The present disclosure relates to a Steam Methane Reformer (SMR). In particular, the present disclosure relates to a SMR with enhanced carbon dioxide (CO2) capture.
Steam methane reformers (SMRs) are generally used to produce a syngas from a gas feedstock such as natural gas or refinery gas. The produced syngas can be further processed within the plant to yield various end products, including purified hydrogen, methanol, carbon monoxide, and ammonia. However, the flue gas produced during the reforming process contains contaminants, such as carbon dioxide, which are known to adversely affect the environment by contributing to overall climate change. SMRs are known to be one of the largest CO2 emitters in refineries. As such, in recent years, many government regulatory bodies have required the reduction in emissions of carbon dioxide, into the atmosphere.
Given the recognition of the harmful effect of carbon dioxide release and recent restrictions on its emission, efforts have been made to efficiently remove carbon dioxide in a purified form from a flue gas produced by a steam reformer plant. By removing carbon dioxide from the flue gas, the carbon dioxide alternatively may be used for other, safer purposes, such as underground storage or oil production needs.
Current methods for CO2 capture from SMRs, such as, for example, using an amine absorption stripper system to remove CO2 from flue gas (post-combustion capture) or using physical or amine-based chemical solvents in a stripper system to remove CO2 from the SMR tail gas (pre-combustion capture), are highly inefficient and costly. The stripping systems are generally too energy-intensive, requiring significant quantities of steam to regenerate the solvents. The state-of-the-art post-combustion method employing molten carbonate fuel cell (MCFC) technology generates power while capturing CO2 from a host plant. The additional power generated beyond the requirements of the system itself provides a source of revenue that offsets system capital and operating costs. In the conventional post-combustion system, flue gas from the SMR containing high levels of CO2 is directed into the MCFC. Due to the high levels of CO2, this method requires a relatively large quantity of MCFC modules, which can be costly and may produce more power than is desirable. As such, conventional MCFC-based CO2 capture systems can be very expensive and may produce excess energy that cannot easily be unloaded.
Embodiments described herein provide a SMR-CO2 capture system that captures CO2 from a tail gas of a pressure swing adsorption (PSA) system of a SMR system, which can, advantageously, help to capture CO2 in a more efficient and cost-effective manner, as compared to some conventional CO2 capture systems.
In some embodiments, a system for capturing CO2 from a SMR system comprises a MCFC, a compressor, a chiller, and a CO2 separator. Exhaust gas from the anode of the MCFC may be mixed with tail gas from a PSA of the SMR system and compressed by the compressor. The mixed, compressed gas may be cooled by the chiller and fed into the CO2 separator. The CO2 separator separates liquefied CO2 from the residual, uncondensed gas.
In various embodiments, the residual gas may be recycled into various parts of the SMR system or the system for capturing CO2. For example, in some embodiments, a portion of the gas may be recycled to an anode gas oxidizer and then to a cathode of the MCFC, and another portion recycled into an anode of the MCFC. In some embodiments, a third portion of the residual gas may be recycled to the PSA of the SMR system to produce more hydrogen, or to a reformer in the SMR system to be burned as fuel. This third portion of residual gas may instead be recycled for use in a PSA outside the SMR system. In some embodiments, a third portion of the residual gas may be recycled to the PSA of the SMR system to produce more hydrogen, and a fourth portion of the residual gas may be recycled to a reformer in the SMR system to be burned as fuel.
In some embodiments, flue gas from a reformer of the SMR system may be vented to the atmosphere. Because the tail gas from the PSA of the SMR system is not burned to fuel the reformer of the SMR system, the flue gas is relatively low in CO2. In other embodiments, the flue gas may be directed to an anode gas oxidizer in the system for capturing CO2 and then to a cathode of the MCFC.
In some embodiments, the MCFC may be sized to power only the system for capturing CO2, only the SMR system, or both. Because the tail gas from the PSA of the SMR system is not burned to fuel the reformer of the SMR system, the MCFC receives a reduced amount of CO2, allowing the MCFC to be sized smaller and reducing excess power generation.
In some embodiments, a system for capturing CO2 from a SMR system comprises a compressor, a chiller, and a CO2 separator, but excludes an MCFC as power for the system may be derived from an external power source such as an existing power plant, utility grid, and/or renewable power such as solar or wind power. Tail gas from a PSA of the SMR system is compressed by the compressor and cooled by the chiller. The CO2 separator separates liquefied CO2 from the residual, uncondensed gas. The uncondensed gas may then be recycled to the PSA of the SMR system and/or to the reformer of the SMR system to be burned as fuel.
