Sorptive gas separation process with concentrated stream recycle

Abstract

A sorptive gas separation process employing a pre-concentration and purification process and systems thereof. Sorptive gas separation processes using partial pressure swing with a solid sorbent for separation of a target component from a multi-component gas stream are provided, along with systems thereof.

Description

[0001] Sorptive Gas Separation Process with Concentrated Stream Recycle

[0002] TECHNICAL FIELD

[0003] The present technology relates generally to sorptive gas separation processes using partial pressure swing with a solid sorbent for separation of a target component from a multi-component gas stream and systems thereof. In particular, it relates to moisture swing sorptive gas separation with product recycle for assisting the overall cycle performance.

[0004] Of particular interest is the application of the technology to the treatment of combustion gases produced by fossil-fuel or bio-fuel combustors and systems. More particularly, the present technology relates to a process of operating a carbon dioxide (CO₂) separation and concentration system whereby a diluted CO₂ stream is utilized to produce a stream with an increased CO₂ concentration incorporating a moisture addition system with a sorptive separator to deliver a high purity CO₂ stream.

[0005] BACKGROUND

[0006] Moisture swing sorptive methods are known in the art for use in sorptive separation of multi-component gas mixtures as disclosed in US Patent 11,117,088 B2, International Publication WO 2022 / 238934 A2, and International Publication WO 2025 / 153969 A1. Temperature swing adsorptive processes can be used for preferentially sorbing a target component of a feed gas mixture on a sorbent material, separating the target or sorbed component from the remaining feed gas components, and subsequently regenerating the sorbent material by desorbing the sorbed component by increasing the temperature of the sorbent material thereby allowing for cyclic reuse of the sorbent material. In some methods, a water stream in the form of steam, may be employed as a regeneration stream to regenerate the sorbent material by supplying heat and / or water to the sorbent. One type of industrial process where gas separation may be desirable includes combustion processes, where an oxidant and a carbon-containing fuel are combusted to generate, for example, heat, a combustion gas stream (also known as a combustion flue gas stream or flue gas stream) and mechanical power, such as through expansion of the combustion gases and / or a suitable working fluid. The separation of one or more gas components from the combustion gas stream may be desirable, such as for example for the removal and / or sequestration of carbon dioxide from the combustion gas stream or flue gas stream.

[0007] In a combustion process and system incorporating temperature swing sorptive gas separation, it may be desirable to reduce the quantity of steam or quantity of steam high in exergy (or useful energy of a steam stream) consumed for regeneration of the sorbent material as the availability of steam may be limited. Thus, when the quantity of steam high in exergy is reduced, the process may require additional energy to generate additional steam and / or steam high in exergy, which may result in reducing the operating cost (or OPEX) of a combustion- system incorporating a moisture or temperature swing sorptive gas separation.

[0008] Additionally, in applications where additional steam generation is desired to enable CO2 separation and recovery, this steam generation may also be associated with the production of additional CO2 that may also need to be mitigated. This can occur, for example, when using an auxiliary boiler powered by natural gas or by increasing the fuel input to the main combustor and / or process to produce more steam for the CO2 separation process. Therefore, advantageous methods to reduce the amount of steam used in the separation process are presented in the invention disclosed herein.

[0009] Sorptive separation systems employing solid sorbent have advantages including a compact footprint for the sorptive separator and contactor(s) with the solid sorbent material. One downside is that heat stored on the solid sorbent may be more difficult to recycle or recover relative to sorptive separation systems employing a liquid sorbent which can be pumped and directed to a heat exchanger. Advantages can be gained from applications where a concentration of a target component such as CO2 in the feed stream is less than 10% on volume basis, and the sorptive gas separation process and sorptive separator employs a physisorbent. Accordingly, such applications are provided herein by the present applicants.

[0010] SUMMARY

[0011] In a first broad aspect, a sorptive gas separation process for separating a first component from a first stream comprising a first component, and a third component, the process can comprise the steps of:

[0012] (a) splitting the first stream into a second stream and a third stream;

[0013] (b) converting the second stream into a fourth stream, converting the third stream into a fifth stream, and at least one of: the converting of the second stream into the fourth stream further comprising removing a second component from or decreasing a concentration of the second component in the second stream to form the fourth stream with a lower concentration of the second component relative to the first stream, and the converting of the third stream into the fifth stream further comprising adding the second component to or increasing a concentration of the second component in the second stream to form the fifth stream with a higher concentration of the second component relative to the first stream;

[0014] (c) admitting the fourth stream into a sorptive separator with a sorbent on and / or in a contactor, contacting the fourth stream with the sorbent, sorbing the first component in the fourth stream on and / or in the sorbent forming a sixth stream from the non-sorbed components of the fourth stream, and recovering the sixth stream from the contactor and / or sorptive separator; (d) admitting the fifth stream into the sorptive separator and / or the contactor, contacting the fifth stream with the sorbent and desorbing the first component sorbed on the sorbent from the fourth stream while sorbing at least a fraction of the second component from the fifth stream, forming a seventh stream comprising the non-sorbed components of the fifth stream, and recovering the seventh stream from the contactor and / or sorptive separator;

[0015] (e) admitting the seventh stream into the sorptive separator and / or the contactor and contacting the seventh stream with the sorbent, sorbing at least a fraction of the first component from the seventh stream on the sorbent, forming an eighth stream from the non-sorbed components of the seventh stream, and recovering the eighth stream from the contactor and / or sorptive separator;

[0016] (f) admitting a regeneration stream or a ninth stream into the sorptive separator and / or the contactor, contacting the regeneration stream or ninth stream comprising the second component with the sorbent, sorbing at least a fraction of the second component from the regeneration stream or the ninth stream on the sorbent and forming a tenth stream enriched in first component relative to the first stream and the seventh stream, and recovering the tenth stream from the contactor and / or sorptive separator.

[0017] In a second broad aspect, a sorptive gas separation system can comprise: (a) a first stream source;

[0018] (b) a stream splitting device fluidly connected to the first stream source; (c) a second component liquid source;

[0019] (d) at least one stream conditioning device fluidly connected downstream of the stream splitting device; (e) at least one flashing or vaporizing device;

[0020] (f) a sorptive separator having an enclosure, a contactor located within the enclosure, at least one sorbent on and / or in the contactor, and at least a first zone, a second zone, a third zone, a fourth zone, and a fifth zone within the enclosure, wherein the first zone, the second zone, the third zone, the fourth zone, and the fifth zone are substantially fluidly separate from each other within the enclosure, and each zone comprise an inlet and an outlet; and the contactor moves through the first zone, the second zone, the third zone, the fourth zone, and the fifth zone within the enclosure;

[0021] (g) at least one fluid connection between an outlet of the at least one stream conditioning device and at least one of the inlet of the first zone, the inlet of the second zone, the inlet of the third zone, the inlet of the fourth zone, and the inlet of the fifth zone of the sorptive separator,

[0022] (h) a fluid connection between an outlet of a zone of the sorptive separator and an inlet of a zone of the sorptive separator;

[0023] (i) a fluid connection between at least the flashing and vaporizing device outlet and the fourth or fifth sorptive separator zone inlet and a fluidic connection from the fourth or fifth sorptive separator zone to collect the purified product stream;

[0024] (j) a fluid connection between the inlet of the fifth zone and a conditioning stream source, and

[0025] (k) a fluid connection between the outlet of the fifth zone and the inlet of the third zone.

[0026] In a third broad aspect, a sorptive gas separation system can comprise: (a) a stream splitting device for dividing a first stream into a second stream and a third stream;

[0027] (b) at least one of a first stream conditioning device fluidly connected downstream of the stream splitting device to receive the second stream and for adjusting a concentration of the second component and / or a temperature of the second stream, and a second stream conditioning device fluidly connected downstream of the stream splitting device to receive the third stream and for adjusting a concentration of the second component and / or the temperature of the third stream;

[0028] (c) at least one flashing or vaporizing device fluidly connected to receive a liquid regeneration stream comprising the second component from a liquid regeneration stream source for converting the second component in the liquid regeneration stream from a liquid phase into a gas phase and forming a ninth stream, and

[0029] (d) a sorptive separator fluidly connected to at least one of the first stream conditioning device for admitting the fourth stream into the sorptive separator and the second stream conditioning device for admitting the fifth stream into the sorptive separator, a sixth stream conduit for recovering the sixth stream from the sorptive separator, the at least one flashing or vaporizing device for admitting the ninth stream into the sorptive separator, a tenth stream conduit for recovering the tenth stream from the sorptive separator, a seventh stream conduit for recovering the seventh stream from the sorptive separator and admitting the seventh stream from the sorptive separator, and an eighth stream conduit for recovering the eighth stream from the sorptive separator, the sorptive separator comprising at least one sorbent for selectively sorbing a first component and a second component. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a graph of sorptive capacity or uptake of a sorbent in cc / g for CO2 versus concentration of a feed stream in % by volume at atmospheric pressure and isothermal conditions at 70 °C. Plots illustrate the sorptive capacity for CO2 of an amine sorbent on a sorbent support and a CALF-20 metal-organic framework sorbent.

