Patent Grant
10427091
The present techniques relate to a method and system associated with swing adsorption processes used in conditioning streams for downstream processing. In particular, the method and system involve a startup mode process for a swing adsorption process, which is further utilized for starting downstream process.
Gas separation is useful in many industries and can typically be accomplished by flowing a mixture of gases over an adsorbent material that preferentially adsorbs one or more gas components while not adsorbing one or more other gas components. The non-adsorbed components are recovered as a separate product.
One particular type of gas separation technology is swing adsorption, such as temperature swing adsorption (TSA), pressure swing adsorption (PSA), partial pressure swing adsorption (PPSA), rapid cycle temperature swing adsorption (RCTSA), rapid cycle pressure swing adsorption (RCPSA), rapid cycle partial pressure swing adsorption (RCPPSA), and not limited to but also combinations of the fore mentioned processes, such as pressure and temperature swing adsorption. As an example, PSA processes rely on the phenomenon of gases being more readily adsorbed within the pore structure or free volume of an adsorbent material when the gas is under pressure. That is, the higher the gas pressure, the greater the amount of readily-adsorbed gas adsorbed. When the pressure is reduced, the adsorbed component is released, or desorbed from the adsorbent material.
The swing adsorption processes (e.g., PSA and/or TSA) may be used to separate gases of a gas mixture because different gases tend to fill the micropore of the adsorbent material to different extents. For example, if a gas mixture, such as natural gas, is passed under pressure through a vessel containing an adsorbent material that is more selective towards carbon dioxide than it is for methane, at least a portion of the carbon dioxide is selectively adsorbed by the adsorbent material, and the gas exiting the vessel is enriched in methane. When the adsorbent material reaches the end of its capacity to adsorb carbon dioxide, it is regenerated by reducing the pressure, thereby releasing the adsorbed carbon dioxide. Then, the adsorbent material is typically purged and repressurized prior to starting another adsorption cycle.
The swing adsorption processes typically involve adsorbent bed units, which include adsorbent beds disposed within a housing and configured to maintain fluids at various pressures for different steps in a cycle within the unit. These adsorbent bed units utilize different packing material in the bed structures. For example, the adsorbent bed units utilize checker brick, pebble beds or other available packing. As an enhancement, some adsorbent bed units may utilize engineered packing within the bed structure. The engineered packing may include a material provided in a specific configuration, such as a honeycomb, ceramic forms or the like.
Further, various adsorbent bed units may be coupled together with conduits and valves to manage the flow of fluids through the cycle. Orchestrating these adsorbent bed units involves coordinating the steps in the cycle for each of the adsorbent bed units with other adsorbent bed units in the system. A complete cycle can vary from seconds to minutes as it transfers a plurality of gaseous streams through one or more of the adsorbent bed units.
As may be appreciated, the removal of contaminants may result in the process operating in different modes, such as a startup mode and a normal operation mode. The startup mode may be utilized to prepare the equipment (e.g., the adsorbent bed and various stream) for the normal operation mode. The normal operation mode may be utilized when the process is receiving various streams, such as the gaseous feed stream, and removing contaminants from the gaseous feed stream to provide a product stream, which may be referred to as steady state. For example, the conventional processes may operate in normal operation mode to treat hydrocarbon containing streams containing water (H2O) or carbon dioxide (CO2) to prepare the stream for downstream processing, such as natural gas liquid recovery (NGL) or liquefied natural gas (LNG) processing. The normal operation modes may be different for each of the respective downstream processes based on the respective specifications that are involved for normal operational mode. For example, a typical LNG specification requires the CO2 content to be less than 50 parts per million molar (ppm).
During the startup mode, the cycle may be different than the cycle utilized for normal operation mode. Conventional systems may utilize a single heating step to regenerate the adsorbent material with high temperatures to remove any contaminants as the startup mode cycle. For example, a startup process involving a mole sieve unit may include heating the bed to temperatures in excess of 550° F.
Unfortunately, conventional startup mode processes have certain limitations. For example, the process in startup mode may involve merely heating the adsorbent material to high temperatures. The heating of the adsorbent material to high temperatures in the conventional approaches typically rely upon dedicated high-temperature startup heaters. These heaters are expensive, involve large capital expenditure and high operational costs. In addition, these heaters increase the weight and footprint of the facility. Further, the cycle time is typically longer than necessary to remove contaminants to ensure sufficient time is provided for downstream equipment to begin operations. In addition, the temperature that the adsorbent material are exposed to may lessen the operational life of the adsorbent material and may lessen the efficiency of the adsorbent material.
Accordingly, there remains a need in the industry for apparatus, methods, and systems that provided enhancements to the start-up processes associated with hydrocarbon recovery processes. In particular, a need exists for enhancements to startup mode processes for rapid cycle swing adsorption processes.
In one or more embodiments, the present techniques comprise a process for removing contaminants from a gaseous feed stream with a swing adsorption process. The process comprising: a) performing a purge step, wherein the purge step comprises passing an external gas stream through an adsorbent bed unit to remove one or more contaminants from an adsorbent bed within a housing of the adsorbent bed unit to form a purge product stream; b) performing one or more adsorption steps, wherein each of the one or more adsorption steps comprise passing a gaseous feed stream through an adsorbent bed unit having an adsorbent bed to separate one or more contaminants from the gaseous feed stream to form a product stream; c) determining whether the product stream is within a specification for a contaminant; d) if the product stream is within the specification, passing the product stream to a downstream process; and e) if the product stream is not within the specification, repeating the steps a) to d) for at least one additional cycle.
In yet another embodiment, a cyclical swing adsorption system is described. The system includes a plurality of manifolds; a plurality of adsorbent bed units coupled to the plurality of manifolds, and an external gas bypass valve in fluid communication with purge manifold and configured to provide a flow passage for an external gas stream from an external gas storage vessel to the purge manifold in a startup mode position and configured to block the flow passage of the external gas stream from the external gas storage vessel to the purge manifold in a normal operation mode position. The plurality of manifolds comprise a feed manifold configured to pass a feed stream to the plurality of adsorbent bed units during an adsorption step, a product manifold configured to pass a product stream from the plurality of adsorbent bed units during the adsorption step, a purge manifold configured to pass a purge stream to the plurality of adsorbent bed units during a regeneration step, a purge product manifold configured to pass a purge product stream from the plurality of adsorbent bed units during the regeneration step. Each manifold of the plurality of manifolds is associated with one swing adsorption process step of a plurality of swing adsorption process steps. Each of the adsorbent bed units comprises a housing; an adsorbent material disposed within the housing; a plurality of valves, wherein at least one of the plurality of valves is associated with one of the plurality of manifolds and is configured to manage fluid flow along a flow path extending between the respective manifold and the adsorbent material.
In certain embodiments, the system or method may include certain variations. The plurality of valves may comprise one or more poppet valves; the plurality of manifolds and/or the plurality of adsorbent bed units may be configured to operate at pressures between 0.1 bar absolute (bara) and 100 bara; the system may include a heating unit disposed upstream of the purge manifold and downstream of the external gas storage vessel, wherein the heating unit may be configured to heat the external gas stream to a temperature in the range between a temperature in the range between 450° F. and the gaseous feed stream temperature or in the range between a temperature in the range between 450° F. and greater than 100° F. of the gaseous feed stream temperature; the system may include a conditioning unit disposed downstream of the purge product manifold and upstream of the external gas storage vessel, wherein the conditioning unit may be configured to remove one or more contaminants from the purge product stream; wherein the plurality of manifolds further comprise a blowdown manifold configured to pass a blowdown stream from the plurality of adsorbent bed units during a blowdown step; and the system may include a liquefied natural gas process unit in fluid communication with the adsorbent bed unit and configured to receive the product stream and separate the product stream into a final product stream and a flash fuel stream, wherein the flash fuel stream may be passed to the purge manifold. Further, the external gas stream may comprise a nitrogen stream comprising predominately nitrogen with less than 0.1 ppm of water, less than 1 ppm of water or less than 10 ppm of water or at least one of nitrogen, methane, helium, hydrogen or any combination thereof.
The foregoing and other advantages of the present disclosure may become apparent upon reviewing the following detailed description and drawings of non-limiting examples of embodiments.
Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. The singular terms “a,” “an,” and “the” include plural referents unless the context clearly indicates otherwise. Similarly, the word “or” is intended to include “and” unless the context clearly indicates otherwise. The term “includes” means “comprises.” All patents and publications mentioned herein are incorporated by reference in their entirety, unless otherwise indicated. In case of conflict as to the meaning of a term or phrase, the present specification, including explanations of terms, control. Directional terms, such as “upper,” “lower,” “top,” “bottom,” “front,” “back,” “vertical,” and “horizontal,” are used herein to express and clarify the relationship between various elements. It should be understood that such terms do not denote absolute orientation (e.g., a “vertical” component can become horizontal by rotating the device). The materials, methods, and examples recited herein are illustrative only and not intended to be limiting.
As used herein, “stream” refers to fluid (e.g., solids, liquid and/or gas) being conducted through various equipment. The equipment may include conduits, vessels, manifolds, units or other suitable devices.
As used herein, “conduit” refers to a tubular member forming a channel through which something is conveyed. The conduit may include one or more of a pipe, a manifold, a tube or the like.
The provided processes, apparatus, and systems of the present techniques may be used in swing adsorption processes that remove contaminants (CO2, H2O, and H2S) from feed streams, such as hydrocarbon containing streams. As may be appreciated and as noted above, the hydrocarbon containing feed streams may have different compositions. For example, the gaseous feed stream may be a hydrocarbon containing stream having greater than one volume percent hydrocarbons based on the total volume of the feed stream. As another example, the hydrocarbon feed streams may vary widely in amount of acid gas, such as from several parts per million acid gas to 90 volume percent (vol. %) acid gas. Non-limiting examples of acid gas concentrations from exemplary gas reserves sources include concentrations of approximately: (a) 4 ppm H2S, 2 vol. % CO2, 100 ppm H2O (b) 4 ppm H2S, 0.5 vol. % CO2, 200 ppm H2O (c) 1 vol. % H2S, 2 vol. % CO2, 150 ppm H2O, (d) 4 ppm H2S, 2 vol. % CO2, 500 ppm H2O, and (e) 1 vol. % H2S, 5 vol. % CO2, 500 ppm H2O. Further, in certain applications the hydrocarbon containing stream may include predominately hydrocarbons with specific amounts of CO2 and/or water. For example, the hydrocarbon containing stream may have greater than 0.00005 volume percent CO2 based on the total volume of the gaseous feed stream and less than 2 volume percent CO2 based on the total volume of the gaseous feed stream; or less than 10 volume percent CO2 based on the total volume of the gaseous feed stream. The processing of feed streams may be more problematic when certain specifications have to be satisfied.
The removal of contaminants may be performed by swing adsorption processes during normal operations to prepare the stream for further downstream processing, such as NGL processing and/or LNG processing. For example, natural gas feed streams for liquefied natural gas (LNG) applications have stringent specifications on the CO2 content to ensure against formation of solid CO2 at cryogenic temperatures. The LNG specifications may involve the CO2 content to be less than or equal to 50 ppm. Such specifications are not applied on natural gas streams in pipeline networks, which may involve the CO2 content up to 2 vol. % based on the total volume of the gaseous feed stream. As such, for LNG facilities that use the pipeline gas (e.g., natural gas) as the raw feed, additional treating or processing steps are utilized to further purify the stream. Further, the present techniques may be used to lower the water content of the stream to less than 0.1 ppm. Exemplary swing adsorption processes and configurations may include U.S. Patent Ser. Nos. 62/213,262; 62/213,267; 62/213,270; 62/213,273; 62/246,916; 62/246,920; and 62/246,922, which are each incorporated by reference herein.
The present techniques provide configurations and processes that are utilized to enhance the startup mode for the swing adsorption process and associated downstream processes. While the normal operation mode processes are described based on steady state operation, startup mode procedures involve different cycles until normal operation mode is begun. The present techniques describes different methods that may be utilized to transition the operation from startup mode to normal operation mode. In startup mode, each of the adsorbent beds utilized in the swing adsorption process is assumed to be in equilibrium with contaminants. For dehydration applications, the contaminant is water (H2O), while for carbon dioxide (CO2) applications, the contaminant is either H2O (e.g., in equilibrium with atmosphere) or CO2 (e.g., in case of a shutdown). Accordingly, the startup mode is utilized to remove contaminants to prepare the adsorbent beds for normal operation mode. In particular, the startup mode sequence may be used for swing adsorption processes (e.g., dehydration and low-level CO2 removal) upstream or integrated with NGL and LNG applications.
