PRODUCING HIGH PURITY HYDROGEN AND CARBON MONOXIDE FROM A HYDROCARBON MATERIAL
20230047197 · 2023-02-16
Inventors
- Jiping Zhang (San Diego, CA, US)
- Jonathan David Sheeder (Escondido, CA, US)
- Robert Schleicher (Carlsbad, CA, US)
- Jonas Opperman (San Diego, CA, US)
Cpc classification
C01B2203/0838
CHEMISTRY; METALLURGY
C01B2203/0272
CHEMISTRY; METALLURGY
B01J19/248
PERFORMING OPERATIONS; TRANSPORTING
Y02E60/36
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J2219/00051
PERFORMING OPERATIONS; TRANSPORTING
C01B2203/0255
CHEMISTRY; METALLURGY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C01B2203/148
CHEMISTRY; METALLURGY
International classification
B01J19/24
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Disclosed are apparatuses, systems, methods, and devices for generating hydrogen pyrolysis of hydrocarbons (methane, diesel, JP8, etc.) in a reactor. The reactor includes multiple channels in parallel. A hydrocarbon flows in a channel and decomposes into hydrogen and carbon. Hydrogen gas flows out and some of the carbon will deposit on the channel wall. Once carbon deposition reaches a predetermined level, the hydrocarbon flow stops, and air or oxygen is caused to flow into the channels to oxidize carbon into carbon monoxide or carbon dioxide and supply heat to neighboring channels. Simultaneously, the hydrocarbon will flow into neighboring channels causing decomposition into hydrogen and carbon in the neighboring channels. When the carbon coating in the neighboring channels reaches a predetermined level, the gas flow is switched again to air or oxygen. In this way, each channel alternates between decomposing the hydrocarbon and oxidizing the deposited carbon.
Claims
1. A method of generating hydrogen gas by recycling energy, comprising: passing a material including one or more hydrocarbon structures through a first conduit that is heated above a desired threshold temperature to cause decomposition of the material into a first mixture that includes a first hydrogen gas and first carbon deposited onto a wall of the conduit; extracting the first hydrogen gas from the first conduit as part of a hydrogen gas output; after stopping the passing the material through the first conduit, causing oxidation of the first carbon deposited on the wall of the first conduit to convert the first carbon into a first carbon oxide gas while generating heat; coupling the heat generated from the first conduit to a second conduit separate from the first conduit; after stopping the passing the material through the first conduit, passing the material including one or more hydrocarbon structures through the second conduit that is heated above the desired threshold temperature by receiving the heat generated from the first conduit to cause decomposition of the material into a second mixture that includes a second hydrogen gas and second carbon deposited onto a wall of the second conduit; extracting the second hydrogen gas from the second conduit as part of the hydrogen gas output; after stopping the passing the material through the second conduit, causing oxidation of the carbon deposited on the wall of the second conduit to convert the second carbon into a second carbon oxide gas while generating heat; and repeating foregoing operations to recycle energy between the first and second conduits to alternatively to extracting the first hydrogen gas from the first conduit and the second hydrogen gas from the second conduit sequentially in time to produce the hydrogen gas output.
2. The method of claim 1, further comprising extracting the first carbon oxide gas from the first conduit and the second carbon oxide gas from the second to produce a carbon oxide gas output.
3. The method of claim 2, further comprising controlling the oxidation in the first and second conduits to render the first and second carbon oxide gases as carbon monoxide.
4. The method of claim 2, further comprising controlling the oxidation in the first and second conduits to render the first and second carbon oxide gases as carbon dioxide.
5. The method of claim 1, wherein the material includes methane.
6. The method of claim 1, wherein the material includes a fluid that includes diesel, gasoline, or kerosene.
7. The method of claim 1, wherein the material includes JP8
8. The method of claim 1, wherein the material includes methane and the decomposition in the first and second conduit occurs in accordance with the endothermic chemical equation:
CH4=C+2H2+75 kJ
9. The method of claim 1, wherein the oxidation is controlled to be:
C+O2=CO2−390 kJ.
10. The method of claim 1, wherein the oxidation is controlled to be:
C+½O2=CO−110 kJ
11. The method of claim 1, wherein the material includes natural gas, propane, ethane, butane, or another hydrocarbon gas.
12. The method of claim 1, wherein the recycling energy between the first and second conduits is a self-sustaining cycle not requiring external heat.