[0031] Figures 2a and 2b are schematic diagrams of a prior art sorptive separation process cycle and an embodiment sorptive separation process cycle of the present invention with a sequence of cycle steps presented from the left to the right. Figure 2a shows the prior art process without splitting of the feed stream. Figure 2b shows an embodiment sorptive separation process of the present invention with splitting of the feed stream and CO2 preconcentration;

[0032] Figures 2c and 2d are graphs showing plots of sorbent loading or uptake of CO2 versus an axial position of a sorbent bed with the inlet on the left side of the graph and an outlet on the right side of the graph. Figure 2c shows sorbent loading of CO2 versus sorbent bed axial position at the end of a first sorption step in the prior art process. Figure 2d shows sorbent loading of CO2 versus sorbent bed axial position at the end of the first and second sorption steps of the embodiment process with recycle of a preconcentrated stream;

[0033] Figure 3 is a schematic diagram of an embodiment sorptive separation process of the present invention with splitting of the feed stream and a process sequence from left to right;

[0034] Figure 4 is a schematic diagram of an embodiment sorptive separation process of the present invention integrating moisture recovery from a fraction of the conditioning stream using membrane moisture exchangers;

[0035] Figure 5 is a schematic diagram of an embodiment sorptive separation process of the present invention integrating moisture recovery from a fraction of the conditioning stream using membrane moisture exchangers and a heat pump with cooling and heating loops for recovering a fraction of the heat of condensation of water from a fraction of the stream and admitting the heat recovered into the second fraction of the stream;

[0036] Figure 6 is a schematic diagram of an embodiment sorptive separation process of the present invention integrating recycling of a fraction of the concentrated CO2 product into a second sorption step;

[0037] Figure 7 is a schematic diagram of an embodiment sorptive separation process of the present invention integrating separation of the effluent of the first pre-concentration step with recycling in reverse order in between a second feed step and the sorbent regeneration and product recovery step;

[0038] Figure 8 is a schematic diagram of an embodiment sorptive separation process of the present invention using two pre-concentration stages for generating three different streams with increasing CO2 concentrations upstream of a CO2 recovery and purification process, and

[0039] Figure 9 is a schematic diagram of an embodiment sorptive separation process of the present invention using two pre-concentration stages and a recovery stage with a recycle stream. The sequence of steps relative to the sorbent contactor is from left to right while feed streams are represented by arrows flowing to the contactor and product streams are represented by arrows flowing away from the contactor.

[0040] DETAILED DESCRIPTION

[0041] Definitions:

[0042] CAPEX: Capital expenditures (CapEx) can be funds used by a company to acquire, upgrade, and maintain capital assets such as property, plants, buildings, technology, or equipment. Condensed form: for a chemical compound, a form different from a gaseous phase, a vapor phase, or a plasma state, for example, a pure liquid phase form, a mixed multicomponent liquid form, an adsorbed form or a non-gaseous complexed form.

[0043] Conditioned stream: A fluid stream where at least one of a temperature, a pressure, and a composition is changed by a conditioning device for forming a conditioned stream Conditioning device: a device for changing at least one of a temperature, a pressure, and a composition of a conditioned flue gas or a conditioned fluid stream recovered from the conditioning device relative to a flue gas or a fluid stream admitted into the conditioning device. Conditioning devices can include, for example, a direct contact cooler (DCC), a heat exchanger (HEX), a mixing device for adding and combining at least one component to a fluid stream admitted into the mixing device, a condensing device for removing a condensable component from a fluid stream admitted into the mixing device, and an evaporator for adding a gaseous component into a fluid stream admitted into the evaporator and converting the fluid stream from a liquid phase to a gas phase.

[0044] COP: Coefficient of Performance. A COP of a heat pump, refrigerator or air conditioning system, is a ratio of an amount of useful heating or cooling provided to an amount of work (energy) required or desired.

[0045] CO2: Carbon dioxide. The terms carbon dioxide and CO2 can be used interchangeably herein.

[0046] DCC: Direct Contact Cooler is a device where a first fluid stream in a gas phase can be contacted with a second fluid stream in a liquid phase and heat is transferred from the first fluid stream in the gas phase to the second fluid stream in the liquid phase. The first fluid stream can be in a liquid phase while the second fluid stream can be in a gas phase. A DCC can also be used as a vaporizer for increasing the moisture content of fluid stream in a gas phase while cooling the fluid stream.

[0047] Evaporator: a device for converting a fraction of a liquid stream into a gas stream for forming a substantially pure stream comprising a vaporized component originating from the liquid stream or a mixture of gases through mixing a vaporized component originating from the liquid stream with another component in another gas stream.

[0048] MOF: Metal-Organic Frameworks (MOFs) are a class of porous materials comprising metal ions or clusters of ions coordinated with organic ligands. MOFs can have a crystalline structure that forms a regular array of cages or channels.

[0049] MT: Metric Ton or 1000 Kilograms (kg).

[0050] OPEX: operating expenses, or OPEX, are expenditures that a company incurs as part of its normal day-to-day operations, such as rent, travel, utilities, salaries, office supplies, maintenance and repairs, property taxes, and depreciation.

[0051] OTSG: Once Through Steam Generator (OTSG) is a combustion device which can use a carbon-containing fuel such as natural gas for producing steam for various applications including oil recovery and naval applications.

[0052] RH: Relative Humidity or RH is a ratio of a partial pressure of water in a gas mixture to a saturation partial pressure of water at a given temperature and pressure.

[0053] Primary flue gas: Flue gas admitted into a CO2 separation system from a flue gas source, for example, an industrial source or flue gas from an industrial process.

[0054] Residual gas: mixture of components not sorbed in and / or on a sorbent in the voids of a sorbent contactor, or sorptive separator.

[0055] Sorbent: a material used to selectively absorb and / or adsorb a target component from a multi-component gas stream. The sorbent is in the form of a solid unless otherwise stated.

[0056] Contactor: a device comprising a sorbent in solid form and flow channels for promoting the mass transfer of a fluid or gas stream to the sorbent. For some configurations, a contactor can direct the flow of the fluid or gas stream between an inlet and an outlet of a sorptive separator. A contactor can include but not limited to, for example, a structured bed configured with repeated elements forming a set of substantially parallel channels between an inlet and an outlet, or a packed bed configured with sorbent particles stacked together with voids between the particles for providing flow channels for the fluids entering and exiting the contactor. The terms sorbent contactor and contactor can be used interchangeably herein.

[0057] Sorptive separator: a device or assembly can comprise at least one contactor with at least one solid sorbent, wherein the contactor can be stationary or moving. A sorptive separator can comprise fluidized solid sorbents, or liquid sorbents where stated.

[0058] Pre-concentrator device or process: a device or process for increasing a concentration of a first component in a fluid stream relative to a multi-component stream forming at least two outlet, effluent, or product streams which can be an outlet, effluent, or product stream enriched in the first component relative to the multi-component stream and an outlet, effluent, or product stream depleted in the first component relative to the multicomponent stream, for example, producing a fluid stream with a concentration of less than 50 volume% of the first component. The pre-concentrator can comprise a sorptive separator, a membrane, or a cryogenic device.

[0059] Purification or recovery device or process: a device or process for increasing a concentration of a first component in a fluid stream relative to a multi-component stream forming at least two outlet, effluent, or product streams, an outlet, effluent, or product stream enriched in a first component relative to a multi-component stream, for example, with a concentration of greater than 80 volume%, and an outlet, effluent, or product stream depleted in the first component relative to the multi-component stream. The purification device can comprise a cryogenic device, a sorptive separator or a membrane.

[0060] Secondary flue gas: A flue gas generated within the sorptive gas separation system as a modified stream, or a new stream or flue gas generated within the separation and purification system.

[0061] VVC: a unit of measure of a sorptive capacity of a contactor, Volume of purified product per Volume of Contactor (or Bed) per Cycle. For example, for separation of CO2 from a feed stream a quantity of CO2 recovered from a sorptive separator per cycle of a sorptive gas separation process in standard volume (liters) per liter of contactor volume. Embodiments disclosed herein relate to the use of a solid physisorbent for separating an acid gas component from a gas mixture. In particular, the separation of CO2 from a flue gas, a biogas, a process gas, a mixture of hydrocarbon or hydrogen with CO2, when the partial pressure of CO2 in the mixture is below 15 kPa or 15% volume concentration at atmospheric pressure.

[0062] A shortcoming of a physisorbent is that its sorption capacity varies strongly with the partial pressure of the sorbate or target component in a gas mixture. The embodiment moisture swing process improves the performance of a physisorbent in applications where a feed stream has a low partial pressure of the sorbate or target component.

[0063] Figure 1 is a graph of sorptive capacity or uptake of a sorbent in cc / g for CO2 on the y-axis versus concentration of a feed stream in % by volume at atmospheric pressure and isothermal conditions at 70 °C on the x-axis. A CALF-20 metal-organic framework sorbent, is shown by a plot 10, illustrating a decline in sorptive capacity at concentrations of less than about 15% CO2 while an amine based sorbent shown as a plot 12 has a relatively higher sorptive capacity at concentrations of less than about 15% CO2.