The startup mode process may involve the use of an external medium to remove one or more contaminants from the adsorbent beds. In the external startup mode, an external medium is used to remove one or more contaminants from the adsorbent beds. The external medium may include the use of an external gas stream that is circulated through the adsorbent beds to remove the one or more contaminants from the adsorbent beds during a regeneration step (e.g., a purge step). The external gas stream may include nitrogen, dry methane or other non-reactive stream under process operating conditions. For example, the external stream may include predominately nitrogen or methane with less than 0.1 ppm of water, less than 1 ppm of water or less than 10 ppm of water. The external gas stream may comprise at least one of nitrogen, methane, helium, hydrogen or any combination thereof.
For example, in dehydration applications, an external gas stream, such as dry nitrogen (e.g., nitrogen stream having less than 0.1 ppm of water, less than 1 ppm of water or less than 10 ppm of water), may be used to remove water from the adsorbent beds during the startup mode. When the dry nitrogen stream is introduced into each of the adsorbent beds, which is at equilibrium with ambient water, some of the water transfers from the adsorbent material in the adsorbent bed to the dry nitrogen stream. The startup mode sequence may involve providing feed to the adsorbent bed during an adsorption step and using the external stream to purge the adsorbent bed during a purge step. The startup mode cycle may continue to use the dry nitrogen until a sufficient amount of water is removed from each of the adsorbent beds and a desired bed profile is achieved for the adsorbent beds. Then, the resulting product stream from the adsorbent beds is within the desired specification (e.g., below the specific contaminant levels for the product stream). In addition, the startup mode may include maintaining the purge step with dry nitrogen to sufficient amounts of moisture, and then start the sequence described above. In such a configuration, the product stream may be within specification from the first cycle.
Once the product stream is within the desired specification, the product stream may be used in the startup mode process for the downstream processes, such as a demethanizer or a liquefaction train. As the downstream processes and units are being started, the adsorbent beds continue to regenerate using the external gas stream, such as the dry nitrogen stream. Alternatively, a heated slip stream from the product side may also be used to regenerate the spent adsorbent beds. As the downstream process begins producing a purge stream, this purge stream may be combined with the external gas stream and the amount of external gas stream utilized in the purge step may be adjusted. Once the downstream processes begin normal operations, the desired purge stream (e.g., within the desired specifications), such as a residue gas stream or fuel gas stream, is provided to the adsorbent bed as part of the normal operation mode. At this point, the adsorbent bed regeneration stream is transitioned from nitrogen to the purge stream from the downstream process.
To facilitate rapid regeneration and minimize the amount of dry nitrogen being utilized during the external startup mode, the operating conditions may be adjusted to manage the removal of contaminants from the adsorbent bed. For example, the flow rate for the gaseous feed stream may be conducted within a flow rate range below the normal operation mode flow ranges (e.g., flow rate at turndown). For example, the flow rates in startup mode may be at about 25% of the normal operation mode flow rate, at about 50% of the normal operation mode flow rate, at about 75% of the normal operation mode flow rate, in a range between 25% and 90% of the normal operation flow rate, in a range between 50% and 90% of the normal operation flow rate, and in a range between 75% and 90% of the normal operation flow rate. Further, the regeneration of the adsorbent bed may be conducted within a pressure range near atmospheric pressure (e.g., in a pressure range between atmospheric pressure and fifty pounds per square inch gauge (psi) above atmospheric pressure) or may be within a pressure range near normal operation mode pressures (e.g., in a pressure range between 75% of normal operation mode pressure and 125% of normal operation mode pressure or at a pressure between atmospheric pressure and normal operating pressure or a pressure close to feed pressure). As an example, the regeneration of the adsorbent bed may be conducted in a pressure range from 300 pounds per square inch gauge (psi) to 650 psi. Also, the temperature of the external medium stream may be provided within a temperature range from (e.g., in a temperature range between 20° Celsius (C) above atmospheric temperature and 150° Celsius (C) above atmospheric temperature). Also, the temperature of the external stream may be in a range between 350° F. and 550° F., in a range between 350° F. and 550° F. or in a range 450° F. and 550° F. in a range between 100° F. and 550° F., in a range between 150° F. and 450° F. or in a range 250° F. and 350° F.
For a dehydration application, the sequence of the cycle for the startup mode may be configured to lessen flaring of gas or completely eliminate flaring of gas. The external sequence may be initiated at turndown. The purge pressure is selected such that the purge product is at the suction pressure of the residue gas compressor. The residue gas compressor is then operated to compress the purge product and recombine with the feed stream either upstream or downstream of a triethylene glycol (TEG) based dehydration unit. Knockout drums may be necessary to remove the excess water gathered from the purge step.
As a specific example, the startup mode process may be used for a cryogenic NGL recovery facility. The external startup process may include passing wet gas to the absorbent units at turndown. Then, the external startup process is utilized to clean the adsorbent beds. The process is continued until product stream is at specification and the desired water profile in the adsorbent bed is achieved. Next, the flow rate of the gas stream entering the adsorbent beds is increased for subsequent cycles. Then, at least a portion of the dry product stream is introduced to the cryogenic NGL recovery facility. As necessary, the purge inlet temperature may be adjusted to achieve the necessary purge to remove the water in the adsorbent beds. With the product stream from the adsorbent beds, the startup sequence for the cryogenic NGL recovery facility is initiated. This cryogenic NGL facility may perform the startup mode using the residue gas compressor to recycle the demethanizer column overhead product with the external stream. Once the NGL recovery facility is approaching specification, a portion of the demethanizer overhead product is mixed with the purge stream from the adsorbent beds in swing adsorption process to increase the flow rate. The heat from the startup heater may be reduced as necessary. Eventually, the overhead product stream from the demethanizer is introduced to the adsorbent beds as a purge stream for the respective cycles and the portion of the external stream from the adsorbent bed being used as the purge stream is lessened and may be eliminated. The process eventually transitions to normal operation mode, which is a steady state with the adsorbent beds purge product gas being provided for sale.
Similarly, the above sequence may be used for the LNG process. However, a source of gas to compress the purge product to feed pressure may not be available with the LNG process during startup mode. As such, some of the purge stream may have to be flared. For the CO2 removal processes, a similar external startup mode sequence may be used. Additionally, a loop heating step may be used to provide the necessary heat to the adsorbent beds.
One or more variants to the procedure noted above may be used to reduce the startup time of the process. The first variant includes heating adsorbent beds to reduce the amount of water in the adsorbent beds, which may be performed initially. In the heating step, the heated stream at low pressure is used as the purge stream for the absorbent beds and removes a large amount of water already adsorbed in the adsorbent beds. A second variant involves performing one or more blowdown steps in the startup mode process to flare or rapidly decrease the partial pressure and reduce the amount of water adsorbed in the adsorbent beds. A third variant involves performing a purge step with dry nitrogen, which may be heated, if necessary, to dry the adsorbent beds.
The present techniques provide a startup mode process that may be utilized to initiate the normal operation mode process for a swing adsorption process, and specifically a rapid cycle adsorption process. The present techniques may include some additional equipment, such as one or more conduits and/or one or more manifolds that provide a fluid path for the external gas stream, an external gas storage tank, a heating unit (furnace and/or heat exchanger), one or more blowers and/or one or more compressors to fluidly communication with one or more adsorbent beds, and/or depressurizing equipment that may be utilized to facilitate the startup mode cycle. In addition, other components and configurations may be utilized to provide the swing adsorption process, such as rapid cycle enabling hardware components (e.g., parallel channel adsorbent bed designs, rapid actuating valves, adsorbent bed configurations that integrate with other processes). Exemplary swing adsorption processes and configurations may also include U.S. Patent Ser. Nos. 62/213,262; 62/213,267; 62/213,270; 62/213,273; 62/246,916; 62/246,920; and 62/246,922, which are each incorporated by reference herein.
In one or more embodiment, a startup mode process for a swing adsorption process may include using an external startup mode. For the external startup mode, the present techniques comprise a process for removing contaminants from a gaseous feed stream with a swing adsorption process, which may be utilized with one or more downstream processes. The process comprising: a) performing a regeneration step (e.g., purge step), wherein the step comprises passing an external gas stream through an adsorbent bed unit to remove contaminants from an adsorbent bed within a housing of the adsorbent bed unit to form a purge product stream; b) performing one or more adsorption steps, wherein each of the one or more adsorption steps comprise passing a gaseous feed stream through an adsorbent bed unit having an adsorbent bed to separate contaminants from the gaseous feed stream to form a product stream; c) determining whether the product stream is within a specification for at least one contaminant; d) if the product stream is within the specification (e.g., is below a certain threshold), passing the product stream to a downstream process; and e) if the product stream is not within the specification (e.g., above a certain threshold), repeating the steps a) to d) for at least one additional cycle.
As another example for the external startup mode, a cyclical swing adsorption system may include a plurality of manifolds; a plurality of adsorbent bed units coupled to the plurality of manifolds, and an external gas bypass valve in fluid communication with purge manifold and configured to provide a flow passage for an external gas stream from an external gas storage vessel to the purge manifold in a startup mode position and configured to block the flow passage of the external gas stream from the external gas storage vessel to the purge manifold in a normal operation mode position. The plurality of manifolds comprise a feed manifold configured to pass a feed stream to the plurality of adsorbent bed units during an adsorption step, a product manifold configured to pass a product stream from the plurality of adsorbent bed units during the adsorption step, a purge manifold configured to pass a purge stream to the plurality of adsorbent bed units during a regeneration step, a purge product manifold configured to pass a purge product stream from the plurality of adsorbent bed units during the regeneration step. Each manifold of the plurality of manifolds is associated with one swing adsorption process step of a plurality of swing adsorption process steps. Each of the adsorbent bed units comprising a housing; an adsorbent material disposed within the housing; a plurality of valves, wherein at least one of the plurality of valves is associated with one of the plurality of manifolds and is configured to manage fluid flow along a flow path extending between the respective manifold and the adsorbent material.
In addition, the system or method may include certain features to enhance the operation of the system or method. For example, the plurality of valves may comprise one or more poppet valves; the plurality of manifolds and/or the plurality of adsorbent bed units may be configured to operate at pressures between 0.1 bar absolute (bara) and 100 bara; the system may include a heating unit disposed upstream of the purge manifold and downstream of the external gas storage vessel, wherein the heating unit is configured to heat the external gas stream to a temperature in the range between a temperature in the range between a temperature in the range between 450° F. and the gaseous feed stream temperature or in the range between 450° F. and greater than 100° F. of the gaseous feed stream temperature; the system may include a conditioning unit disposed downstream of the purge product manifold and upstream of the external gas storage vessel, wherein the conditioning unit is configured to remove one or more contaminants from the purge product stream; the plurality of manifolds may further comprise a blowdown manifold configured to pass a blowdown stream from the plurality of adsorbent bed units during a blowdown step; and the system may include a liquefied natural gas process unit in fluid communication with the adsorbent bed unit and configured to receive the product stream and separate the product stream into a final product stream and a flash fuel stream, wherein the flash fuel stream is passed to the purge manifold. Further, the external gas stream comprises a nitrogen stream comprising predominately nitrogen with less than 0.1 ppm of water, or may comprise a nitrogen stream comprising predominately nitrogen with less than 10 ppm of water. The external gas stream may be a nitrogen containing stream having greater than one volume percent nitrogen based on the total volume of the feed stream. Also, the method may include mixing a slip stream from the downstream process with the external gas stream prior to performing the purge step and/or adjusting the amount of external gas stream utilized in the performing a purge step based on the amount of the slip stream from the downstream process. The slip stream may be an overhead stream, such as overhead stream from NGL or fuel from LNG.
In other certain embodiments, the startup mode for the swing adsorption process may be integrated with downstream equipment and processes. The downstream equipment and processes may include control freeze zone (CFZ) applications, nitrogen removal unit (NRU), cryogenic NGL recovery applications, LNG applications, and other such applications. Each of these different applications may include different specifications for the feed stream in the respective process. For example, the startup process may involve dehydration upstream of a cryogenic NGL process or an LNG process and may be integrated with the respective downstream equipment. As another example, the startup process may involve CO2 removal upstream of a cryogenic NGL process or the LNG process and may be integrated with respective downstream equipment. The startup method may include using an external medium as part of the process, which may be a dry nitrogen stream. Further, the startup mode may be integrated with downstream processes, such as cryogenic NGL processes and/or LNG processes. In addition, the startup mode process may involve performing the startup mode cycle with minimal flaring or no flaring.