14. An apparatus for generating hydrogen gas, comprising: a chamber structured to include a hollow interior, a silicon carbide interior wall and exterior wall with silicon between the interior wall and the exterior wall; a fluid supply system coupled to the chamber to controllably supply selected fluids including gases and/or liquids into the chamber, including a first fluid which can be decomposed into hydrogen and carbon and a first gas containing oxygen that reacts with carbon to release heat and generate a second gas; and a control system coupled to the fluid supply system to sequentially control supplying of the fluids into the chamber, wherein control system controls the fluid supply system to cause the first fluid to pass through the chamber thereby causing decomposition of the first fluid into a generated hydrogen gas and carbon which is deposited onto the interior wall of the chamber, and to stop supplying of the first fluid and after stopping the first fluid, the gas supply system causes the first gas to pass through the chamber to cause the carbon to react with oxygen in the first gas thereby releasing heat to heat the chamber and the second gas.
15. The apparatus of claim 14, further comprising: one or more temperature sensors to sense the temperature of the chamber, wherein the fluid supply system includes: a valve to control a flow of the first fluid; another valve to control a flow of the first gas; and wherein the control system includes a processor and memory including executable instructions, wherein the executable instructions are configured to at least control the valve and the other valve to produce the generated hydrogen gas and the second gas.
16. The apparatus of claim 14, wherein the first fluid is methane, and wherein heat from the chamber causes decomposition of the methane into carbon and hydrogen gas
17. The apparatus of claim 14, wherein the first fluid is diesel, gasoline, or kerosene.
18. The apparatus of claim 14, wherein the first fluid is JP8
19. The apparatus of claim 14, wherein the first gas is oxygen
20. The apparatus of claim 14, wherein the second gas is carbon monoxide
21. The apparatus of claim 14, wherein the second gas is carbon dioxide.
22. The apparatus of claim 14, wherein the first gas is air.
23. The apparatus of claim 14, wherein the first fluid is natural gas, propane, ethane, butane, or another hydrocarbon gas.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0008]
[0009]
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DETAILED DESCRIPTION
[0019] The disclosed subject matter includes designs of a channel reactor and methods of producing hydrogen from pyrolysis of hydrocarbons (methane, diesel, JP8, etc.). In implementations, the structure of the reactor can include multiple channels in parallel and may have every other channel connected at both ends. Such a reactor may be initially heated to a high temperature (e.g., >1400° C.). A hydrocarbon gas can be directed to flow in a channel and can be decomposed into hydrogen and carbon within the channel. The hydrogen gas from this decomposition can be extracted out of the channel and be collected and some of the carbon from this decomposition will deposit on the inner wall of the channel. Once carbon deposition on the inner wall of the channel reaches a predetermined level, the hydrocarbon flow stops. To continue the hydrogen production, the flow of hydrogen gas is terminated and is replaced by directing a flow air or oxygen into the channel to oxidize deposited carbon on the inner wall into carbon monoxide or carbon dioxide while generating heat which is supplied to neighboring channels. Simultaneously, the hydrocarbon gas will be directed to flow into neighboring channels causing hydrocarbon decomposition into hydrogen and carbon in the neighboring channels to produce hydrogen gas and carbon. When the carbon coating on the inner walls in the neighboring channels reaches a predetermined level, the gas flow in those channels is switched again to air or oxygen. In this way, each channel alternates between decomposing the hydrocarbon and oxidizing the deposited carbon. In some example embodiments, at any one time every other channel is decomposing the hydrocarbon and the alternate channels are oxidizing the deposited carbon. The foregoing process is thus a repeatable process cycle to produce hydrogen and carbon monoxide or carbon dioxide. One of the benefits of the process is that hydrogen is produced continuously without needing to switch gases.
[0020] Since the reaction is exothermic, the generated heat as a byproduct of such reaction may be beneficially used or recycled within the hydrogen production system or may be used to supply heat to another system. For example, the generated heat may be used to burn feedstock hydrocarbons or hydrogen that is produced in the channels.
[0021] The disclosed technology can be used generate H.sub.2 and CO for distribution on demand, a desirable feature for various applications. For example, the disclosed technology can be used to produce hydrogen for use in a vehicle.
[0022] Hydrocarbons such as methane, diesel, and JP8 can be fully converted into pure H.sub.2 and carbon (e.g., more than 99.5%) at a temperature greater than 1400 C with a resident time of less than 0.1 seconds without a catalyst. The CO production can be controlled to have a very high purity of the produced CO (e.g., a purity more than 99%) by controlling O.sub.2 flow.
[0023] Methane can be decomposed into C and H.sub.2 while releasing 75 kJ of heat (endothermic) according to the following chemical reaction:
CH.sub.4=C+2H.sub.2+75 kJ Equation 1.
[0024] As described above, deposited carbon reacts with O.sub.2 to produce CO and heat (exothermic) according to:
C+½O.sub.2=CO−110 kJ Equation 2.
[0025] In addition, deposited carbon reacts with O.sub.2 to produce CO2 and heat (exothermic) according to:
C+O.sub.2=CO.sub.2−390 kJ Equation 3.