[0064] The embodiment processes disclosed herein enable use of physisorbents, the CALF-20 sorbent, or similar MOFs for separation of a target or first component, for example, CO₂, by combining a pre-concentration process (using diluted steam stream as a fraction of a regeneration stream for forming a concentrated stream with an enriched concentration of the first component or CO2) with subsequently a purification process for forming a high purity stream with a high concentration of the first component or CO2 (for example, with equal to or greater than 90% volume on a dry basis) using partial pressure swing of a second component or water. The pre-concentration process and purification process can be carried out substantially in parallel within a device, such as a sorptive separator with at least one sorbent contactor which can move or rotate, and the at least one sorbent contactor or portions of the at least one sorbent contactor can be sequentially exposed to different process steps and streams. A pre-concentration process or step can be beneficial for separating a first component or CO2 from a diluted stream. For example, a process stream with 8% CO₂ is split into two streams, a first influent stream (or a first fraction of the flue or feed stream) and a second influent stream (or a second fraction of the flue or feed stream), and admitted into a sorptive separator comprising a physisorbent, or MOF such as a CALF-20 sorbent to form two product streams: a first effluent stream with a 2% CO₂ concentration and a second effluent stream with a 14% CO₂ concentration of about equal flow rates. The first and second effluent streams can be admitted into different sections of the sorptive separator sequentially with the stream with a 2% CO₂ concentration added first and then the stream with a 14% CO₂ concentration added second. The CO2 saturated sorbents are then regenerated by exposure to a regeneration stream or steam thus forming a concentrated CO2 stream.

[0065] The effect of saturating the sorbent contactor with a stream without splitting and with a concentration of 8% CO₂ may result in 0.5 mmol / g of CO₂ being loaded on the sorbent, while saturating the sorbent contactor with a second effluent stream after splitting with a concentration of 14% CO₂ may result in 0.75 mmol / g of CO₂ being loaded on the sorbent. The higher sorbent loading enables greater energy efficiency during regeneration, for example, when adding steam for regeneration of the sorbent. The amount of CO₂ recovered per process cycle can increase faster than the amount of steam added per process cycle for supplying the heat of desorption for CO₂. This can result in a specific energy reduction per unit weight of CO₂ recovered. A preconcentration process and integration into a two-stage system is disclosed in International Publication WO 2025 / 153969 A1.

[0066] In one aspect the embodiment sorptive separation process can comprise steps of concentrating a fraction of the flue gas or feed stream while partially depleting another fraction of the feed stream preferably using energy stored as chemical potential within a fraction of the flue gas or feed gas stream before directing both fractions to a second stage recovery and purification process.

[0067] The embodiment sorptive separation process discloses integration of a preconcentration process (using a second fraction of the feed stream for regeneration of the sorbent) with a subsequent purification process in a (single) sorptive separator with one or more sorbent contactors moving between the preconcentration process and the purification process rather than using two separate sorptive separators each with their own sorbent contactor. Employing a sorptive separator and moving the at least one sorbent contactor between both processes can enable the transfer and use of heat from one process to another, for example, transferring heat between the preconcentration process and the purification process through heat stored on the sorbent or sorbed components, and can enable novel recycling of one or more effluent streams relative to the prior art of using two sorbent separators with individual sorbent contactors which are not physically connected. Another difference as compared to the prior art is the embodiment process can comprise recycling of a preconcentrated stream within a purification process either before a first regeneration step (using diluted steam in a second fraction of the feed stream comprising the first component or CO2) or after the first regeneration step.

[0068] In another aspect, recycling of streams containing CO2 from the second concentration or purification process produced during the regeneration and conditioning steps can assist the first concentration stage or preconcentration process by adding heat into the sorbent or by assisting in flushing non-sorbed components from voids of the sorbent contactor and / or sorptive separator which can increase the purity or concentration of a product stream recovered during a second regeneration step.

[0069] In an embodiment, a sorptive gas separation process for separating a first component from a first stream (or a feed stream) comprising a first component, and a third component, the process can comprise the steps of:

[0070] (a) splitting the first stream into a second stream (or a first fraction of the feed stream) and a third stream (or a second fraction of the feed stream);

[0071] (b) converting the second stream into a fourth stream, converting the third stream into a fifth stream, and at least one of: the converting of the second stream into the fourth stream further comprising removing a second component from or decreasing a concentration of the second component in the second stream to form the fourth stream with a lower concentration of the second component relative to the first stream, and the converting of the third stream into the fifth stream further comprising adding the second component to or increasing a concentration of the second component in the second stream to form the fifth stream with a higher concentration of the second component relative to the first stream;

[0072] (c) admitting the fourth stream into a sorptive separator with a sorbent on and / or in a contactor, contacting the fourth stream with the sorbent, sorbing the first component in the fourth stream on and / or in the sorbent forming a sixth stream from the non-sorbed components of the fourth stream, and recovering the sixth stream from the contactor and / or sorptive separator;

[0073] (d) admitting the fifth stream into the sorptive separator and / or the contactor, contacting the fifth stream with the sorbent and desorbing the first component sorbed on the sorbent from the fourth stream while sorbing at least a fraction of the second component from the fifth stream, forming a seventh stream comprising the non-sorbed components of the fifth stream, and recovering the seventh stream from the contactor and / or sorptive separator;

[0074] (e) admitting the seventh stream into the sorptive separator and / or the contactor and contacting the seventh stream with the sorbent, sorbing at least a fraction of the first component from the seventh stream on the sorbent, forming an eighth stream from the non-sorbed components of the seventh stream, and recovering the eighth stream from the contactor and / or sorptive separator;

[0075] (f) admitting a regeneration stream or a ninth stream into the sorptive separator and / or the contactor, contacting the regeneration stream or ninth stream comprising the second component with the sorbent, sorbing at least a fraction of the second component from the regeneration stream or the ninth stream on the sorbent and forming a tenth stream enriched in first component relative to the first stream and the seventh stream, and recovering the tenth stream from the contactor and / or sorptive separator.

[0076] In embodiments, the sorptive gas separation process can further comprise at least one of the following:

[0077] • wherein step (c) through step (f) are sequential;

[0078] • controlling a composition of the ninth stream to comprise a concentration of the second component of equal to or greater than 30% volume and controlling at least one of a flow rate, a contact times and a pressure of the seventh stream and the ninth stream for forming a heat of adsorption of the second component on the sorbent generated in step (f) which is greater than a heat of adsorption on the sorbent of the first component generated in step (e);

[0079] • wherein the first component is CO2;

[0080] • wherein the first stream (or the feed stream) further comprising the second component;

[0081] • wherein the second component is water;

[0082] • wherein the third component is nitrogen;

[0083] • controlling a quantity of steam in the fifth stream for obtaining a concentration of CO₂ in the seventh stream which is greater than 50% to 400% or 50% to 200% of a concentration of CO₂ in the first stream;

[0084] • recovering heat while reducing a temperature of the second stream in the first conditioning device and transferring the recovered heat into the fifth stream in the second conditioning device using heat exchangers which can be fluidly connected to at least one heat pump;

[0085] • in a step (g) admitting a conditioning stream or an eleventh stream into the sorptive separator and / or the contactor, contacting the conditioning stream or eleventh stream with the sorbent, desorbing at least a fraction of the second component on and / or in the sorbent, forming a twelfth stream, and directing at least a fraction of the twelfth stream to a moisture exchange membrane or a water selective sorbent separate of the sorptive separator, recovering water from the twelfth stream and transferring the recovered water into the fifth stream;

[0086] • wherein the sorbent comprises at least one of a metal-organic framework material, a covalent organic framework material, a porous carbon material, a zeolite, a functionalized polymer, a porous inorganic material;

[0087] • wherein the sorbent comprises CALF-20, or a metal organic framework sorbent comprising Zinc ions, triazolate ligands and oxalate ligands;

[0088] • wherein during step (c) an average temperature of the sorbent is at a temperature of equal to or less than 80 °C and during step (e) a temperature of the sorbent is equal to or greater than 100 °C;

[0089] • admitting the second stream (first fraction of the feed stream or dry influent stream) and admitting the third stream (second fraction of the feed stream or a wet influent stream) into the sorptive separator and / or the contactor in a counter-flow direction relative to each other, and

[0090] • recovering equal to or greater than 25% of the first component in the seventh stream from the fifth stream.

[0091] During a regeneration step, while flushing the void(s) of the contactor of residual gas, a significant amount of CO2 can be liberated from the sorbent. This can concentrate CO2 at an end of a contactor and thereby during a subsequent regeneration step this can enable the recovery of a high purity CO2 stream.

[0092] The first fraction of the feed stream or the fourth stream and the second fraction of the feed stream or the fifth stream can flow in a counter-flow direction relative to each other in the sorptive separator and / or the contactor. The counter-flow orientation may drive a first component or CO2 loading gradient in a contactor towards the outlet of the contactor while the second component or water accumulates toward an inlet of the contactor.