In certain embodiments, the system utilizes a combined swing adsorption process, which combines TSA and PSA, for treating of pipeline quality natural gas to remove contaminants for the stream to satisfy LNG specifications. The swing adsorption process, which may be a rapid cycle process, is used to treat natural gas that is at pipeline specifications (e.g., a feed stream of predominately hydrocarbons along with less than or equal to about 2% volume CO2 and/or less than or equal to 4 ppm H2S) to form a stream satisfying the LNG specifications (e.g., less than 50 ppm CO2 and less than about 4 ppm H2S). The product stream, which may be the LNG feed stream, may have greater than 98 volume percent hydrocarbons based on the total volume of the product stream, while the CO2 and water content are below certain thresholds. The LNG specifications and cryogenic NGL specifications may involve the CO2 content to be less than or equal to 50 ppm, while the water content of the stream may be less than 0.1 ppm. Further, the gaseous feed stream may include hydrocarbons and H2O. For example, the gaseous feed stream may be that the H2O is in the range of 0.2 parts per million volume to saturation levels in the gaseous feed stream or the H2O is in the range of 100 parts per million volume to 1500 parts per million volume.
In certain aspects, as described further below, the present techniques may involve using a high temperature stream that is provided to the adsorbent beds as part of the purge step to heat the adsorbent bed. The stream, which may be referred to as the purge stream (e.g., the external stream), may be heated to temperature may be less than 550° F., may be less than 500° F., less than 450° F. or may be less than 350° F., and may be greater than 50° F. of the gaseous feed stream temperature, greater than 100° F. of the gaseous feed stream temperature or greater than 250° F. of the gaseous feed stream temperature. For example, the stream used during the purge step of the startup mode cycle may be a temperature in the range between 500° F. and greater than 50° F. of the gaseous feed stream temperature, in the range between 450° F. and the gaseous feed stream temperature, in the range between a temperature in the range between 450° F. and greater than 100° F. of the gaseous feed stream temperature or 400° F. and greater than 200° F. of the gaseous feed stream temperature. The stream (purge stream or external stream) pressure may be in the range between 0.01 bara and 100 bara, between 1 bara and 80 bara, or between 2 bara and 50 bara.
Further, the present techniques may not remove all of the contaminant (e.g., H2O and CO2) adsorbed in the bed during the purge step of the startup mode process, but remove a portion of the contaminants such that the product end of the adsorbent bed has a contaminant loading sufficiently low to provide a product stream with less than specifications. Accordingly, the product end of the adsorbent bed may be maintained nearly free of contaminants (e.g., the CO2 loading for the region near the product end is less than 1 millimole per gram (mmol/g), less than 0.5 mmol/g or less than 0.1 mmol/g). The loading level of contaminant may be lower on the feed side of the adsorbent bed during the purge step, but the length of adsorbent bed that contains contaminants is reduced during the purge step. For example, a feed region may be a specific portion of the adsorbent bed from the feed end of the adsorbent bed to 10% of the bed length, from the feed end of the adsorbent bed to 25% of the bed length or from the feed end of the adsorbent bed to 40% of the bed length. The product region may be a specific portion of the adsorbent bed from the product end of the adsorbent bed to 10% of the bed length, from the product end of the adsorbent bed to 25% of the bed length or from the product end of the adsorbent bed to 40% of the bed length. The movement of the contaminants front back during purge step and forward during the adsorption step is the basis of the swing capacity of the process. In part, this is achieved by using a limited, cost effective quantity of purge gas in the purge steam along with the heating of the adsorbent bed in this process and configuration.
The present techniques may involve using two or more adsorbent beds, which are operated on similar cycle that are performing different steps of the cycles (e.g., not synchronized with each other) to maintain a steady flow of fluids for the various streams (e.g., feed stream, product stream, heating stream, and purge stream).
Further, in other embodiments, the pressure of the different streams may be varied. For example, the feed stream may involve a feed pressure that is within the in the range between 0.01 bara and 100 bara, between 1 bara and 80 bara, or between 2 bara and 50 bara, but is not necessarily limited to this range. The feed temperature may be in the range between 0° F. and 200° F., in the range between 20° F. and 175° F. or in the range between 40° F. and 150° F. The blowdown pressure, heating pressure, and purge pressure may be adjusted depending on the cycle, may depend upon the adsorbent material being utilized and/or may range from vacuum to feed pressure. For example, if the adsorbent material is zeolite 4A, the blowdown pressure range may be between 0.01 bara to 50 bara, or more preferably in a range between 1 bara and 15 bara. This example may depend on the feed concentration of CO2. Also, in other embodiments, the depressurization steps may be adjusted such that the pressure swing is achieved in stages to vary the amount of methane desorbing during each step, if any. Additionally, a heating loop may be introduced and the heating pressure in the heating loop may be operated at a pressure different from the purge pressure or blowdown pressure in the respective steps. Also, certain embodiments may include no pressure swing, but may rely upon temperature swing for the regeneration step. Similarly, in the other embodiments, no temperature swing may be performed and the regeneration step may be performed by pressure swing.
Furthermore, the above process may be used for startup mode processes that separate two or more contaminants from the feed stream (e.g., two swing adsorption processes operated in series with each other). For example, the feed stream may subjected to a dehydration swing adsorption process, then a CO2 removal swing adsorption process, and the resulting product may be subjected to a downstream process, such as cryogenic NGL or LNG recovery. The startup mode for the dehydration and the CO2 removal processes may involve external startup processes. As one example, the dehydration process may involve the external startup process. Then, once the product stream satisfies the desired specification for water removal, the product stream may be used by the CO2 removal as part of the external startup stream. Alternatively, the dehydration process may involve the external startup process and the CO2 removal process may perform another external startup mode process and may mix the purge stream with the feed stream to the dehydration process.
In certain configurations, an integrated rapid cycle adsorption system may be utilized to remove multiple contaminants (e.g., water and CO2). Suitable adsorbent material or adsorbent layers may be utilized to provide the dehydration, which may be the same or different from the adsorbent material used to in the removal of other contaminants, such as CO2.
Moreover, the present techniques may include a specific process flow during normal operation mode to remove contaminants, such as CO2 and/or water. For example, the process may include an adsorbent step and a regeneration step, which form the cycle. The adsorbent step may include passing a gaseous feed stream at a feed pressure and feed temperature through an adsorbent bed unit to separate one or more contaminants from the gaseous feed stream to form a product stream. The feed stream may be passed through the adsorbent bed in a forward direction (e.g., from the feed end of the adsorbent bed to the product end of the adsorbent bed). Then, the flow of the gaseous feed stream may be interrupted for a regeneration step. The regeneration step may include one or more depressurization steps, one or more heating steps, and/or one or more purge steps. The depressurization steps, which may be or include a blowdown step, may include reducing the pressure of the adsorbent bed unit by a predetermined amount for each successive depressurization step, which may be a single step and/or multiple steps. The depressurization step may be provided in a forward direction or may preferably be provided in a countercurrent direction (e.g., from the product end of the adsorbent bed to the feed end of the adsorbent bed). The heating step may include passing a heating stream into the adsorbent bed unit, which may be a recycled stream through the heating loop and is used to heat the adsorbent material. The purge step may include passing a purge stream into the adsorbent bed unit, which may be a once through purge step and the purge stream may be provided in countercurrent flow relative to the feed stream. The purge stream may be provided at a purge temperature and purge pressure, which may include the purge temperature and purge pressure being similar to the heating temperature and heating pressure used in the heating step. Then, the cycle may be repeated for additional streams. Additionally, the process may include one or more re-pressurization steps after the purge step and prior to the adsorption step. The one or more re-pressurization steps may be performed, wherein the pressure within the adsorbent bed unit is increased with each re-pressurization step by a predetermined amount with each successive re-pressurization step. The cycle duration for normal operation mode may be for a period greater than 1 second and less than 600 seconds, for a period greater than 2 second and less than 300 seconds, for a period greater than 2 second and less than 180 seconds, for a period greater than 5 second and less than 150 seconds or for a period greater than 5 second and less than 90 seconds.
In other configurations, the startup mode may involve lower flow rates and longer cycles. For example, the initial flow rate may be 25% of the normal flow rate utilized during normal operations, which may have a startup mode cycle time of four times the normal operation model cycle time. This initial flow rate may be increased in a steady manner or in various increments until the normal operation mode is reached. By way of example, the startup mode cycle duration may be for a period greater than 1 second and less than 2400 seconds, for a period greater than 1 second and less than 1500 seconds, for a period greater than 1 second and less than 600 seconds, for a period greater than 2 second and less than 800 seconds, for a period greater than 2 second and less than 400 seconds, for a period greater than 5 second and less than 150 seconds or for a period greater than 5 second and less than 90 seconds.
In yet other configurations, the startup mode may involve installation of adsorbent beds that are partially or completely devoid of the contaminant being removed. By way of example, if the swing adsorption process is primarily configured to remove water, then a partially or totally dehydrated adsorbent bed may be installed in the system. During the start mode, a feed stream is passed to the adsorbent bed, which may be as a wet gas, and a product stream, which may be a dry stream, is conducted away and may be used as a purge stream to a different adsorbent bed. Alternatively, another method may involve installation of an adsorbent bed in the swing adsorption process that is treated or conditioned such that the contaminant replaces a different molecule that is already adsorbed on the adsorbent bed. By way of example, if the swing adsorption process is primarily configured to remove CO2, then the adsorbent bed may include adsorbed particles, such as water, which may be installed in the system. During the start mode, a feed stream is passed to the adsorbent bed, which may include the CO2 contaminants, and a product stream may be conducted away and may be used as a purge stream to a different adsorbent bed.
In certain configurations, a process for removing contaminants from a gaseous feed stream with a swing adsorption process is described. The process comprising: a) performing a purge step, wherein the purge step comprises passing an external gas stream through an adsorbent bed unit to remove one or more contaminants from an adsorbent bed within a housing of the adsorbent bed unit to form a purge product stream; b) performing one or more adsorption steps, wherein each of the one or more adsorption steps comprise passing a gaseous feed stream through an adsorbent bed unit having an adsorbent bed to separate one or more contaminants from the gaseous feed stream to form a product stream; c) determining whether the product stream is within a specification for a contaminant; d) if the product stream is within the specification, passing the product stream to a downstream process; and e) if the product stream is not within the specification, repeating the steps a) to d) for at least one additional cycle.
The process may include various configuration changes to enhance the operations. For example, the process may further comprising mixing a slip stream from the downstream process with the external gas stream prior to performing the purge step; adjusting the amount of external gas stream utilized in the performing a purge step based on the amount of the slip stream from the downstream process; heating the external gas stream prior to passing the external gas stream through an adsorbent bed unit; wherein the external gas stream is heated to a temperature in the range between 500° F. and greater than 50° F. of the gaseous feed stream temperature or to a temperature in the range between 450° F. and the gaseous feed stream temperature; heating the purge product stream, wherein the purge product stream is heated to a temperature 10° F. greater than the dew point of the purge product stream; separating one or more contaminants from the purge product stream to form conditioned purge product stream and mixing the conditioned purge product stream with external gas source stream to form the external gas stream; wherein the purge stream is passed in a countercurrent direction relative to the direction of the feed stream and wherein a temperature differential exists at the end of the purge step in a range between 100° F. and 400° F., wherein the temperature differential is the difference in temperatures between a feed end of the adsorbent bed and a product end of the adsorbent bed; wherein the cycle duration is for a period greater than 1 second and less than 2400 seconds or is greater than 2 seconds and less than 800 seconds; wherein the gaseous feed stream is a hydrocarbon containing stream having greater than one volume percent hydrocarbons based on the total volume of the feed stream; wherein the gaseous feed stream comprises hydrocarbons and CO2, wherein the CO2 content is in the range of two hundred parts per million volume and less than or equal to about 2% volume of the gaseous feed stream; wherein the adsorbent bed unit is configured to lower the carbon dioxide (CO2) level to less than 50 parts per million; wherein the gaseous feed stream comprises hydrocarbons and H2O, wherein the H2O is in the range of 0.2 parts per million volume to saturation levels in the gaseous feed stream; wherein the gaseous feed stream comprises hydrocarbons and H2O, wherein the H2O is in the range of 100 parts per million volume to 1500 parts per million volume; passing the product stream from the adsorbent bed unit to a liquefied natural gas (LNG) process unit and separating a flash fuel stream from the LNG process unit to be utilized as at least a portion of the purge stream; passing the product stream from the adsorbent bed unit to a cryogenic natural gas liquid recovery (NGL) process unit and separating an overhead stream from the NGL process unit to be utilized as at least a portion of the purge stream; wherein the external gas stream is a nitrogen containing stream having greater than one volume percent nitrogen based on the total volume of the feed stream; wherein the external gas stream comprises a predominately nitrogen stream comprising less than 0.1 ppm of water or less than 10 ppm of water; and/or wherein the external gas stream comprises at least one of nitrogen, methane, helium, hydrogen or any combination thereof.
