Patent Grant
9034078
Provided is a parallel channel adsorbent contactor apparatus and system along with swing adsorption processes related thereto. More particularly, provided are one or more adsorbent contactors of stacked modules, which are loaded together in a swing adsorption vessel. The fabrication, use and regeneration of the swing adsorption vessel is also described to enhance the process.
Gas separation is utilized in many industries and can typically be accomplished by passing a mixture of gases over an adsorbent material in an adsorbent contactor that preferentially adsorbs more readily adsorbed components relative to less readily adsorbed components of the mixture. One type of gas separation technology is swing adsorption. For example, the pressure-swing adsorption (PSA) process adsorbs impurities from a gaseous stream into an adsorbent material in one step and releases the impurities in a subsequent step of a cycle. As another example, the temperature-swing adsorption (TSA) process, which may include PSA process steps, utilizes heating and cooling to enhance the effectiveness of this gas purification.
The use of the swing adsorption hardware may involve large diameter beds to minimize the number of total beds for any given application. However, manufacture and installation of large diameter beds is a difficult engineering problem, which often results in a compromise design at a smaller diameter. As a result multiple beds are often needed to achieve the same process goal. This typically results in greater expense and a larger equipment footprint.
Conventional swing adsorption vessels contain a plurality of individual monolith adsorbent contactors within a cylindrical vessel. The monolith contactors have multiple substantially parallel gas flow channels running along the longitudinal axis of the contactor, with an adsorbent material lining the walls of the open channels. Various engineering problems limit the flow through capacity of such adsorption vessels. For example, larger contactors often provide unintentional and undesirable gaseous stream paths in regions between adjacent contactors. This creates a significant problem because it is difficult to maximize the monoliths process area, while providing a robust mechanical support and hold-down structure aimed at retaining the monoliths in place during the unit operating cycles.
These problems may be further complicated by the swing adsorption process. For example, TSA processes have to overcome substantial challenges in designing equipment to achieve these process needs. Some of the challenges include: (a) rapid cycling of pressure; (b) rapid cycling of temperatures; (c) high area density requirements; and/or (d) forming sufficient microchannels with sufficient adsorbent material. Accordingly, there remains a need in the art for monolith designs that mitigate at least the above-mentioned problems, especially those associated with undesirable gaseous steam paths between contactors.
In one embodiment, a method of fabricating an adsorbent contactor is described. The method comprises obtaining two or more plates, wherein each of the two or more plates have a plurality of gaseous openings and at least one utility fluid opening; aligning the two or more plates, wherein the plurality of gaseous openings are substantially oriented along a common axis for each of the plurality of gaseous openings; diffusion bonding the aligned plates to form a module; and wash coating the plurality of gaseous openings within the module with an adsorbent material. The method may also include photo-chemical etching the two or more plates to form the plurality of gaseous openings and wherein diffusion bonding involves applying a substantial and uniform pressure across the plates inside an oven heated to approximately 70% of the melting point of the plate material.
In yet another embodiment, a method of fabricating a swing adsorption vessel is described. The method comprises obtaining two or more plates, wherein each of the two or more plates have a plurality of gaseous openings and at least one utility fluid opening; aligning the two or more plates, wherein the plurality of gaseous openings are substantially oriented along a common axis for each opening; diffusion bonding the aligned plates to form a module; and wash coating the plurality of gaseous openings within the module with an adsorbent material; and disposing the module within a housing. The method may include repeating the method to provide another module and stacking the modules, wherein the plurality of gaseous openings of each of the modules are substantially oriented along the common axis for each opening.
A method of processing a gaseous stream to remove contaminants, comprising: a) passing a gaseous stream through the swing adsorption vessel to remove contaminants from the gaseous stream, wherein the swing adsorption vessel has a plurality of stacked modules having a plurality of gaseous openings with an adsorbent material disposed within the plurality of gaseous openings and configured to adsorb at least a portion of the contaminants in the gaseous stream, and wherein each module is formed from two or more plates that are diffusion bonded together; b) passing a utility fluid through a swing adsorption vessel, wherein the plurality of stacked modules have at least one utility fluid opening and wherein the utility fluid and the gaseous stream are maintained separate from each other; c) stopping the flow of the gaseous stream through the swing adsorption vessel; and d) performing one or more of a depressurization step, a blow-down step, and a repressurization step. The method may include e) determining whether production is complete; f) if production is not complete; repeating steps a) to e); and g) if production is complete, regenerating the adsorbent material in the swing adsorption vessel. Further, the method may include regenerating the adsorbent material in the swing adsorption vessel, which includes removing the swing adsorption vessel from operation; removing the adsorbent contactor from the swing adsorption vessel; separating the plurality of stacked modules; removing the adsorbent material from each of the modules; disposing adsorbent material within the plurality of gaseous openings; and reassembling the plurality of stacked modules into the swing adsorption vessel.
In one or more embodiments, the method may include combining equipment with the adsorption contactor or module disposed within a housing to form the swing adsorption vessel. The method may include securing one or more baffles between at least one of the modules to manage the flow path of the utility fluid through the modules; securing one or more manifolds between at least one of the modules to manage the flow path of the utility fluid through the modules; securing one or more baffle arrangements to an inlet nozzle and an outlet nozzle, respectively, to provide a utility fluid flow path into one module and out of the one module or another module.
In one or more embodiments, the apparatus may be further defined to enhance operation. For example, the adsorbent contactor may include five to fifty modules within a stack or may include ten to twenty modules in a stack. In another embodiment, the plurality of gaseous openings of the module may be substantially oriented along the common axis that is in a direction perpendicular to the diffusion-bonded interfaces between the two or more plates. Further, in other embodiments, the at least one utility fluid opening of the module are substantially oriented along the common axis that is in a direction parallel to the diffusion-bonded interfaces between the two or more plates. In certain embodiments, the module has a high area density in the range of 1200 to 4000 m2/m3, in the range of 1500 to 3500 m2/m3, or in the range of 2000 to 3000 m2/m3. Also, in other embodiments, the module may have a thickness in the range of 20 mm to 200 mm.