[0093] In one embodiment, a sorptive gas separation process is provided for separating a first component from a first stream comprising a first component, and a second component, the process can comprise the following steps:

[0094] (a) splitting the first stream (a feed stream) into a second stream (a first fraction of the feed stream) and a third stream (a second fraction of the feed stream); (b) converting the second stream into a fourth stream, converting the third stream into a fifth stream, and at least one of: the converting of the second stream into the fourth stream further comprising removing the second component from or decreasing a concentration of the second component in the second stream to form the fourth stream with a lower concentration of the second component relative to the first stream, and the converting of the third stream into the fifth stream further comprising adding the second component to or increasing a concentration of the second component in the second stream to form the fifth stream with a higher concentration of the second component relative to the first stream;

[0095] (c) admitting the fourth stream into a sorptive separator with a sorbent on and / or in a contactor, contacting the fourth stream with the sorbent, sorbing the first component in the fourth stream on and / or in the sorbent forming a sixth stream from the non-sorbed components of the fourth stream, and recovering the sixth stream from the contactor and / or sorptive separator;

[0096] (d) admitting the fifth stream into the sorptive separator and / or contactor, contacting the fifth stream with the sorbent and desorbing the first component sorbed on the sorbent from the fourth stream while sorbing at least a fraction of the second component from the fifth stream, forming a seventh stream comprising the non-sorbed components of the fifth stream, and recovering the seventh stream from the contactor and / or sorptive separator;

[0097] (e) admitting the seventh stream into the sorptive separator and / or contactor and contacting the seventh stream with the sorbent, sorbing at least a fraction of the first component from the seventh stream on the sorbent, forming an eighth stream from the non-sorbed components of the seventh stream, and recovering the eighth stream from the contactor and / or sorptive separator; (f) admitting a regeneration stream or a ninth stream into the sorptive separator and / or contactor, contacting the regeneration stream or ninth stream comprising the second component with the sorbent, sorbing at least a fraction of the second component from the regeneration stream or the ninth stream on the sorbent and forming a tenth stream enriched in first component relative to the first stream and the seventh stream, and recovering the tenth stream from the contactor and / or sorptive separator.

[0098] In aspects, step (c) through step (f) are sequential.

[0099] In an embodiment, the sorptive gas separation process can further comprise a step of removing the second component from the tenth stream. In one aspect, the tenth stream can have a concentration of the first component or CO2 of equal to or greater than 90 % volume after removing the second component.

[0100] In an embodiment, the process can further comprise a step of controlling and / or adjusting a composition of the ninth stream to have a concentration of the second component of equal to or greater than 30% by volume. In another embodiment, the process can further comprise a step of controlling the at least one of the flow rate, contact time and pressures of the seventh stream and the ninth stream, such that the heat of adsorption of the second component on the sorbent generated in step (f) is greater than the heat of adsorption on the sorbent of the first component generated in step (e).

[0101] In an embodiment, further comprising prior to step (e), removing at least a portion or reduce a concentration of the second component from the seventh stream. In an embodiment, the sorptive separator comprises at least a first zone, a second zone, a third zone, and a fourth zone, the first zone, the second zone, the third zone, and the fourth zone are configured sequentially in the sorptive separator, and performing step (c) in the first zone, step (d) in the third zone, step (e) in the second zone, and step (f) in the fourth zone.

[0102] In an embodiment, the sorptive separator comprises at least a first contactor, a second contactor, a third contactor, and a fourth contactor, the first contactor, the second contactor, the third contactor, and the fourth contactor are configured sequentially in the sorptive separator, and performing step (c) in the first contactor, step (d) in the third contactor, step (e) in the second contactor, and step (f) in the fourth contactor. In an embodiment of the sorptive gas separation process, the first component is CO₂, the second component is H₂O or water.

[0103] In one aspect, the first stream is a combustion gas stream, a flue gas stream, a process gas stream, a biogas stream, or an air stream. In one aspect, the first stream further comprising a third component or nitrogen.

[0104] In an embodiment, the sorptive gas separation process further comprising at least one of in step (c) admitting the fourth stream into the sorptive separator and / or the contactor and in step (d) admitting the fifth stream into the sorptive separator and / or contactor wherein the fifth stream is in a counter flow direction in the sorptive separator and / or contactor in relation to the fourth stream; in step (d) admitting the fifth stream into the sorptive separator and / or contactor and in step (e) admitting the seventh stream into the sorptive separator and / or contactor, wherein the seventh stream is in a counter flow direction in the sorptive separator and / or contactor in relation to the fifth stream; and in step (d) admitting the fifth stream into the sorptive separator and / or contactor and in step (f) admitting the regeneration stream or the ninth stream into the sorptive separator and / or contactor, wherein the nineth stream is in a co-flow direction in the sorptive separator and / or contactor in relation to the fifth stream.

[0105] In an embodiment, the sorptive gas separation process further comprising after step (f) a step (g) admitting a first conditioning stream or an eleventh stream into the sorptive separator and / or contactor, contacting the eleventh stream with the sorbent and desorbing the second component sorbed on the sorbent from the ninth stream, forming a twelfth stream enriched in the second component relative to at least one of the third stream or the fifth stream, and recovering the twelfth stream from the contactor and / or sorptive separator. In aspects, the sorptive separator further comprise a fifth zone, and performing the admitting of the eleventh stream is into the fifth zone and the recovering of the twelfth stream is from the fifth zone. In further aspects the fifth zone is configured sequentially to the fourth zone in the sorptive separator. In another aspect, at least a portion of the twelfth stream is admitted into the third zone. In other aspects, step (a) to step (g) are sequential, and step (a) to step (g) are sequential and repeated.

[0106] In an embodiment, the sorptive gas separation process further comprising after step (g) a step (h), admitting a second conditioning stream or a thirteenth stream into the sorptive separator and / or contactor, contacting the thirteenth stream with the sorbent and desorbing the second component sorbed on the sorbent, forming a fourteenth stream enriched in the second component relative to at least one of the third stream or the fifth stream, and recovering the fourteenth stream from the contactor and / or sorptive separator. In aspects, the sorptive separator further comprise a sixth zone, and performing the admitting of the thirteenth stream is into the sixth zone and the recovering of the fourteenth stream is from the sixth zone. In further aspects the sixth zone is configured sequentially to the fifth zone in the sorptive separator. In other aspects, step (a) to step (h) are sequential, and step (a) to step (h) are sequential and repeated.

[0107] In an embodiment, the sorptive gas separation process further comprising in step (f), admitting the regeneration stream or the ninth stream into the sorptive separator and / or contactor and in step (g) admitting the first conditioning stream or the eleventh stream into the sorptive separator and / or contactor, wherein the eleventh stream is in a counter flow direction in the sorptive separator and / or contactor in relation to the nineth stream; and in step (g) admitting the first conditioning stream or the eleventh stream into the sorptive separator and / or contactor and in step (h) admitting the second conditioning stream or the thirteenth stream into the sorptive separator and / or contactor, wherein the thirteenth stream is in a co-flow direction in the sorptive separator and / or contactor in relation to the eleventh stream.

[0108] In an embodiment, the sorptive gas separation process further comprises recovering a fraction of the second component, water, or second component in a vapor phase from an exhaust stream or preferably a fourteenth stream, using, for example, a membrane moisture exchange, and adding the recovered second component or water to the third stream or fifth stream.

[0109] This embodiment is particularly advantageous for a conditioning step, for example, step (g) or step (h), where the twelfth stream or fourteenth stream comprise a high partial pressure of the second component and a large fraction of this second component can be transferred to the third stream without compressing the fourteenth stream.

[0110] For example, in applications where the first stream comprises a concentration of the second component or water of less than about 20%, a portion of the twelfth stream or fourteenth stream may have a concentration of water of greater than about 40% which may be separated and used.

[0111] In an embodiment, the process can further comprise recovering heat from the second stream while cooling the second stream in the first conditioning device. In one aspect, transferring the recovered heat to the fifth stream in the second conditioning device using heat exchangers fluid ically connected to at least one heat pump.

[0112] In an embodiment of the sorptive gas separation process, a plurality of conditioning steps may be employed for recovering a plurality of conditioning effluent streams, with decreasing temperature and partial pressure in the second component. In this case, multiple selective membranes can be used in series to increase the recovery of the second component from the recovered conditioning effluent streams.

[0113] In an embodiment of the sorptive gas separation process, the sorbent is at least one of a metal-organic framework material, CALF-20, a covalent organic framework material, a porous carbon material, a zeolite material, a polymer, or a porous inorganic material. CALF-20 is a metal-organic framework comprising zinc ions, triazolate ligands and oxalate ligands.

