cross-contamination of H2 and O2 into the O2 and H2 generating chambers, respectively. The lower portion of the H2 and O2 generating chambers can include apertures that are on or in the side walls of each chamber and that are positioned anywhere in the bottom half of the reactor such as at half the height of the chambers or less. In some instances, the apertures or conduit can be positioned on the side wall of each chamber proximate the bottom of the chamber. In some embodiments, the aperture is a hole or a plurality of holes (e.g., a screen) in the H2 and O2 impermeable material that separates the H2 generating chamber with the O2 generating chamber.
In another aspect of the invention a water-splitting process for production of H2 and O2 is described. The process can include providing an electrolyte solution to any of the water-splitting systems of the present invention. The electrolyte solution can include, water, a purge gas, and an electrolyte. The electrolyte solution in the H2 generating chamber and the electrolyte solution in the O2 generating chamber can be subjected to conditions sufficient to produce a H2 containing aqueous electrolyte solution and an O2 containing aqueous electrolyte solution. The purge gas, at least a portion of the generated H2, and at least a portion of the generated O2 can be dissolved in each of the aqueous electrolyte solutions. In certain instances, a majority of or all of the generated H2 and/or generated O2 can be dissolved in the aqueous electrolyte solution. The H2 containing aqueous electrolyte solution and/or the O2 containing aqueous electrolyte solution can be subjected to conditions suitable to produce a purge gas containing aqueous electrolyte solution, a gaseous H2 stream, and a gaseous O2 stream. In some embodiments, the purge gas containing aqueous electrolyte solution can be provided to the H2 generating chamber of the water-splitting system, the O2 generating chamber of the water-splitting system, or both. The purge gas containing aqueous electrolyte solution can be free of H2 and O2. In other instances, the purge gas containing aqueous electrolyte solution can include H2 and O2 in molar H2/O2 ratio under the flammability limit. The purge gas can by any gas, preferably an inert gas, most preferably nitrogen N2. The purge gas can reduce or limit contamination of H2 into the O2 containing aqueous electrolyte stream, O2 into the H2 containing aqueous electrolyte stream, or both. Water-splitting conditions can include a pressure of 0.010 MPa to 2.1 MPa, a temperature of 5° C. to 100° C., a pH of 0 to 14, or a combination thereof. Step (c) can include compressing the H2 containing aqueous electrolyte solution stream to produce a gaseous H2 stream and the electrolyte solution and/or (i) collecting the H2 containing aqueous electrolyte solution stream in the H2 reservoir, the O2 containing aqueous electrolyte solution stream in the O2 reservoir or both; (ii) separating the H2 gaseous stream from the H2 containing aqueous electrolyte solution and the O2 gaseous stream from the O2 containing aqueous electrolyte solution, or both; (iii) forming an aqueous electrolyte solution comprising residual H2, O2, or both; and (iv) purging the step (iii) aqueous electrolyte solution with the purge gas to form the purge gas containing aqueous electrolyte solution. In some embodiments, the process includes providing a purge gas to the H2 generating chamber, the O2 generating chamber, or both and/or providing the purged electrolyte solution to the H2 generating chamber and the O2 generating chamber.
