Patent Grant
10016715
Provided are encased parallel channel adsorbent contactor apparatus and systems and swing adsorption processes related thereto. More particularly, provided are one or more encased adsorbent contactors which are loaded and sealed together in a swing adsorption vessel such that substantially the entire feed stream should pass into the channels of the contactors and not through unintended gaseous stream paths between contactors.
Gas separation is important in many industries and can typically be accomplished by flowing 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 of the more important types of gas separation technology is swing adsorption.
Users of swing adsorption hardware prefer to use 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.
There remains a need in the art for monolith designs that mitigate the above mentioned problems, especially those associated with undesirable gaseous steam paths between contactors.
Other related applications in the technical area include U.S. Patent Application Nos. 61/447,806, 61/447,812, 61/447,824, 61/447,848, 61/447,869, 61/447,835, and 61/447,877, each of which is herein incorporated by reference in its entirety.
Provided are encased parallel channel adsorbent contactor apparatus and systems and swing adsorption processes related thereto. Swing adsorption contactor systems include: a plurality of hollow rigid liners each having an inner surface and open axial ends, adjacent liners being fixedly connected to each other; a monolith adsorbent contactor being disposed within each liner, each monolith adsorbent contactor having an outer surface spaced from the inner surface of the liner; a bonding agent being disposed in the space between the outer surface of the monolith adsorbent contactor and the inner surface of the liner to form a seal to prevent gaseous flow in the space.
Also, in accordance with the present invention, a method of assembling a swing adsorption contactor system is provided that comprises the steps of: fixedly connecting a plurality of hollow rigid liners to each other, wherein each of the liners has an inner surface and open axial ends; placing a monolith adsorbent contactor within each liner, each monolith adsorbent contactor having an outer surface, wherein the placing step includes spacing the outer surface of each monolith adsorbent contactor from the inner surface of each liner; placing a bonding agent in the space between the outer surface of the monolith adsorbent contactor and the inner surface of the liner to form a seal to prevent gaseous flow in the space.
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, will 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, 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.
This invention relates to an enhanced swing adsorption contactor system. This system includes monolith adsorbent contactor liners and the installation of a plurality of the liners into a cylindrical vessel or an irregular shaped containment boundary, preferably a swing adsorption vessel. There are several benefits of the present invention over the prior art. For example, the swing adsorption vessels can be optimized overall by limiting the cross sectional area of non-process material. The present invention also provides a means of achieving both accurate and repeatable fabrication and installation results. Further, the internal mechanical support and hold-down structures for an assembly of lined monolith contactors of the present invention are also simplified. The undesirable stray gaseous stream paths between contactors of conventional assemblies are substantially eliminated. Another benefit of the present invention over the prior art is providing a cost effective robust means of anchoring the monolith contactors in a gaseous process environment. Still another benefit of the present invention is providing a direct scale-up relationship between a smaller demonstration unit and the full size commercial unit. An individual adsorbent monolith having a metallic liner can be equal in size for both given applications.
The lined monolith adsorbent contactors of the present invention can also be constructed to accommodate numerous geometric shapes without the need of relying on specialized fabrication tools, assembly techniques or industry know-how. The contactor liners of the present invention 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 100° C. and pressures up to 1200 pounds per square inch absolute (psia) (8274 kilo Pascal absolute (kPaa)). Stainless steels are the most preferred materials for use as liners of the present invention. The wall thickness of the liners of the present invention may be from about 3/32 to 3/16 inch (in) (0.02381 to 0.004762 meters (m)), preferably from ⅛ to ¼ in (0.003175 to 0.000625 m), and more preferably from 1/16 to ⅛ in (0.001587 to 0.003175 m). The liners of the present invention can be brake-bent from flat plate or can begin with commercially available shaped pipe with post fabrication steps.
This invention can be better understood with reference to the figures hereof.
The individual metallic liners can be deployed into an assembly fixture jig (not shown), which represents the inside geometry of the intended pressure boundary (e.g., which may be similar to the pressure vessel 11). The design shown in these figures (see
The bonding agent may be a polymer-based composition, e.g., thermoplastic and thermosets, adhesive compositions, such as contact adhesives or hot melt adhesives, rubber, i.e., natural or synthetic, elastomers, or combination thereof. Also, the bonding agent may include a heavy petroleum wax (e.g. Apiezon), bitumen, asphalt, etc. and the like.