[0114] In an embodiment, a sorptive gas separation system can comprise:

[0115] (a) a first stream (or a feed stream) source;

[0116] (b) a stream splitting device fluidly connected to the first stream source for splitting a first stream into a second stream (or first fraction of the first stream) and a third stream (or a second fraction of the first stream);

[0117] (c) a second component liquid source;

[0118] (d) at least one stream conditioning device fluidly connected downstream of and / or to the stream splitting device for adjusting a temperature and a concentration of a second component of at least one of the second stream (or the first fraction of the first stream) and the third stream (or the second fraction of the first stream) and increasing a concentration of the second component in the third stream (or the second fraction of the first) relative to a concentration of the second component in the second stream (or first fraction of the first stream);

[0119] (e) at least one flashing or vaporizing device for converting a fluid stream having the second component in a liquid phase into a vapor stream or a gas phase for forming, for example, a regeneration stream or a nineth stream; (f) a sorptive separator having an enclosure, a contactor located within the enclosure, at least one sorbent on and / or in the contactor, and at least a first zone, a second zone, a third zone, a fourth zone, and a fifth zone within the enclosure, wherein the first zone, the second zone, the third zone, the fourth zone, and the fifth zone are substantially fluidly separate from each other within the enclosure, and each zone comprise an inlet and an outlet; and the contactor moves through the first zone, the second zone, the third zone, the fourth zone, and the fifth zone within the enclosure; (g) at least one fluid connection between an outlet of the at least one stream conditioning device and the sorptive separator;

[0120] (h) a fluid connection between an outlet of a zone of the sorptive separator and an inlet of a zone of the sorptive separator;

[0121] (i) a fluid connection between the at least one flashing or vaporizing device and the inlet of the fourth zone, and

[0122] (j) a fluid connection between the inlet of the fifth zone and a conditioning stream source and a fluid connection between the outlet of the fifth zone and the inlet of the third zone for recovering the conditioning stream effluent. In an embodiment, a sorptive gas separation system can further comprise at least one of: a first stream conditioning device; a second stream conditioning device; a fluid connection between an outlet of the first stream conditioning device and the inlet of the first zone; a fluid connection between an outlet of the second stream conditioning device and the inlet of the third zone; a fluid connection between an outlet of the second stream conditioning device and the inlet of the second zone, and a fluid connection from the outlet of the fourth zone to an end use for recovering the purified product stream.

[0123] In other embodiments, at least one of:

[0124] • the at least one flashing or vaporizing device can be fluidly connected to receive a carrier gas from a carrier gas supply for diluting the fluid stream having the second component in a vapor or gas phase with the carrier gas;

[0125] • the zones are stationary and the contactor moves;

[0126] • the sorptive separator further comprising a plurality of contactors, wherein the plurality of contactors are stationary and the zones move;

[0127] • wherein the sorptive contactor cycles between sorbing and desorbing the first component within two minutes, one minute, or thirty seconds;

[0128] • wherein the sorbent is physisorbent, a metal organic framework sorbent or a CALF-20 sorbent, and • in (h) the fluidic connection is between at least one of the following: the outlet of the first zone and the inlet of the second zone inlet; the outlet of the first zone and the inlet of the third zone; the outlet of the first zone and the inlet of the fourth zone; the outlet of the first zone and the inlet of the fifth zone; the outlet of the second zone and the inlet of the third zone; the outlet of the second zone and the inlet of the fourth zone; the outlet of the second zone and the inlet of the fifth zone; the outlet of the third zone and the inlet of the fourth zone; the outlet of the third zone and the inlet of the fifth zone, and the outlet of the fourth zone and the inlet of the fifth zone. In an embodiment, a sorptive gas separation system of the present invention, the system comprises:

[0129] (a) a stream splitting device for dividing a first stream into a second stream and a third stream;

[0130] (b) at least one of a first stream conditioning device fluidly connected downstream of the stream splitting device to receive the second stream and for adjusting a concentration of the second component and / or a temperature of the second stream, and a second stream conditioning device fluidly connected downstream of the stream splitting device to receive the third stream and for adjusting a concentration of the second component and / or the temperature of the third stream;

[0131] (c) at least one flashing or vaporizing device fluidly connected to receive a liquid regeneration stream comprising the second component from a liquid regeneration stream source for converting the second component in the liquid regeneration stream from a liquid phase into a gas phase and forming a ninth stream, and

[0132] (d) a sorptive separator fluidly connected to at least one of the first stream conditioning device for admitting the fourth stream into the sorptive separator and the second stream conditioning device for admitting the fifth stream into the sorptive separator, a sixth stream conduit for recovering the sixth stream from the sorptive separator, the at least one flashing or vaporizing device for admitting the ninth stream into the sorptive separator, a tenth stream conduit for recovering the tenth stream from the sorptive separator, a seventh stream conduit for recovering the seventh stream from the sorptive separator and admitting the seventh stream from the sorptive separator, and an eighth stream conduit for recovering the eighth stream from the sorptive separator, the sorptive separator comprising at least one sorbent for selectively sorbing a first component and a second component.

[0133] In embodiments of the sorptive gas separation system, the sorptive separator further comprising a first zone, a second zone, a third zone and a fourth zone. In aspects of the embodiments, the first zone is fluidly connected to the first stream conditioning device and the sixth stream conduit, the second zone is fluidly connected to the seventh stream conduit and the eighth stream conduit, the third zone is fluidly connected to the second stream conditioning device and the seventh stream conduit, the fourth zone is fluidly connected the at least one flashing or vaporizing device and the tenth stream conduit. In further aspects, the first zone, the second zone, the third zone and the fourth zone are configured in sequential order.

[0134] In embodiments of the sorptive gas separation system, at least one of the third zone and the fourth zone is fluidly connected to the eighth stream conduit, or the second zone for admitting the eighth stream into at least one of the third zone and the fourth zone.

[0135] In embodiments of the sorptive gas separation system, the sorptive separator is fluidly connected to a conditioning stream source for admitting at least one conditioning stream, for example, at least one of an eleventh stream and a thirteenth stream, into the sorptive separator, and at least one of a twelfth stream conduit for recovering a twelfth stream and a fourteenth stream conduit for recovering a fourteenth stream from the sorptive separator. In further embodiments, the sorptive separator further comprising at least one of a fifth zone and a sixth zone, the at least one of the fifth zone and the sixth zone is or are fluidly connected to the conditioning stream source for admitting at least one of an eleventh stream into the fifth zone and a thirteenth stream into the sixth zone, and fluidly connected to at least one of the twelfth stream conduit for recovering the twelfth stream from the fifth zone of the sorptive separator and a fourteenth stream conduit for recovering the fourteenth stream from the sixth zone of the sorptive separator. In one aspect the fifth zone and / or twelfth stream conduit is fluidly connected to the third zone.

[0136] Figures 2a and 2b presents a comparison of a prior art process shown in Figure 2a where a feed stream or a first stream with diluted concentration of CO2 is separated from the first stream with one sorption step as compared to the embodiment sorptive separation process shown in Figure 2b where a plurality of sorption steps and regeneration steps are used in the sorption separation process.

[0137] Figure 2a shows influent streams admitted into, and effluent streams recovered from, a sorptive separator 150 with zones or sections 150a, 150b, 150c, 150d, 150e, 150f, and 150g with one or more sorbent contactors moving sequentially and cyclically between the zones or sections. A first stream 101 comprising a first component or CO2 is conditioned through a stream conditioning device or a DCC 102 before contacting a sorbent contactor within process section 150a and forming an exhaust or an eighth stream 118 which can be directed to a stack. A fraction of exhaust or an eighth stream 118a can be recycled as an effluent stream 119 to an inlet of section 150a. Nineth stream 115 recovered from section 150e is admitted into section 150b to purge the non-sorbed gas in the void(s) of the sorbent contactor. In section 150c, a regeneration stream 106a comprising second component vapor or steam is admitted to start the regeneration of the sorbent contactor with the first component or CO2, and flushing non-adsorbed components from the sorbent contactors. The product stream or reflux stream from section 150c is combined with the effluent stream of section 150b and compressed with a fan 153 and recycled into the separation process with the first stream 101. In section 150d, regeneration stream 106b comprising second component vapor or steam is admitted for completing the regeneration of the sorbent contactor, the effluent is then directed to a stream conditioning device or DCC 102b to form a product or tenth stream 107 that is recovered and comprise concentrated first component or CO2. Conditioning or thirteenth stream 108a is heated or dried in stream conditioning device 152a with the effluent stream of stream conditioning device 152a split and admitted in sections 150e and 150f. The effluent from section 150e typically comprise a second component concentration greater than 30% and form the nineth stream 115. The effluent of section 150f is recovered as conditioning effluent or fourteenth stream 109, it also contains significant concentration of second component with greater than 10% concentration which may be recovered. Conditioning or thirteenth stream 108b is heated or dried in stream conditioning device 152b before admitting in section 150g, the effluent of this section exhaust or eighth stream 118 can be directed to a stack.