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.
Monolith adsorbent contactors are defined herein is a subset of adsorbent contactors comprising structured (engineered) adsorbents in which substantially parallel flow channels are incorporated into the adsorbent structure. These flow channels may be formed by a variety of means, including extruded ceramic monoliths, bundles of hollow fibers, spiral wound adsorbent layers, stacked layers of adsorbent sheets with and without spacers, stacking plates and/or modules and other methods. In addition to the adsorbent material, the structure may contain items such as, but not limited to, support materials, heat sink materials, void reduction components, and other materials. Exemplary contactors are described in U.S. Patent App. Pub. No. 2008/0282892, which is incorporated by reference herein.
The present techniques are directed to an enhanced adsorbent contactor for use in swing adsorption processes, which adsorbent contactors contain a plurality of flow channels. Further, these contactors may also contain 20 volume percent (vol. %) or less, preferably 15 vol. % or less, more preferably 10 vol. % or less, and most preferably 5 vol. % or less of their open pore volume in pores in the mesopore and macropore size range. The term “adsorbent contactor” as utilized herein includes both structured and unstructured adsorbent contactors. The preferred contactors of the present disclosure are a type of structured adsorbent contactor entitled herein as “parallel channel contactors” for use in thermal swing adsorption (TSA) and various types of pressure swing adsorption processes including conventional pressure swing adsorption (PSA), and partial pressure swing or displacement purge adsorption (PPSA) technologies. These swing adsorption processes can be conducted with rapid cycles, in which case they are referred to as rapid cycle thermal swing adsorption (RCTSA), rapid cycle pressure swing adsorption (RCPSA), and rapid cycle partial pressure swing or displacement purge adsorption (RCPPSA) technologies. The term swing adsorption processes is taken to include all of these processes (i.e. TSA, PSA, PPSA, RCTSA, RCPSA, and RCPPSA) including combinations of these processes. Such processes involve efficient contact of a gas mixture with a solid adsorbent material. It should also be noted that unless otherwise noted herein or by reference to specific “geometric shapes” (in which case apply only to structured adsorbent contactors), that all preferred embodiments as described in this application, such as, but limited to, contactor voidages, separation components and efficiencies, operating conditions, preferred materials, etc., apply to both structured and unstructured adsorbent contactors of the present techniques as described herein. Other related applications in the technical area include Intl. Patent Application Nos. 2012/026797; 2012/026799; 2012/026801; 2012/026802; 2012/026803; and 2012/0267804 each of which is herein incorporated by reference in its entirety.
As noted above, the PSA process involves removing impurities (e.g., CO2, H2S) in a gaseous stream (e.g., a natural gas stream) are adsorbed into an adsorbent material (e.g., Zeolite) under high pressure. This step is followed by a depressurization step in which the impurities are released from the adsorbent material into a tail gas stream. This process is repeated through rapid cycles, which is roughly, once every 10 to 20 seconds (sec) to remove these impurities from the gaseous stream.
The PSA process for Advanced Kinetics Separation (AKS) has been demonstrated to remove CO2 from hydrocarbon containing streams (e.g., natural gas streams). However, this process is limited in its effectiveness in removing H2S from such streams. As such, PSA alone is only able to handle certain fields with a limited amount of H2S. In fact, some of the gas production streams contain up to 22% (by mass) of H2S, which has to be decreased to several parts per million (ppm) in the purified stream for certain processes.
Accordingly, as the PSA does not appear to provide enough H2S removal, other processes may be utilized, such as TSA and/or other scrubbers. Conventional processes typically involve scrubbers (e.g., Amine systems) to remove the H2S contaminates. These other systems require more energy as compared to a TSA process along with greater plot space and equipment compared to the TSA process.
The TSA process involves a heating step (e.g., during removal of impurities from adsorbent material, which is typically at a lower pressure) and a cooling step (e.g., prior to adsorption of impurities into adsorbent material, which is typically at a higher pressure). This heating and cooling of the exchanger substantially enhances effectiveness of this gas purification as compared to a PSA process without the temperature swing. The TSA process is also more beneficial in removing H2S from the gas stream for which PSA alone is inadequate. For this process, the temperature swing occurs inside of the PSA cycle at low pressure. Other related applications in the technical area include U.S. Patent Application Pub. Nos. 20080314244; 20080282888; and 20080314245, each of which is herein incorporated by reference in its entirety.
However, TSA processes have to overcome substantial challenges in designing equipment to achieve these process needs. As a specific example, some of the challenges include: (a) rapid cycling of pressure (from 1 bar to 85 bar, for example), (b) rapid heating and cooling requirements (each phase being about 20 seconds (sec) in duration), (c) need a high area density (e.g., in the range of 1200 to 4000 m2/m3, in the range of 1500 to 3500 m2/m3, or in the range of 2000 to 3000 m2/m3) to minimize thermal mass through the use of microchannels, (d) wash-coating techniques to apply a very thin and uniform layer of adsorbent in micro-channels, and/or (e) maximizing the depth of micro-channels to carry out wash-coating. Currently it is challenging to coat the inside of the small channels to lengths greater than 2 inches (in.) (50 millimeters (mm)), or even greater than 6 in. (150 mm).
Accordingly, in one or more embodiments, a diffusion-bonded exchanger design with micro-channels may be utilized to enhance the process. However, this diffusion-bonded exchanger design has several limitations. For example, these limitations include: (a) the channel length is generally greater than the current maximum limitation of two-inch (50 mm) depth; (b) the micro-channels have a semi-circular cross-section that is less conducive to high-quality wash-coating methods, and (c) the area density is less than 1000 m2/m3, which is significantly less than 1200 to 4000 m2/m3 provided by the present techniques, discussed further below.