Once the assembly is removed from the fixture jig, it can be concentrically positioned in the pressure vessel. The annular gap between the pressure vessel inside surface and the assembly outermost material can be filled in a similar manner with a viscous bonding agent, as one example. The dispensable paraffin can be melted and drained from the pressure vessel to expose the axial ends of the monolith adsorbent contactor 10 in the assembly. The resulting exemplary monolith contactor assembly is shown in
The provided adsorbent contactors are 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, i.e., the higher the gas pressure, the greater the amount readily-adsorbed gas 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, 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
Another feature of the apparatus shown in
One possible alternative embodiment is shown in
An individual adsorbent bed assembly is shown in
Each adsorbent bed assembly can be first fitted with the requisite reciprocating valves and then placed in the bed support structure 1601-1607 mounted on the skid 1610, which is shown in
The piping, valves, and headers for a complete skid as connected are shown in
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
Concept A: using one or more kinetic swing adsorption process, such as pressure swing adsorption (PSA), thermal swing adsorption (TSA), calcination, and partial pressure swing or displacement purge adsorption (PPSA), including combinations of these processes; each swing adsorption process may be utilized with rapid cycles, such as using one or more rapid cycle pressure swing adsorption (RC-PSA) units, with one or more rapid cycle temperature swing adsorption (RC-TSA) units or with one or more rapid cycle partial pressure swing adsorption (RC-PPSA) units; exemplary kinetic swing adsorption processes are described in U.S. Patent Application Publication Nos. 2008/0282892, 2008/0282887, 2008/0282886, 2008/0282885, and 2008/0282884 which are each herein incorporated by reference in its entirety;
Concept B: removing acid gas with RC-TSA using advanced cycles and purges as described in U.S. patent application No. 61/447,848, filed Mar. 1, 2011, which is herein incorporated by reference in its entirety;
Concept C: using a mesopore filler to reduce the amount of trapped methane in the adsorbent and increase the overall hydrocarbon recovery, as described in U.S. Patent Application Publication Nos. 2008/0282892, 2008/0282885, 2008/028286, each of which is herein incorporated by reference in its entirety. The non-sweepable void space present within the adsorbent channel wall is can be defined by the total volume occupied by mesopores and macropores. 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 angstrom 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. The non-sweepable void space is defined herein as the open pore volume occupied by pores in the absorbent 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 absorbent material including associated mesopores and macropores in the absorbent structure. The non-sweepable void space, hereafter referred to collectively as mesopores, can be reduced by filling the mesopores between the particles to reduce the open volume while allowing rapid gas transport throughout the adsorbent layer. This filling of the non-sweepable void space is desired to reduce to acceptable levels the quantity of desired product lost during the rapid desorption step as well as to allow a high degree of adsorbent bed purity following desorption. Such mesopore filling can be accomplished in a variety of ways. For example, a polymer filler can be used with rapid diffusion of H2S and CO2, such as a silicon rubber or a polymer with intrinsic porosity. Alternatively, a pyrolitic carbon having mesoporosity and/or microporosity could be used to fill the void space. Still another way is by filling the void space with inert solids of smaller sizes, or by filling the void space with a replenishable liquid through which the desired gases rapidly diffuse (such as water, solvents, or oil). Preferably, the void space within the adsorbent wall is reduced to less than about 40 volume percent (vol. %), preferably to less than 30 vol. %, and more preferably to less than 20 vol. %, and even more preferably to less than 10 vol. % and most preferably less than about 5 vol % of the open pore volume;
Concept D: choosing an appropriate adsorbent materials to provide high selectivity and minimize adsorption (and losses) of methane and other hydrocarbons, such as one or more of the zeolites described in U.S. Patent Application Publication Nos. 2008/0282887 and 2009/0211441, each of which is herein incorporated by reference in its entirety.
Preferred adsorbents for the removal of acid gases are selected from a group consisting of mesoporous or microporous materials, with or without functionality for chemical reactions with acid gases. Examples of materials without functionality include cationic zeolites and stannosilicates. Functionalized materials that chemically react with H2S and CO2 exhibit significantly increased selectivity for H2S and CO2 over hydrocarbons. Furthermore, they do not catalyze undesirable reactions with hydrocarbons that would occur on acidic zeolites. Functionalized mesoporous adsorbents are also preferred, wherein their affinity toward hydrocarbons is further reduced compared to unfunctionalized smaller pore materials, such as zeolites.
Alternatively, adsorption of heavy hydrocarbons can be kinetically suppressed by using small-pore functionalized materials, in which diffusion of heavy hydrocarbons is slow compared to H2S and CO2. Care should also be taken to reduce condensation of hydrocarbons with carbon contents equal to or above about 4 (i.e., C4+ hydrocarbons) on external surfaces of H2S and CO2 selective adsorbents.