[0138] Figure 2b presents for the novel and inventive process inlet and outlet streams into a sorptive separator 150 with a plurality of process sections or zones 150a, 150b, 150c, 150d, 150e, 150f, and 150g with one or more sorbent contactors moving cyclically and sequentially in this order between sections. A feed stream or a first stream 101 comprising a first component or CO2 can be split into two fractions, a first fraction of the feed stream or a second stream 101a which can be conditioned through a stream conditioning device or DCC 102 before contacting one or more sorbent contactors within process section or zone 150a and forming an exhaust or eighth stream 118 which can be directed to a stack, and a second fraction of the feed stream or a second stream 101b. In section 150b, seventh stream 105 the effluent of section or zone 150c is admitted in the sorbent contactors, the effluent of section or zone 150b may be direct as a fraction or in full as exhaust or eighth stream 118 to a stack and discarded. A fraction of exhaust or eighth stream 118 can be mixed with an influent stream to section or zone 150a or a fourth stream. In section or zone 150c, second fraction of the feed stream or second stream 101b is mixed with ninth stream 115 and the effluent from section or zone 150d before admitting into sorbent contactors. An effluent of section or zone 150c is seventh stream 105. In section or zone 150d, a regeneration stream 106a comprising second component vapor or steam is admitted to start the regeneration of sorbent contactors, the product stream of section or zone 150d or a reflux stream is combined with second fraction of the feed stream or second stream 101b and (nineth stream 115). In section or zone 150e, regeneration stream 106b comprising second component vapor or steam is admitted for completing the regeneration of sorbent contactors, the effluent stream is then directed to a stream conditioning device or DCC 102b to form a product or a tenth stream 107 which can be recovered and comprise concentrated first component or CO2. Conditioning or thirteenth stream 108a is heated or dried in a stream conditioning device 152a. The effluent from section or zone 150f typically comprise a second component concentration greater than 30% volume and form the stream (nineth stream 115). Conditioning or thirteenth stream 108b is heated or dried in stream conditioning device 152b before admitting in section orzoe 150g. The effluent of section or zone 150g is recovered as conditioning effluent or fourteenth stream 109, which can contain a significant concentration of the second component, for example, greater than 10% which may be recovered.

[0139] Figure 2c presents simulated sorbent contactor loading of the process depicted in Figure 2a (on a y-axis 23, arbitrary unit) of a first component and a second component at selected steps of the process versus the axial position through the contactor (on a x-axis 24) with inlet of the contactor on the left side of the graph and outlet on the right side of the graph. CO2 loading of the sorbent contactor exiting section or zone 150a in Figure 2a is represented as a curve 20. A curve 25a and a curve 25b represents a water loading profile through the sorbent contactor.

[0140] Figure 2d presents simulated sorbent contactor loading of the process depicted in Figure 2b (on a y-axis 23, arbitrary unit) of a first component and a second component at selected steps of the process versus the axial position through the sorbent contactor (on a x-axis 24) with inlet of the contactor on the left side of the graph and outlet on the right side of the graph. CO2 loading of the sorbent contactor exiting section 150a is shown as a curve 21 and exiting section 150b is shown as a curve 22. A water loading profile through the sorbent contactor is shown as a curve 26a and a curve 26b.

[0141] The scale of y-axis 23 in Figures 2a and 2b was kept constant to enable comparison for both simulation results. The CO2 loading from curves 20a and 20b are similar to curve 21, while curve 22 present a cumulative increase of about 50% in CO2 on average for the sorbent contactor with greater gains in sorbent loading for CO2 near the inlet which is drier (with less adsorbed water) than the outlet of the contactor as shown in curves 26a and 26b. At this stage of the cycle, the regeneration of the sorbent becomes significantly energy efficient. It should be noted that in the next step a large fraction of this additional CO2 loaded on the sorbent is stripped from the sorbent contactor in section or zone 150d to form a portion of the feed stream of section or zone 150c, so the benefit of the cycle is not quite as large as it would have been without that intermediate step. However, this sorption / desorption loop acts as a refluxing loop and can help minimize the steam use in regeneration stream 106 by pre-heating the sorbent. This can enable a reduction in steam used in regeneration streams 106a and 106b in the embodiment sorptive separation process versus the prior art process which was a complex seven-step cycle with internal stream recycling.

[0142] Additional quantitative comparative analysis of the cycle presented in Figures 2a and 2b will be presented when discussing the simulation method and results below.

[0143] Figure 3 presents a simplified flow diagram for an embodiment sorptive gas separation process using a wet and a hot influent or feed stream as part of the regeneration stream and / or a preconcentration stream for separation of CO2 from a gas mixture. A flue gas or a feed stream 101 comprising CO2 is split into two fractions; a first fraction of the feed stream or second stream 101a is directed to a first stream conditioning device or a direct contact cooler (DCC) 102 for decreasing its temperature as well as removing some of its moisture content and thus forming a fourth stream 103, and a second fraction of the feed stream or fifth stream 101b can be optionally conditioned through a second conditioning device or a stream conditioning device 111 or mixed with steam to form a fifth stream 104. Flue gas or a feed stream 101 can comprise water or moisture. Both fourth stream 103 and fifth stream 104 can be contacted sequentially with a contactor within a sorptive separator 150. In a first step or step (c) CO2 is removed from the fourth stream 103, in the second step or step (e) CO2 is removed from the seventh stream 105 by contacting a seventh stream 105 which with the sorbent. Seventh stream 105 can have a CO2 concentration greater than a CO2 concentration of fourth stream 103 and fifth stream 104. In the third step or step (d), fifth stream 104 is mixed with ninth stream 115 before contacting with the sorbent and forming stream seventh stream 105. Stream 105 can optionally be mixed with ninth stream 115 which is the effluent of an eleventh stream 114 contacting sorbent contactor 150 in a fifth process step or step (g).

[0144] In a fourth step or step (f), a regeneration stream 106 comprising steam with greater than 30% volume concentration is contacted with the sorbent contactor and produces a product or tenth stream 107 enriched in CO2. Tenth stream 107 can be recovered for further processing, storage, or end use of the CO2. In a fifth step or step (g), an eleventh stream 114 is admitted in sorbent contactor and forms nineth stream 115 enriched in moisture relative to eleventh stream 114. In a sixth step or step (h), a conditioning or a thirteenth stream 108 with a moisture content below 5% volume is admitted into sorbent contactor removing water from sorbent contactor. A conditioning effluent or fourteenth stream 109 recovered from sorbent contactor can be enriched in water relative to conditioning or a thirteenth stream 108.

[0145] Fifth stream 104 may be further enriched in water through admitting steam, vaporization of water in a direct liquid I gas contactor circulating hot water, or via a membrane moisture exchanger. Regeneration stream 106 may be formed in a vaporizer or flashing device from an aqueous liquid regeneration stream 116.

[0146] Figure 3 illustrates a novel aspect of the process with a loop of CO2 sorption-desorption using a wet feed stream in a third step comprising CO2 with fifth stream 104 forming a seventh stream 105 enriched in CO2 which can be recycled into sorbent contactor during a second step prior to the third step.

[0147] Figure 4 illustrates further integration of membrane moisture exchangers into the process to moisturize fifth stream 104 in place of directly mixing nineth stream 115 shown in Figure 3. In Figure 4, a membrane moisture exchanger 120 and a membrane moisture exchanger 121 are placed in series to incrementally increase the moisture content of fifth stream 104. As conditioning effluent or fourteenth stream 109 can be segmented into a fraction with decreasing moisture content based upon time of contact within sorbent contactor with the conditioning or thirteenth stream 108, a first fraction of conditioning effluent or fourteenth stream 109 may be used as a feed or influent stream to membrane moisture exchanger 121. The other streams and steps are substantially the same as shown in Figure 3. The benefit of integrating membrane moisture exchangers is that a moisture content of conditioning effluent or fourteenth stream 109 may range from 50% to 10%. Addition of moisture in fifth stream 104 from nineth stream 115) in a counter flow direction and conditioning effluent or fourteenth stream 109 enables a large fraction of moisture recovered at minimized cost relative to using a chiller and heating the recovered water to form steam or diluted steam.

[0148] The temperature of the fifth stream 104 can be maintained greater than 60 °C or greater than 70 °C, to enable fifth stream 104 to transfer a large fraction of its water content to the sorbent in the third step.

[0149] In most applications, achieving this temperature using a cross exchanger for heat and moisture from conditioning effluent or fourteenth stream 109 can be enabled by the heat in fourteenth stream 109 exiting sorptive separator 150 at temperatures in the range of 70 °C to 140 °C.

[0150] For gas turbine applications, the exhaust stream itself is typically at a temperature greater than 150 °C or enough heat to add at least 6% of the volume of water into the stream leading through adiabatic vaporization which would provide about a total of 16% volume water mixture post vaporization.

[0151] Figure 5 illustrates integration of heat pumps, enabling greater steam addition in fifth stream 104 with a heat pump 122 for recovering heat with a fluid loop 123 connected to stream conditioning device or DCC 102 and admitting the recovered heat into a stream conditioning device or direct contact heater (DCH) 111. The heat transferred is used to provide latent heat of phase change for vaporizing water, fluid loop 123 and a fluid loop 124 can be used to transfer heat or energy between heat pump 122 and stream conditioning device or DCC 102 and DCH 111. The other streams and process steps stay substantially the same as Figure 4.