In some embodiments, a method comprises mixing anode exhaust gas from the anode of a MCFC with tail gas from the PSA of a SMR system, compressing the mixed gas with a compressor, cooling the mixed gas with a chiller, separating liquefied CO2 from residual, uncompressed gas in a separator, and collecting the liquefied CO2. In some embodiments, the residual gas may be recycled in varying amounts to an anode gas oxidizer coupled to a cathode of the MCFC, the anode of the MCFC, the PSA of the SMR system, and/or to a reformer of the SMR system to be burned as fuel.
The foregoing is a summary of the disclosure and thus by necessity contains simplifications, generalizations, and omissions of detail. Consequently, those skilled in the art will appreciate that the summary is illustrative only and is not intended to be in any way limiting. Other aspects, features, and advantages of the devices and/or processes described herein, as defined by the claims, will become apparent in the detailed description set forth herein and taken in conjunction with the accompanying drawings.
The disclosure will become more fully understood from the following detailed description, taken in conjunction with the accompanying figures, wherein like reference numerals refer to like elements, in which:
Referring generally to the figures, disclosed herein are various embodiments of an enhanced SMR-CO2 capture system capable of capturing CO2 in a more efficient and cost-effective manner, as compared to some conventional CO2 capture systems. The various embodiments disclosed herein may be capable of increasing the amount of CO2 captured, improving efficiency of capturing CO2, increasing the amount of hydrogen produced, and/or reducing costs associated with capturing CO2. In the various embodiments disclosed herein, like reference numerals refer to like elements between Figures, but are increased by 200 from figure to figure (e.g., PSA 450 in
Generally speaking, in a typical SMR unit of a SMR-CO2 capture system, natural gas is reacted with water to form hydrogen and CO2. Some methane is unconverted and some carbon monoxide is also generated in the process. These impurities, along with any water that is not separated out by condensation, are normally removed from the hydrogen using a PSA system, which can desorb these impurities at atmospheric pressure to generate a PSA tail gas that is generally high in CO2 and also contains CO, methane, and hydrogen. Typically, the PSA tail gas is recycled as fuel in the SMR unit, where the gases are combusted with air to provide the heat needed for the endothermic reforming reaction. This reaction produces a flue gas having relatively high CO2 content that can be directed to an MCFC for subsequent CO2 capture. In this type of system configuration, the size of the MCFC is dictated, in part, by the amount (or percentage) of CO2 to be transferred to the anode of the MCFC from the flue gas received from the SMR unit (e.g., 70%-90% of the CO2).
However, the composition of the PSA tail gas is very similar to the shifted anode exhaust gas of the MCFC in the CO2 capture system. Thus, Applicant advantageously determined that the PSA tail gas could be mixed directly with the anode exhaust gas of the MCFC before being compressed and cooled to separate the CO2 from the gas, instead of recycling the PSA tail gas in the SMR unit. In this manner, the size of the MCFC is not dictated by the PSA tail gas from the SMR unit, since the CO2 that is normally contained in the flue gas from the PSA tail gas is mixed with the anode exhaust gas downstream of the MCFC for subsequent CO2 capture instead. Accordingly, the overall cost of the system can be reduced by selecting a smaller sized MCFC that can, for example, produce just enough power for the chiller and other electrical loads of the CO2 capture system, the SMR system itself, or both, as discussed in greater detail below.
In some implementations, the system can also be configured to direct the flue gas from the SMR unit to the MCFC for additional CO2 capture. In some implementations, the unused fuel from the anode of the MCFC containing hydrogen and carbon monoxide can be directed from a CO2 capture tail gas to the PSA to increase the hydrogen production of the system. In some implementations, power is purchased from an external source instead of using an MCFC to power the CO2 capture system.
The shifted gas is then sent via shift gas line 240 to a PSA system 250 where the hydrogen is separated from the residual methane and CO in the gas along with the CO2 produced from the reforming and shift reactions. The residual gases are recycled as fuel to the reformer 230 via a recycling line 260, where the gases are combusted with air supplied by an air supply line 270 to provide the heat needed for the endothermic reforming reaction. All of the CO2 generated in the production of the hydrogen is vented in the reformer flue gas as a mixture of N2, CO2, and H2O with some NOx.
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The outlet stream is then compressed by a compressor 130 and then cooled by, for example, a chiller 135. The compressed and cooled outlet stream is then transferred to a CO2 separator 140. In the compressed and cooled outlet stream, about 60% to about 90% of the CO2 is condensed as a liquid and separated from a residual CO2 capture tail gas containing hydrogen, any unconverted CO, the remaining uncondensed CO2, and methane. The residual CO2 capture tail gas is partially recycled to the anode 122 via a recycle line 142 to be used as fuel in the MCFC 120. The remainder of the residual CO2 capture tail gas is sent to the AGO 110 to help prevent buildup of inert gases, such as nitrogen, and to heat up the gas in the AGO 110 by combusting the remaining hydrogen gas from the residual CO2 capture tail gas. This recycling has the advantage of increasing the amount of CO2 recovered from the anode exhaust.