The present techniques relate to an enhanced swing adsorption system. This system includes the fabrication of an adsorbent contactor and/or swing adsorption vessel, use of such vessel and regeneration of such vessel. The swing adsorption vessel may include an adsorbent contactor formed from various plates and/or modules (e.g., stack of modules and/or plates). These plates and modules may include gaseous channels for a gaseous stream passing through at least a portion of the adsorbent contactor and utility fluid channels for a utility fluid passing through at least a portion of the adsorbent contactor. The gaseous channels may be utilized to remove contaminants from a gaseous stream (e.g., natural gas stream) during an adsorption step and release the contaminants during regeneration steps (e.g., depressurization steps, purge steps and/or blow down steps). The utility fluid channels may be utilized to pass a utility fluid (e.g., water) to heat and cool the modules.
There are several benefits of the present techniques over the prior art. For example, the use of thin plates in the fabrication process provides flexibility forming the adsorbent contactor (e.g., the size and direction of the openings) and the associated dimensions of the adsorbent contactor (e.g., the size of the adsorbent contactor is not limited by material or fabrication techniques, as it is a modular configuration). In particular, the fabrication technique may provide smaller opening depths of bonded plates (e.g., the channels in the modules may be in the range from 1 inch to 6 inches, or 1 inch to 2 inches), which provide flexibility in the process for applying the adsorbent material. Further, the method may involve a specific sequence to further enhance the fabrication of the absorbent contactor. As an example, the gaseous openings may be formed prior to diffusion-bonding of the different thin plates. Then, a wash coating process may be applied following the diffusion-bonding to limit any potential damage to the adsorbent material. Also, the fabrication may provide additional flexibilities with the spacing of openings to further enhance the thermal efficiencies and the openings may be oriented parallel or perpendicular to the diffusion bonding. Moreover, the modular arrangement provides a simplified technique for regeneration of the adsorbent material, which may be performed once the adsorbent material has exceeded its use.
The structure of parallel channel contactors, including fixed surfaces on which the adsorbent or other active material is held, provides significant benefits over previous conventional gas separation methods, such as vessels containing adsorbent beads or extruded adsorbent particles. “Parallel channel contactors” are defined herein as a subset of adsorbent contactors comprising structured (engineered) adsorbents in which substantially parallel flow channels are incorporated into the adsorbent structure. These flow channels may be formed by a variety of means, many of which are described herein and in addition to the adsorbent material, the adsorbent structure may contain items such as, but not limited to, support materials, heat sink materials, void reduction components, etc., which are described more fully herein.
The adsorbent contactor of the present techniques can be made from any suitable material that is able to withstand the operating conditions and environment of their intended use, preferably swing adsorption conditions. Such conditions include temperatures up to 300° C. or up to 350° C. and pressures up to 1200 pounds per square inch absolute (psia) (8274 kilo Pascal absolute (kPaa)). Preferably, the temperature is in the range of 30° C. to 350° C. or even in the range of 30° C. to 150° C.
In certain embodiments, the adsorbent contactor may be five to fifty modules stacked together or even 10 to 20 modules stacked together. Each module may have a high area density in the range of 1200 to 4000 m2/m3, in the range of 1500 to 3500 m2/m3, or in the range of 2000 to 3000 m2/m3. Further, the module has thickness in the range of 20 mm to 200 mm. The present techniques can be better understood with reference to the
To pass a gaseous stream through the adsorbent contactor 102, a gas inlet portion 110 and a gas outlet portion 112 may be formed in the housing 104. The gaseous stream may flow through the gas inlet portion 110 into the channels formed through the adsorbent contactor 102 and be conducted away from the adsorbent contactor 102 via the gas outlet portion 112. The channels in the adsorbent contactor 102 are the space formed to provide a passage for gaseous flow through the adsorbent contactor 102. The term “space” means a region or volume, which may be bounded by one or more objects.
For certain applications, a utility fluid (e.g., water) may also be passed through the swing adsorption vessel 100. To pass the utility fluid through the adsorbent contactor 102, a utility inlet portion 114 and a utility outlet portion 116 may be formed in the housing 104. The utility fluid may flow through the utility inlet portion 112 into utility channels formed through the adsorbent contactor 102 and be conducted away from the adsorbent contactor 102 via the utility outlet portion 116. The utility channels in the adsorbent contactor 102 are the space formed to provide a passage for utility flow through the adsorbent contactor 102.
While the monolith adsorbent contactor 102 of the swing adsorption vessel 100 may be fabricated in a variety of different methods, the use of stacked modules may provide certain enhancements for the swing adsorption process. In particular, the formation of modules from various plates may be utilized to reduce leaks and provide gaseous openings that may be coated with adsorbent material. Such a design may be provided with a baffle arrangement. The local flow configuration may be a cross-flow (usually, less desirable), but the overall flow may be configured to be a parallel flow configuration.
The method 200 may begin at block 202 with two or more plates are formed. The formation of the plates may include forming or obtaining plates having a predetermined thickness, cutting along the outer boundary using laser machine or a shearer, and forming (e.g., drilling, etching or sintering) openings into the plates to provide the specific pattern for the configuration, and other fabrication steps to fabricate the plates. The thickness of the plates may depend upon the method of forming the openings (e.g., the drilling process or sintering process). This drilling process may include (a) photo-chemical etching (PCE), (b) electrical-discharge machining (EDM), (c) laser-drilling, and (d) stamping, while the sintering process, which does not involve drilling, forms the openings via a mold (in the form of precisely aligned pins) used for this process. Preferably, the PCE process may be utilized as it is more reliable and an economical approach. Once the plates are formed, two or more plates may be aligned into a module, as shown in block 204. The alignment of the two or more plates may include stacking one or more types of plates into a stack and/or adjusting the openings of the plates to be substantially oriented with each other within a specific threshold. The adjusting the openings of the plates may include inserting a pin through one or more openings and/or inserting the plates into a container that aligns edges of the plates with each other. Then, the aligned plates are diffusion bonded to each other to form a module, as shown in block 206. The diffusion bonding process generally involves the application of a substantial and uniform pressure across the plates inside an oven heated to approximately 70% of the melting point of the plate material. In other words, the temperature required depends on the metallurgy, while the pressure depends on the metallurgy involved as well as the plate thicknesses involved and the needed bond strength. The diffusion-bonding process has been a well-known art in the industry.
