Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
  • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
  • B01D53/047—Pressure swing adsorption
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
  • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
  • B01D53/047—Pressure swing adsorption
  • B01D53/0473—Rapid pressure swing adsorption
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/10—Working-up natural gas or synthetic natural gas
  • C10L3/101—Removal of contaminants
  • C10L3/102—Removal of contaminants of acid contaminants
  • C10L3/104—Carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2256/00—Main component in the product gas stream after treatment
  • B01D2256/24—Hydrocarbons
  • B01D2256/245—Methane
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/30—Sulfur compounds
  • B01D2257/304—Hydrogen sulfide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/50—Carbon oxides
  • B01D2257/502—Carbon monoxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2259/00—Type of treatment
  • B01D2259/40—Further details for adsorption processes and devices
  • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
  • B01D2259/40035—Equalization
  • B01D2259/40041—Equalization with more than three sub-steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2259/00—Type of treatment
  • B01D2259/40—Further details for adsorption processes and devices
  • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
  • B01D2259/40043—Purging
  • B01D2259/40049—Purging with more than three sub-steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2259/00—Type of treatment
  • B01D2259/40—Further details for adsorption processes and devices
  • B01D2259/406—Further details for adsorption processes and devices using more than four beds
  • B01D2259/4063—Further details for adsorption processes and devices using more than four beds using seven beds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

• 61/448, 125 entitled APPARATUS AND SYSTEMS HAVING COMPACT CONFIGURATION MULTIPLE SWING ADSORPTION BEDS AND METHODS RELATED THERETO, filed March 1, 201 1, and U.S. Patent Application No. 61/594,824, entitled METHODS OF REMOVING CONTAMINANTS FROM A HYDROCARBON STREAM BY SWING ADSORPTION AND RELATED APAPRATUS AND SYSTEMS, filed February 3, 2012, each of which is herein incorporated by reference in its entirety.
• This invention relates to a swing adsorption process for removal of contaminants, e.g., CO 2 and 3 ⁇ 4S, from hydrocarbon streams through a combination of a selective features, such as system configurations, adsorbent structures and materials, and/or cycle steps.
• a selective features such as system configurations, adsorbent structures and materials, and/or cycle steps.
• PSA pressure swing adsorption
• PSA processes can be used to separate gases within a gas mixture because different gases tend to fill the micropore or free volume of the adsorbent to different extents.
• a gas mixture such as natural gas
• a vessel containing a polymeric or microporous adsorbent that is more selective towards carbon dioxide, for example, than it is for methane
• at least a fraction of the carbon dioxide is selectively adsorbed by the adsorbent, and the gas exiting the vessel is enriched in methane.
• the bed reaches the end of its capacity to adsorb carbon dioxide, it is regenerated by reducing the pressure, thereby releasing the adsorbed carbon dioxide. It is typically then purged and repressurized and ready for another adsorption cycle.
• Achieving high recovery and high purity in separation processes at high pressures is especially beneficial in natural gas processing operations.
• Many natural gas fields contain significant levels of CO 2 , as well as other contaminants, such as H 2 S, N 2 , H 2 O mercaptans and/or heavy hydrocarbons that have to be removed to various degrees before the gas can be transported to market.
• methane is the valuable component and acts as a light component in swing adsorption processes. Small increases in recovery of this light component can result in significant improvements in process economics and also serve to prevent unwanted resource loss.
• a swing adsorption process for removing contaminants, e.g., CO 2 , from hydrocarbon streams, such as natural gas streams, which process comprises: a) subjecting a natural gas stream comprising methane and CO 2 to an adsorption step by introducing it into the feed input end of an adsorbent bed comprised of an adsorbent material selective for adsorbing CO 2 , which adsorbent bed having a feed input end and a product output end and which adsorbent bed is operated at a first pressure and at a first temperature wherein at least a portion of said CO 2 is adsorbed by the adsorbent bed and wherein a gaseous product rich in methane and depleted in CO 2 exits the product output end of said adsorbent bed, wherein said adsorbent material is porous and contains an effective amount of non-adsorbent mesopore filler material, and wherein the adsorption step
• Figure 1 hereof is a representation of one embodiment of a parallel channel adsorbent contactor that can be used in the present invention.
• This contactor is in the form of a monolith that is directly formed from a microporous adsorbent and containing a plurality of parallel gas channels.