Non-limiting example of functional groups suitable for use herein include primary, secondary, tertiary and other non-protogenic, basic groups such as amidines, guanidines and biguanides. Furthermore, these materials can be functionalized with two or more types of functional groups. To obtain substantially complete removal of H2S and CO2 from natural gas streams, an adsorbent material preferably is selective for H2S and CO2 but has a low capacity for both methane and heavier hydrocarbons (C2+). In one or more embodiments, it is preferred to use amines, supported on silica based or other supports because they have strong adsorption isotherms for acid gas species. They also have high capacities for such species, and as a consequence of their high heats of adsorption, they have a relatively strong temperature response (i.e. when sufficiently heated they readily desorb H2S and CO2 and can thus be used without excessive temperature swings). Preferred are adsorbents that adsorb in the 25° C. to 70° C. range and desorb in the 90° C. to 140° C. range. In systems requiring different adsorbents for CO2 and H2S removal, a layered bed comprising a suitable adsorbent for the targeted species may be desirable.
For CO2 removal from natural gas, it is preferred to formulate the adsorbent with a specific class of 8-ring zeolite materials that has a kinetic selectivity. The kinetic selectivity of this class of 8-ring zeolite materials allows CO2 to be rapidly transmitted into zeolite crystals while hindering the transport of methane so that it is possible to selectively separate CO2 from a mixture of CO2 and methane. For the removal of CO2 from natural gas, this specific class of 8-ring zeolite materials preferably has a Si/Al ratio from about 1 to about 25. In other preferred embodiments, the Si/Al ratio of the zeolite material is from 2 to about 1000, preferably from about 10 to about 500, and more preferably from about 50 to about 300. It should be noted that as used herein, the term Si/Al is defined as the molar ratio of silica to alumina of the zeolitic structure. This preferred class of 8-ring zeolites that are suitable for use herein allow CO2 to access the internal pore structure through 8-ring windows in a manner such that the ratio of single component diffusion coefficients for CO2 over methane (i.e., DCO2/DCH4) is greater than 10, preferably greater than about 50, and more preferably greater than about 100 and even more preferably greater than 200.
In many instances, nitrogen also has to be removed from natural gas or gas associated with the production of oil to obtain high recovery of a purified methane product from nitrogen containing gas. There have been very few molecular sieve sorbents with significant equilibrium or kinetic selectivity for nitrogen separation from methane. For N2 separation from natural gas it is also preferred to formulate the adsorbent with a class of 8-ring zeolite materials that has a kinetic selectivity. The kinetic selectivity of this class of 8-ring materials allows N2 to be rapidly transmitted into zeolite crystals while hindering the transport of methane so that it is possible to selectively separate N2 from a mixture of N2 and methane. For the removal of N2, from natural gas, this specific class of 8-ring zeolite materials also has a Si/Al ratio from about 2 to about 1000, preferably from about 10 to about 500, and more preferably from about 50 to about 300. This preferred class of 8-ring zeolites that are suitable for use herein allow N2 to access the internal pore structure through 8-ring windows in a manner such that the ratio of single component diffusion coefficients for N2 over methane (i.e., DN2/DCH4) is greater than 5, preferably greater than about 20, and more preferably greater than about 50 and even more preferably greater than 100. Resistance to fouling in swing adsorption processes during the removal N2 from natural gas is another advantage offered by this class of 8-ring zeolite materials.