In yet other configurations, a cyclical swing adsorption system is described. The system may include: a plurality of manifolds, wherein the plurality of manifolds comprise a feed manifold configured to pass a feed stream to the plurality of adsorbent bed units during an adsorption step, a product manifold configured to pass a product stream from the plurality of adsorbent bed units during the adsorption step, a purge manifold configured to pass a purge stream to the plurality of adsorbent bed units during a regeneration step, a purge product manifold configured to pass a purge product stream from the plurality of adsorbent bed units during the regeneration step, each manifold of the plurality of manifolds is associated with one swing adsorption process step of a plurality of swing adsorption process steps; a plurality of adsorbent bed units coupled to the plurality of manifolds, each of the adsorbent bed units comprising: a housing; an adsorbent material disposed within the housing; a plurality of valves, wherein at least one of the plurality of valves is associated with one of the plurality of manifolds and is configured to manage fluid flow along a flow path extending between the respective manifold and the adsorbent material; an external gas bypass valve in fluid communication with purge manifold and configured to provide a flow passage for an external gas stream from an external gas storage vessel to the purge manifold in a startup mode position and configured to block the flow passage of the external gas stream from the external gas storage vessel to the purge manifold in a normal operation mode position.
The system may include various configuration changes to enhance the operations. For example, the cyclical swing adsorption system may include that the plurality of valves comprise one or more poppet valves; may include that the plurality of adsorbent bed units are configured to operate at pressures between 0.1 bar absolute (bara) and 100 bara; may further include a heating unit disposed upstream of the purge manifold and downstream of the external gas storage vessel, wherein the heating unit is configured to heat the external gas stream to a temperature in the range between a temperature in the range between 450° F. and the gaseous feed stream temperature; may further include a conditioning unit disposed downstream of the purge product manifold and upstream of the external gas storage vessel, wherein the conditioning unit is configured to remove one or more contaminants from the purge product stream; may include that the plurality of manifolds further comprise a blowdown manifold configured to pass a blowdown stream from the plurality of adsorbent bed units during a blowdown step; may further include a liquefied natural gas process unit in fluid communication with the adsorbent bed unit and configured to receive the product stream and separate the product stream into a final product stream and a flash fuel stream, wherein the flash fuel stream is passed to the purge manifold; may further comprising a cryogenic natural gas liquid recovery (NGL) process unit in fluid communication with the adsorbent bed unit and configured to receive the product stream and separate the product stream into a final product stream and a residue gas stream, wherein the residue gas stream is passed to the purge manifold; and/or may further include a heating jacket disposed adjacent to the adsorbent bed unit and configured to heat the adsorbent bed.
In one or more embodiments, the present techniques can be used for any type of swing adsorption process. Non-limiting swing adsorption processes for which the present techniques may be used include pressure swing adsorption (PSA), vacuum pressure swing adsorption (VPSA), temperature swing adsorption (TSA), partial pressure swing adsorption (PPSA), rapid cycle pressure swing adsorption (RCPSA), rapid cycle thermal swing adsorption (RCTSA), rapid cycle partial pressure swing adsorption (RCPPSA), as well as combinations of these processes. For example, the preferred swing adsorption process may include a combined pressure swing adsorption and temperature swing adsorption, which may be performed as a rapid cycle process. Exemplary swing adsorption processes are further described in U.S. Patent Ser. Nos. 62/213,262; 62/213,267; 62/213,270; 62/213,273; 62/246,916; 62/246,920; and 62/246,922 and U.S. Patent Application Publication Nos. 2008/0282892, 2008/0282887, 2008/0282886, 2008/0282885, 2008/0282884 and 20140013955, which are each herein incorporated by reference in their entirety.
Further still, in one or more embodiments, a variety of adsorbent materials may be used to provide the mechanism for the separations. Examples include zeolite 3A, 4A, 5A, ZK4 and MOF-74. However, the process is not limited to these adsorbent materials, and others may be used as well. The present techniques may be further understood with reference to the
In this system, the adsorbent bed units, such as adsorbent bed unit 102, may be configured for a cyclical swing adsorption process for removing contaminants from feed streams (e.g., fluids, gaseous or liquids). For example, the adsorbent bed unit 102 may include various conduits (e.g., conduit 104) for managing the flow of fluids through, to or from the adsorbent bed within the adsorbent bed unit 102. These conduits from the adsorbent bed units 102 may be coupled to a manifold (e.g., manifold 106) to distribute the flow to, from or between components. The adsorbent bed within an adsorbent bed unit may separate one or more contaminants from the feed stream to form a product stream. As may be appreciated, the adsorbent bed units may include other conduits to control other fluid steams as part of the process, such as purge streams, depressurizations streams, and the like. In particular, the adsorbent bed units may include startup mode equipment, such as one or more heating units (not shown), one or more external gas source manifolds, which may be one of the manifolds 106) and one or more expanders, as noted further below, which is used as part of the startup mode for the adsorbent beds. Further, the adsorbent bed unit may also include one or more equalization vessels, such as equalization vessel 108, which are dedicated to the adsorbent bed unit and may be dedicated to one or more step in the swing adsorption process. The equalization vessel 108 may be used to store the external stream, such as nitrogen for use in the startup mode cycle.
As an example, which is discussed further below in
The adsorbent bed comprises a solid adsorbent material capable of adsorbing one or more components from the feed stream. Such solid adsorbent materials are selected to be durable against the physical and chemical conditions within the adsorbent bed unit 102 and can include metallic, ceramic, or other materials, depending on the adsorption process. Further examples of adsorbent materials are noted further below.
The upper head 218 and lower head 220 contain openings in which valve structures can be inserted, such as valve assemblies 222 to 240, respectively (e.g., poppet valves). The upper or lower open flow path volume between the respective head 218 or 220 and adsorbent bed 210 can also contain distribution lines (not shown) which directly introduce fluids into the adsorbent bed 210. The upper head 218 contains various openings (not show) to provide flow passages through the inlet manifolds 242 and 244 and the outlet manifolds 248, 250 and 252, while the lower head 220 contains various openings (not shown) to provide flow passages through the inlet manifold 254 and the outlet manifolds 256, 258 and 260. Disposed in fluid communication with the respective manifolds 242 to 260 are the valve assemblies 222 to 240. If the valve assemblies 222 to 240 are poppet valves, each may include a disk element connected to a stem element which can be positioned within a bushing or valve guide. The stem element may be connected to an actuating means, such as actuating means (not shown), which is configured to have the respective valve impart linear motion to the respective stem. As may be appreciated, the actuating means may be operated independently for different steps in the process to activate a single valve or a single actuating means may be utilized to control two or more valves. Further, while the openings may be substantially similar in size, the openings and inlet valves for inlet manifolds may have a smaller diameter than those for outlet manifolds, given that the gas volumes passing through the inlets may tend to be lower than product volumes passing through the outlets.
In swing adsorption processes, the cycle involves two or more steps that each has a certain time interval, which are summed together to be the cycle time or cycle duration. These steps include regeneration of the adsorbent bed following the adsorption step using a variety of methods including pressure swing, vacuum swing, temperature swing, purging (via any suitable type of purge fluid for the process), and combinations thereof. As an example, a PSA cycle may include the steps of adsorption, depressurization, purging, and re-pressurization. When performing the separation at high pressure, depressurization and re-pressurization (which may be referred to as equalization) may be performed in multiple steps to reduce the pressure change for each step and enhance efficiency. In some swing adsorption processes, such as rapid cycle swing adsorption processes, a substantial portion of the total cycle time is involved in the regeneration of the adsorbent bed. Accordingly, any reductions in the amount of time for regeneration results in a reduction of the total cycle time. This reduction may also reduce the overall size of the swing adsorption system.
Further, in startup mode for the swing adsorption process, one or more of the manifolds and associated valves may be utilized as a dedicated flow path for one or more startup streams. For example, during the adsorption or feed step, the manifold 242 and valve assembly 222 may be utilized to pass the feed gas stream to the adsorbent bed 210, while the valve assembly 236 and manifold 256 may be used to conduct away the product stream from the adsorbent bed 210. During the regeneration or purge step, the manifold 244 and valve assembly 224 may be utilized to pass the external gas stream to the adsorbent bed 210, while the valve assembly 236 and manifold 256 may be used to conduct away the purge product stream from the adsorbent bed 210. Accordingly, the manifold 244 and valve assembly 224 may be utilized for startup mode processes, but remain inactive during normal operation mode. As may be appreciated, the purge stream may be configured to flow counter current to the feed stream in other embodiments.
Alternatively, the startup mode for the swing adsorption process may involve sharing one or more of the manifolds and associated valves during the normal operation mode and during startup mode. For example, the manifold 242 and valve assembly 222 may be utilized to feed the gaseous feed stream to the adsorbent bed 210 during startup mode and during normal operations, while the valve assembly 236 and manifold 256 may be used to conduct away the product stream from the adsorbent bed 210 may be used to conduct away the product stream during startup mode and during normal operation mode. During the regeneration or purge step, the manifold 254 and valve assembly 232 may be utilized to pass the external gas stream to the adsorbent bed 210 for startup mode and to pass the purge stream to the adsorbent bed 210 for normal operation mode, while the valve assembly 226 and manifold 248 may be used to conduct away the purge product stream from the adsorbent bed 210 during startup mode and normal operation mode. Beneficially, this configuration may be utilized to lessen any additional valves or connections for startup mode for adsorbent bed unit configurations that are subject to space limitations on the respective heads.
During normal operation mode, a gaseous feed stream may be subject to various processes to form a NGL stream or a LNG stream. For example, the process may include a mercury removal unit to remove mercury from an input stream; a filter to remove both particular and liquid droplets; a swing adsorption unit to remove one or more contaminants, such as H2O, CO2 and sulfur containing species; a LNG process unit or NGL process unit to process the resulting stream into a final product that may be used for sales, shipment or storage. In addition, the configuration may include one or more of a heating loop, a compressor, a heating unit and/or a storage vessel.
As noted above, the present techniques include various procedures that may be utilized for the startup mode of the swing adsorption process. The startup mode may include an external startup mode. The external startup mode may include performing an adsorption step and then a regeneration step for each of the adsorbent beds. The adsorption step may include passing a gaseous feed stream through the adsorbent bed to adsorb one or more contaminants from the gaseous feed stream and conducting away the resulting product stream from the adsorbent bed unit. The resulting product stream may be passed to downstream processing equipment. The regeneration step may include passing an external stream through the adsorbent bed to remove one or more contaminants from the adsorbent bed unit (e.g., a portion of the contaminants within the adsorbent bed unit or within the voids of the adsorbent bed) and conduct away the purge product stream from the adsorbent bed unit. The purge product stream may be set to flare or may be combined with fuel gas.