With the module formation stage complete, the modules are formed into a stack of modules (e.g., adsorbent contactor). At block 208, the modules may be wash-coated with an adsorbent material. The wash coating process may include dip coating, spray coating or electro-chemical deposition, and other suitable techniques. Then, at block 210, the modules are stacked to form the adsorbent contactor. The stacking of the adsorbent contactors may include forming the seal mechanisms for the stack of modules. The seal mechanism may include machining one or more of the modules to form grooves for a gasket, laser welding the modules into the stack of modules. As may be appreciated, the forming the seal mechanism may be performed prior to the wash coating for certain embodiments. The stacking the modules may include aligning the modules to have the openings of the modules concentrically disposed along a common axis through the openings of the modules. Further, each module may be configured to have substantially similar total thickness without any deformations or warping. Otherwise, the module may be machined on a milling machine with a small cut to achieve the high tolerances for each module. Then, the plates should be cleaned to remove any metal shavings. The shavings may be removed by using a high-pressure jet of air or, preferably, nitrogen or steam.
With the stack formation stage complete, the swing adsorption vessel is formed. At block 212, equipment may be combined with the adsorption contactor to form the swing adsorption vessel. As an example, the adsorption contactor may be disposed within a housing, the housing may be secured to maintain certain pressures, and conduits and/or lines may be fluidly connected to the housing. Further, baffles may be secured to between certain modules to manage the flow path of the certain streams, such as the utility fluid. At the bottom and at the top of the vessel, special baffle arrangements (not shown) may be utilized to facilitate the inlet and outlet nozzles, respectively, away from the shell girth flanges and to allow utility fluid flow in and out of the bottom-most and top-most modules. On the other hand, inlet and outlet nozzles may be provided on the bottom and top plates 507 and 506. In another example, the adsorbent contactor may be disposed between two pressure plates. Then, manifolds may be coupled to the modules to provide fluid flow path through one or more modules of the adsorbent contactor.
Beneficially, this fabrication method provides various enhancements. For example, the embodiments allow efficient use of modules of limited length. This provides flexibility in the fabrication process. For example, if a wash-coating process is utilized, it should be subsequent to the formation of the modules and/or stack of modules.
Also, the openings in the plates are formed prior to diffusion bonding. As a specific example, the wash-coating process may follow the diffusion-bonding processes because the coatings may be damaged by high temperatures in the diffusion-bonding process, as the wash-coating of channels having a small diameter may be limited to only a few inches so conventional diffusion-bonded heat exchangers designs for these applications is problematic. If the wash-coating depth within the channels can be increased substantially, the number of modules can be decreased thereby decreasing the number of gaskets needed; this may lessen potential leaks. However, the number of gaskets needed may be determined by the wash-coating limitations. For example, if a wash-coat is applied to a depth of 6 inches (in.) instead of 2 in., the number of gaskets may be decreased by a factor of about three and thereby decrease the leak probability by a factor of three. This aspect may also include wash-coating of modules to provide a layer of adsorbent material in each gaseous opening. This may be achieved prior to assembly of the modules into the swing adsorption vessel (e.g., the exchanger unit).
Also, this modular arrangement provides a technique of potential regeneration of the adsorbent material, which may be at least once a year or at least once every two years. To regenerate the modules, high-pressure steam may be applied across the top and bottom surfaces of the modules. Thus, this configuration provides a mechanism for regeneration.
Further, the fabrication method provides flexibility in the configuration of the openings, which may be in the same direction as the pressure force used in the diffusion bonding process. Conventional diffusion bonded heat exchangers have both sets of channels perpendicular to the pressure force during diffusion bonding, which results in a larger metal thickness being required to withstand those pressures. In the configuration outlined in this invention, the distance between any two pairs of openings has no impact on the pressure-integrity concern, but the distance from the edge of the first row of gaseous openings to the edge of the utility fluid opening is a factor; this region involves diffusion-bonding with high reliability; the integrity of this region may be improved by providing a thin layer of brazing material on the inside surfaces of the channels for the utility fluid; this would be achieved following the diffusion-bonding process and the machining of gasket grooves; such an approach is readily feasible as the brazing temperature is generally much less than that required for diffusion bonding. In the present techniques, the pressure-containing forces may be applied in a direction perpendicularly to the diffusion-bonded interfaces; such an arrangement is less likely to lead to de-bonding of these interfaces that may otherwise lead to leaks. On the other hand, if a conventional diffusion-bonded design is used to fabricate a two-inch deep module (to satisfy wash-coating requirements), all of the bonded interfaces may be arranged in the vertical direction (e.g., considering the apparatus outlined in
As another benefit, the dense spacing of the openings may reduce the time for heat transfer; this results from the reduced distances over which heat has to be conducted as well as from the reduced “thermal mass” resulting from a reduction in metal volume. This aspect is useful because rapid-cycle processes are sensitive to the heat transfer.
Finally, the present techniques provide a mechanism for regeneration of the modules, which is not provided from conventional techniques. For example, the modules or sub-modules may have the adsorbent material removed once it has become ineffective. Then, the new adsorbent material may be applied to the sub-modules and/or plates to reuse the underlying structure. This regeneration of the modules may reduce equipment and operational costs, which includes one embodiment as noted below in
As an example,
In this process the swing adsorption vessel is removed from operation, as shown in block 222. The removal from operation may include closing valves to prevent flow of the gaseous stream and/or utility fluid stream to the vessel, for example. Then, the adsorbent contactor is removed from the swing adsorption vessel, as shown in block 224. This removal of the adsorbent contactor may include removal of conduits, baffles, manifolds, housing and other equipment that is disposed around or associated with the adsorbent contactor. The removal process may include transporting the adsorbent contactor from the vessel to another location for regeneration.
Once the adsorbent contactor is removed from the swing adsorption vessel, the adsorbent contactor may be regenerated. At block 226, the modules and/or plates of the adsorbent contactor may be separated. The separation may include removing a portion of the module or otherwise removing the bonding between the plates and/or modules. Then, the adsorbent material is removed from the plates and/or modules, as shown in block 228. The removal of the adsorbent material may include hydro-blasting the modules and/or plates to remove the adsorbent, heating the modules or plates to remove the adsorbent material and/or other suitable methods to separate the adsorbent material from the plates or modules.