In the context of the present invention, 20 embodiments are described. Embodiment 1 describes a water-splitting system for the production of hydrogen (H2) gas and oxygen (O2) gas from an aqueous electrolyte solution, the system comprising a reactor comprising: a H2 generating chamber comprising a cathode and at least a first fluid inlet fluidly coupled to a purged electrolyte source, a purge gas source, or a combination thereof, and an O2 generating chamber comprising an anode in electrical communication with the cathode and at least a first fluid inlet fluidly coupled to the purged electrolyte source, the purge gas source, or a combination thereof, wherein the H2 and O2 generating chambers are not separated by a H2 or an O2 gas permeable material. Embodiment 2 is the water-splitting system of embodiment 1, wherein the H2 or O2 gas permeable material is a membrane, an ionic bridge, or both. Embodiment 3 is the water-splitting system of any one of embodiments 1 to 2, further comprising a H2 reservoir fluidly coupled to the H2 generating chamber, the purged electrolyte source and an H2 product outlet. Embodiment 4 is the water-splitting system of embodiment 3, further comprising a H2 purification system, preferably a H2 permeable membrane, fluidly coupled to the H2 product outlet. Embodiment 5 is the water-splitting system any one of embodiments 1 to 4, further comprising an O2 reservoir fluidly coupled to the O2 generating chamber, the purged electrolyte source, and an O2 product outlet. Embodiment 6 is the water-splitting system of embodiment 5, further comprising an O2 purification system, preferably an O2 permeable membrane, fluidly coupled to the O2 product outlet. Embodiment 7 is the water-splitting system of any one of embodiments 1 to 6, wherein purged electrolyte source is fluidly coupled to the purge gas source. Embodiment 8 is the water-splitting system of any one of embodiments 1 to 7, wherein the first fluid inlets are fluidly coupled to the purged electrolyte source, and wherein the H2 generating chamber further comprises a second inlet and/or the O2 generating chamber further comprises a second inlet, each second inlet fluidly coupled to the purge gas source. Embodiment 9 is the water-splitting system of any one of embodiments 1 to 8, wherein the H2 generating chamber and the O2 generating chamber are fluidly coupled by at least one aperture positioned at a lower portion of both chambers, the at least one aperture sized to allow transport of ions between each chamber. Embodiment 10 is the water-splitting system of any one of embodiments 1 to 9, further comprising a conduit coupled to the H2 generating chamber and the O2 generating chamber, the conduit comprising a first aperture coupled to the H2 generating chamber and a second aperture coupled to the O2 generating chamber. Embodiment 11 is the water-splitting system of any one of embodiments 1 to 10, wherein the anode and the cathode are comprised in a H2 and/or O2 gas impermeable material positioned at least partially between the H2 generating chamber and the O2 generating chamber. Embodiment 12 is the water-splitting system of embodiment 11, wherein the anode comprises a photo-reduction catalyst in fluid communication with a purged electrolyte solution from the purged electrolyte source, and the H2 generating chamber is in communication with an electromagnetic radiation source. Embodiment 13 is the water-splitting system of any one of embodiments 11 to 12, wherein the cathode comprises a photo-oxidation catalyst in fluid communication with a purged electrolyte solution from the purged electrolyte source, and the O2 generating chamber is in communication with an electromagnetic radiation source. Embodiment 14 is the water-splitting system of any one of embodiments 11 to 13, wherein the H2 generating chamber and the O2 generating chamber are fluidly coupled by at least one aperture positioned at a lower portion of both chambers, and wherein the at least one aperture is comprised in the H2 and/or O2 gas impermeable material.
Embodiment 15 is a water-splitting system for the production of hydrogen (H2) gas and oxygen (O2) gas from an aqueous electrolyte solution, the system comprising: a reactor comprising: a H2 generating chamber comprising a cathode and at least a first fluid inlet fluidly coupled to a purged electrolyte source, a purge gas source, or a combination thereof; and an O2 generating chamber fluidly coupled to the H2 generating chamber, the O2 generating chamber comprising an anode in electrical communication with the cathode and at least a first fluid inlet fluidly coupled to the purged electrolyte source, the purge gas source, or a combination thereof, wherein the H2 and O2 generating chambers are not separated by a H2 or an O2 gas permeable material.