As an example,
The process begins by performing the startup mode process for the adsorbent bed units of the swing adsorption process, as shown in blocks 302 to 308. At block 302, a regeneration step is performed for the adsorbent bed with an external stream. The external stream may include nitrogen or methane and may be a dry stream (e.g., less than 10 ppm of water, less than 1 ppm of water, or less than 0.1 ppm of water). The regeneration step, which may be one or more purge steps may include passing the external stream through the adsorbent bed to create a purge product stream that is conducted away from the adsorbent bed unit. The product purge stream may include the external stream and a portion of the contaminants within the adsorbent bed. This product purge stream may be intermingled with a fuel gas stream or may be flared. Further, the external stream may be subjected to a heating step prior to being passed to the adsorbent bed. The heating step may heat the external stream to a temperature less than 550° F., less than 500° F., less than 450° F. or less than 350° F., and may be greater than 50° F. of the gaseous feed stream temperature, greater than 100° F. of the gaseous feed stream temperature or greater than 250° F. of the gaseous feed stream temperature. For example, the external stream used during the purge step may be a temperature in the range between 500° F. and greater than 50° F. of the gaseous feed stream temperature, in the range between a temperature in the range between 450° F. and greater than 100° F. of the gaseous feed stream temperature, in the range between 450° F. and the gaseous feed stream temperature or 400° F. and greater than 200° F. of the gaseous feed stream temperature. The heating of the external stream may include passing the stream through a heat exchanger or similar heating unit to increase the temperature of the external stream. At block 304, an adsorption step is performed for the adsorbent bed. The adsorption step may include passing a gaseous feed stream through the adsorbent bed to remove one or more contaminants from the gaseous feed stream and to create a product stream that is conducted away from the adsorbent bed unit. At block 306, the product stream may be measured. The product stream may be measured by taking samples, using a moisture analyzer, using a gas chromatograph or using another gas component analysis equipment. Then, at block 308, a determination may be made whether the product stream is within specification. This determination may include analyzing the product stream to determine the level of one or more of the contaminants within the product stream. If the product stream is within specification (e.g., contaminants are at or below a specific threshold), the product stream may be passed to downstream processes. However, if the product stream is not within specifications (e.g., contaminants are above a specific threshold), the product stream may be recycled to be intermingled with the gaseous feed stream and utilized as part of the adsorption step, as shown in block 304.
Once the adsorbent bed units are passing the product stream to the downstream process, the product stream may be used with the downstream equipment, as shown in blocks 310 to 316. At block 310, the startup mode for the downstream equipment may begin. The startup mode for the downstream equipment may involve various steps prior to the passing of product stream to the downstream equipment or may begin once the product stream is passed to the downstream equipment. The downstream processes may include a CFZ process, a cryogenic NGL recovery process, or an LNG process, with the associated equipment for each. Further, during the downstream startup mode sequence, the adsorbent bed units may continue to utilize the external stream for the purge step. At block 312, a purge stream may be passed to the adsorbent bed units from the downstream process. The purge stream may include an overhead stream or a slip stream from the downstream process. By way of example, the purge stream from an NGL facility may be the demethanizer overhead, or the purge stream may be a fuel gas stream for an LNG facility. Then, at block 314, the amount of external stream utilized in the purge step may be adjusted. The adjustment may be based on the amount of the purge stream being provided to the adsorbent bed units. For example, the flow rate of the external stream may be lowered by 10%, 50%, or 90% based on the amount of purge stream from the downstream processes and the desired flow rate. At block 316, the flow of the external stream may be interrupted. The flow of the external stream may be interrupted once the downstream process is producing a sufficient amount of purge stream at conditions close to steady operating conditions.
Once the startup mode process is complete, the normal operation mode may begin, as shown in block 318. At block 318, normal operation mode is begun. The normal operation mode may include passing the gaseous feed stream is passed to the adsorbent bed units for the swing adsorption process to remove contaminants and pass the product stream to the downstream process. Then, the downstream process may pass the product stream through the various downstream equipment to produce a final product stream. The downstream process may also pass a purge stream to the swing adsorption process, which may be utilized during the regeneration step to remove contaminants from the adsorbent beds within the adsorbent bed units.
As a specific example, the feed stream may be a natural gas stream that predominately contains hydrocarbons, the external stream may be a nitrogen stream and the contaminants within the adsorbent bed may be water. During the purge step for the respective adsorbent bed, the nitrogen stream is passed through the adsorbent bed and water interacts with the nitrogen stream to form the purge product stream, which includes the nitrogen and the portion of the water removed from the adsorbent bed.
In addition, the product stream from the adsorbent bed units may be utilized in the startup mode process for one or more downstream units, such as a demethanizer or a liquefaction train. As the downstream processes and units are being started, the spent adsorbent beds may be regenerated using the dry nitrogen stream as the purge stream. The dry nitrogen stream may be heated. Alternatively, a heated slip stream from the product side may also be used to regenerate the adsorbent beds during the purge step. Once the downstream processes begin normal operation mode, the purge stream may be adjusted to be provided from a residue gas stream, a fuel gas stream or other suitable stream from one of the downstream processes.
In certain embodiments, the purge product stream may be subjected to processes to remove the contaminants from the external stream, such that the cleaned purge product stream may be recycled to the adsorbent bed units as the external stream or intermingled with the external stream. For example, if the external stream is a nitrogen stream and the contaminant is water, the purge product stream may be heated and then may be subjected to a pressure drop to separate the water from the nitrogen in the purge product stream. In this manner, the nitrogen may be regenerated and recycled to the adsorbent beds to remove additional water from the adsorbent beds during a subsequent purge step.
As further enhancements, the operating conditions may be adjusted during the external startup mode to manage the removal of contaminants from the adsorbent beds. By way of example, flow rate may be in a range between 25 and 1000 million standard cubic feet per day (MSCFD) during normal operation mode, while the flow rate may be in the range between 6.25 and 500 MSCFD for startup mode. The flow rate may be increased during subsequent purge steps until normal operation mode flow rates are reached. Also, the pressure range of the external stream may be in a pressure range between atmospheric pressure and fifty psi above atmospheric pressure. In addition, the temperature of the external stream may be within a temperature range between 20° Celsius (C) above atmospheric temperature and 150° C. above atmospheric temperature. Further, the temperature of the external stream may be less than 550° F., less than 500° F., less than 450° F. or less than 350° F., and may be the gaseous feed stream temperature, greater than 50° F. of the gaseous feed stream temperature, greater than 100° F. of the gaseous feed stream temperature or greater than 250° F. of the gaseous feed stream temperature. For example, the external stream used during the purge step may be a temperature in the range between 500° F. and greater than 50° F. of the gaseous feed stream temperature, in the range between a temperature in the range between 450° F. and the gaseous feed stream temperature; in the range between 450° F. and greater than 100° F. of the gaseous feed stream temperature or 400° F. and greater than 200° F. of the gaseous feed stream temperature.
To support the external startup mode process, a configuration of the swing adsorption process may include additional bypass conduits and manifold to pass the external stream to the adsorbent bed units during the purge step. The external stream may be provided from an external source vessel through an external source conduit that is in fluid communication with purge manifold. In addition, the configuration may include one or more heating units that are upstream of the purge manifold and configured to heat the external stream prior to passing through the adsorbent bed units and/or that are downstream of the purge product manifold and configured to heat the purge product stream. The heating unit may include a heat exchanger, a furnace, or the like. The configuration may also include one or more separation units configured to separate one or more contaminants from the purge product stream. The separation units may be a flash separation vessel that is configured to lower the pressure of the stream to separate the contaminants from the remaining portion of the purge product stream or may be an adsorption unit that interacts with the contaminants to separates the contaminants from the remaining portion of the purge product stream. The contaminants may be conducted away from the process, while the remaining portion of the purge product stream may be passed to one or more regeneration units. The regeneration units may be utilized to further purify the remaining portion of the purge product stream and/or compress the remaining portion of the purge product stream to form the external stream that is passed to the adsorbent beds.
In certain embodiments, the external stream may be further conditioned prior to being provided to a subsequent adsorbent bed unit during its regeneration step, as the purge stream. The heating step may heat the external stream to a temperature less than 550° F., less than 500° F., less than 450° F. or less than 350° F., and may be greater than 50° F. of the gaseous feed stream temperature, greater than 100° F. of the gaseous feed stream temperature or greater than 250° F. of the gaseous feed stream temperature. For example, the external stream used during the purge step may be a temperature in the range between 500° F. and greater than 50° F. of the gaseous feed stream temperature, in the range between a temperature in the range between 450° F. and the gaseous feed stream temperature; in the range between 450° F. and greater than 100° F. of the gaseous feed stream temperature or 400° F. and greater than 200° F. of the gaseous feed stream temperature. The heating of the external stream may include passing the stream through a heat exchanger or similar heating unit to increase the temperature of the external stream. Further, the external stream may be subjected to a depressurization step prior to being passed to the adsorbent bed unit performing its regeneration step. The depressurization step, which may be prior to the heating step or following the heating step, may lower the pressure of the external stream to a pressure in the range from between 0.1 bar absolute (bara) and 100 bara, which is lower than the pressure of the external stream prior to the depressurization step. The pressure may be lowered by at least 10%, by at least 20% or at least 30% relative to the pressure of the product stream exiting the adsorbent bed. The depressurizing of the external stream may include passing the stream through an expander or flash separation vessel to lower the pressure of the external stream.
As further enhancements, the operating conditions may be adjusted during the startup mode to manage the removal of contaminants from the adsorbent bed units. By way of example, the flow rate may be in a range between 25 and 1000 million standard cubic feet per day (MSCFD) during normal operation mode, while the flow rate may be in the range between 6.25 and 500 MSCFD for startup mode. The flow rate may be increased during subsequent purge steps until normal operation mode flow rates are reached. Also, the pressure range of the external stream may be in a pressure range between atmospheric pressure and fifty psi above atmospheric pressure. In addition, the temperature of the external stream may be within a temperature range between 20° Celsius (C) above atmospheric temperature and 100° Celsius (C) above atmospheric temperature.
In addition, the purge product may be subject to conditioning steps, such as for recovering hydrocarbons from the regeneration step. For example, the purge product stream may be cooled or compressed to remove contaminants and may be recycled to be at least a portion of the feed stream or to be at least a portion of the product stream. By way of example, a flash separation may be utilized to remove contaminants. In other configurations, the purge product stream is heated to a temperature 5° F. greater than the dew point of the purge product stream; 10° F. greater than the dew point of the purge product stream; or 20° F. greater than the dew point of the purge product stream. By heating the purge product stream above the dew point, the heated purge product stream may be used in a subsequent process, such as a gas turbine.
To support the startup mode process, a configuration of the swing adsorption process may include additional bypass conduits and manifold to pass the external stream or a portion of the external stream to adsorbent bed units during their regeneration step. The configuration may also include one or more heating units that are upstream of the purge manifold and configured to heat the external stream prior to passing through the adsorbent bed units and/or that are downstream of the purge product manifold and configured to heat the purge product stream. The heating unit may include a heat exchanger, a furnace, or the like. The configuration may also include one or more depressurization units configured to lower the pressure of the external stream. The depressurization units may include one or more expanders and/or one or more separation units. The separation units, which may be a flash separation vessel, may be configured to separate one or more contaminants from the external stream. Further, the configuration may include one or more regeneration units that are configured to purify the purge product stream to remove contaminants from the purge product stream. By way of example, the configuration may include an external gas bypass valve in fluid communication with purge manifold and configured to provide a flow passage for an external gas stream from an external gas storage vessel to the purge manifold in a startup mode position and configured to block the flow passage of the external gas stream from the external gas storage vessel to the purge manifold in a normal operation mode position.
Exemplary embodiments of steps that may be performed in the startup mode process are shown in
In
As may be appreciated, the startup mode process may include various combination of steps to perform the startup mode process. The startup modes may use these different step to manage the startup mode sequence. For example, the blowdown step may be performed after the purge step for the respective adsorbent bed units.
In addition, as another enhancement, the present techniques may include other enhancements. For example, a heating jacket or blanket may be used to provide additional heat to the adsorbent bed unit. The additional heat may be used during startup mode to further provide heat to the adsorbent bed. Specifically, the heating jacket may be disposed adjacent to the adsorbent bed unit and/or manifolds and conduits fluidly coupled to the adsorbent bed unit and configured to heat the adsorbent bed, which may be an electric heating configuration.
In one or more embodiments, the material may include an adsorbent material supported on a non-adsorbent support. The adsorbent materials may include alumina, microporous zeolites, carbons, cationic zeolites, high silica zeolites, highly siliceous ordered mesoporous materials, sol gel materials, aluminum phosphorous and oxygen (ALPO) materials (microporous and mesoporous materials containing predominantly aluminum phosphorous and oxygen), silicon aluminum phosphorous and oxygen (SAPO) materials (microporous and mesoporous materials containing predominantly silicon aluminum phosphorous and oxygen), metal organic framework (MOF) materials (microporous and mesoporous materials comprised of a metal organic framework) and zeolitic imidazolate frameworks (ZIF) materials (microporous and mesoporous materials comprised of zeolitic imidazolate frameworks). Other materials include microporous and mesoporous sorbents functionalized with functional groups. Examples of functional groups include primary, secondary, tertiary amines and other non protogenic basic groups such as amidines, guanidines and biguanides.