Following the removal of the old adsorbent material, the plates or modules may be taken through similar steps in the fabrication process of
In operation, the swing adsorption vessel may be useful in adsorptive kinetic separation processes, for development and production of hydrocarbons, such as gas and oil processing. Particularly, the provided apparatus and system may be useful for the rapid, large scale, efficient separation of a variety of target gases from gas mixtures. In such processes, the swing adsorption vessel may be utilized to withstand the large forces applied to the adsorbent contactor (e.g., stack of plates or modules) during rapid cycle swing adsorption processes. In particular, the apparatus may be utilized in a TSA processes that utilizes lower temperatures to adsorb gases within the pore structure or free volume of an adsorbent material. By cyclically swinging the temperature of an adsorbent bed, the TSA processes can be used to separate gases in a mixture when used with an adsorbent that is selective for one or more of the components of a gas mixture. This process is further enhanced by the utility fluid utilized in this apparatus.
As an example,
To begin, the swing adsorption vessel is operated in a production mode. During the production mode, a utility fluid and a gaseous stream are provided to the swing adsorption vessel during an adsorption step, as shown in block 242. This providing may include passing the gaseous stream through the gaseous openings to remove contaminates from the gaseous stream, and passing the utility fluid through the utility openings. Each of these streams may be maintained separate from each other to prevent mixing of the streams, but may utilize the modules to transfer heat from one stream to the other, depending on the temperature differences of the step in the cycle. The gaseous stream may include natural gas stream with the adsorption material being configured to remove contaminants and heavy hydrocarbons, i.e., hydrocarbons having at least two carbon atoms. The adsorbent material may be configured to remove contaminants for dew point control, sweetening/detoxification, corrosion protection/control, dehydration, heating value improvements, conditioning, and purification. Exemplary “not to exceed” product (or “target”) gas specifications include: (a) 2 volume percent (vol. %) CO2, 4 ppm H2S, (b) 50 ppm CO2, 4 ppm H2S, or (c) 1.5 vol. % CO2, 2 ppm H2S. At block 244, the gaseous stream is stopped. This may include diverting the gaseous stream to another swing adsorption vessel and/or closing a valve to hinder the flow of the gaseous stream to the swing adsorption vessel.
During the non-production mode, one or more depressurization/desorption steps, one or more blow-down steps, and one or more repressurization steps may be utilized to remove the contaminates within the swing adsorption vessel. At block 246, one or more depressurization steps are performed. The depressurization steps may be stored into individual tanks for the subsequent repressurization steps. Then, at block 248, one or more blow-down steps may be performed. Then, one or more repressurization steps may be performed in block 250. The repressurization steps may utilize gas stored in individual vessels from one or more of the depressurization steps.
Then, a determination is made whether the production is complete, as shown in block 252. If the production is not complete, the method may repeat the process by providing a utility fluid and a gaseous stream to the swing adsorption vessel during an adsorption step, as shown in block 242. If the production is complete, the production is stopped and the swing adsorption vessel may be regenerated, as shown in block 254. The stopping of the production may include adjusting valves to prevent fluids from entering the swing adsorption vessel. The regeneration may include the regeneration method as noted above for
To manage the flow of fluids through the monolith adsorbent contactor, the channels may be provided by forming holes and/or voids within different layers and/or modules of the adsorbent contactor. As an example,
In the top plate 306 of the adsorbent contactor, the one or more gaseous holes 302 and utility fluid hole 304 may be formed into a specific pattern or configuration. The one or more gaseous holes 302 may have diameter in the range 0.2 mm to 5 mm or in the range 0.3 mm to 1 mm or in the range 0.3 mm to 2 mm. As a specific example of the configuration, the different gaseous openings 302 may be formed in the top plate in a parallel configuration. In this configuration, eight rows of openings 302a (which are divided by a line of symmetry 312) are located in an interior region of the top plate 306, while four rows of openings 302b are disposed adjacent to an edge region. These openings 302a and 302b are separated by the utility fluid opening 304. In this configuration, the utility fluid opening 304 may be utilized to heat and/or cool the four rows of openings 302a and 302b adjacent to the utility fluid opening 304. The number of rows of openings that is associated with the utility fluid opening may be subject to an optimization calculation based on heat conduction time in the solid, which is dependent on the opening diameter. The diameter of the openings 302a and 302b and the pitch of the openings 302a and 302b may, preferably, be less than a millimeter, while the width of the utility fluid opening 304 may be less than or equal to 2 millimeters (mm). The dimensions of the openings 302a and 302b provide a high surface area for the gaseous stream (e.g., 1000 to 4000 m2/m3). In this manner, the area density may be maximized to increase the effectiveness of the exchanger (e.g., a reduced “thermal mass”), while also minimizing the overall cost.
To further enhance the flow of the gaseous steam, different gaseous opening configurations may be utilized for the gaseous channels in the plates or modules. As an example,
In the top plate 356 of the adsorbent contactor, the one or more gaseous holes 352 and utility fluid hole 354 may be formed into a specific pattern or configuration. As a specific example in this embodiment, the different gaseous openings 352 may be formed in the top plate. 356 in an alternate triangular arrangement or configuration. In this configuration, two rows of openings 352b (which are separated from the gaseous openings 352a by a line of symmetry 362) are located in an interior region of the top plate 356, while two rows of gaseous openings 352c are disposed adjacent to an edge region. The utility fluid opening 354b is disposed between these openings 352b and 352c. In this configuration, the utility fluid opening 354b may be utilized to heat and/or cool the four rows of openings 352b and 352c adjacent to the utility fluid opening 354b. The number of rows of openings that is associated with the utility fluid opening may be subject to an optimization calculation based on heat conduction time in the solid, which is dependent on the opening diameter. The utility fluid opening 354a may be utilized to heat and/or cool the four rows of openings 352a and another not shown adjacent to the utility fluid opening 254a.