• Figure 4 hereof is an enlarged view of a small area of a cross-section of the contactor of Figure 1 hereof showing adsorbent layered channel walls.
• Figures 12a and 12b are charts showing an arrangement of steps for sixteen adsorbent bed assemblies in a three-pressure equalization RC-PSA cycle.
• Figures 13a and 13b are schematic diagrams of the adsorbent structures and bed.
• Figure 16 shows an exemplary cycle schedule for the rerun RC-PSA system in
• Figure 18 shows an exemplary cycle schedule for the rerun RC-PSA system utilizing equalization tanks.
• Figure 19 shows the pressure versus time relationship for an exemplary vacuum RC-PSA cycle described in Figure 9.
• Figure 20 shows an exemplary cycle schedule for the vacuum RC-PSA described in Figure 9.
• Figure 21 is an illustration of an elevation view of an exemplary hydrocarbon treating apparatus comprised of a swing adsorption system with fourteen adsorbent bed assemblies arranged in two levels of seven beds equally spaced around the central valve and flow distribution assembly.
• Figure 22 is an illustration of a plan view of an exemplary hydrocarbon treating apparatus comprised of a swing adsorption system with fourteen adsorbent bed assemblies arranged in two levels of seven beds equally spaced around the central valve and flow distribution assembly.
• Figure 23 is a three-dimensional diagram of another exemplary hydrocarbon treating apparatus comprised of a swing adsorption system with seven adsorbent bed assemblies arranged in two rows.
• Figures 24A, 24B, and 24C are top, side, and bottom views, respectively, of an individual adsorbent bed assembly from the exemplary hydrocarbon treating apparatus in Figure 23.
• Figure 25 is a three-dimensional diagram of individual adsorbent bed support structures attached to the skid base for the exemplary hydrocarbon treating apparatus of Figure 23.
• RC-PSA systems are provided that produce high purity product streams from high-pressure natural gas, while recovering over 99% of the hydrocarbons.
• a product with less than 10 ppm H 2 S can be produced from a natural gas feed stream that contains less than 1 mole percent H 2 S.
• the methane is adsorbed onto the adsorbent material, because materials with relatively low selectivity are employed in conventional PSA systems and the swing capacity is such that the effective ratio for CO 2 versus methane molecules entering and leaving the absorbent materials is around 5-10.
• the swing capacity is such that the effective ratio for CO 2 versus methane molecules entering and leaving the absorbent materials is around 5-10.
• Performance could be further enhanced by adding factors multiple blow-down steps and/or a series RC-PSA arrangement and/or dedicated equalization tanks for each equalization step.
• both high recovery and high purity could be achieved by combining factors rapid cycle times; purge with exhaust; vacuum regeneration; selection of adsorbent material; structured adsorbent contactors; arrangement of adsorbent material within the contactor; and utilization of a mesopore filler to reduce macropore and mesopores within contactor.
• Performance could be further enhanced by adding factors, such as multiple blow-down steps and/or a series RC- PSA arrangement and/or dedicated equalization tanks for each equalization step
• This contaminant- rich purge stream sweeps methane from the flow channels and void spaces between adsorbent particles and/or the contactor structure, so that the methane can be recycled or captured and other process, thereby reducing the loss of the product gases to the exhaust stream.
• This purge step substantially increases the recovery of the product gases.
• Non-limiting examples of such gases 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.
• the preferred source for the clean gas is to utilize a portion of the product stream, which is let down to the appropriate pressure to use for the purge.
• the pressure of the purge is selected typically at the lowest depressurization pressure, although any pressure level between the lowest depressurization pressure and feed pressure can be used.
• the purge pressure is primarily selected to lessen the flow rate required for the purge.
• the blow-down step may be performed from both the feed and the product sides of a composite adsorbent bed containing a first portion of bed having an amine functionalized adsorbent material for H 2 S removal and a second portion of the bed having DDR adsorbent bed for CO 2 removal from natural gas.
• the gas of the feed stream which may be referred to as feed gas, contacts the amine functionalized adsorbent bed first and breakthrough of H 2 S occurs before the feed gas contacts the DDR adsorbent bed where breakthrough of CO 2 occurs.
• certain embodiments may formulate the adsorbent with a specific class of 8-ring zeolite materials that has a kinetic selectivity for CO 2 over methane.