In one or more embodiments, the adsorbent bed unit may be utilized to separate contaminants from a feed stream during normal operation mode. The method may include passing a gaseous feed stream at a feed pressure through an adsorbent bed unit having an adsorbent contactor to separate one or more contaminants from the gaseous feed stream to form a product stream, wherein the adsorbent contactor has a first portion and a second portion; interrupting the flow of the gaseous feed stream; performing a depressurization step, wherein the depressurization step reduces the pressure within the adsorbent bed unit; performing an optional heating step, wherein the heating step increases the temperature of the adsorbent bed unit to form a temperature differential between the feed end of the adsorbent bed and the product end of the adsorbent bed; and performing a purge step, wherein the purge step reduces the pressure within the adsorbent bed unit; performing a re-pressurization step, wherein the re-pressurization step increases the pressure within the adsorbent bed unit; and repeating the steps a) to e) for at least one additional cycle.
Further, in one or more embodiments, the adsorbent bed unit may include an adsorbent bed that can be used for the separation of a target gas form a gaseous mixture. The adsorbent is usually comprised of an adsorbent material supported on a non-adsorbent support, or contactor. Such contactors contain substantially parallel flow channels wherein 20 volume percent, preferably 15 volume percent or less of the open pore volume of the contactor, excluding the flow channels, is in pores greater than about 20 angstroms. A flow channel is taken to be that portion of the contactor in which gas flows, if a steady state pressure difference is applied between the point or place at which a feed stream enters the contactor and the point or place at which a product stream leaves the contactor. In the contactor, the adsorbent is incorporated into the wall of the flow channel.
In one or more embodiments, when using RCTSA or an integrated RCPSA and RCTSA process, the total cycle times are typically less than 600 seconds, preferably less than 400 seconds, preferably less than 300 seconds, preferably less than 250 seconds, preferably less than 180 seconds, more preferably less than 90 seconds, and even more preferably less than 60 seconds. In other embodiment, the rapid cycle configuration may be operated at lower flow rates during startup mode as compared to normal operation mode, which may result in the cycle durations being longer than the cycle durations during normal operation mode. For example, the startup mode cycle duration may be for a period greater than 1 second and less than 2400 seconds, for a period greater than 1 second and less than 1500 seconds, for a period greater than 1 second and less than 1000 seconds, for a period greater than 1 second and less than 600 seconds, for a period greater than 2 second and less than 800 seconds, for a period greater than 2 second and less than 400 seconds, for a period greater than 5 second and less than 150 seconds or for a period greater than 5 second and less than 90 seconds.
In view of the many possible embodiments to which the principles of the disclosed invention may be applied, it should be recognized that the illustrative embodiments are only preferred examples of the invention and should not be taken as limiting the scope of the invention.
This application claims the benefit of U.S. Provisional Patent Application 62/343,426, filed May 31, 2016, entitled APPARATUS AND SYSTEM FOR SWING ADSORPTION PROCESSES, the entirety of which is incorporated by reference herein.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1868138 | Fisk | Jul 1932 | A |
| 3103425 | Meyer | Sep 1963 | A |
| 3124152 | Payne | Mar 1964 | A |
| 3142547 | Marsh et al. | Jul 1964 | A |
| 3508758 | Strub | Apr 1970 | A |
| 3594983 | Yearout | Jul 1971 | A |
| 3602247 | Bunn et al. | Aug 1971 | A |
| 3788036 | Lee et al. | Jan 1974 | A |
| 3967464 | Cormier et al. | Jul 1976 | A |
| 4187092 | Woolley | Feb 1980 | A |
| 4261815 | Kelland | Apr 1981 | A |
| 4324565 | Benkmann | Apr 1982 | A |
| 4325565 | Winchell | Apr 1982 | A |
| 4329162 | Pitcher | May 1982 | A |
| 4340398 | Doshi et al. | Jul 1982 | A |
| 4386947 | Mizuno et al. | Jun 1983 | A |
| 4421531 | Dalton, Jr. et al. | Dec 1983 | A |
| 4445441 | Tanca | May 1984 | A |
| 4461630 | Cassidy et al. | Jul 1984 | A |
| 4496376 | Hradek | Jan 1985 | A |
| 4631073 | Null et al. | Dec 1986 | A |
| 4705627 | Miwa et al. | Nov 1987 | A |
| 4711968 | Oswald et al. | Dec 1987 | A |
| 4737170 | Searle | Apr 1988 | A |
| 4770676 | Sircar | Sep 1988 | A |
| 4783205 | Searle | Nov 1988 | A |
| 4784672 | Sircar | Nov 1988 | A |
| 4790272 | Woolenweber | Dec 1988 | A |
| 4814146 | Brand et al. | Mar 1989 | A |
| 4816039 | Krishnamurthy et al. | Mar 1989 | A |
| 4877429 | Hunter | Oct 1989 | A |
| 4977745 | Heichberger | Dec 1990 | A |
| 5110328 | Yokota et al. | May 1992 | A |
| 5125934 | Krishnamurthy et al. | Jun 1992 | A |
| 5169006 | Stelzer | Dec 1992 | A |
| 5174796 | Davis et al. | Dec 1992 | A |
| 5224350 | Mehra | Jul 1993 | A |
| 5229089 | Ramachandran | Jul 1993 | A |
| 5234472 | Krishnamurthy et al. | Aug 1993 | A |
| 5292990 | Kantner et al. | Mar 1994 | A |
| 5306331 | Auvil et al. | Apr 1994 | A |
| 5354346 | Kumar | Oct 1994 | A |
| 5365011 | Ramachandran et al. | Nov 1994 | A |
| 5370728 | LaSala et al. | Dec 1994 | A |
| 5486227 | Kumar | Jan 1996 | A |
| 5547641 | Smith et al. | Aug 1996 | A |
| 5565018 | Baksh et al. | Oct 1996 | A |
| 5672196 | Acharya et al. | Sep 1997 | A |
| 5700310 | Bowman et al. | Dec 1997 | A |
| 5733451 | Coellner et al. | Mar 1998 | A |
| 5735938 | Baksh et al. | Apr 1998 | A |
| 5750026 | Gadkaree et al. | May 1998 | A |
| 5769928 | Leavitt | Jun 1998 | A |
| 5779768 | Anand | Jul 1998 | A |
| 5792239 | Reinhold, III et al. | Aug 1998 | A |
| 5807423 | Lemcoff et al. | Sep 1998 | A |
| 5811616 | Holub et al. | Sep 1998 | A |
| 5827358 | Kulish et al. | Oct 1998 | A |
| 5906673 | Reinhold, III et al. | May 1999 | A |
| 5912426 | Smolarek et al. | Jun 1999 | A |
| 5914294 | Park et al. | Jun 1999 | A |
| 5924307 | Nenov | Jul 1999 | A |
| 5935444 | Johnson et al. | Aug 1999 | A |
| 5968234 | Midgett, II et al. | Oct 1999 | A |
| 5976221 | Bowman et al. | Nov 1999 | A |
| 5997617 | Czabala et al. | Dec 1999 | A |
| 6007606 | Baksh et al. | Dec 1999 | A |
| 6011192 | Baker et al. | Jan 2000 | A |
| 6023942 | Thomas et al. | Feb 2000 | A |
| 6053966 | Moreau et al. | Apr 2000 | A |
| 6063161 | Keefer et al. | May 2000 | A |
| 6096115 | Kleinberg | Aug 2000 | A |
| 6099621 | Ho | Aug 2000 | A |
| 6129780 | Millet et al. | Oct 2000 | A |
| 6136222 | Friesen et al. | Oct 2000 | A |
| 6147126 | DeGeorge et al. | Nov 2000 | A |
| 6152991 | Ackley | Nov 2000 | A |
| 6156101 | Naheiri | Dec 2000 | A |
| 6171371 | Derive et al. | Jan 2001 | B1 |
| 6176897 | Keefer | Jan 2001 | B1 |
| 6179900 | Behling et al. | Jan 2001 | B1 |
| 6183538 | Naheiri | Feb 2001 | B1 |
| 6194079 | Hekal | Feb 2001 | B1 |
| 6210466 | Whysall et al. | Apr 2001 | B1 |
| 6231302 | Bonardi | May 2001 | B1 |
| 6245127 | Kane et al. | Jun 2001 | B1 |
| 6284021 | Lu et al. | Sep 2001 | B1 |
| 6311719 | Hill et al. | Nov 2001 | B1 |
| 6345954 | Al-Himyary et al. | Feb 2002 | B1 |
| 6398853 | Keefer et al. | Jun 2002 | B1 |
| 6402813 | Monereau et al. | Jun 2002 | B2 |
| 6406523 | Connor et al. | Jun 2002 | B1 |
| 6425938 | Xu et al. | Jul 2002 | B1 |
| 6432379 | Heung | Aug 2002 | B1 |
| 6436171 | Wang et al. | Aug 2002 | B1 |
| 6444012 | Dolan et al. | Sep 2002 | B1 |
| 6444014 | Mullhaupt et al. | Sep 2002 | B1 |
| 6444523 | Fan et al. | Sep 2002 | B1 |
| 6444610 | Yamamoto | Sep 2002 | B1 |
| 6451095 | Keefer et al. | Sep 2002 | B1 |
| 6457485 | Hill et al. | Oct 2002 | B2 |
| 6464761 | Bugli | Oct 2002 | B1 |
| 6471749 | Kawai | Oct 2002 | B1 |
| 6471939 | Boix et al. | Oct 2002 | B1 |
| 6488747 | Keefer | Dec 2002 | B1 |
| 6497750 | Butwell et al. | Dec 2002 | B2 |
| 6500234 | Ackley et al. | Dec 2002 | B1 |
| 6500241 | Reddy | Dec 2002 | B2 |
| 6500404 | Camblor Fernandez et al. | Dec 2002 | B1 |
| 6503299 | Baksh et al. | Jan 2003 | B2 |
| 6506351 | Jain et al. | Jan 2003 | B1 |
| 6514318 | Keefer | Feb 2003 | B2 |
| 6514319 | Keefer et al. | Feb 2003 | B2 |
| 6517609 | Monereau et al. | Feb 2003 | B1 |
| 6531516 | Davis et al. | Mar 2003 | B2 |
| 6533846 | Keefer et al. | Mar 2003 | B1 |
| 6565627 | Golden et al. | May 2003 | B1 |
| 6565635 | Keefer et al. | May 2003 | B2 |
| 6565825 | Ohji et al. | May 2003 | B2 |
| 6572678 | Wijmans et al. | Jun 2003 | B1 |
| 6579341 | Baker et al. | Jun 2003 | B2 |