Beneficially, this configuration provides the openings for the gas flow are in the same direction as the imposed pressure force used in the diffusion bonded process. This allows the openings to be spaced very close together and reduces the time for heat transfer, which is sensitive in the rapid-cycle process operation. As noted above, conventional diffusion bonded heat exchangers have both sets of channels perpendicular to the pressure force during diffusion bonding, which results in a larger metal thickness being required to withstand those pressures. In this configuration, the distance between any two pairs of openings does not factor into the pressure-integrity concern, but the distance from the edge of the first row of gaseous openings to the edge of the utility fluid opening is a factor; as this region involves diffusion-bonding with high reliability.
To view the channels formed by these various openings, the adsorbent contactor may be formed by one or more plates and/or one or more modules (e.g., two or more combined plates) that are stacked together. As an example,
In certain embodiments, another type of plate may be utilized with the plates noted above to provide fluid flow for the utility fluid. This third type of plate may be similar to the plates 404 with utility fluid openings 406, but areas near the edge area may be removed to provide direct access into the utility fluid opening. As an example, following assembly (with very high tolerance) and diffusion-bonding of the thin plates into a module, a portion of the plates may be milled to reveal the utility fluid opening. Following the diffusion-bonding step to form a module, a thin layer of high-temperature solder may be provided on the surfaces forming the utility fluid channels.
As an alternative embodiment,
As shown in this figure, the utility fluid openings 456 that form the utility fluid channels are made of grooves or openings that may be machined or etched on the plate surface. These grooves are made in halves, which differ for the different plates 454 and 455 (e.g., one half on one plate and the other on the adjacent plate). By matching the two openings from the plates 454 and 455, a larger flow area is provided, which may be useful for thinner plates. For thicker plates, a single groove thickness may suffice for the utility fluid channel. As an example, if the plate is about 0.4 mm thick, the utility fluid opening has thickness may be as small as 2 plates×0.4 mm thickness×0.5 (fraction of plate thickness for channel)=0.4 mm, which is generally too thin; for a utility fluid such as water. Accordingly, the utility fluid opening should have a thickness of 1 mm or larger to avoid excessive pressure drop. That is, for thinner plates, the utility fluid opening may be limited by the available design pressure drop.
The stacking of the plates may also involve different aspects to further enhance the process. For example, in one or more embodiments, two or more plates or modules may be diffusion-bonded to provide a greater thickness for the final absorbent contactor and to seal the plates together in an effective manner. The thickness of this plate or module may be determined by the wash-coating-depth limitations or other processing steps. For thicker modules or plates, equipment interconnectivity may benefit from a deeper wash-coating ability. A thicker module (e.g., 150 mm or 6 in.) may provide easier attachment of the utility fluid (e.g., water) manifolds described below.
Further still, a mechanism for aligning the different plates may also be utilized to enhance the plate configuration. That is, each plate or module may include a locator members (e.g., locator pins or the like) to align a neighboring plate or module. These locator members may include extensions or notches that provide for alignment of the openings. As such, the locator members may be assembled together in the manner that the gas openings and/or utility fluid (e.g., water) are aligned with sufficient accuracy.
As another aspect, the plates or modules may be formed in a manner that a gasket may be utilized to seal the flow of fluids through the appropriate channels. Accordingly, one or more plates, such as the top and bottom plates or certain plates, may also include a recessed gasket seating areas. The recessed gasket seating areas may be formed through high-precision milling processes, such that the plates or modules may be assembled into a leak-tight heat exchanger unit.
As an example,
To compensate for thermal expansion and/or contraction, as well as to compensate for any dimensional differences that may otherwise not provide adequate leak-tightness, the swing adsorption vessel 500 may include a housing having an expansion joint 516 and a first housing section 518 and a second housing section 520. The expansion joint 516 may be disposed between the first housing section 518 and the second housing section 520 and be configured to expandable and contract along an axis, which may be substantially parallel with the stack of modules 502. The expansion joints, which are known in the art and are described by the Expansion Joints Manufacturers Association (EJMA), may be welded to the housing sections. These housing sections 518 and 520 may be utilized with the expansion joint 516 to provide a shell or barrier between locations external to an interior region formed by the housing and the plates 506 and 507. The housing may form a physical barrier for the utility fluid and/or the gaseous stream to maintain such fluid within the interior region, with the exception of provided passages. The utility fluid may enter and leave through the cylindrical walls of the housing sections 518 and/or 520 or through pressure plates 506 and/or 507. If the utility fluid stream penetrates through the cylindrical walls, baffle arrangements (not shown) should be utilized to accommodate flow into first module 502 at the bottom and at the top, respectively, for inlet and outlet.
To manage the flow of the gaseous stream through the swing adsorption vessel 500, various openings may be utilized to provide a flow path for the gaseous stream. For example, the first pressure plate 506 and a second pressure plate 507 may have machined slots (not shown) to provide a flow path for a gaseous stream through the first pressure plate 506 and a second pressure plate 507. The modules 502 may include channels 508 to provide a flow path for the gaseous stream through the modules 502. Gaskets 504 may also be disposed between the modules 502 to manage the flow of fluids between the modules 502. Overall leak tightness is achieved through the use of long bolts and nuts (not shown) across the two pressure plates 506 and 507 to apply sufficient compression of the gaskets 504.
To manage the flow of the utility fluid, gaskets 504 and baffles 514 (e.g., baffles 514a and 514b) are disposed at least partially between certain modules 502. The gaskets 504 hinder inter-mixing of gas and utility fluid within the modules 502, while the baffles 514 are utilized to manage the flow of the utility fluid through the modules, which may include a variety of different configurations. For example, the first baffle 504a may pass the utility fluid from a first module to a second module, as indicated by arrow 510. Then, the second baffle 504b may be utilized to pass the utility fluid from the second module to a third module, as indicated by arrow 512. Further, is should be noted that two types of gaskets may be utilized. These types of gaskets include: (a) the gaskets that are located between the modules as well as the top and bottom modules and the pressure plates (e.g., gaskets utilized to retain the gas within the modules), and (b) the gaskets that are located between the pressure plates and the shell girth flanges (e.g., the gaskets utilized to maintain the utility fluid within the vessel).
