WO2023215875A1 - Sorbants contenant du phénol, systèmes comprenant des sorbants, et procédés utilisant les sorbants - Google Patents

Sorbants contenant du phénol, systèmes comprenant des sorbants, et procédés utilisant les sorbants Download PDF

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WO2023215875A1
WO2023215875A1 PCT/US2023/066672 US2023066672W WO2023215875A1 WO 2023215875 A1 WO2023215875 A1 WO 2023215875A1 US 2023066672 W US2023066672 W US 2023066672W WO 2023215875 A1 WO2023215875 A1 WO 2023215875A1
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sorbent
tert
butyl
phenol
amine
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PCT/US2023/066672
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English (en)
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Miles SAKWA-NOVAK
Eric PING
Joan LUCAS
Abigayle CLABAUGH
Cassandra HERTZ
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Global Thermostat Operations, Llc.
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Publication of WO2023215875A1 publication Critical patent/WO2023215875A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • 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
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/34—Specific shapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/34—Specific shapes
    • B01D2253/342—Monoliths
    • B01D2253/3425—Honeycomb shape
    • 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
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • 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
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings
    • 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

  • CO 2 emissions are caused by burning fossil fuels, solid waste, and trees as well as through the manufacture of cement and other materials.
  • One way to decrease the amount of CO 2 in the atmosphere is to capture CO 2 using materials having an affinity for CO 2 .
  • sorbents and contactors methods of using sorbents and contactors to capture CO 2 , structures including the sorbent, and systems and devices using sorbents and contactors to capture CO 2 .
  • the present disclosure provides for a sorbent comprising: a CO 2 -philic phase and a support, wherein the CO 2 -philic phase includes CO 2 binding molecules and phenol containing molecules.
  • the CO 2 binding molecules include CO 2 binding moieties.
  • the present disclosure provides for a contactor, comprising a structure and the sorbent as described above or herein.
  • the present disclosure provides for a system for capturing CO 2 from a gas, optionally the gas is ambient air, comprising: a first device configured to introduce the gas to the sorbent or contactor as described above or herein to bind CO2 to the sorbent; a second device configured to heat the sorbent containing bound CO 2 to at least a first temperature to release the CO 2 ; and a third device configured to collect the released CO 2 .
  • the present disclosure provides for a method of capturing CO 2 from gas, optionally the gas is ambient air, comprising: introducing the ambient air to the sorbent as described above or herein to bind CO 2 to the sorbent; heating the sorbent to at least a first temperature to controllably release the CO 2 ; and collecting the CO 2 in a CO 2 collection device.
  • the present disclosure provides for a system for implement the method of as described above or herein.
  • Figure 1A shows a schematic of how amine moieties bind CO 2 into the form of a carbamate.
  • Figure 1B is a schematic of a sorbent system comprised of support and CO 2 -philic phase. Together, the support and CO 2 -philic phase comprise a sorbent.
  • Figure 2 is a schematic of honeycomb monolith contactor comprised of a substrate and a sorbent washcoat.
  • Figure 3 illustrates some phenol additive molecules that were evaluated.
  • Figure 4 illustrates mass loss curves during exposure of sorbents created with improved CO 2 -philic phases containing PEI and phenol additives and unmodified PEI to diluted air while ramping the temperature from room temperature to 900° C.
  • the phenols are present at a ratio of 0.1 mol/mol N in PEI.
  • Figure 5 illustrates heat flow (DSC) curves during exposure of sorbents created with improved CO 2 -philic phases containing PEI and phenol additives and unmodified PEI to diluted air while ramping the temperature from room temperature to 900° C.
  • the phenols are present at a ratio of 0.1 mol/mol N in PEI.
  • Figure 6 illustrates transient mass change profiles from TGA CO 2 uptake experiments at 400 ppm CO 2 (DAC conditions) utilizing improved sorbents containing PEI and phenol additives; each at 0.1 mol additive/mol PEI, and all supported in a mesoporous alumina.