• the kinetic selectivity of this class of 8-ring zeolite materials allows CO 2 to be rapidly transmitted (diffused) into zeolite crystals while hindering the transport of methane so that it is possible to selectively separate CO 2 from a mixture of CO 2 and methane.
• this specific class of 8-ring zeolite materials has a Si/Al ratio from about 2 to about 1000, preferably from about 10 to about 500, and more from about 50 to about 300.
• Non-limiting construction methods include spiral winding a single sheet made from a mixed matrix of adsorbent, mesopore filler and thermal mass; wash-coating a mixed matrix of adsorbent and mesopore filler to a thin metal sheet and then spiral winding the sheet; spiral winding a thin metal sheet or mesh and then wash-coating a mixed matrix of adsorbent and mesopore filler to the spiral wound assembly.
• Providing a small gap between adjacent segments preferably less than 1000 ⁇ , or preferably less than 500 ⁇ , and even more preferably less than 200 ⁇ , allows for redistribution of gas between segments, which may lessen any effects of maldistribution within the flow channels of the structured contactors.
• this effective purge of the H 2 S adsorbing segment of the composite bed may be more effective if H 2 S is not allowed to breakthrough into the DDR segments of the bed during the adsorption step so that the CO 2 in the DDR segments of the bed are substantially free of H2S.
• the product recovery of an RC-PSA system can also be enhanced by use of a mesopore filler, as above noted in feature B4, which may be used to reduce the void space in the adsorbent bed.
• a mesopore filler as above noted in feature B4, which may be used to reduce the void space in the adsorbent bed.
• a mesopore filler is described in U.S. Patent Application Publication Nos. 2008/0282892, 2008/0282885 and 2008/028286, each of which is herein incorporated by reference in its entirety.
• acid gas may be removed from a natural gas stream to produce a high purity methane stream in the first RC-PSA unit of this system.
• Acid gas from the first RC-PSA unit may contain a fraction of methane, which can be removed using a second RC-PSA unit.
• the methane product from the second RC-PSA unit may be recycled or utilized elsewhere in the facility and the acid gas may be exhausted from the second RC- PSA unit or conducted away for disposal.
• the overall RC-PSA system achieves high product recovery and high product purity even for high pressure natural gas.
• the time interval for equalization steps between an adsorbent bed and an equalization tank is typically shorter than the time required for equalization between two adsorbent beds, and therefore the total cycle time can be decreased.
• the amount of adsorbent material utilized within an adsorbent bed is reduced and the overall size and weight of the swing adsorption system can be reduced, while the performance may be enhanced (e.g., lower purge flow rates, lower recycle compression, etc.).
• the amount of piping and valves for the RC-PSA system is reduced because bed to bed connections are not required for the equalization steps.
• the methane recovery is increased by utilizing two PSA units in series (feature CI) to capture methane lost into the acid gas stream from the first PSA unit 801 using a second PSA unit 821.
• the PSA system can also utilize equalization tanks (feature C2) to reduce the cycle time and enhance the productivity.
• Performance and details of the RC-PSA system 800 are described in Examples 3 and 4 for processing natural gas with 12% CO 2 and 0.01-0.1% H 2 S to produce methane with less than 1.5% CO 2 and less than 4 ppm H 2 S while achieving over 99% recovery.
• both high methane recovery and high product purity are achieved in a single PSA unit 900.
• This PSA unit is operated in rapid cycle mode (feature Al) with a recovery purge (feature A2) at an appropriate intermediate pressure (feature A5) followed by blow-down to vacuum pressure (feature A4) to achieve high product purity.
• a structured adsorbent contactor (feature B2) is used with two specific materials for kinetic separation of CO 2 and equilibrium adsorption of H 2 S (feature Bl) arranged in the contactor in two separate segments (feature B3) and incorporating mesopore filler to reduce the void volume (feature B4) and enhance recovery.
• Equalization tanks (feature C2) can also be utilized to reduce the cycle time required and thereby enhance the productivity of the system.
• the layer may also contain a mesopore filler material, which decreases the void space in the layer to less than 30% by volume, or more preferably 20% by volume, or even more preferably 10% by volume, or most preferably less than 4% by volume.
• the average thickness of the layer may be in a range from 25 to 450 microns, preferably in a range from 30 to 200 microns, and most preferably 50 to 125 microns.