Embodiment 16 is a water-splitting process for the production of hydrogen (H2) gas and oxygen (O2) gas, the process comprising: (a) providing an electrolyte solution to each of the H2 generating chamber and the O2 generating chamber of the water-splitting system of any one of embodiments 1 to 15, the electrolyte solution comprising water, a purge gas, and an electrolyte; (b) subjecting the electrolyte solution in the H2 generating chamber and the electrolyte solution in the O2 generating chamber to conditions sufficient to produce a H2 containing electrolyte solution in the H2 generating chamber and an O2 containing electrolyte solution in the O2 generating chamber, wherein at least a portion of the generated H2 is dissolved in the H2 containing aqueous electrolyte solution, and at least a portion of the generated O2 is dissolved in the O2 containing electrolyte solution; and (c) subjecting the H2 containing electrolyte solution and/or the O2 containing electrolyte solution to conditions suitable to produce a purge gas containing electrolyte solution, a gaseous H2 stream, a gaseous O2 stream, or combinations thereof. Embodiment 17 is the process of embodiment 16, further comprising providing the purge gas containing electrolyte solution to the H2 generating chamber of the water-splitting system, the O2 generating chamber of the water-splitting system, or both, wherein the purge gas containing electrolyte solution comprises H2 and O2 in a molar H2/O2 ratio under the explosion limit. Embodiment 18 is the process of any one of embodiments 16 to 17, wherein the purge gas comprises any gas, preferably an inert gas, most preferably nitrogen N2, and wherein the purge gas is at least partially or fully solubilized in the aqueous electrolyte solution. Embodiment 19 is the process of any one of embodiments 16 to 18, wherein the water-splitting conditions comprise a pressure of 0.010 MPa to 2.1 MPa, a temperature of 5° C. to 100° C., a pH of 0 to 14, or a combination thereof. Embodiment 20 is the process of any one of embodiments 16 to 19, wherein the purge gas reduces contamination of H2 into the O2 containing aqueous electrolyte stream, O2 into the H2 containing aqueous electrolyte stream, or both. Embodiment 21 is the process of any one of embodiments 16 to 20, wherein step (c) comprises compressing the H2 containing aqueous electrolyte solution stream to produce a gaseous H2 stream and the electrolyte solution comprising the purge gas. Embodiment 22 is the process of any one of embodiments 16 to 21, wherein step (c) comprises: (i) collecting the H2 containing aqueous electrolyte solution stream in the H2 reservoir, the O2 containing aqueous electrolyte solution stream in the O2 reservoir or both; (ii) separating the H2 gaseous stream from the H2 containing aqueous electrolyte solution and the O2 gaseous stream from the O2 containing aqueous electrolyte solution, or both; (iii) forming an aqueous electrolyte solution comprising residual H2, O2, or both; and (iv) purging the step (iii) aqueous electrolyte solution with the purge gas to form the purge gas containing aqueous electrolyte solution. Embodiment 23 is the process of any one of embodiments 16 to 22, further comprising: providing a purge gas to the H2 generating chamber, the O2 generating chamber, or both; and providing the purged electrolyte solution to the H2 generating chamber and the O2 generating chamber. Embodiment 24 is the process of any one of embodiments 16 to 23, wherein step (b) further comprises flowing the a portion of the electrolyte solution between the H2 generating chamber and the O2 generating chamber through at least one of the apertures of embodiments 10, 11, or 15.
The following includes definitions of various terms and phrases used throughout this specification.
The phrase “electromagnetic radiation” refers to all wavelengths of light unless specified otherwise. Non-limiting example of wavelengths of light include radio wave, microwave, infrared, visible light, ultraviolet, X-ray, and gamma radiation, or any combination thereof. In some preferred instances, the electromagnetic radiation can include visible light or ultraviolet light or a combination of the two.
The term “coupled” is defined as connected, although not necessarily directly, and not necessarily mechanically; two items that are “coupled” may be unitary with each other.
The terms “about” or “approximately” are defined as being close to the value, term, or phrase that follows, as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
The terms “wt. %,” “vol. %,” or “mol. %” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt. % of component.
The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.
The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.
The use of the words “a” or “an” when used in conjunction with any of the terms “comprising,” “including,” “containing,” or “having” in the claims, or the specification, may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”
The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
The photoelectrochemical systems of the present invention can “comprise,” “consist essentially of,” or “consist of” particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase “consisting essentially of,” in one non-limiting aspect, a basic and novel characteristic of the photoelectrochemical water-splitting systems of the present invention are their abilities to produce high purity H2 and O2 in a continuous manner. In certain instances, the H2 and O2 generating chambers can be separate chambers, but are not separated by H2 and O2 permeable membranes and/or an ionic bridge.
Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.
Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.
A discovery has been made that provides a solution to the inefficiencies of water-splitting systems (e.g., PEC systems and/or an electrolysis systems). The discovery is premised on a reactor that does not require the use of a H2 and/or O2 gas permeable material such as a membrane or an ionic bridge. In lieu of such a membrane, a reactor of the present invention can provide purged electrolyte solution to a hydrogen generating chamber and an oxygen generating chamber with a minimal amount of H2 or O2 cross contamination in the respective chambers.