[0152] Fluid loop 123 can be operated at an average temperature of 40 °C while fluid loop 124 can be operated at an average temperature of 70 °C. With a 30 °C approach temperature the heat pump COP can be as high as 5, making the cost of adding moisture to the wet stream as low as about 123kWh per MT of steam added. Figure 6 is similar to Figure 3 but illustrates adding a fraction of the product or tenth stream 107a into the seventh stream 105. Recycling a fraction of the product or tenth stream 107a can increase the amount of product or CO2 within the product loop formed by CO2 stored on and / or in the sorbent in sorptive separator 150 from the second step to the third step while the recycle of tenth stream 107a moves CO2 in the opposite direction or from third step to second step. While recycling can initially decrease the product fraction exiting the system, as the recycled CO2 does not exit the loop described above, it will eventually result in the product fraction exiting with the sorbent in the fourth step in product or tenth stream 107 to stay constant by dynamically adjusting the amount of CO2 within the “sorption / desorption reflux” loop.

[0153] If the fraction of the product or tenth stream 107a is large, some CO2 can be lost via exhaust or eighth stream 118 during the second step.

[0154] Figure 7 illustrates another process scheme where instead of looping CO2 backward relative to the order of contacting sorbent with the streams or moving the sorbent contactor in a sorptive separator, the effluent of the pre-concentration step is recycled at a latter point in the sequence. For this to work, a fourth fraction of the feed stream 101 d is created and admitted in a sixth step. A first fraction of the feed stream or a second stream 101a is cooled and dried in a stream conditioning device or DCC 102 and split into two fractions, a third fraction of the feed stream 101c and fourth fraction of the feed stream 101 d. In a first step, third fraction of the feed stream 101c is admitted into sorbent contactors and optionally an effluent stream 119 can be mixed with fourth fraction of the feed stream 101c to maximize recovery of CO2. In a second step second fraction of the feed stream or third stream 101b which can contain a high fraction of moisture is admitted into sorbent contactors forming sequentially an effluent stream 125a and an effluent stream 125b. In a third step, fourth fraction of the feed stream 101d is admitted into the sorbent contactors with the effluent being directed to first step or directed as exhaust or eighth stream to the stack and discarded. In a fourth step, the effluent streams of the second step effluents stream 125a and effluents stream 125b are admitted into sorbent contactors to increase the CO2 loading of the sorbent forming an effluent exhaust or eighth stream 118 directed to the stack. In a fifth step a regeneration stream 106 enriched in steam is admitted into the sorbent contactor forming an effluent product or tenth stream 107 enriched in CO2. In a sixth step, a conditioning or thirteenth stream 108 is admitted into sorbent contactors forming conditioning effluent or fourteenth stream 109 enriched in steam relative to conditioning or thirteenth stream 108. The process can repeat with the sorbent contactors returning to the first step.

[0155] The main difference between the processes illustrated in Figures 3 through 6 is a further separation of the pre-concentration steps and the product purification step by the addition of a dried feed stream or fourth fraction of the feed stream 101 d before admitting of the preconcentrated feed. This process uses a single conditioning step or sixth step for removing moisture from the sorbent contactors and differs from the prior art disclosing two separate sorptive separators to carry out preconcentration and purification steps.

[0156] Figure 8 illustrates a sorptive gas separation process with two sequential pre-concentration steps followed by a recovery step where multiple streams comprising diluted CO2 are added sequentially to sorbent contactors before product recovery and conditioning of the sorbent. For ease of representation, the process is shown as carried out in a sorptive separator 150x, a sorptive separator 150y, and a sorptive separator 150z.

[0157] Table 1 bellow presents estimated flow rates and CO2 concentrations for the feed gas and the effluent from a first pre-concentration stage and a second preconcentration stage.

[0158] Stream First Stream § Stream Stream Stream

[0159] stream 131 § 132 141 142

[0160] 101

[0161] Flow “““Yggg" “""““444"

[0162] kmol / h

[0163]

[0164] %CO2 4.70% 2.40% 9.80% 4.70% 16.50%

[0165] In this example, CO2 is concentrated about 2 times in the first preconcentration stage and 1.7 times in the second concentration stage thus allowing a feed with 4.7% CO2 to be upgraded into a stream comprising about 16.5% CO2. Figure 9 illustrates how a two-stage preconcentration process could be deployed in a single rotary sorptive separator. In this process example, the feed 101 is split between two feed fraction one cooled and dried in stream conditioning device 102a before being admitted into sorbent contactors in a first step, and the second fraction added to the stream conditioning device (111a) where water or moisture is added.

[0166] These two fractions form a stream 131 and a stream 132. Stream 132 is split and contacted through stream conditioning devices 102b and 111b to produce respectively dried and moisturized stream contacting the sorbent contactors in a third and fourth steps. The effluent of the third and fourth steps are respectively stream 141 and a stream (142). Stream 141 can have a concentration od CO2 about the same as feed or first stream 101, stream 141 can be recycled and blended with first stream 101. Stream 142 can be recycled and sent to a stream conditioning device or DCC 102c. In, the fifth step a conditioning or thirteenth stream 108 is admitted in the sorbent contactors and form an effluent exhaust or eighth stream 118 directed to a stack.

[0167] The combination of steps 1 to 5 can be described as a preconcentration process 901 forming two streams, a partially depleted CO2 stream as a stream 131 and a CO2 enriched stream as a stream 142. Steps 6 to 9 can be described as a product recovery process 902. A sixth step stream 131 can be contacted with sorbent contactors forming an effluent exhaust or eighth stream 118 directed to a stack. In a seventh step, stream 142 is contacted with stream conditioning device 102c and admitted into sorbent contactors forming an effluent exhaust or eighth stream 118 directed to a stack. In an eighth step, regeneration stream 106 enriched in steam is admitted into sorbent contactors to form a product or tenth stream 107 enriched in CO2. In a ninth step, a conditioning or thirteenth stream 108 is admitted into sorbent contactor forming a conditioning effluent or fourteenth stream 109 enriched in steam.

[0168] Steps 1 through 5 integrate a plurality of product recycle loops which can provide high recovery through the pre-concentration steps. This can reduce the amount of sorbent drying performed in the fifth step.

[0169] Similarly to the examples provided in Figures 4 and 5, a heat pump with DCC and DCH, or use of membrane moisture exchangers for transfer of moisture can also be used to minimize the energy supplied to the sorption separation system using the two-stage pre-concentration process described above coupled with the high purity recovery process. While the number of gas to liquid contactors or gas to gas contactors can be increased, some of the liquid circulation loops and the heat pumps may be shared by a plurality of process step. For example, the liquid flowing into the DCC which comes in contact with fourth stream 103, fluid loop 123 and heat pump 122 may be delivered from a single pump with connections either in series or in parallel with a common liquid return circuit sharing a common cooling system. An enclosure of a DCC may be shared with three inlet and outlets to provide three separate gas cooling and drying circuits as long as the pressure difference between the streams is maintained below 10kPa to reduce OPEX.

[0170] The previous examples provided in Figures 2 through 9 are for illustrative purposes and are not meant to capture all different possible configurations suitable for use in a single stage or multi-stage pre-concentration process using partial pressure swing combined with a product recovery stage using the same set of sorbents. The skilled artisan will understand that other configurations are possible while still falling within the scope of the present invention.

[0171] Numerical simulations following a single sorbent contactor through all of the process step for 100 cycles or more as needed to reach steady state model outputs were carried out using a performance model for sorbent contactor comprising CALF-20 sorbent, with about 80% sorbent loading with a contactor density of about 280 kg / m3 and 1 meter contactor flow length, fitted with empirical data for kinetics and equilibrium CO2 and water sorption versus temperature, partial pressure and sorbent saturation (loading) versus adsorbed CO2 and water. The isotherm for CO2 uptake of the sorbent contactor containing MOF is provided in Figure 1. Figures 2c and 2d provide a snapshot of CO2 and water loading across the contactor.

[0172] Separate simulations of the prior art process as illustrated in Figure 2a and the inventive embodiment sorptive separation process illustrated in Figure 2b were carried out for a flue gas or first stream gas with a concentration of CO2 of 4.7% and a 10.5%. Table 2 compares the key performance indicators (KPIs) computed for the two processes with the same concentration of CO2 of 4.7%.

[0173] Current New Cycle

[0174] Baseline

[0175] i KPI / simulation 4.7% CO2 Feed,

[0176]

[0177] i case 4.7% s

[0178] CO2 15% CO2 recycled

[0179] Feed stream

[0180]

[0181] i Cycle capacity 1.41. „

[0182] | (VVC) | | Steam Ratio (SR) 3.72 2.88

[0183] | CO2 Purity% 98% 95%

[0184] | CO2 Recovery% 93% 90%

[0185]

[0186] i.

[0187] Table 3 compares the key performance indicators (KPIs) computed for the two processes with a flue gas or first stream with the same concentration of CO2 of 10.5%.