  • Figures 7A-7D illustrate the extent of oxidation over time of PEI, determined via the differential scanning calorimetry method described herein and discussed in the referenced publication (solid lines, DSC), and via the loss of amine efficiency (datapoints, AE) at ( Figure 7A) 5%, ( Figure 7B) 17%, and ( Figure 7C) 30% O 2 concentration; ( Figure 7D) extent of oxidation with different PEI pore fillings.
  • Figure 8 illustrates transient oxidation curves for PEI and PEI with phenol additive tested under 20% CO 2 , 17% O 2 , balance N 2 at 125 °C, all sorbents are in a mesoporous alumina, additive ratios are 0.1 mol additive / mol PEI.
  • Figure 9 illustrates transient oxidation curves for PEI and PEI with phenol additive tested under 17% O 2 , balance N 2 at 137.5 °C, all sorbents are in a mesoporous alumina, additive ratios are 0.1 mol additive / mol PEI.
  • Figure 10 illustrates mass loss curve (dashed line) and heat flow (DSC, solid line) of honeycomb monolith containing PEI + Phenol 12 during exposure to diluted air while ramping the temperature to 900 °C.
  • DETAILED DISCLOSURE Embodiments of the present disclosure provide for phenol containing sorbents (also referred to herein as “sorbent” or “sorbents”) and contactors, methods of using sorbents and contactors to capture CO 2 , structures including the sorbent, and systems and devices using the sorbents and contactors to capture CO 2 .
  • the methods, systems, and sorbents of the present disclosure can be advantageous over current technologies since they are relatively more robust and reduce the cost of capturing CO 2 , in particular from ambient air.
  • the present disclosure provides for sorbents having a support and a CO 2 -philic phase that includes phenol containing molecules, which leads to a sorbent that is effective for capturing CO 2 .
  • the present disclosure provides for sorbents (also referred to herein as “sorbent” or “sorbents”) and contactors, methods of using sorbents and contactors to capture CO 2 , structures including the sorbent, and systems and devices using sorbents and contactors to capture CO 2 .
  • the present disclosure is directed to multiple types of sorbents and structures that will be described below and herein.
  • the present disclosure provides for sorbents and contactors that include a CO 2 -philic phase and a support.
  • the CO 2 -philic phase includes CO 2 binding molecules and phenol containing molecules.
  • the CO 2 -philic phase can be a homogeneous mixture or a heterogeneous mixture.
  • the CO 2 binding molecules contain CO 2 binding moieties.
  • the ratio of the amount of phenol containing molecules to CO 2 binding moieties can be about 0.0001 to 1 mole phenol containing molecule to mole CO 2 binding moiety or about 0.01 to 0.5 mole phenol containing molecule to mole CO 2 binding moiety.
  • the phenol containing molecules can act as a stabilizer for the CO 2 binding molecules to improve its stability thereby creating an improved CO 2 -philic phase.
  • an effective CO 2 sorbent is formed.
  • a structured support also referred to as a formed support or as a structure, refers to a support that has been formed into a structure where the structure is, at standard conditions, a solid body. Supports can also be unstructured, at standard conditions having a powdery consistency. When a support is referred to without mention to a structure, forming, or being formed or structured, it can refer to supports that are either structured or unstructured.
  • Structured supports can take the form of a homogeneous solid body (i.e., comprised predominantly of support but also containing components that allow it to remain a stable body at standard conditions) or as a coating on a substrate, whereby the substrate has a different composition than the coating and provides the mechanical stability to the coating. It can be useful to utilize a structured support with a CO 2 -philic phase as a contactor in a process for removing CO 2 from a gas stream such as ambient air. Contactors provide a geometry to a CO 2 -philic phase such that considerations such as pressure drop, throughput, and/or mass transfer rates can be optimized.
  • the CO2 binding molecules can be an amine or an amine polymer.
  • the amine or amine polymer can contain primary amines, secondary amines, tertiary amines, or a mixture of any combination of primary, secondary, and tertiary amines.