These and other non-limiting aspects of the present invention are discussed in further detail in the following sections with reference to the FIGS. The systems and methods of described in
Referring to
O2 generating chamber 108 can include anode 124 capable of oxidizing OH− in electrolyte solution 114 to O2. In some embodiment anode 124 include a photocatalyst capable of catalyzing generation of O2 from water and electrolyte solution 114. Anode 124 and cathode 112 can be electrically coupled through circuit 126. Circuit 126 can be a wire (e.g., copper wire) that connects the two electrodes. In some embodiments, circuit 126 can include a power source to supply electricity to one or more electrons. It should be understood, that one of skill in the art can electrically connect the cathode and anode as needed depending on the chosen electrode or catalyst. O2 generating chamber 108 can include O2 outlet 128 and electrolyte solution outlet 130. O2 outlet 128 can allow generated O2 to be removed from the O2 generating chamber and be in fluid communication with purification systems and/or collection systems (not shown). Electrolyte solution outlet 130 can be in fluid communication with electrolyte source 104 via piping 132 to allow O2 containing electrolyte solution to be removed from O2 generating chamber 108 and be provided to electrolyte source 104.
Electrolyte source 104 can include electrolyte solution inlet 134, purge gas (e.g., N2, argon, inert gas, or other gases) inlet 136, and electrolyte solution outlet 138. Electrolyte solution inlet 134 can be in fluid communication with piping 120 and/or other piping that allow gas containing (e.g., H2 and/or O2) electrolyte solutions and/or fresh electrolyte solution to enter electrolyte source 104. Purge gas inlet 136 can be in fluid communication with sparging system (not shown) capable of delivering a sufficient amount of purge gas to substantially or completely remove (degas) dissolved reactive gases (e.g., H2 and/or O2), forming degassed electrolyte solution 140. In certain instances, the purge gas can be any gas that does not react with the water-splitting materials or reagents (e.g., cathode material, anode material, intermediate reactants, products, or water). Non-limiting examples of purge gas include nitrogen (N2), helium (H2), argon (Ar), carbon dioxide (CO2), hydrocarbon gases (e.g., methane, ethane, propane and butane). In a preferred embodiment, N2 is used as the purge gas. System 100 can include fluid mover 146 (e.g., a pump). Degassed electrolyte solution 140 can be moved using fluid mover 146 to H2 generating chamber electrolyte inlet 142, O2 generating chamber inlet 144, via degassed electrolyte solution outlet 138 and piping 148, 150, and 152. Piping 148, 150, and 152 can fluidly couple the H2 generating chamber with the O2 generating chamber. In some embodiments, pressure from purge gas entering inlet 136 is sufficient to move the electrolyte solution to the various chambers. Removing the H2 and O2 from the electrolyte solution can minimize or inhibit cross-contamination of H2 into the O2 generating chamber and/or O2 into the H2 generating chamber. Such cross contamination can cause formation of water molecules from reactions of H+ and or OH− with the generated O2, H2 respectively. The reactive gas mixture can be removed from the electrolyte source via reactive gas outlet 154. Reactive gas mixture can be a mixture of H2, O2 and purge gas and have a molar H2 to O2 ratio under the flammability limit. Reactive gas outlet 154 can be in fluid communication with a collection unit, purification unit, transportation line, or the like. In some embodiments, system 100 is an electrolysis system or a photoelectrochemical system.
In some embodiments, the water-splitting system includes a H2 reservoir and an O2 reservoir fluidly coupled to the electrolyte source and the H2 generating chamber and the O2 generating chamber. Inclusion of H2 and O2 reservoirs can allow for separation of the H2 gas and/or O2 gas from the H2 and O2 containing electrolyte solutions prior to the electrolyte solution entering electrolyte source 104. Referring to
O2 reservoir 204 can be in fluid communication with O2 generating chamber 108 of reactor 102 via O2 outlet 128, piping 218, and reservoir O2 inlet 220. As O2 is generated in O2 generation chamber 108, a mixture of electrolyte solution with dissolved and free O2 can exit the O2 generation chamber and enter O2 reservoir. In O2 reservoir 204, aqueous electrolyte droplets separate from the gaseous O2. In some embodiments, the purge gas can enter O2 generating chamber 108 through inlet 144 or a second inlet (not shown) and purge or sweep gaseous O2 from O2 generating chamber 108 into O2 reservoir 204. Addition of the purge gas into O2 generating chamber 106 can saturate the anode with purge gas and inhibit OH-ions present to combine with any H+ present to form H2O. Gaseous O2 can exit O2 reservoir 204 via O2 outlet 222 and be in fluid communication with O2 permeable membrane 224 via piping 226. Membrane 224 can be an O2 permeable membrane capable of separating O2 from the purge gas and/or trace amounts of H2.