[0188] Current New Cycle

[0189] Baseline

[0190] i

[0191]

[0192] KPI / simulation 10.5% CO2 Feed,

[0193] i case 10.5% i

[0194] CO2 30% CO2 recycled

[0195] Feed stream

[0196]

[0197] i Cycle capacity 2.6 „ „

[0198] | (VVC) | i Steam Ratio

[0199]

[0200] (SR) I? 1.4

[0201] | CO2Purity% 95.1% 95.6% | |

[0202]

[0203] CO2 Recovery% 87% 87% I The KPIs illustrate the energy saving in the CO2 recovery step afforded by the pre-concentration step. As the pre-concentration step is performed using less energy supplied and lower exergy energy than the purification step, it leads to a net gain of 0.8 SR units or about 2GJ / MT of CO2 for the 4.7% CO2 feed and a gain of about 0.3 SR units or about 0.8GJ / MT of CO2 for the 10.5% CO2 feed.

[0204] This corresponds to an OPEX savings of about $10 / MT of CO2 for the flue gas or first stream with a concentration of CO2 of 4.7% when that energy is derived from natural gas and at an estimate cost of $5 / GJ for the natural gas. Higher OPEX savings are likely for higher natural gas costs. Another aspect of the embodiment is the preconcentration process CO2 release step may use lower exergy heat than the CO2 recovery step at greater than 90% purity. In some cases, only waste heat is used for the pre-concentration process.

Claims

What is claimed is:

1. A sorptive gas separation process for separating a first component from a first stream comprising a first component, and a third component, the process comprising:(a) splitting the first stream into a second stream and a third stream;(b) converting the second stream into a fourth stream, converting the third stream into a fifth stream, and at least one of: the converting of the second stream into the fourth stream further comprising removing a second component from or decreasing a concentration of the second component in the second stream to form the fourth stream with a lower concentration of the second component relative to the first stream, and the converting of the third stream into the fifth stream further comprising adding the second component to or increasing a concentration of the second component in the second stream to form the fifth stream with a higher concentration of the second component relative to the first stream;(c) admitting the fourth stream into a sorptive separator with a sorbent on and / or in a contactor, contacting the fourth stream with the sorbent, sorbing the first component in the fourth stream on and / or in the sorbent forming a sixth stream from the non-sorbed components of the fourth stream, and recovering the sixth stream from the contactor and / or sorptive separator;(d) admitting the fifth stream into the sorptive separator and / or the contactor, contacting the fifth stream with the sorbent and desorbing the first component sorbed on the sorbent from the fourth stream while sorbing at least a fraction of the second component from the fifth stream, forming a seventh stream comprising the non-sorbed components of the fifth stream, and recovering the seventh stream from the contactor and / or sorptive separator;(e) admitting the seventh stream into the sorptive separator and / or the contactor and contacting the seventh stream with the sorbent, sorbing at least a fractionof the first component from the seventh stream on the sorbent, forming an eighth stream from the non-sorbed components of the seventh stream, and recovering the eighth stream from the contactor and / or sorptive separator; (f) admitting a regeneration stream or a ninth stream into the sorptive separator and / or the contactor, contacting the regeneration stream or ninth stream comprising the second component with the sorbent, sorbing at least a fraction of the second component from the regeneration stream or the ninth stream on the sorbent and forming a tenth stream enriched in first component relative to the first stream and the seventh stream, and recovering the tenth stream from the contactor and / or sorptive separator.

2. The sorptive gas separation process of claim 1, further comprising controlling a composition of the ninth stream to comprise a concentration of the second component of equal to or greater than 30% volume and controlling at least one of a flow rate, a contact times and a pressure of the seventh stream and the ninth stream for forming a heat of adsorption of the second component on the sorbent generated in step (f) which is greater than a heat of adsorption on the sorbent of the first component generated in step (e).

3. The process of claim 1 or 2, wherein the first stream further comprise the second component.

4. The process of any one of claims 1 to 3, wherein the first component is CO2 and the second component is water.

5. The process of claim 4, further comprising controlling a quantity of steam in the fifth stream for obtaining a concentration of CO2 in the seventh stream which is greater than 50% to 400% of a concentration of CO2 in the first stream.

6. The process of claims 1 to 5, further comprising recovering heat while reducing a temperature of the second stream in the first conditioning device and transferring the recovered heat into the fifth stream in the second conditioning device using heat exchangers fl uidical ly connected to at least one heat pump.

7. The process of claims 1, further comprising in a step (g) admitting a conditioning stream or a eleventh stream into said sorptive separator and / or said contactor, contacting the conditioning stream or eleventh stream with the sorbent, desorbing at least a fraction of the second component on and / or in the sorbent, forming a twelfth stream, and directing at least a fraction of the twelfth stream to a moisture exchange membrane or a water selective sorbent, recovering water from the twelfth stream and transferring the recovered water into the fifth stream.

8. The process of claims 1 to 7, wherein the sorbent comprises at least one of a metal organic framework material, a covalent organic network material, a porous carbon material, a zeolite, a functionalized polymer, a porous inorganic material.

9. The process of claim 8, wherein the sorbent comprises CALF-20, or a metal organic framework sorbent comprising zinc ions, triazolate ligands and oxalate ligands.

10. A sorptive gas separation system comprising:(a) a first stream source;(b) a stream splitting device fluidly connected to the first stream source;(c) a second component liquid source;(d) at least one stream conditioning device fluidly connected downstream of the stream splitting device;(e) at least one flashing or vaporizing device;(f) a sorptive separator having an enclosure, a contactor located within the enclosure, at least one sorbent on and / or in the contactor, and at least a first zone, a second zone, a third zone, a fourth zone, and a fifth zone within the enclosure, wherein the first zone, the second zone, the third zone, the fourth zone, and the fifth zone are substantially fluidly separate from each other within the enclosure, and each zone comprise an inlet and an outlet; and the contactor moves through the first zone, the second zone, the third zone, the fourth zone, and the fifth zone within the enclosure;(g) at least one fluid connection between an outlet of the at least one stream conditioning device and at least one of the inlet of the first zone, the inlet of the second zone, the inlet of the third zone, the inlet of the fourth zone, and the inlet of the fifth zone of the sorptive separator,(h) a fluid connection between an outlet of a zone of the sorptive separator and an inlet of a zone of the sorptive separator;(i) a fluid connection between at least the flashing and vaporizing device outlet and the fourth or fifth sorptive separator zone inlet and a fluidic connection from the fourth or fifth sorptive separator zone to collect the purified product stream;(j) a fluid connection between the inlet of the fifth zone and a conditioning stream source, and(k) a fluid connection between the outlet of the fifth zone and the inlet of the third zone.

11. The sorptive gas separation system of claim 10, further comprising a first stream conditioning device and a fluid connection between an outlet of the first stream conditioning device and the inlet of the first zone.

12. The sorptive gas separation system of claim 10 or 11, further comprising a second stream conditioning device and a fluid connection between an outlet of the second stream conditioning device with the inlet of the third zone wherein the sorptive separator comprising a moving contactor and the sorptive separator has at least five sorptive contactors.

13. The sorptive gas separation system of any one of claims 10 to 12, wherein the at least one flashing or vaporizing device is fluidly connected to receive a carrier gas from a carrier gas supply.

14. The sorptive gas separation system of 10 to 13, wherein the sorbent comprises a metal organic framework sorbent or a CALF-20 sorbent.

15. The sorptive gas separation system of 10 to 14, wherein in (h) the fluidic connection is between at least one of the following: the outlet of the first zone and the inlet of the second zone inlet; the outlet of the first zone and the inlet of the third zone; the outlet of the first zone and the inlet of the fourth zone; the outlet of the first zone and the inlet of the fifth zone; the outlet of the second zone and the inlet of the third zone; the outlet of the second zone and the inlet of the fourth zone; the outlet of the second zone and the inlet of the fifth zone; the outlet of the third zone and the inlet of the fourth zone; the outlet of the third zone and the inlet of the fifth zone, and the outlet of the fourth zone and the inlet of the fifth zone.

16. A sorptive gas separation system comprising:(a) a stream splitting device for dividing a first stream into a second stream and a third stream;(b) at least one of a first stream conditioning device fluidly connected downstream of the stream splitting device to receive the second stream and for adjusting a concentration of the second component and / or a temperature of the second stream, and a second stream conditioning device fluidly connected downstream of the stream splitting device to receive the third stream and for adjusting a concentration of the second component and / or the temperature of the third stream;(c) at least one flashing or vaporizing device fluidly connected to receive a liquid regeneration stream comprising the second component from a liquid regeneration stream source for converting the second component in the liquid regeneration stream from a liquid phase into a gas phase and forming a ninth stream, and(d) a sorptive separator fluidly connected to at least one of the first stream conditioning device for admitting the fourth stream into the sorptive separator and the second stream conditioning device for admitting the fifth stream into the sorptive separator, a sixth stream conduit for recovering the sixth streamfrom the sorptive separator, the at least one flashing or vaporizing device for admitting the ninth stream into the sorptive separator, a tenth stream conduit for recovering the tenth stream from the sorptive separator, a seventh stream conduit for recovering the seventh stream from the sorptive separator and admitting the seventh stream from the sorptive separator, and an eighth stream conduit for recovering the eighth stream from the sorptive separator, the sorptive separator comprising at least one sorbent for selectively sorbing a first component and a second component.

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