  • the amine polymer can be branched, hyperbranched, dendritic, or linear.
  • the CO 2 binding moieties are the amine moieties on the amine molecule or polymer.
  • the amine moieties can interact with CO 2 to form carbamate, carbonate, or bicarbonate species.
  • Figure 1A shows a schematic of how amine moieties bind CO 2 into the form of a carbamate.
  • Primary amines are defined as having the chemical structure –NH 2 R 1 , where R 1 is an alkyl group such as CH 2 or CH 3 .
  • Secondary amines are defined as having the chemical structure –NHR 1 R 2 , where R 1 and R 2 are independently selected from an alkyl group such as CH 2 or CH 3 .
  • Tertiary amines are defined as having the chemical structure –NR 1 R 2 R 3 , where R 1 , R 2 , and R 3 are independently selected from an alkyl group such as CH 2 or CH 3 .
  • Linear amine polymers can be defined as containing only primary amines, secondary amines, or both primary and secondary amines. The ratio of secondary to primary amines can be about 0.5 to 10,000.
  • the linear amine polymer can have a molecular weight of about 100 to 100,000 g/mol, about 200 to 30,000 g/mol or about 600 to 5,000 g/mol.
  • Branched amine polymers can be defined as containing any number of primary, secondary, and tertiary amines, which does not overlap linear amine polymers or dendritic amine polymers.
  • the ratio of primary, secondary, and tertiary can be about 10:80:10 to 60:10:30, about 60:30:10 to 30:50:20, or about 45:45:10 to 35:45:20.
  • the chemical structures of branched amine polymer can vary greatly and can be very complex.
  • the branched amine polymer can have a molecular weight of about 100 to 100,000 g/mol, about 200 to 30,000 g/mol or about 600 to 5,000 g/mol.
  • Dendritic amine polymers can be defined as containing only primary and tertiary amines, where groups of repeat units are arranged in a manner that is necessarily symmetric in at least one plane through the center (core) of the molecule, where each polymer branch is terminated by a primary amine, and where each branching point is a tertiary amine.
  • the core or central linkage is the same as the branching amines (e.g., ethylenimine core and ethylenimine branches, propylenimine core and propylenimine branches).
  • the ratio of primary to tertiary can be about 1 to 3.
  • the dendritic amine polymer can have a molecular weight of about 100 to 100,000 g/mol, about 200 to 30,000 g/mol or about 280 to 3,000.
  • Hyperbranched amine polymers can be defined as having chemical structure resembling dendritic amine polymer, but containing defects in the form of secondary amines (e.g., linear subsections as would exist in a branched polymer), in such a way that provides a random chemical structure instead of a symmetric chemical structure.
  • the hyperbranched amine polymers do not overlap branch amine polymers or dendritic polymers.
  • the ratio of primary to secondary to tertiary can be about 65:5:30 to 30:10:60.
  • the hyperbranched amine polymer can have a molecular weight of about 100 to 100,000 g/mol, about 200 to 30,000 g/mol or about 600 to 10,000 g/mol.
  • linear, hyperbranched and branched amine polymers have secondary amines and dendritic amines do not, which may be advantageous since secondary amines bond strongly to CO 2 .
  • the amine polymer can be polyethylenimine, polypropylenimine, polyallylamine, polyvinylamine, polyglycidylamine, polystyrene-divinylbenzene polymer functionalized with amine such as alkylbenzylamine moieties, or other amine polymer, where each can be branched, hyperbranched, dendritic, or linear.
  • the size e.g., length, molecular weight
  • amount e.g., number of distinct amine polymers
  • type of amine polymer can be selected based on the desired characteristics of the porous structure (e.g., CO 2 absorption, regenerative properties, oxidative stability, loading, and the like).