• the adsorbent material is a zeolite and has a kinetic selectivity ratio for CO 2 greater than 50, preferably greater than 100 and even more preferably greater than 200.
• the kinetic selectivity ratio is the rate of diffusion for the contaminant, such as CO 2 , divided by the rate of diffusion for the product, such as methane.
• the change in average loading of CO 2 and H 2 S in the adsorbent along the length of the channels is preferably greater than 0.2 millimoles per gram (mmole/gram), more preferably greater than 0.5 mmole/gram, and most preferably greater than 1 mmole/gram, where average loading is represented as the millimoles of contaminant adsorbed per gram of the adsorbent.
• the RC-PSA unit 701 is operated by rapidly cycling through a series of steps that include adsorption followed by multiple steps to regenerate the adsorbent bed prior to the adsorption step on the subsequent cycle.
• the same series of steps are executed continuously by each adsorbent bed and the timing of the cycle for each bed may be synchronized with other beds to provide continuous flow of feed stream, product, and purge streams. Selection of the precise steps and cycle timing depends on the gas composition of the feed stream, product specifications, contaminant disposition, and overall hydrocarbon recovery.
• fourteen adsorbent beds are required to complete the cycle for continuous flow operation.
• the timing of cycles between adsorbent beds is also synchronized such that the first equalization step El for one bed coincides with the re-pressurization step Rl for another bed so that the gas withdrawn during the depressurization step is used to re- pressurize another bed.
• adsorbent bed 7 in Figure 11a undergoes the equalization step El at the same time that adsorbent bed 2 is undergoing the re-pressurization step Rl .
• R2 Re-pressurize the first adsorbent bed from about 1.2 bar a to about 19 bar a using gas withdrawn from yet another adsorbent bed undergoing step E2 step (counter-current flow);
• FR Re-pressurize the first adsorbent bed from about 35.5 bar a to about 55 bar a with gas from the feed conduit (co-current flow).
• the total time interval for all of the equalization steps is less than ten times, preferably less than five times that of the adsorption step. Most preferably, the total time for all of the equalization steps is less than that of the adsorption step. It is also preferred that the total time for all of the re-pressurizing steps is less than ten times, preferably less than five times that of the adsorption step. It is most preferred that the total time for all of the re-pressurizing steps be less than that of the adsorption step.
• each adsorbent bed is the same as Example 1, including flow channel dimensions, adsorbent bed length, adsorbent material, mesopore filler, etc.
• the number of adsorbent beds has increased from fourteen to sixteen to accommodate the modified cycle, which utilizes three equalization steps instead of two equalization steps as in Example 1.
• the natural gas feed stream containing CO 2 and H 2 S enters the first RC-PSA unit 801 via conduit 802 and a purified product stream enriched in methane exits via conduit 803 at a slightly reduced pressure due to pressure drop across the adsorbent beds, valves and piping internal to the RC-PSA unit 801. Acid gas removed from the feed stream is desorbed at a low pressure and the exhaust gas exits the unit via conduit 807. To provide high product purity in RC-PSA unit 801, a portion of the product stream is removed via conduit 804 and reduced in pressure to be used as a product purge in the adsorbent beds 801.
• a portion of the acid gas is removed via conduit 812 and compressed in compressor 814 to be used as a recovery purge that enters the RC- PSA unit 821 via conduit 815.
• This stream is enriched in acid gas, and is used to sweep methane from the flow channels and void spaces in the adsorbent layer to enhance recovery of the system.
• the outlet from this purge step exits the RC-PSA unit 821 via conduit 816 and is combined with the product from conduit 810, and the combined stream in conduit 817 contains the recovered hydrocarbons to be used for fuel gas or other purposes within the facility.
• the remainder off the acid gas is disposed of via conduit 813 by venting or compressing and re-injecting.
• Each RC-PSA unit 801 is comprised of ten adsorbent beds, each of which is comprised of a structured contactor with a plurality of gas flow channels.
• the gas flow channels are substantially square as shown in Figure 13a, with a height 1301 of 225 ⁇ and a width of 225 ⁇ .
• the total length of the gas flow channels is 1.1 m, and the total diameter of each adsorbent bed is 1.2 m.