In a preferred embodiment, H2S is selectively removed with a non-aqueous sorbent comprising a basic non-protogenic nitrogenous compound supported on a marcroporous, mesoporous, or microporous solid. The non-protogenic nitrogenous compound selectively reacts with at least a portion of the H2S in the feed gas mixture. Examples of suitable porous solid supports include activated charcoal or solid oxides (including mixed oxides), such as alumina, silica, silica-alumina or acidic or non-acidic zeolites. The basic non-protogenic nitrogenous compound may simply be physically sorbed on the support material (e.g. by impregnation or bonded with or grafted onto it by chemical reaction with the base itself or a precursor or derivative in which a substituent group provides the site for reaction with the support material in order to anchor the sorbent species onto the support). Bonding is not, however, required for an effective solid phase sorbent material. Support materials which contain reactive surface groups, such as the silanol groups found on zeolites and the M41S silica oxides are capable of reacting with siloxane groups in compounds, such as trimethoxysilylpropyldimethylamine. Non-protogenic nitrogenous compounds do not enter into chemisorption reactions with CO2 in the absence of water although they do undergo reaction with H2S. This differential chemical reactivity is used to make the separation between the H2S and the CO2. A wide variety of basic nitrogen-containing compounds may be used as the essential sorbent. If desired, a combination of such compounds may be used. The requirement for the desired selectivity for H2S adsorption is that the nitrogenous groups be non-protogenic, that is, incapable of acting as a proton donor. The nitrogenous groups therefore do not contain an acidic, dissociable hydrogen atom, such as nitrogen in a primary or secondary amine. It is not required that the whole compound be aprotic, only that the nitrogen-containing groups in the compound be non-protogenic. Non-protogenic nitrogen species cannot donate an H+ (proton), which is a prerequisite for the formation of carbamates as a route for the CO2 chemisorption reaction in the absence of water; they are non-nucleophilic under the prevailing reaction conditions. Suitable nitrogenous compounds include tertiary amines such as triethylamine, triethanolamine (TEA), methyldiethanolamine (MDEA), N-methyl diethanolamine (CH3N(C2H4OH)2), NNN′N′-tetrakis (2-hydroxyethyl) ethylenediamine as well as non-protogenic nitrogenous bases with cyclic, multicyclic, and acyclic structures, such as imines, heterocyclic imines and amines, amidines (carboxamidines) such as dimethylamidine, guanidines, triazabicyclodecenes, imidazolines, and pyrimidines. Compounds such as the N,N-di(lower alkyl) carboxamidines where lower alkyl is preferably C1-C6 alkyl, N-methyltetrahydropyrimidine (MTHP), 1,8-diazabicyclo[5.4.0]-undece-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), substituted guanidines of the formula (R1R2N)(R3R4N)C═N—R5 where R1, R2, R3 and R4 are preferably lower alkyl (C1-C6) and R5 is preferably H or lower alkyl (C1-C6), such as 1,1,3,3-tetramethylguanidine and biguanide, may also be used. Other substituent groups on these compounds such as higher alkyl, cycloalkyl, aryl, alkenyl, and substituted alkyl and other structures may also be used.
Another class of materials that is capable of removing H2S and CO2, from natural gas streams is cationic zeolites. Selectivity of these materials for H2S and CO2 depends on the framework structure, choice of cation, and the Si/Al ratio. In a preferred embodiment the Si/Al ratio for cationic materials is in a range from 1 to 50 and more preferably a range from 1 to 10. Examples of cationic zeolite include zeolites, 4A, 5A and faujasites (Y and X). It is preferred to use these materials for selectively removing H2S and CO2 after the feed stream has been dehydrated.
Other non-limiting examples of preferred selective adsorbent materials for use in embodiments herein include microporous materials such as zeolites, AlPOs, SAPOs, MOFs (metal organic frameworks), ZIFs (zeolitic imidazolate frameworks, such as ZIF-7, ZIF-8, ZIF-22, etc.) and carbons, as well as mesoporous materials such as the amine functionalized MCM materials. For the acidic gases such as hydrogen sulfide and carbon dioxide which are typically found in natural gas streams, adsorbent such as cationic zeolites, amine-functionalized mesoporous materials, stannosilicates, carbons are also preferred;
Concept E: depressurizing one or more RC-PSA units in multiple steps to intermediate pressures so that the acid gas exhaust can be captured at a higher average pressure, thereby decreasing the compression required for acid gas injection. Pressure levels for the intermediate depressurization steps may be matched to the interstage pressures of the acid gas compressor(s) to optimize the overall compression system;
Concept F: using exhaust or recycle streams to minimize processing and hydrocarbon losses, such as using exhaust streams from one or more RC-PSA units as fuel gas instead of re-injecting or venting;
Concept G: using multiple adsorbent materials in a single bed to remove trace amounts of a first contaminant, such as H2S, before removal of a second contaminant, such as CO2; such segmented beds may provide rigorous acid gas removal down to ppm levels with RC-PSA units with minimal purge flow rates;
Concept H: using feed compression before one or more RC-PSA units to achieve a desired product purity;
Concept I: contemporaneous removal of non-acid gas contaminants such as mercaptans, COS, and BTEX; selection processes and materials to accomplish the same;
Concept J: using structured adsorbents for gas-solid contactors to minimize pressure drop compared to conventional packed beds;
Concept K: selecting a cycle time and cycle steps based on adsorbent material kinetics;
Concept L: using a process and apparatus that uses, among other equipment, two RC-PSA units in series, wherein the first RC-PSA unit cleans a feed stream down to a desired product purity and the second RC-PSA unit cleans the exhaust from the first unit to capture methane and maintain high hydrocarbon recovery; use of this series design may reduce the need for a mesopore filler;
Concept M: using parallel channel contactors, wherein gas/solid contacting takes place in relatively small diameter adsorbent-lined channels. This structure of the contactor provides the benefits of rapid adsorption kinetics through minimization of gas film resistance and high gas-solid communication. A preferred adsorber design generates a sharp adsorption front.