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According to another representative embodiment, the size of the MCFC 520 is configurable to offset the power consumed by the CO2 capture system 500 and the SMR system 600. In this configuration, a relatively large percentage of the normally emitted CO2 (e.g., about 60% to about 70%) would still be captured by the system, but the capital cost would be significantly reduced and the need to export power to a third party would be eliminated or reduced.
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According to a representative embodiment, tail gas from a PSA in a SMR system is mixed directly with an anode exhaust gas from the anode of an MCFC, where the mixture can be compressed and its temperature lowered by a chiller, such that liquefied CO2 can be separated from the mixture to be captured. The CO2 from the combustor of the reformer of the SMR system, i.e. the flue gas from the SMR system, is not directed to the MCFC for CO2 capture, as compared to some conventional SMR-CO2 capture systems. In this way, the size of the MCFC is independent of the flue gas from the SMR reformer and instead is governed by the CO2 capture from the PSA tail gas, thereby reducing the overall cost of the system while still providing CO2 capture.
According to another representative embodiment, flue gas from a SMR system is sent to the cathode of an MCFC, and tail gas from a PSA of the SMR system is mixed directly with an anode exhaust from the anode of the MCFC for capturing CO2. In this way, the MCFC can be sized to be smaller than in a typical SMR-CO2 capture system, since the tail gas containing about 50-60% of the CO2 normally present in the flue gas to be captured by the MCFC is directed to the anode exhaust of the MCFC instead. Thus, this exemplary system can provide relatively high CO2 capture while reducing overall cost of the system.
According to another representative embodiment, flue gas from a SMR system is sent to the cathode of an MCFC, and tail gas from a PSA of the SMR system is mixed directly with an anode exhaust from the anode of the MCFC for capturing CO2. A portion of the unused fuel from the anode of the MCFC, following removal of CO2 and containing hydrogen and carbon monoxide (CO), can be directed from the CO2 capture tail gas to the PSA to increase the hydrogen production of the system. In this manner, this exemplary system can provide for relatively high CO2 capture and increased hydrogen production, while reducing overall cost of the system.
According to another representative embodiment, the tail gas from a PSA of the SMR system is compressed and its temperature lowered by a chiller using an external power source (and, in cases where an absorption chiller is used, an external heat source), such that the liquefied CO2 can be separated from the gas for capturing CO2. The unused fuel from the CO2 capture tail gas containing hydrogen, CO, residual CO2, and other non-condensable gases may be directed to the PSA so as to increase the hydrogen production of the system, and/or to the reformer of the SMR system, helping to prevent build-up of inert gases in the SMR system. In this manner, this exemplary system can provide a lower-cost option for capturing CO2, as compared to some conventional SMR-CO2 capture systems.
Disclosed herein are various embodiments of an enhanced SMR-CO2 capture system capable of capturing CO2 in a more efficient and cost-effective manner, as compared to some conventional CO2 capture systems using MCFC. The various embodiments disclosed herein may be capable of increasing the amount of CO2 captured, improving efficiency of capturing CO2, increasing the amount of hydrogen produced, and/or reducing costs associated with capturing CO2.
As utilized herein, the terms “approximately,” “about,” “substantially”, and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numerical ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and claimed are considered to be within the scope of the invention as recited in the appended claims.
The terms “coupled,” “connected,” and the like as used herein mean the joining of two members directly or indirectly to one another. Such joining may be stationary (e.g., permanent) or moveable (e.g., removable or releasable). Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate members being attached to one another.
References herein to the positions of elements (e.g., “top,” “bottom,” “above,” “below,” etc.) are merely used to describe the orientation of various elements in the Figures. It should be noted that the orientation of various elements may differ according to other exemplary embodiments, and that such variations are intended to be encompassed by the present disclosure.
It is important to note that the construction and arrangement of the various exemplary embodiments are illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter described herein. For example, elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes and omissions may also be made in the design, operating conditions and arrangement of the various exemplary embodiments without departing from the scope of the present invention. For example, the heat recovery heat exchangers may be further optimized.
This application is a divisional of U.S. patent application Ser. No. 17/194,597, filed Mar. 8, 2021, which claims the benefit of and priority to U.S. Provisional Application No. 62/987,985, filed Mar. 11, 2020, both of which are incorporated by reference herein in their entireties.
Number | Date | Country | |
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62987985 | Mar 2020 | US |
Number | Date | Country | |
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Parent | 17194597 | Mar 2021 | US |
Child | 18626547 | US |