| 6593541 | Herren | Jul 2003 | B1 |
| 6595233 | Pulli | Jul 2003 | B2 |
| 6605136 | Graham et al. | Aug 2003 | B1 |
| 6607584 | Moreau et al. | Aug 2003 | B2 |
| 6630012 | Wegeng et al. | Oct 2003 | B2 |
| 6631626 | Hahn | Oct 2003 | B1 |
| 6641645 | Lee et al. | Nov 2003 | B1 |
| 6651645 | Nunez-Suarez | Nov 2003 | B1 |
| 6660064 | Golden et al. | Dec 2003 | B2 |
| 6660065 | Byrd et al. | Dec 2003 | B2 |
| 6692626 | Keefer et al. | Feb 2004 | B2 |
| 6712087 | Hill et al. | Mar 2004 | B2 |
| 6742507 | Keefer et al. | Jun 2004 | B2 |
| 6746515 | Wegeng et al. | Jun 2004 | B2 |
| 6752852 | Jacksier et al. | Jun 2004 | B1 |
| 6770120 | Neu et al. | Aug 2004 | B2 |
| 6773225 | Yuri et al. | Aug 2004 | B2 |
| 6802889 | Graham et al. | Oct 2004 | B2 |
| 6814771 | Scardino et al. | Nov 2004 | B2 |
| 6835354 | Woods et al. | Dec 2004 | B2 |
| 6840985 | Keefer | Jan 2005 | B2 |
| 6866950 | Connor et al. | Mar 2005 | B2 |
| 6889710 | Wagner | May 2005 | B2 |
| 6890376 | Arquin et al. | May 2005 | B2 |
| 6893483 | Golden et al. | May 2005 | B2 |
| 6902602 | Keefer et al. | Jun 2005 | B2 |
| 6916358 | Nakamura et al. | Jul 2005 | B2 |
| 6918953 | Lomax, Jr. et al. | Jul 2005 | B2 |
| 6921597 | Keefer et al. | Jul 2005 | B2 |
| 6974496 | Wegeng et al. | Dec 2005 | B2 |
| 7025801 | Monereau | Apr 2006 | B2 |
| 7027929 | Wang | Apr 2006 | B2 |
| 7029521 | Johansson | Apr 2006 | B2 |
| 7074323 | Ghijsen | Jul 2006 | B2 |
| 7077891 | Jaffe et al. | Jul 2006 | B2 |
| 7087331 | Keefer et al. | Aug 2006 | B2 |
| 7094275 | Keefer et al. | Aug 2006 | B2 |
| 7097925 | Keefer et al. | Aug 2006 | B2 |
| 7112239 | Kimbara et al. | Sep 2006 | B2 |
| 7117669 | Kaboord et al. | Oct 2006 | B2 |
| 7122073 | Notaro et al. | Oct 2006 | B1 |
| 7128775 | Celik et al. | Oct 2006 | B2 |
| 7144016 | Gozdawa | Dec 2006 | B2 |
| 7160356 | Koros et al. | Jan 2007 | B2 |
| 7160367 | Babicki et al. | Jan 2007 | B2 |
| 7166149 | Dunne et al. | Jan 2007 | B2 |
| 7172645 | Pfister et al. | Feb 2007 | B1 |
| 7189280 | Alizadeh-Khiavi et al. | Mar 2007 | B2 |
| 7250073 | Keefer et al. | Jul 2007 | B2 |
| 7250074 | Tonkovich et al. | Jul 2007 | B2 |
| 7255727 | Monereau et al. | Aug 2007 | B2 |
| 7258725 | Ohmi et al. | Aug 2007 | B2 |
| 7276107 | Baksh et al. | Oct 2007 | B2 |
| 7279029 | Occhialini et al. | Oct 2007 | B2 |
| 7285350 | Keefer et al. | Oct 2007 | B2 |
| 7297279 | Johnson et al. | Nov 2007 | B2 |
| 7311763 | Neary | Dec 2007 | B2 |
| RE40006 | Keefer et al. | Jan 2008 | E |
| 7314503 | Landrum et al. | Jan 2008 | B2 |
| 7354562 | Ying et al. | Apr 2008 | B2 |
| 7387849 | Keefer et al. | Jun 2008 | B2 |
| 7390350 | Weist, Jr. et al. | Jun 2008 | B2 |
| 7404846 | Golden et al. | Jul 2008 | B2 |
| 7438079 | Cohen et al. | Oct 2008 | B2 |
| 7449049 | Thomas et al. | Nov 2008 | B2 |
| 7456131 | Klett et al. | Nov 2008 | B2 |
| 7510601 | Whitley et al. | Mar 2009 | B2 |
| 7527670 | Ackley et al. | May 2009 | B2 |
| 7553568 | Keefer | Jun 2009 | B2 |
| 7578864 | Watanabe et al. | Aug 2009 | B2 |
| 7604682 | Seaton | Oct 2009 | B2 |
| 7637989 | Bong | Dec 2009 | B2 |
| 7641716 | Lomax, Jr. et al. | Jan 2010 | B2 |
| 7645324 | Rode et al. | Jan 2010 | B2 |
| 7651549 | Whitley | Jan 2010 | B2 |
| 7674319 | Lomax, Jr. et al. | Mar 2010 | B2 |
| 7674539 | Keefer et al. | Mar 2010 | B2 |
| 7687044 | Keefer et al. | Mar 2010 | B2 |
| 7713333 | Rege et al. | May 2010 | B2 |
| 7717981 | LaBuda et al. | May 2010 | B2 |
| 7722700 | Sprinkle | May 2010 | B2 |
| 7731782 | Kelley et al. | Jun 2010 | B2 |
| 7740687 | Reinhold, III | Jun 2010 | B2 |
| 7744676 | Leitmayr et al. | Jun 2010 | B2 |
| 7744677 | Barclay et al. | Jun 2010 | B2 |
| 7758051 | Roberts-Haritonov et al. | Jul 2010 | B2 |
| 7758988 | Keefer et al. | Jul 2010 | B2 |
| 7763098 | Alizadeh-Khiavi et al. | Jul 2010 | B2 |
| 7763099 | Verma et al. | Jul 2010 | B2 |
| 7792983 | Mishra et al. | Sep 2010 | B2 |
| 7793675 | Cohen et al. | Sep 2010 | B2 |
| 7806965 | Stinson | Oct 2010 | B2 |
| 7819948 | Wagner | Oct 2010 | B2 |
| 7828877 | Sawada et al. | Nov 2010 | B2 |
| 7828880 | Moriya et al. | Nov 2010 | B2 |
| 7854793 | Rarig et al. | Dec 2010 | B2 |
| 7858169 | Yamashita | Dec 2010 | B2 |
| 7862645 | Whitley et al. | Jan 2011 | B2 |
| 7867320 | Baksh et al. | Jan 2011 | B2 |
| 7902114 | Bowie et al. | Mar 2011 | B2 |
| 7938886 | Hershkowitz et al. | May 2011 | B2 |
| 7947118 | Rarig et al. | May 2011 | B2 |
| 7947120 | Deckman et al. | May 2011 | B2 |
| 7959720 | Deckman et al. | Jun 2011 | B2 |
| 8016918 | LaBuda et al. | Sep 2011 | B2 |
| 8034164 | Lomax, Jr. et al. | Oct 2011 | B2 |
| 8071063 | Reyes et al. | Dec 2011 | B2 |
| 8128734 | Song | Mar 2012 | B2 |
| 8142745 | Reyes et al. | Mar 2012 | B2 |
| 8142746 | Reyes et al. | Mar 2012 | B2 |
| 8192709 | Reyes et al. | Jun 2012 | B2 |
| 8210772 | Gillecriosd | Jul 2012 | B2 |
| 8227121 | Adams et al. | Jul 2012 | B2 |
| 8262773 | Northrop et al. | Sep 2012 | B2 |
| 8262783 | Stoner et al. | Sep 2012 | B2 |
| 8268043 | Celik et al. | Sep 2012 | B2 |
| 8268044 | Wright et al. | Sep 2012 | B2 |
| 8272401 | McLean | Sep 2012 | B2 |
| 8287629 | Fujita et al. | Oct 2012 | B2 |
| 8319090 | Kitamura | Nov 2012 | B2 |
| 8337594 | Corma Canos et al. | Dec 2012 | B2 |
| 8361200 | Sayari et al. | Jan 2013 | B2 |
| 8361205 | Desai et al. | Jan 2013 | B2 |
| 8377173 | Chuang | Feb 2013 | B2 |
| 8444750 | Deckman et al. | May 2013 | B2 |
| 8470395 | Khiavi et al. | Jun 2013 | B2 |
| 8480795 | Siskin et al. | Jul 2013 | B2 |
| 8512569 | Eaton et al. | Aug 2013 | B2 |
| 8518356 | Schaffer et al. | Aug 2013 | B2 |
| 8529662 | Kelley et al. | Sep 2013 | B2 |
| 8529663 | Reyes et al. | Sep 2013 | B2 |
| 8529664 | Deckman et al. | Sep 2013 | B2 |
| 8529665 | Manning et al. | Sep 2013 | B2 |
| 8535414 | Johnson et al. | Sep 2013 | B2 |
| 8545602 | Chance et al. | Oct 2013 | B2 |
| 8551444 | Agnihotri et al. | Oct 2013 | B2 |
| 8573124 | Havran et al. | Nov 2013 | B2 |
| 8591627 | Jain | Nov 2013 | B2 |
| 8591634 | Winchester et al. | Nov 2013 | B2 |
| 8616233 | McLean et al. | Dec 2013 | B2 |
| 8657922 | Yamawaki et al. | Feb 2014 | B2 |
| 8673059 | Leta et al. | Mar 2014 | B2 |
| 8680344 | Weston et al. | Mar 2014 | B2 |
| 8715617 | Genkin et al. | May 2014 | B2 |
| 8752390 | Wright et al. | Jun 2014 | B2 |
| 8778051 | Weist, Jr. et al. | Jul 2014 | B2 |
| 8784533 | Leta et al. | Jul 2014 | B2 |
| 8784534 | Kamakoti et al. | Jul 2014 | B2 |
| 8784535 | Ravikovitch et al. | Jul 2014 | B2 |
| 8795411 | Hufton et al. | Aug 2014 | B2 |
| 8808425 | Genkin et al. | Aug 2014 | B2 |
| 8808426 | Sundaram | Aug 2014 | B2 |
| 8814985 | Gerds et al. | Aug 2014 | B2 |
| 8852322 | Gupta et al. | Oct 2014 | B2 |
| 8858683 | Deckman | Oct 2014 | B2 |
| 8875483 | Wettstein | Nov 2014 | B2 |
| 8906138 | Rasmussen et al. | Dec 2014 | B2 |
| 8921637 | Sundaram et al. | Dec 2014 | B2 |
| 8939014 | Kamakoti et al. | Jan 2015 | B2 |
| 9005561 | Leta | Apr 2015 | B2 |
| 9017457 | Tammera | Apr 2015 | B2 |
| 9028595 | Sundaram et al. | May 2015 | B2 |
| 9034078 | Wanni et al. | May 2015 | B2 |
| 9034079 | Deckman et al. | May 2015 | B2 |
| 9050553 | Alizadeh-Khiavi et al. | Jun 2015 | B2 |
| 9067168 | Frederick et al. | Jun 2015 | B2 |
| 9095809 | Deckman et al. | Aug 2015 | B2 |
| 9108145 | Kalbassi et al. | Aug 2015 | B2 |
| 9120049 | Sundaram et al. | Sep 2015 | B2 |
| 9126138 | Deckman et al. | Sep 2015 | B2 |
| 9162175 | Sundaram | Oct 2015 | B2 |
| 9168485 | Deckman et al. | Oct 2015 | B2 |
| 20010047824 | Hill et al. | Dec 2001 | A1 |
| 20020053547 | Schlegel et al. | May 2002 | A1 |
| 20020124885 | Hill et al. | Sep 2002 | A1 |
| 20020162452 | Butwell et al. | Nov 2002 | A1 |
| 20030075485 | Ghijsen | Apr 2003 | A1 |
| 20030129101 | Zettel | Jul 2003 | A1 |
| 20030131728 | Kanazirev et al. | Jul 2003 | A1 |
| 20030145726 | Gueret et al. | Aug 2003 | A1 |
| 20030170527 | Finn et al. | Sep 2003 | A1 |
| 20030202918 | Ashida et al. | Oct 2003 | A1 |
| 20030205130 | Neu et al. | Nov 2003 | A1 |
| 20030221555 | Golden | Dec 2003 | A1 |
| 20030223856 | Yuri et al. | Dec 2003 | A1 |
| 20040099142 | Arquin et al. | May 2004 | A1 |
| 20040118277 | Kim | Jun 2004 | A1 |
| 20040118747 | Cutler et al. | Jun 2004 | A1 |
| 20040197596 | Connor et al. | Oct 2004 | A1 |
| 20040232622 | Gozdawa | Nov 2004 | A1 |
| 20050014511 | Spain | Jan 2005 | A1 |
| 20050109419 | Ohmi et al. | May 2005 | A1 |
| 20050114032 | Wang | May 2005 | A1 |
| 20050129952 | Sawada et al. | Jun 2005 | A1 |
| 20050145111 | Keefer et al. | Jul 2005 | A1 |
| 20050150378 | Dunne et al. | Jul 2005 | A1 |
| 20050229782 | Monereau et al. | Oct 2005 | A1 |
| 20050252378 | Celik et al. | Nov 2005 | A1 |
| 20060048648 | Gibbs et al. | Mar 2006 | A1 |
| 20060049102 | Miller et al. | Mar 2006 | A1 |
| 20060076270 | Poshusta et al. | Apr 2006 | A1 |