H2 reservoir 202 and O2 reservoir 204 can be in fluid communication with electrolyte source inlet 146 via piping 228 and 230, respectively. Electrolyte source 104 can receive electrolyte solution from H2 reservoir 202, O2 reservoir 204, or both. Such an electrolyte solution can have dissolved H2 and O2 in the solution. The dissolved H2 and O2 can be removed from the electrolyte solution to produce a degassed electrolyte solution that can be returned to H2 generating chamber and O2 generating chamber via piping 146, 148 and 150 as described for system 100.
In some embodiments, the H2 generating chamber and the O2 generating chamber can be in direct fluid communication with each other. By way of example, the two chambers can include an aperture that connects the two chambers. The aperture can be any size or shape (e.g., parabolic, circular, elliptical, trapezoid, parallelogram, square, rectangular, polygonal, or the like). The aperture can be sized to be sufficient to allow mass transport of ions (H+) and (OH−) at a rate sufficient to sustain a water-splitting reaction. Such sizing can be determined by known engineering methods depending on the size of the reactor.
In some embodiments of the present invention, the water-splitting system includes a H2 and/or O2 impermeable material. Referring to
In some embodiments, the water-splitting system of the present invention can have a stacked configuration as shown in
In some embodiments, the water-splitting system of the present invention can have a reactor having a stacked configuration that includes inlets for purge gas and electrolyte solution and outlets for H2 containing electrolyte solution and O2 containing electrolyte solution as shown in
1. Polymeric Materials
As discussed above, the systems of the present invention can be made from transparent or opaque polymeric materials. Non-limiting examples of polymeric materials include thermoset and thermoplastic materials. The polymeric material can include a thermoplastic polymer, such as, for example, polyethylene terephthalate, polycarbonate (PC), polybutylene terephthalate (PBT), poly(1,4-cyclohexylidene cyclohexane-1,4-dicarboxylate) (PCCD), glycol-modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine or polyetherimide (PEI) or a derivative thereof, a thermoplastic elastomer (TPE), a terephthalic acid (TPA) elastomer, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), a polyamide (PA), polystyrene sulfonate (PSS), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), a copolymer thereof, or a blend thereof. The polymeric material can comprise a thermoset material, such as, for example, an unsaturated polyester resin, a polyurethane, bakelite, duroplast, urea-formaldehyde, diallyl-phthalate, epoxy resin, an epoxy vinylester, a polyimide, a cyanate ester of a polycyanurate, dicyclopentadiene, a phenolic, a benzoxazine, a co-polymer thereof, or a blend thereof. In a preferred embodiments, the entire or portions of the PEC system is made from PMMA.
Polycarbonate polymers suitable for use in the present disclosure can have any suitable structure. For example, such a polycarbonate polymer can include a linear polycarbonate polymer, a branched polycarbonate polymer, a polyester carbonate polymer, or a combination thereof. Such a polycarbonate polymer can include a polycarbonate-polyorganosiloxane copolymer, a polycarbonate-based urethane resin, a polycarbonate polyurethane resin, or a combination thereof.