It is preferred to have very rapid gas to adsorbent kinetics, i.e. the length through which the target species (e.g., target gas) diffuses to make contact with the adsorbent wall is kept short, preferably less than 1000 microns, more preferably less than 200 microns, and most preferably less than 100 microns. Favorable adsorbent kinetics may be realized by, while limiting bed pressure drop to acceptable values, utilizing parallel channel contactors wherein the feed and purge gases are confined to a plurality of very narrow (1000 to 30 micron diameter) open channels that are lined to an effective thickness of the adsorbent material.
By “effective thicknesses” we mean a range of about 500 microns to 5 microns for most applications. In the most limiting case of laminar gas flow, the very narrow channels limit the maximum diffusion distance for a trace species to no more than half the diameter of the channel. Even when adsorbing the desired species at the leading edge of the adsorption front, where their concentrations approach zero in the gas phase, a sharp adsorption front can be maintained by using such small diameter parallel channel structured adsorption bed configurations. Such a configuration can be in the form of multiple independent parallel channels, or in the form of very wide, very short channels as may be achieved by using a spiral wound design;
Concept N: a means for rapidly heating and cooling the adsorbent bed structure so that adsorption can occur at a lower temperature and desorption at a higher temperature. The adsorption step then occurs at high pressure and the higher temperature desorption step can optionally take place at a reduced pressure in order to increase adsorbent swing capacity. Depending upon adsorbent properties, it may be desirable to use a bed architecture suitable for either an externally temperature controlled or internally temperature controlled scheme.
By “internal temperature control” we mean the use of a heating and cooling fluid media, either gaseous or liquid, preferably liquid, that can be circulated through the same adsorbent lined channels that are utilized for the gaseous feed flow. Internal temperature control requires that the adsorbent material not be adversely affected by the temperature control fluid and that the temperature control fluid be easily separated from the previously adsorbed species (H2S and CO2) following the heating step. Further, for internal temperature control, the pressure drop across each of the parallel channels in the structured bed during the gaseous feed adsorption step is preferably sufficiently high to clear each channel (or the single channel in the case of spiral wound designs) of the temperature control fluid. Additionally, internal fluid flow temperature designs preferably utilize an adsorbent that does not strongly adsorb the temperature control fluid so that H2S and CO2 may be usefully adsorbed even in the presence of the temperature control fluid.
Non-limiting examples of such adsorbents include amine functionalized microporous and mesoporous adsorbents. A non-limiting example of such a system would be the use of supported amines on a water stable support with the use of hot and cold water (pressurized liquid or used as steam for heating) for heating and cooling. Whereas liquid water may be left within the adsorbent wall during the adsorption step, if the thickness of the adsorbent wall is kept small (less than 1000 microns, preferably less than 200 microns, and most preferably less than 100 microns) it may be possible for H2S and CO2 to diffuse through the liquid water in time scales less than 1 minute, more preferred less than 10 seconds to become adsorbed by the supported amine. Following the desorption step, H2S and CO2 can be easily separated using distillation or other methods known to those skilled in the art.
By “external temperature control” we mean an adsorbent bed structure where the heating and cooling fluid is kept from contact with the gas-carrying adsorbent channels. Such a structure can resemble a tube and shell heat exchanger, plate and frame heat exchanger or hollow fibers with a fluid impermeable barrier layer on the outer diameter or on the inner diameter, or any other suitable structures. In order to obtain rapid heating and cooling, the distance through which the heat diffuses from the temperature control fluid to the adsorbent layer should be kept to a minimum, ideally less than 10,000 microns, more preferably less than 1000 microns, most preferably less than 200 microns. A non-limiting example of such an external temperature control bed design would be the use of hollow fibers with a fluid impermeable barrier layer on the outer diameter wherein the hollow fibers are comprised of a mixed matrix system of polymeric and supported amine adsorbents. Feed gas would be passed through the inner diameter of the porous fiber to be adsorbed by the adsorbent at lower temperatures, while cool temperature control fluid is flowing over the fibers outer diameters. Desorption would be accomplished by passing hot temperature control fluid, preferably in a counter-current direction over the fibers outer diameter, thus heating the adsorbent. The cycle is completed by exchanging the hot temperature control fluid with cold fluid to return the fiber containing the adsorbent to the desired adsorption temperature.