[0026] Heat alone can be sufficient for methane or other hydrocarbons (HCs) to undergo pyrolysis with either partial oxidation of carbon as expressed in Equation 2, or full oxidation of carbon as expressed in Equation 3. Equations 1-3 do not produce water, so heating efficiency is relatively high.
[0027] To produce CO, the partial oxidation of carbon in the chemical reaction in Equation 2 may be used. Alternatively, oxygen-containing air may be used to fully oxidize carbon in the oxidation process in Equation 3 which releases more heat that the partial oxidation in the process in Equation 2.
[0028] In some implementations, heat exchanger (HX) may be used to improve efficiency by recovering heat from outlet gases.
[0029] If other hydrocarbons are used, more CO may be produced and more heat will be generated according to:
C.sub.xH.sub.2y=xC+yH.sub.2+xQ(y<=2x, and Q<=75 kJ) Equation 4.
[0030]
[0031]
[0032] At first alternate times, reactor 210 is configured to receive an input hydrocarbon 212A such as methane (CH.sub.4) shown and produce H.sub.2 gas 214A via decomposition according to Equation 1. Also, at a first alternate times reactor 220 is configured to receive an input of O.sub.2 222A which reacts with carbon deposited on the walls of reactor 220 to produce CO gas 224A via partial oxidation according to Equation 2.
[0033] At second alternate times, reactor 210 is configured to receive an input of O.sub.2 212B which reacts with carbon deposited on the walls of reactor 220 to produce CO gas 214B via partial oxidation according to Equation 2. Also, at a second alternate times reactor 220 is configured to receive an input hydrocarbon 222B such as methane (CH.sub.4) shown and produce H.sub.2 gas 224B via decomposition according to Equation 1.
[0034] First and second alternate times may be interleaved in the sense that a first alternate time is followed by a second alternate time, which in turn is followed by another first alternate time. In this way, each channel reactor is repetitively alternated between receiving a hydrocarbon and producing H.sub.2 gas, and receiving O.sub.2 and producing CO gas.
[0035] Adjacent channels such as channels 210 and 220 shown in
[0036] In some implementations, the channels may be made from silicon carbide (SiC) which is compatible with high operating temperature and as well as being chemically compatible. For example, carbon will build-up on the walls of a SiC channel during decomposition in the pyrolysis phase that will react with O.sub.2 during the oxidation phase. Some example embodiments include silicon encapsulated by SiC. For example, the channel wall material may be SiC on exposed surfaces with Si inside the SiC. An advantage of Si encapsulation is that Si has a high latent heat (˜1800 kJ/kg) and high thermal conductivity which aids in keeping the channel walls at a constant and uniform temperature even with an unstable flow.
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[0041] Shown in
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[0044] The cross flow-channels provide more convenient access to input and output ports and for connection to heat exchange (HX) devices. The cross-flow reactor may be configured with the reactor tubes surrounded by Si. The Si acts as a heat transfer and heat storage media to keep reactor at a uniform and constant temperature such as 1414 C which corresponds to the melting point of Si.
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[0048] When oxygen flows into the reactor at certain times, such as between T.sub.1 to T.sub.2 and T.sub.3 to T.sub.4, sufficient carbon can be deposited on the wall to keep the ratio of C:O at or greater than 1, and the CO production will dominate at high temperatures with only a trace of CO.sub.2.
[0049] In the first two cycles which are T.sub.0 to T.sub.2 and T.sub.2 to T.sub.4, when the oxygen flow is close to the end of the cycle, most of the carbon is already burned and the small amount of carbon left is not enough to hold the ratio of C:O to be at or greater than 1, thus resulting in CO.sub.2 being produced. The CO.sub.2 production occurs for a short time and after the cycle has ended, the gas flow switches to methane. At the end of the cycle, some carbon is probably still present but there is no oxygen to form CO.sub.2. This is why the CO.sub.2 production tends to be brief in time within a cycle and looks like a sharp spike in
[0050] For the third cycle which begins at T.sub.4, not all the carbon produced from methane decomposition is coated on the channel walls and some of the carbon flows out with hydrogen as dust resulting in CO.sub.2 that is produced far from the cycle end.
[0051] For pure CO production, the O.sub.2 flow should be stopped before CO.sub.2 is produced.
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[0053] While this patent document contains many specifics, these should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features that may be specific to particular embodiments of particular inventions. Certain features that are described in this patent document in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.
[0054] Similarly, while operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. Moreover, the separation of various components in the embodiments described in this patent document should not be understood as requiring such separation in all embodiments.
[0055] Only a few implementations and examples are described, and other implementations enhancements and variations can be made based on what is described and illustrated in this patent document.