Such a polycarbonate polymer can include an aromatic polycarbonate resin. For example, such aromatic polycarbonate resins can include the divalent residue of dihydric phenols bonded through a carbonate linkage and can be represented by the formula:
where Ar is a divalent aromatic group. The divalent aromatic group can be represented by the formula: —Ar1—Y—Ar2—, where Ar1 and Ar2 each represent a divalent carbocyclic or heterocyclic aromatic group having from 5 to 30 carbon atoms (or a substituent therefor) and Y represents a divalent alkane group having from 1 to 30 carbon atoms. For example, in some embodiments, —Ar1—Y—Ar2— is Ar1—C(CH3)—Ar2, where Ar1 and Ar2 are the same. As used herein, “carbocyclic” means having, relating to, or characterized by a ring composed of carbon atoms. As used herein, “heterocyclic” means having, relating to, or characterized by a ring of atoms of more than one kind, such as, for example, a ring of atoms including a carbon atom and at least one atom that is not a carbon atom. “Heterocyclic aromatic groups” are aromatic groups having one or more ring nitrogen, oxygen, or sulfur atoms.
In some embodiments, Ar1 and Ar2 can each be substituted with at least one substituent that does not affect the polymerization reaction. Such a substituent can include, for example, a halogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, or a nitro group.
Aromatic polycarbonate resins suitable for use in the present disclosure can be commercially available, such as, for example, Lexan® HF1110, available from SABIC Innovative Plastics (U.S.A.), or can be synthesized using any method known by those skilled in the art. Polycarbonate polymers for use in the present disclosure can have any suitable molecular weight; for example, an average molecular weight of such a polycarbonate polymer can be from approximately 5,000 to approximately 40,000 grams per mol (g/mol).
2. Electrolyte Solution
The electrolyte solution can be an aqueous solution that has a pH of 0 to 14. In some embodiments, the electrolyte solution is a buffer solution have a pH of 6 to 7.5, or greater than, equal to, or between any two of 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4 and 7.5. The amount of electrolyte solution can be varied to fit the system. In some embodiments, an amount of electrolyte in the H2 and O2 reservoirs is minimal. By way of example, the amount of electrolyte is at least 5 vol % of the total volume of the reservoirs. In some embodiments, the amount of electrolyte solution in the reactor is 5 to 100% of the volume of the reactor. The electrolyte solution can be an aqueous solution of inorganic salts. The inorganic salts can have positive (K+, Na+, NH4+, Ca2+) and negative (NO3−, SO42−, PO43−, H2PO4−, HPO42−) ions that do not involve any kind of redox reaction under water oxidation condition in order to avoid possible redox reaction except pure water splitting reaction. Non-limiting examples of buffer solutions include phosphonium salts, sulfate salts, carbonate salts, and mixtures thereof.
3. Anode, Cathode, and Photocatalysts
Any anode or cathode material known for water-splitting reactions can be used. Non-limiting examples of anode material include metal oxides. Non-limiting examples of cathode material include metals or metal alloys. The metal oxide and metals can include platinum (Pt), cobalt (Co), molybdenum (Mo), nickel (Ni), iron (Fe, tungsten (W), tin (Sn), ruthenium (Ru), irdium (Ir), copper (Cu), manganese (Mn), chromium (Cr), zinc (Zn), cerium (Ce), lanthanum (La) or oxides, or alloys thereof. Non-limiting examples of oxygen evolution catalysts include Ir, Ru, Co, Co/phosphorus (P), CoFe, Cu, Fe, FeMn, Ni, NiCe, NiCo, NiCr, NiFe, NiCe, NiCeCoCe, NiLa, NiMoFe, NiSn, NiZn, or oxides thereof, or combinations thereof. Non-limiting examples of hydrogen evolution catalysts can include, Pt, Co, CoMo, CoNiFe, Fe, FeMo, Mo/sulfur (S), Ni, NiCo, NiFe, NiMo, NiMoC, NiMoFe, NiSn, NiW, or combinations thereof.
The photocatalysts useful in the present invention is suitable to generate H2 and O2 from water. By way of example, Z-scheme catalysts using two different semiconductor materials. In a preferred embodiment, the anodic catalyst can include metal oxides and the cathodic catalyst can include metal/metal alloy. Non-limiting examples semiconductor materials include strontium (Sr), titanium (Ti), Co, and thallium (Tl), and arsenic (As). Dopants such as phosphorous (P), sulfur (S) and barium (Ba) can be added. Non-limiting examples of semiconductor-type catalysts include SrTiO3, BaTiO3, GaN, CoPS, GaAs, GaAs/InGaP, NiMo/GaAs, InGaP/TiO2Ni, or combinations thereof. The photocatalysts can have layers of metals, metal oxides, and other materials of various thicknesses (e.g., 1 nm to 300 microns or any value there between. For example, a cathodic photocatalyst can include a bottom Ga layer, a InGaAs layer, a Tl layer, backsurface field layer (BSF), two InGaAs layers, an InGaP layer, a Tl layer, a BSF layer, two InGaP layers, an AlInP layer, and a top layer of InGaAs. In another example, an anodic photocatalyst can include be a p-n junction type catalyst that can include a GaAs layer on a support with InAlP layer, InGaP layer, a InGaP layer, a AlInGaP layer, a AlGaAs layer, an InGaP layer, an InAlP layer, a GaAs layer, a InGa P layer, a GaAs layer, and a Ni substrate layer as the top layer.