In a preferred embodiment, the rate of heat flow in the system would be such that a sharp temperature gradient in the temperature control fluid would be established during heating and cooling such that the sensible heat of the system can be recuperated within the adsorbent bed structure. For such a non-limiting hollow fiber example, the useful fiber outer diameter dimension is less than 20,000 microns, preferably less than 2000 microns, and most preferably less than 1000 microns. The useful hollow fiber inner diameters (the feed gas channels) is less than 10,000 microns, preferably less than 1000 microns, and most preferably less than 500 microns as suitable based on the desired adsorption and desorption cycle times, feed adsorbed species concentrations, and adsorbent layer swing capacity for those species.
In some embodiments, it is advantageous to keep the ratio of non-adsorbing thermal mass in the adsorbent bed to adsorbent as low as possible. This ratio is preferably be less than 20, more preferably less than 10, and most preferred less than 5. In this manner, the sensible heat of the system that is swung in each cycle may be kept to a minimum;
Concept O: A relatively low flow of about 0.01 to 5 vol. % of the total feed of a clean gas substantially free of H2S or CO2 is utilized as a purge gas. Non-limiting examples of such gases (i.e., “clean gas”) include methane and nitrogen that are maintained flowing through the parallel channels in a direction counter-current to the feed direction during at least a portion of the desorption steps of the process. It is preferred that the flow rate of this clean gas be sufficient to overcome the natural diffusion of the desorbing H2S and CO2 to maintain the product end of the adsorbing channel in a substantially clean condition. That is, the purge stream should have sufficient flow rate to sweep the desorbing CO2 and H2S from the channels and/or pores. It is this counter-current purge flow during desorption that ensures that on each subsequent adsorption cycle there is no breakthrough of target species, such as H2S or CO2 into the product stream. A further benefit or objective of the clean purge is to assist in desorption of contaminants by reducing the partial pressure of contaminants in the flow channels of the adsorbent bed. This lessening of the partial pressure may be utilized to drive the contaminants from the adsorbent bed.
A preferred cycle and bed design for the practice of the present invention is that the product end of the adsorbent channels (i.e. the end opposite the end where feed gases enter) have a low, or ideally essentially zero concentration of adsorbed H2S and CO2. In this manner, and with suitable structured channels as described above, the H2S and CO2 are rigorously removed from the feed gas stream. The downstream end of the bed can be kept clean as described by maintaining a low flow of a clean fluid substantially free of H2S and CO2, in a counter-current direction relative to the feed direction, during the desorption step(s), or more preferably, during all the heating and cooling steps in the cycle. It is further preferred that during the adsorption step, the adsorption part of the cycle be limited to a time such that the advancing adsorption front of H2S and CO2 loaded adsorbent not reach the end of the channels, i.e. adsorption to be halted prior to H2S and/or CO2 breakthrough so that a substantially clean section of the adsorbent channel remains substantially free of target species. With reasonably sharp adsorption fronts, this allows more than 50 vol. % of the adsorbent to be utilized, more preferred more than 75 vol. %, and most preferred more than 85 vol. %.
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.
Additional embodiments A-T are provided as follows:
A swing adsorption contactor system comprising: a plurality of hollow rigid liners each having an inner surface and open axial ends, adjacent liners being fixedly connected to each other; a monolith adsorbent contactor being disposed within each liner, each monolith adsorbent contactor having an outer surface spaced from the inner surface of the liner; and a bonding agent disposed in the space between the outer surface of the monolith adsorbent contactor and the inner surface of the liner to form a seal to prevent gaseous flow in the space.
The swing adsorption contactor system of Embodiment A, wherein the monolith adsorbent contactor includes a stack of at least two monolith adsorbent contactors.
The swing adsorption contactor system of Embodiment B, wherein the stack of at least two monolith adsorbent contactors are held together by tape about adjacent axial ends of the two monolith adsorbent contactors.
The swing adsorption contactor system of any of Embodiments A-C, wherein each liner has integral stand-offs that project in the axial direction from each axial end of the liner.
The swing adsorption contactor system of any of Embodiments A-D, wherein each liner and monolith adsorbent contactor has a mating polygonal cross-section shape.
The swing adsorption contactor system of any of Embodiments A-E, wherein the bonding agent is a polymer-based composition, e.g., thermoplastic and thermosets, adhesive compositions, such as contact adhesives or hot melt adhesives, rubber, i.e., natural or synthetic, elastomers, or combination thereof.
The swing adsorption contactor system of any of Embodiments A-F, wherein the bonding agent is curable, e.g., acrylics, urethanes, and epoxies.
The swing adsorption contactor system of Embodiments G, wherein the curable bonding agent is semi-rigid when cured.