• the structured contactor may be segmented along its length so that each segment has a plurality of flow channels and the gas passes sequentially from flow channels in one segment to flow channels in a separate segment. There may be from 1 to 10 segments along the length of the contactor.
• E4 Depressurize the first adsorbent bed from about 22 bar a to about 15.24 bar a sending gas to another adsorbent bed to pressurize it from about 8.05 bar a to about 15.24 bar a (co-current flow);
• R5 Re-pressurize the first adsorbent bed from about 1.4 bar a to about 8.1 bar a with gas from the E5 step of yet another adsorbent bed (counter-current flow);
• R2 Re-pressurize the first adsorbent bed from about 22 bar a to about 28.7 bar a with gas from the E2 step of yet another adsorbent bed (counter-current flow);
• R5 Re-pressurize for 0.5 seconds
• Rl Re-pressurize for 0.5 seconds
• Rl Re-pressurize the first adsorbent bed from about 12.7 bar a to about 26.1 bar a with gas from the El step of yet another adsorbent bed (counter-current flow);
• FR Re-pressurize the first adsorbent bed from about 26.1 bar a to about 45 bar a with feed gas (co-current flow).
• FIG. 9 is a simplified process flow diagram for the RC-PSA system 900, in which the RC-PSA unit 910 is in fluid communication with various conduits 901-905 and associated compressors 906a-906b.
• the system 900 is interconnected to manage the flow of fluids through the system to perform various cycle steps which are described below.
• the RC-PSA unit 910 is comprised of twelve adsorbent beds, each of which is comprised of a structured contactor with a plurality of gas flow channels.
• the gas flow channels are square as shown in Figure 13 a, with a height 1301 of 225 ⁇ and a width of 225 ⁇ .
• the total length of the gas flow channels is 1.1 m, and the total diameter of each adsorbent bed is 1.2 m.
• the structured contactor maybe segmented along its length so that each segment has a plurality of flow channels and the gas passes sequentially from flow channels in one segment to flow channels in a separate segment. There may be from 1 to 10 segments along the length of the contactor.
• the total pressure drop along the length of the adsorbent bed during the adsorption step is around 1 bar.
• Gas flow channels in the structured adsorbent contactor are formed from a layer containing adsorbent material which may be on our part of at least a fraction of the structured contactor walls.
• the layer may also contain a mesopore filler material which decreases the void space in the layer to less than about 20%.
• the average thickness of the layer is 150 ⁇ , dimension 1302 in Figure 13a.
• two different adsorbent materials are utilized in a composite bed to enable near complete removal of H 2 S to produce a high purity methane product.
• an amine functionalized adsorbent is utilized which selectively adsorbs H 2 S.
• E2 Depressurize the adsorbent bed about 73 bar a to 59 bar a sending gas to equalization tank M2;
• R3 Re-pressurize the first adsorbent bed from about 36 bar a to about 45 bar a with gas from M3 ;
• H12 Hold for 0.1 seconds
• Rl Repressurize for 0.2 seconds
• each adsorbent bed operates independently and the timing of cycles for different adsorbent beds are not synchronized to allow equalization between adsorbent beds. Synchronization of adsorbent beds is only necessary for providing continuous feed and product flow.
• FIG. 21 and 22 Another feature of the apparatus shown in Figures 21 and 22 relates to a method of coordinating the activation mechanism of the reciprocating valve to either open or close at several predetermined physical locations on the rotary valve itself.
• a reliable and repeatable means of replicating precise operable coordination between the open or closed ports of the respective valves is provided for the adsorption cycle.
• This embodiment uses a traveling magnet assigned as a transmitter location, which is aligned to a fixed magnetic assigned as a receiving location.
• a generated flux signal between the magnets activates a specified mechanized driver of a given reciprocating valve for a specified duration.
• the art of generating and reading the change in a magnetic flux signal is scientifically recognized as the Hall Effect.
• the hydrocarbon treating apparatus shown in Figures 21 and 22 can be implemented in many different configurations.
• the fourteen individual adsorbent bed assemblies may be arranged in two skids, each of the skids containing seven of the individual adsorbent bed assemblies arranged in two rows.
• One of the exemplary skids is shown in Figure 23.
• Multiple reciprocating (or poppet) valves are arranged on the top and bottom of each vessel and connected via piping and headers above and below the adsorbent bed assemblies.