Systems 100, 200, 300 and 400 can have photocatalysts arranged as shown in
In some embodiments, photocatalysts can be are used either for generating H2 or O2 and they can separated from corresponding counter electrodes. The photocatalysts (e.g., 112 and/or 124) and corresponding electrodes (e.g., 112 and/or 124) can be connected through circuit 126 (e.g. a copper wire). The photocatalyst can be based on tandem, Z-scheme or multi-junction structures. In some embodiments, circuit 126 can be attached to impermeable material 402 or conduit 302. Referring to
Referring to
4. Gas Selective Membranes for Gas Phase Separation
Hydrogen selective and oxygen selective membranes used to purify the generated H2 and/or O2 can be manufactured or be obtained from commercial sources. Non-limiting examples of commercial membrane sources are Air Products (U.S.A.), Membrane Technology Research, Inc. (U.S.A.), Air Liquid (U.S.A.), UBE Industries, LTD. (JAPAN), or the like.
Non-limiting examples of materials that compose the hydrogen separation membrane include polymeric and carbon membranes. Polymeric membranes typically achieve hydrogen selective molecular separation via control of polymer free volume. Polymeric membranes may be comprised, for example, of glassy polymers, epoxies, polysulfones, polyimides (e.g., polyimide membrane from UBE, or Proteus™ membranes from Membrane Technology and Research, Inc., and other materials, and may include crosslinks and matrix fillers of non-permeable (e.g., dense clay) and permeable (e.g., zeolites) varieties to modify polymer properties. Carbon membranes are generally microporous and substantially graphitic layers of carbon prepared by pyrolysis of polymer membranes or hydrocarbon layers. Carbon membranes may include carbonaceous or inorganic fillers, and are generally applicable at both low and high temperature. The hydrogen separation membrane may be a dense membrane composed only of the above-mentioned materials, or may be a dense thin membrane composed of the above-mentioned materials supported on a porous body. In the case of the former, the thickness of the hydrogen separation membrane is preferably 0.1 μm or more and more preferably 0.5 μm to 5 μm from the viewpoints of mechanical strength and hydrogen permeability. In the case of the latter, the thickness of the thin membrane is 0.1 to 25 μm or more and more preferably 0.1 μm to 2 μm from the viewpoint of processability.
In cases where the hydrogen separation membrane includes the dense thin membrane composed of the above-described materials and the porous body supporting the membrane thereon, the replacement of gaseous species tends to be inhibited on the side of the porous body and, thus, it is preferable for a dense thin membrane to be the side contacted with a mixed gas, and a porous body to be the side contacted with permeated hydrogen.
Oxygen selective membranes can include a perfluorocarbon material, a polysiloxane material, a fluorinated polysiloxane material, a perfluorinated polyethers material, and an alkyl methacrylate-based copolymeric material. Oxygen selective membranes are available from commercial sources. For example, Sepuran® membranes from Evonik Industries (Austria) can be used. In some embodiments, oxygen can be released to the environment.