A method of assembling a swing adsorption contactor system comprising the steps of: fixedly connecting a plurality of hollow rigid liners to each other, wherein each of the liners has an inner surface and open axial ends; placing a monolith adsorbent contactor within each liner, each monolith adsorbent contactor having an outer surface, wherein the placing step includes spacing the outer surface of each monolith adsorbent contactor from the inner surface of each liner; placing a bonding agent in the space between the outer surface of the monolith adsorbent contactor and the inner surface of the liner to form a seal to prevent gaseous flow in the space.
The method of assembling a swing adsorption vessel of Embodiment I, wherein the bonding agent is a polymer-based composition, e.g., thermoplastic and thermosets, adhesive compositions, such as contact adhesives or hot melt adhesives, rubber, e.g., natural or synthetic, elastomers, or combination thereof.
The method of assembling a swing adsorption vessel of Embodiment I or J, wherein the bonding agent is curable, e.g., acrylics, urethanes, and epoxies.
The method of assembling a swing adsorption vessel of Embodiment K, wherein the curable bonding agent is semi-rigid when cured.
The method of assembling a swing adsorption vessel of any of Embodiments I-L, wherein the swing adsorption vessel has a housing that receives the plurality of hollow rigid liners, further comprising the step of: placing a protective ring of wax within the housing at its base before the plurality of hollow rigid liners are placed within the housing so that the ring of wax deforms and seals the bottom of the space between the outer surface of the monolith adsorbent contactor and the inner surface of each liner.
The method of assembling a swing adsorption vessel of any of Embodiment I-M, further comprising the step of placing a protective layer of wax on the top axial end of each monolith adsorbent contactor before the placing of a bonding agent step.
The method of assembling a swing adsorption vessel of Embodiment N, further comprising the step of:
melting both the protective layer of wax on the top axial end of each monolith adsorbent contactor and the protective ring of wax within the housing after the step of permitting the curable bonding agent to cure into a semi-rigid material.
A method of processing hydrocarbons comprising the steps of: (a)
providing an apparatus comprising the swing adsorption contactor system of any of embodiments A-H or as shown in the attached figures, (b) recovering at least 5 million, or at least 15 million, or at least 25 million, or at least 50 million, or at least 100 million, or at least 500 million, or at least 1 billion, or at least 2 billion standard cubic feet per day (SCFD) of natural gas.
The method of Embodiment P, wherein one or more additional steps utilize a kinetic swing adsorption process selected from the group consisting of: pressure swing adsorption (PSA), thermal swing adsorption (TSA), calcination, partial pressure swing or displacement purge adsorption (PPSA), and combinations of these processes.
The method of Embodiment Q, wherein one or more swing adsorption process utilizes rapid cycles.
The method of any of Embodiments P-R, wherein a gaseous feed stream is processed to achieve: (a) a desired dew point, (b) a desired level of detoxification, (c) a desired corrosion protection composition, (d) a desired dehydration level, (e) a desired gas heating value, (f) a desired purification level, or (g) combinations thereof.
A hydrocarbon treating apparatus comprising: an apparatus comprising the swing adsorption contactor system of any of embodiments A-H or as shown in the attached figures, wherein the hydrocarbon treating apparatus capacity is at least 5 million, or at least 15 million, or at least 25 million, or at least 50 million, or at least 100 million, or at least 500 million, or at least 1 billion, or at least 2 billion standard cubic feet per day (SCFD) of natural gas.
Additional embodiments 1 to 14 are provided in the following paragraphs:
1. A swing adsorption contactor system comprising: a plurality of hollow rigid liners, each liner having an inner surface that defines an interior region, a first open axial end along a longitudinal axis, a second open axial end along the longitudinal axis opposite the first open axial end, and an outer surface external to the interior region; a plurality of monolith adsorbent contactors, wherein one of the plurality of monolith adsorbent contactors is disposed within one of the plurality of liners, the one monolith adsorbent contactor having a body that defines at least one passage through the body along the longitudinal axis and an outer surface of the body; and a bonding agent being disposed between the outer surface of the monolith adsorbent contactor and the inner surface of the liner to hinder gaseous flow between the monolith adsorbent contactor and the hollow rigid liner.
2. The swing adsorption contactor system according to paragraph 1, wherein the two or more of the plurality of monolith adsorbent contactors are stacked together along the same longitudinal axis within one of the plurality of hollow rigid liners.
3. The swing adsorption contactor system according to paragraph 2, wherein the stacked monolith adsorbent contactors are coupled via tape about adjacent ends.
4. The swing adsorption contactor system according to any one of paragraphs 1 to 3, further comprising two or more of the plurality of hollow rigid liners being adjacent to each other being fixedly connected to each other.