As a specific example, the swing adsorption vessel 500 may include diffusion bonded modules 502 formed from two or more plates, which may be formed into a stack of modules 502 that is 1 meter in height, as indicated by the dimension line 523. The modules may include gaseous openings 508 that have a diameter of 300 to 1000 micrometers and utility fluid openings (not shown) may have a height of 30 millimeters, as shown by dimension line 524. The openings may be provided along the entire edge surface of the module. Accordingly, the opening may be about 30 mm in height by about 960 mm in length. The horizontal dimension may be determined by the module size minus about 40 mm (hence, above shown 960 mm assumes a module size of 1 m (module width)×1 m (module depth)×50 mm (module height)).
This vessel may be configured to maintain a pressure up to or equal to 85 bar gauge. The vessel may be maintained within an enclosed housing to provide utility fluid flow path through the modules or may include a manifold and conduits to manage the flow of the utility fluid. As an example, the utility fluid and the gaseous stream may be operated at different pressures or pressures that are substantially similar. In particular, the pressure of the gaseous stream may vary during the different steps (e.g., within a range from 0 to 85 bar gauge (barg)), while the utility fluid may be at pressures from 0 to 10 barg (e.g., for water).
In certain embodiments, a gap (e.g., an “air gap”) may be provided between two adjacent modules 502. This gap may be provided by means of spacers or the like. Such a gap may be advantageous in some embodiments to provide a region that provides mixing of the gas streams and also minimizes flow maldistributions. The gaskets 504 may be configured to maintain separate flow for the gaseous stream and the utility fluid.
As another example,
However, in this embodiment, the manifolds 602, such as manifolds 602a and 602b, for example, are utilized instead of an enclosed housing and baffles. In this embodiment, each module 502 has at least one manifold 602 that is utilized to direct the utility fluid through the module 502. For example, this embodiment include an inlet manifold 602a, an outlet manifold 602d, and various return manifolds, such as manifolds 602b and 602c, which are disposed between adjacent modules. The inlet manifold 602a is configured to provide the utility fluid to the first module, while the return manifold 602b is provided to pass the utility fluid from the first manifold to a second manifold, as indicated by arrow 606. The return manifold 602c is configured to provide to pass the utility fluid from the second manifold to a third manifold, as indicated by arrow 608. This flow continues to the outlet manifold 602d, which is configured to conduct away the utility fluid from the swing adsorption vessel 600. The manifolds 602 may be welded to the module 502 and/or the manifolds 602 may be secured to the module 502 via studs, bolts or the like. The design shown in
To secure the manifolds to the modules, various techniques may be utilized. In particular, the manifolds may be welded to one or more modules based on the specific configuration. As an example,
As another example,
As an example, the extended plates 803 may be extended by about 25 mm (1 in.) around the outer periphery; this extension may be utilized for laser-welding to provide adequate sealing between the modules 802. The extended portion may serve as a lip seal that is formed by a variety of techniques, such as (a) using larger plates for the top and bottom regions of the module representing the lip-seal area, and/or (b) using the same size plates, but machine out the excess material leaving behind the lip seal portions. For example, in certain embodiments, the lip-seal may be removed, wash-coating may be regenerated, and lip seal re-welded thereby extending the useful life span of the modules. The weld 804 may be located at the end of the plates to minimize wastage during weld removal and re-welding.
In one or more embodiments, the swing adsorption vessel may be utilized to withstand the large forces applied to the adsorbent contactor (e.g., stack of plates or modules) during rapid cycle swing adsorption processes. Any number of contactors can be stacked together depending on the intended adsorbent bed height. The swing adsorption vessel may be useful in adsorptive kinetic separation processes, apparatus, and systems for development and production of hydrocarbons, such as gas and oil processing. Particularly, the provided processes, apparatus, and systems are useful for the rapid, large scale, efficient separation of a variety of target gases from gas mixtures.
The provided adsorbent contactors described above are useful in swing adsorption processes. Non-limiting swing adsorption processes 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 such as pressure/temperature swing adsorption.
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 (e.g., the higher the gas pressure, the greater the amount of gas readily-adsorbed). When the pressure is reduced, the adsorbed component is released, or desorbed.
PSA processes may be used to separate gases of a gas mixture because different gases tend to fill the micropore of the adsorbent to different extents. If a gas mixture, such as natural gas, is passed under pressure through a vessel containing a polymeric or microporous adsorbent that is more selective towards carbon dioxide than it is for methane, at least a portion of the carbon dioxide may be selectively adsorbed by the adsorbent, and the gas exiting the vessel may be enriched in methane. When the adsorbent reaches the end of its capacity to adsorb carbon dioxide, it is regenerated by reducing the pressure, thereby releasing the adsorbed carbon dioxide. The adsorbent is then typically purged and repressurized and ready for another adsorption cycle.
TSA processes rely on the phenomenon that gases at lower temperatures are more readily adsorbed within the pore structure or free volume of an adsorbent material compared to higher temperatures, i.e., when the temperature of the adsorbent is increased, the adsorbed gas is released, or desorbed. By cyclically swinging the temperature of an adsorbent bed, TSA processes can be used to separate gases in a mixture when used with an adsorbent that is selective for one or more of the components of a gas mixture.
Swing adsorption processes typically take place in a vessel containing one or more adsorbent beds. In multi-bed systems each bed may undergo a different step in an adsorption cycle, such as an adsorption step, one or more depressurization/desorption steps, one or more blow-down steps, and one or more repressurization steps. The flow of fluid to and from each bed is typically controlled by a valve, such as a poppet valve and/or a rotary valve assembly.