C. Method of Producing H2 and O2 from Water
The water-splitting systems of the present invention can be used to produce H2 and O2 from water. With reference to
In reactor 102, current and/or electromagnetic radiation can be applied to anode 124 to generated electrons, which travel through circuit 126 to cathode 112 to generate H2. In some embodiments, both anode and cathode photocatalysts can receive electromagnetic radiation. In other embodiments, voltage and light are applied. When electromagnetic radiation is used, the source of the electromagnetic radiation can be natural (e.g., sunlight) or artificial (e.g., a lamp). A non-limiting example of an artificial source is a UV lamp that provides light at 300 to 400 nm. Excitation of the photocatalyst 112 in the presence of water can generate hydrogen ion (H+). Conditions for the water-splitting can include temperature and pressure. The reaction temperature can be greater than, equal to, or between any two of 5° C., 10° C., 20° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C. and 100° C. The reaction pressure can be greater than, equal to, or between any two of 0.01 MPa, 0.1 MPa, 0.5 MPa, 1 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2.0 MPa and 2.1 MPa.
As H2 and O2 are generated, electrolyte solution 114 having H2 and O2 dissolved therein exits chambers 104 and 106 and enters H2 reservoir 202 and O2 reservoir 204, respectively. In some embodiments, electrolyte solution 114 exiting H2 generating chamber 106 passes through a compressor and gaseous H2 is separated from the electrolyte solution and enters purification unit 212. In some embodiments, a compressor is not used. In H2 reservoir 202, dissolved H2 is released from the electrolyte solution producing an electrolyte solution that can have less than 0.2 ppm or 0 to 0.2 ppm dissolved H2 remaining. Released H2 can exit H2 reservoir 202 and enter purification and/or collection unit 212. In some embodiments, released H2 can be provided directly to other units or used as a fuel. In O2 reservoir 204, dissolved O2 is released from the electrolyte solution producing an electrolyte solution that can have 0.2 ppm to 0.4 ppm or greater than, equal to, or between any two of 0.2 ppm, 0.25 ppm, 0.3 ppm, 0.35 ppm and 4 ppm of O2 remaining. Released O2 can exit O2 reservoir 202 and enter purification and/or collection unit 214. In some embodiments, released O2 can be provided directly to other units for use as an oxidant. Release of H2 and O2 can be facilitated by purging, compression, heating or any known techniques to degas an aqueous solution.
The electrolyte solutions can exit reservoirs 202, 204, and enter electrolyte source 104. As shown in the
The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.
A water-splitting system included a reactor having electrolyte (200 mL, 0.1 M Na2SO4), an anode (Pt coated-Ni mesh) in an O2 generating chamber, a cathode (GaAs based triple junction solar cell) in an H2 generating chamber. The H2 generating chamber connected to a H2 reservoir and the O2 generating chamber were connected to an O2 reservoir. The reactor and the H2 and O2 reservoirs were connected to an electrolyte reservoir. The reactor was irradiated with a solar simulator at the intensity of 1 Sun (100 mW/cm2). The light intensity reaching the reactor was maintained at 100 mW/cm2 by adjusting the distance between the lamp and the reactor cell. The distance range was typically between is between 20 cm to 50 cm depending on the desired light flux. The rate of pumping of the electrolyte solution through the system was about 100 mL/min. No nitrogen purge was used. In the absence of a nitrogen purge, 75% H2/O2 separation was achieved (Table 1). Solar To Hydrogen (STH) was 7.5% at pH=7 under one sun. Table 1 lists the total water splitting results with multi-junction system using the membrane-less reactor without the N2 purging during the water-splitting reaction. From the data, it was determined that the dissolved H2 gas was transferred from the H2 reservoir (Compartment 1) to the O2 reservoir (Compartment 2) via the O2 chamber (See,
Using the experimental reactor system of Example, 1 the cross-over of H2 to the O2 chamber was studied as a function of nitrogen flow. In this study, H2 was injected into the H2 reservoir (C1 in
Using the experimental design of Example, 3, the performance/efficiency of the separation of H2 and O2 of the reactor system in the presence of both gases was evaluated. H2 and O2 were injected into H2 reservoir (C1,
Based on the data, the low amount of H2 and O2 crossing resulted in a H2/O2 oxygen mixture with low H2 and O2 ratios, which was under the explosion limit (5%). As a result, the H2 rich gas mixture of H2, O2 and N2 can be further separated by conventional gas separation membrane to obtain high purity H2 when needed.
This application claims the benefit of priority of U.S. Provisional Patent Application No. 62/570,971 filed Oct. 11, 2017, which is hereby incorporated by reference in its entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2018/057846 | 10/10/2018 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62570971 | Oct 2017 | US |