5. The swing adsorption contactor system according to any one of paragraphs 1 to 4, wherein each liner has a mating polygonal cross-section shape.
6. The swing adsorption contactor system according to any one of paragraphs 1 to 5, wherein at least one liner has integral stand-offs that project in the axial direction from each axial end of the liner.
7. The swing adsorption contactor system according to paragraphs 1 to 6, wherein the bonding agent is semi-rigid when cured.
8. A method of assembling a swing adsorption contactor system comprising: providing a plurality of hollow rigid liners, each hollow rigid liner having an inner surface that defines an interior region, a first open axial end along a longitudinal axis, a second open axial end along the longitudinal axis opposite the first open axial end, and an outer surface external to the interior region; placing one of a plurality of monolith adsorbent contactors within one of plurality of hollow rigid liners, the one monolith adsorbent contactor having a body that defines at least one passage through the body along the longitudinal axis and an outer surface of the body; and bonding the one of the plurality of monolith adsorbent contactors with the one of plurality of hollow rigid liners via a bonding agent that is disposed between the outer surface of the monolith adsorbent contactor and the inner surface of the hollow rigid liner, wherein the bonding agent hinders the flow of fluids between the monolith adsorbent contactor and the hollow rigid liner.
9. The method of assembling a swing adsorption vessel according to paragraph 8, further comprising curing bonding agent into a semi-rigid material.
10. The method of assembling a swing adsorption vessel according to paragraphs 8 to 9, further comprising melting both the protective layer of wax on the top axial end of each monolith adsorbent contactor and the protective ring of wax within the housing after curing the bonding agent.
11. The method of assembling a swing adsorption vessel according to any one of paragraphs 8 to 10, wherein the swing adsorption vessel has a housing that receives the plurality of hollow rigid liners, further comprising placing a protective ring of wax between the plurality of hollow rigid liners and the housing so that the protective ring of wax deforms and seals the region between the outer surface of the monolith adsorbent contactor and the inner surface of the liner.
12. The method of assembling a swing adsorption vessel according to any one of paragraphs 8 to 11, further comprising placing a protective layer of wax on the top axial end of each monolith adsorbent contactor before the placing of a bonding agent step.
13. The method of assembling a swing adsorption vessel according to any one of paragraphs 8 to 12, further comprising fixedly connecting two of more of the plurality of hollow rigid liners to each other.
14. The method of assembling a swing adsorption vessel according to any one of paragraphs 8 to 13, wherein fixedly connecting further comprises welding the outer surface of the two of more of the plurality of hollow rigid liners.
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 is a continuation application of U.S. Ser. No. 13/979,623, which is the National Stage of International Patent Application Publication No. PCT/US2012/026797, filed Feb. 27, 2012, which claims the priority benefit of U.S. Patent Application No. 61/448,117 entitled APPARATUS AND SYSTEMS HAVING AN ENCASED ADSORBENT CONTACTOR AND SWING ADSORPTION PROCESSES RELATED THERETO, filed on Mar. 1, 2011, the entirety of each is incorporated by reference herein. This application is related to U.S. patent application No. 61/448,120 entitled APPARATUS AND SYSTEMS HAVING A RECIPROCATING VALVE HEAD ASSEMBLY AND SWING ADSORPTION PROCESSES RELATED THERETO, filed Mar. 1, 2011; U.S. patent application No. 61/448,121 entitled METHODS OF REMOVING CONTAMINANTS FROM A HYDROCARBON STREAM BY SWING ADSORPTION AND RELATED APPARATUS AND SYSTEMS, filed Mar. 1, 2011; U.S. patent application No. 61/448,123 entitled APPARATUS AND SYSTEMS HAVING A ROTARY VALVE ASSEMBLY AND SWING ADSORPTION PROCESSES RELATED THERETO, filed Mar. 1, 2011; U.S. patent application No. 61/448,125 entitled APPARATUS AND SYSTEMS HAVING COMPACT CONFIGURATION MULTIPLE SWING ADSORPTION BEDS AND METHODS RELATED THERETO, filed Mar. 1, 2011, and U.S. patent application No. 61/594,824 entitled METHODS OF REMOVING CONTAMINANTS FROM A HYDROCARBON STREAM BY SWING ADSORPTION AND RELATED APPARATUS AND SYSTEMS, filed Feb. 3, 2012, each of which is herein incorporated by reference in its entirety.
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| Number | Date | Country | |
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| 20160236135 A1 | Aug 2016 | US |
| Number | Date | Country | |
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| 61448117 | Mar 2011 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13979623 | US | |
| Child | 15141276 | US |