• Each adsorbent bed assembly can be first fitted with the requisite reciprocating valves and then placed in the bed support structure 2501-2507 mounted on the skid 2510, which is shown in Figure 25. Once the seven adsorbent bed assemblies are set in their respective support structure 2501-2507, the bed assemblies can be interconnected via piping and headers.
• the bed support structures 2501-2507 may be configured to permit movement to allow for thermal expansion or contraction of the piping system associated with the bed assembly. While the individual bed support structures 2501-2507 are fixed to the skid base 2510, the adsorbent bed assemblies, which are noted in other figures, may be disposed into the bed support structure 2501-2507 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.
• Adsorptive kinetic separation processes, apparatus, and systems, as described above, are useful 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.
• 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.
• an adsorbent material preferably is selective for H 2 S and CO 2 but has a low capacity for both methane and heavier hydrocarbons (C 2 +).
• 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.
• N 2 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 N 2 to be rapidly transmitted into zeolite crystals while hindering the transport of methane so that it is possible to selectively separate N 2 from a mixture of N 2 and methane.
• this specific class of 8-ring zeolite materials also has a Si/Al ratio from about
• 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 H 2 S, before removal of a second contaminant, such as CO 2 ; such segmented beds may provide rigorous acid gas removal down to ppm levels with RC-PSA units with minimal purge flow rates;
• 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 (H 2 S and CO 2 ) following the heating step.
• 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.
• internal fluid flow temperature designs preferably utilize an adsorbent that does not strongly adsorb the temperature control fluid so that H 2 S and CO 2 may be usefully adsorbed even in the presence of the temperature control fluid.
• 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 H 2 S and CO 2 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.
• H 2 S and CO 2 can be easily separated using distillation or other methods known to those skilled in the art.
• 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 CO 2 .
• the H 2 S and CO 2 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 H 2 S and CO 2 , 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.
• the adsorption part of the cycle be limited to a time such that the advancing adsorption front of H 2 S and CO 2 loaded adsorbent not reach the end of the channels, i.e. adsorption to be halted prior to H2S and/or CO 2 breakthrough so that a substantially clean section of the adsorbent channel remains substantially free of target species.
• 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.%.
• Embodiment A A swing adsorption process of removing one or more contaminants from a natural gas stream comprising the step of:
• Embodiment C The swing adsorption process of removing one or more contaminants from a natural gas stream of Embodiment A, wherein the contaminant is CO 2 .
• Embodiment D The swing adsorption process of removing one or more contaminants from a natural gas stream of any of Embodiments A-C, wherein said adsorbent material is porous and contains an effective amount of non-adsorbent mesopore filler material.
• Embodiment E The swing adsorption process of removing one or more contaminants from a natural gas stream of any of Embodiments A-D, wherein the adsorption step is performed for a period of less than about 60 seconds, or less than about 50 seconds, less than about 40 seconds, less than about 30 seconds, less than about 20 seconds, less than about 10 seconds, less than about 5 seconds.
• Embodiment I The swing adsorption process of removing one or more contaminants from a natural gas stream of any of Embodiments F-H, wherein the one or more equalization steps of step (f) are 2 to 20 steps or 2 to 15 steps or 2 to 10 steps or 2 to 5 steps and the pressure is increased by a predetermined amount with each successive step.
• Embodiment J The swing adsorption process of removing one or more contaminants from a natural gas stream of any of Embodiments A-I, further comprising the step of:
• a cyclical swing adsorption process for removing contaminants from a gaseous feed stream, the process comprising: a) passing a gaseous feed stream at a feed pressure through an adsorbent bed for an adsorption time interval greater than 0.1 or 1 second and less than 60 seconds to separate one or more contaminants from the gaseous feed stream to form a product stream; b) interrupting the flow of the gaseous feed stream; c) performing a plurality of depressurization steps, wherein each depressurization step reduces the pressure within the adsorbent bed from a depressurization initial pressure to a depressurization final pressure; d) passing a purge stream into the adsorbent bed to remove hydrocarbons from the adsorbent bed; e) subjecting the purged adsorbent bed to one or more blow-down steps, wherein each blow-down step reduces the pressure within the adsorbent bed from a blow-down initial pressure to a blow-down final pressure; f
• a cyclical pressure swing adsorption process for removing contaminant from a gaseous feed stream comprising:

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