| 20060099096 | Shaffer et al. | May 2006 | A1 |
| 20060105158 | Fritz et al. | May 2006 | A1 |
| 20060162556 | Ackley et al. | Jul 2006 | A1 |
| 20060165574 | Sayari | Jul 2006 | A1 |
| 20060169142 | Rode et al. | Aug 2006 | A1 |
| 20060236862 | Golden et al. | Oct 2006 | A1 |
| 20070084241 | Kretchmer et al. | Apr 2007 | A1 |
| 20070084344 | Moriya et al. | Apr 2007 | A1 |
| 20070222160 | Roberts-Haritonov et al. | Sep 2007 | A1 |
| 20070253872 | Keefer et al. | Nov 2007 | A1 |
| 20070261550 | Ota | Nov 2007 | A1 |
| 20070261557 | Gadkaree et al. | Nov 2007 | A1 |
| 20070283807 | Whitley | Dec 2007 | A1 |
| 20080051279 | Klett et al. | Feb 2008 | A1 |
| 20080072822 | White | Mar 2008 | A1 |
| 20080128655 | Garg et al. | Jun 2008 | A1 |
| 20080282883 | Rarig et al. | Nov 2008 | A1 |
| 20080282884 | Kelley et al. | Nov 2008 | A1 |
| 20080282885 | Deckman et al. | Nov 2008 | A1 |
| 20080282886 | Reyes et al. | Nov 2008 | A1 |
| 20080282887 | Chance et al. | Nov 2008 | A1 |
| 20080282892 | Deckman et al. | Nov 2008 | A1 |
| 20080289497 | Barclay et al. | Nov 2008 | A1 |
| 20080307966 | Stinson | Dec 2008 | A1 |
| 20080314550 | Greco | Dec 2008 | A1 |
| 20090004073 | Gleize et al. | Jan 2009 | A1 |
| 20090014902 | Koivunen et al. | Jan 2009 | A1 |
| 20090025553 | Keefer et al. | Jan 2009 | A1 |
| 20090025555 | Lively et al. | Jan 2009 | A1 |
| 20090037550 | Mishra et al. | Feb 2009 | A1 |
| 20090071333 | LaBuda et al. | Mar 2009 | A1 |
| 20090079870 | Matsui | Mar 2009 | A1 |
| 20090107332 | Wagner | Apr 2009 | A1 |
| 20090151559 | Verma et al. | Jun 2009 | A1 |
| 20090162268 | Hufton et al. | Jun 2009 | A1 |
| 20090180423 | Kroener | Jul 2009 | A1 |
| 20090241771 | Manning et al. | Oct 2009 | A1 |
| 20090284013 | Anand et al. | Nov 2009 | A1 |
| 20090294366 | Wright et al. | Dec 2009 | A1 |
| 20090308248 | Siskin et al. | Dec 2009 | A1 |
| 20090314159 | Haggerty | Dec 2009 | A1 |
| 20100059701 | McLean | Mar 2010 | A1 |
| 20100077920 | Baksh et al. | Apr 2010 | A1 |
| 20100089241 | Stoner et al. | Apr 2010 | A1 |
| 20100186445 | Minta et al. | Jul 2010 | A1 |
| 20100212493 | Rasmussen et al. | Aug 2010 | A1 |
| 20100251887 | Jain | Oct 2010 | A1 |
| 20100252497 | Ellison et al. | Oct 2010 | A1 |
| 20100263534 | Chuang | Oct 2010 | A1 |
| 20100282593 | Speirs et al. | Nov 2010 | A1 |
| 20100288704 | Amsden et al. | Nov 2010 | A1 |
| 20110011803 | Koros | Jan 2011 | A1 |
| 20110020202 | Gadkaree et al. | Jan 2011 | A1 |
| 20110031103 | Deckman et al. | Feb 2011 | A1 |
| 20110067440 | Van Aken | Mar 2011 | A1 |
| 20110067770 | Pederson et al. | Mar 2011 | A1 |
| 20110146494 | Desai et al. | Jun 2011 | A1 |
| 20110150756 | Adams et al. | Jun 2011 | A1 |
| 20110217218 | Gupta et al. | Sep 2011 | A1 |
| 20110277620 | Havran et al. | Nov 2011 | A1 |
| 20110277630 | Greenough | Nov 2011 | A1 |
| 20110291051 | Hershkowitz et al. | Dec 2011 | A1 |
| 20110296871 | Van Soest-Vercammen et al. | Dec 2011 | A1 |
| 20110308524 | Brey et al. | Dec 2011 | A1 |
| 20120024152 | Yamawaki et al. | Feb 2012 | A1 |
| 20120031144 | Northrop et al. | Feb 2012 | A1 |
| 20120067216 | Corma-Canos et al. | Mar 2012 | A1 |
| 20120152115 | Gerds et al. | Jun 2012 | A1 |
| 20120222551 | Deckman | Sep 2012 | A1 |
| 20120222552 | Ravikovitch et al. | Sep 2012 | A1 |
| 20120222553 | Kamakoti et al. | Sep 2012 | A1 |
| 20120222554 | Leta et al. | Sep 2012 | A1 |
| 20120222555 | Gupta et al. | Sep 2012 | A1 |
| 20120255377 | Kamakoti et al. | Oct 2012 | A1 |
| 20120272823 | Halder et al. | Nov 2012 | A1 |
| 20120308456 | Leta et al. | Dec 2012 | A1 |
| 20120312163 | Leta et al. | Dec 2012 | A1 |
| 20130061755 | Frederick et al. | Mar 2013 | A1 |
| 20130095996 | Buelow et al. | Apr 2013 | A1 |
| 20130225898 | Sundaram et al. | Aug 2013 | A1 |
| 20140013955 | Tammera et al. | Jan 2014 | A1 |
| 20140060326 | Sundaram et al. | Mar 2014 | A1 |
| 20140157984 | Deckman et al. | Jun 2014 | A1 |
| 20140157986 | Ravikovitch et al. | Jun 2014 | A1 |
| 20140208797 | Kelley et al. | Jul 2014 | A1 |
| 20140216254 | Tammera et al. | Aug 2014 | A1 |
| 20150013377 | Oelfke | Jan 2015 | A1 |
| 20150068397 | Boulet et al. | Mar 2015 | A1 |
| 20150101483 | Perry et al. | Apr 2015 | A1 |
| 20150196870 | Albright et al. | Jul 2015 | A1 |
| 20150328578 | Deckman et al. | Nov 2015 | A1 |
| 20160023155 | Ramkumar et al. | Jan 2016 | A1 |
| 20160129433 | Tammera et al. | May 2016 | A1 |
| 20160166972 | Owens et al. | Jun 2016 | A1 |
| 20160236135 | Tammera et al. | Aug 2016 | A1 |
| 20160332105 | Tammera et al. | Nov 2016 | A1 |
| 20160332106 | Tammera et al. | Nov 2016 | A1 |
| 20170136405 | Ravikovitch et al. | May 2017 | A1 |
| 20170266604 | Tammera et al. | Sep 2017 | A1 |
| 20170282114 | Owens et al. | Oct 2017 | A1 |
| 20170341011 | Nagavarapu et al. | Nov 2017 | A1 |
| 20170341012 | Nagavarapu et al. | Nov 2017 | A1 |
| 20180001301 | Brody et al. | Jan 2018 | A1 |
| 20180056229 | Denton et al. | Mar 2018 | A1 |
| 20180056235 | Wang et al. | Mar 2018 | A1 |
| 20180169565 | Brody et al. | Jun 2018 | A1 |
| 20180169617 | Brody et al. | Jun 2018 | A1 |
| 20180339263 | Dehaas et al. | Nov 2018 | A1 |
| Number | Date | Country |
|---|---|---|
| 2297590 | Sep 2000 | CA |
| 2237103 | Dec 2001 | CA |
| 0225736 | Jun 1987 | EP |
| 0257493 | Feb 1988 | EP |
| 0262934 | Apr 1988 | EP |
| 0426937 | May 1991 | EP |
| 0904827 | Mar 1999 | EP |
| 1018359 | Jul 2000 | EP |
| 1045728 | Nov 2000 | EP |
| 1577561 | Sep 2005 | EP |
| 1674555 | Jun 2006 | EP |
| 2823872 | Jan 2015 | EP |
| 2854819 | May 2003 | FR |
| 2924951 | Jun 2009 | FR |
| 58-114715 | Jul 1983 | JP |
| 59-232174 | Dec 1984 | JP |
| 60-189318 | Dec 1985 | JP |
| 2002-253818 | Oct 1990 | JP |
| 04-180978 | Jun 1992 | JP |
| 06006736 | Jun 1992 | JP |
| 2011-169640 | Jun 1999 | JP |
| 2011-280921 | Oct 1999 | JP |
| 2000-024445 | Aug 2001 | JP |
| 2002-348651 | Dec 2002 | JP |
| 3477280 | Dec 2003 | JP |
| 2006-016470 | Jan 2006 | JP |
| 2006-036849 | Feb 2006 | JP |
| 2008-272534 | Nov 2008 | JP |
| WO2002024309 | Mar 2002 | WO |
| WO2002073728 | Sep 2002 | WO |
| WO2005090793 | Sep 2005 | WO |
| WO2011139894 | Nov 2011 | WO |
| WO2012032325 | Mar 2012 | WO |
| WO2016076994 | May 2016 | WO |
| Entry |
|---|
| U.S. Appl. No. 15/233,617, filed Aug. 10, 2016, Johnson et al. |
| U.S. Appl. No. 15/233,623, filed Aug. 10, 2016, McMahon et al. |
| U.S. Appl. No. 15/233,631, filed Aug. 10, 2016, Marshall et al. |
| U.S. Appl. No. 15/233,640, filed Aug. 10, 2016, Nagavarapu et al. |
| U.S. Appl. No. 15/284,960, filed Oct. 4, 2016, Fowler et al. |
| U.S. Appl. No. 15/284,973, filed Oct. 4, 2016, Fowler et al. |
| U.S. Appl. No. 15/284,982, filed Oct. 4, 2016, Fowler et al. |
| U.S. Appl. No. 16/252,975, filed Jan. 21, 2019, Krishna Nagavarapu et al. |
| U.S. Appl. No. 16/258,266, filed Jan. 25, 2019, Barnes et al. |
| U.S. Appl. No. 16/263,940, filed Jan. 31, 2019, Johnson. |
| U.S. Appl. No. 62/783,766, filed Dec. 21, 2019, Fulton et al. |
| ExxonMobil Research and Engineering and QuestAir (2008) “A New Commercialized Process for Lower Cost H2 Recovery—Rapid Cycle Pressure Swing Adsorption (RCPSA),” Brochure, 4 pgs. |
| Farooq, S. et al. (1990) “Continuous Countercurrent Flow Model for a Bulk PSA Separation Process,” AIChE J., v36 (2) p. 310-314. |
| FlowServe (2005)“Exceeding Expectations, US Navy Cuts Maintenance Costs With Flowserve GX-200 Non-Contacting Seal Retrofits,” Face-to-Face, v17.1, 8 pgs. |
| GE Oil & Gas (2007) “Dry Gas Seal Retrofit,” Florene, Italy, www.ge.com/oilandgas, 4 pgs. |
| Hopper, B. et al. (2008) “World's First 10,000 psi Sour Gas Injection Compressor,” Proceedings of the 37th Turbomachinery Symosium, pp. 73-95. |
| Kikkinides, E. S. et al. (1995) “Natural Gas Desulfurization by Adsorption: Feasibility and Multiplicity of Cyclic Steady States,” Ind. Eng. Chem. Res. V. 34, pp. 255-262. |
| Rameshni, Mahin “Strategies for Sour Gas Field Developments,” Worley Parsons-Brochure, 20 pgs. |
| Reyes, S. C. et al. (1997) “Frequency Modulation Methods for Diffusion and Adsorption Measurements in Porous Solids,” J. Phys. Chem. B. v101, pp. 614-622. |
| Ruthven, D. M. et al. (1996) “Performance of a Parallel Passage Adsorbent Contactor,” Gas. Sep. Purif., vol. 10, No. 1, pp. 63-73. |
| Stahley, J. S. (2003) “Design, Operation, and Maintenance Considerations for Improved Dry Gas Seal Realiability in Centrifugal Compressors,” Dresser-Rand, Tech. Paper 134, 15 pages. |
| Suzuki, M. (1985) “Continuous-Countercurrent-Flow Approximation for Dynamic Steady State Profile of Pressure Swing Adsorption” AIChE Symp. Ser. v81 (242) pp. 67-73. |
| Number | Date | Country | |
|---|---|---|---|
| 20170341011 A1 | Nov 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62343426 | May 2016 | US |