The provided processes, apparatus, and systems may be used to prepare natural gas products by removing contaminants and heavy hydrocarbons, i.e., hydrocarbons having at least two carbon atoms. The provided processes, apparatus, and systems are useful for preparing gaseous feed streams for use in utilities, including separation applications such as dew point control, sweetening/detoxification, corrosion protection/control, dehydration, heating value improvements, conditioning, and purification. Examples of utilities that utilize one or more separation applications include generation of fuel gas, seal gas, non-potable water, blanket gas, instrument and control gas, refrigerant, inert gas, and hydrocarbon recovery. Exemplary “not to exceed” product (or “target”) gas specifications include: (a) 2 vol. % CO2, 4 ppm H2S, (b) 50 ppm CO2, 4 ppm H2S, or (c) 1.5 vol. % CO2, 2 ppm H2S.
The provided processes, apparatus, and systems may be used to remove acid gas from hydrocarbon streams. Acid gas removal technology becomes increasingly beneficial as remaining gas reserves exhibit higher concentrations of acid gas, e.g., sour gas resources. Hydrocarbon feed streams vary widely in amount of acid gas, such as from several parts per million acid gas to 90 vol. % acid gas. Non-limiting examples of acid gas concentrations in natural gas from exemplary gas reserves include concentrations of at least: (a) 1 vol. % H2S, 5 vol. % CO2, (b) 1 vol. % H2S, 15 vol. % CO2, (c) 1 vol. % H2S, 60 vol. % CO2, (d) 15 vol. % H2S, 15 vol. % CO2, and (e) 15 vol. % H2S, 30 vol. % CO2. For these streams, the hydrocarbons may include remaining portions of the total volume of the stream.
An exemplary hydrocarbon treating apparatus is shown in
As may be appreciated, various other alternative embodiments may also be possible. For example, in another embodiment the adsorbent bed assemblies may be arranged in one or more skids, each of the skids containing two or more individual adsorbent bed assemblies. Multiple reciprocating (or poppet) valves may be arranged on the top and bottom of each vessel and connected via piping and headers above and below the adsorbent bed assemblies. For each individual adsorbent bed assembly, various feed piping may pass the gaseous feed stream to the adsorbent bed assembly and the product stream may be removed via the bottom piping. The feed gas enters and exhaust gas exits through the piping and valves on the top of the vessel. Product gas exits the adsorbent vessel through one of the valves and piping systems on the bottom of the vessel. While the individual bed support structures are fixed to the skid base, the adsorbent bed assemblies, which are noted in other figures, may be disposed into the bed support structure without being rigidly attached or securely fixed. Therefore, the entire adsorbent bed assembly can move freely within the bed support structure to accommodate thermal expansion or contraction of the piping and minimize stresses on the piping and valves.
One or more of the following Concepts A-O may be utilized with the processes, apparatus, and systems, provided above, to prepare a desirable product stream while maintaining high hydrocarbon recovery;
The processes, apparatus, and systems provided herein are useful in large gas treating facilities, such as facilities that process more than five million standard cubic feet per day (MSCFD) of natural gas, or more than 15 MSCFD of natural gas, or more than 25 MSCFD of natural gas, or more than 50 MSCFD of natural gas, or more than 100 MSCFD of natural gas, or more than 500 MSCFD of natural gas, or more than one billion standard cubic feet per day (BSCFD) of natural gas, or more than two BSCFD of natural gas.
Compared to conventional technology, the provided processes, apparatus, and systems require lower capital investment, lower operating cost, and less physical space, thereby enabling implementation offshore and in remote locations, such as Arctic environments. The provided processes, apparatus, and systems provide the foregoing benefits while providing high hydrocarbon recovery as compared to conventional technology.
Swing adsorption processes are all well known to those having ordinary skill in the art and they can be applied to remove a variety of target gases from a wide variety of gas mixtures. It is possible to significantly improve the recovery percentage of the light component of a gas mixture by use of the present invention. The “light component” as utilized herein is taken to be the species, or molecular component, or components that are not preferentially taken up by the adsorbent in the adsorption step of the process. Conversely, the “heavy component” as utilized herein is taken to be the species, or molecular component, or components that are preferentially taken up by the adsorbent in the adsorption step of the process. The total recovery of the light component achieved in the swing adsorption process can be greater than about 80 vol. %, more preferably greater than about 85 vol. %, even more preferably greater than about 90 vol. %, and most preferably greater than about 95 vol. % of the content of the light component introduced into the process. Recovery of the light component is defined as the time averaged molar flow rate of the light component in the product stream divided by the time averaged molar flow rate of the light component in the feedstream. Similarly, recovery of the heavy component is defined as the time averaged molar flow rate of the heavy component in the product stream divided by the time averaged molar flow rate of the heavy component in the feedstream.
The adsorbent contactors of the present disclosure may also contain a very low volume fraction of open mesopores and macropores. That is, the structured bed adsorbent contactors of the present invention contain less than about 20 vol. %, preferably less than about 15 vol. %, more preferably less than about 10 vol. %, and most preferably less than about 5 vol. % of their pore volume in open pores in the mesopore and macropore size range. Mesopores are defined by the IUPAC to be pores with sizes in the 20 to 500 angstrom size range. Macropores are defined herein to be pores with sizes greater than 500 angstroms and less than 1 micron. Because the flow channels are larger than 1 micron in size, they are not considered to be part of the macropore volume. By open pores we mean mesopores and macropores that are not occupied by a blocking agent and that are capable of being occupied, essentially non-selectively, by components of a gas mixture. Different test methods as described below are to be used to measure the volume fraction of open pores in a contactor depending on the structure of the contactor.
Open pore volume (in percent or volume percent) is defined herein as the volume of the pores in the adsorbent that are between 20 angstroms and 10,000 angstroms (1 micron) in diameter divided by the total volume of the contactor that is occupied by the adsorbent material including associated mesopores and macropores in the adsorbent structure. “Swept volumes” such as engineering flow channels as well as the volume occupied by any non-adsorbent material, such as but not limited to, support materials, blocking agents, thermal masses, etc., are not included in the amount of volume occupied by the adsorbent material.
Additional embodiments 1 to 35 are provided as follows:
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 61/697,169, filed Sep. 5, 2012, entitled APPARATUS AND SYSTEMS HAVING AN ADSORBENT CONTACTOR AND SWING ADSORPTION PROCESSES RELATED THERETO, the entirety of which is incorporated by reference herein.
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