  • the phenol containing molecules can include one or more of the following: pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (commercial name Irganox 1010), DL-a-tocopherol, butylhydroxytoluene, 2,6-di-tert-butyl-4-methyoxyphenol, tertbutylhydroquinone, 2(3)-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-1 ,4-dihydroxybenzene, 3- tert-butyl-4-hydroxyanisole, pyrrogallol, n-propyl gallate, 2,2’-methylenebis(6-tert-butyl-4- methylphenol), 2-tert-butyl-4-methylphenol, 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)-5-[(Irg
  • the phenol containing molecules is selected from: pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (commercial name Irganox 1010), DL-a-tocopherol, butylhydroxytoluene, 2,6-di-terf-butyl-4- methyoxyphenol, tert-butylhydroquinone, 2(3)-tert-butyl-4-methoxyphenol, 2,2’-methylenebis(6- tert-butyl-4-methylphenol), 2-naphthol, L-ascorbic acid, 4,4’-thiodiphenol, hesperetin, and 4,4’- thiobis-(2-tert-butyl-5-methylphenol).
  • pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)
  • the phenol containing molecules is selected from: butylhydroxytoluene, 2-naphthol, L-ascorbic acid, tert-butylhydroquinone, and 4,4’-thiobis- (2-tert-butyl-5-methylphenol).
  • the addition of phenol containing molecules to the CO 2 -philic phase allows for the ability to tune the properties of the CO 2 -philic phase.
  • the amount, type, and mixture quantity of phosphite molecule can be tuned and changed to achieve the desired properties of the CO 2 -philic phase.
  • Tuning the CO 2 -philic phase can result in one or a combination of the following that yield an improved CO 2 sorbent: increased lifetime due to a reduction in the rate of oxidative degradation, increase in amine efficiency of the sorbent, increase in the CO 2 swing capacity of the sorbent in an adsorption/desorption process, and/or increase in the equilibrium capacity of the sorbent.
  • phenols that are marketed as antioxidants, such as pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (commercial name Irganox 1010), hesperetin, and 2(3)-tert-butyl-4-methoxyphenol.
  • phenols are primary antioxidants that have been shown to be effective over a wide range of temperatures and are typically used to stabilize polyolefins and styrene-based plastics.
  • their effectiveness in amine polymers that are used to create effective CO 2 -phillic phases in CO 2 sorbents is not obvious.
  • Evaluating the oxidative stability of materials in environments that contain oxygen and CO 2 is useful due to the fact that during regeneration processes, desorbed CO 2 is present at different concentrations in addition to oxygen at elevated temperatures, and can impact the stability of the material.
  • evaluating the oxidative stability of materials with oxygen only (CO 2 -free air) is a useful way to evaluate the shelf life of a material when it is stored at ambient conditions.
  • the CO 2 -philic phase (e.g., homogeneous or heterogeneous combination of the phenol amine containing molecules and the CO 2 binding molecules) can be homogeneous or heterogeneous.
  • the phenol containing molecules and the CO 2 binding molecules can be present in a variety of ways.
  • the phenol containing molecules and the CO 2 binding molecules can be mixed and then applied or incorporated with the structure.
  • the phenol containing molecules and the CO 2 binding molecules can be applied or incorporated separately but once applied or incorporated, the phenol containing molecules and the CO 2 binding molecules form the CO 2 -philic phase.
  • the phenol containing molecules and the CO 2 binding molecules can be applied or incorporated separately to form a layer of the CO 2 -philic phase on a support, such as on the surface of pores of the support.
  • a mixture of the phenol containing molecules and the CO 2 binding molecules can be applied to form a layer on a support (e.g., such as on the surface of pores of the support), and optionally one or both of the phenol containing molecules and the CO 2 binding molecules can be applied or incorporated separately onto the layer on the support (e.g., such as on the surface of pores of the support).
  • one of both of the phenol containing molecules and the CO 2 binding molecules can be used to form a part of or all of the support, where CO 2 -philic phase functions as described herein.
  • CO 2 -philic phase functions as described herein.
  • the sorbent includes the CO 2 -philic phase (e.g., homogeneous or heterogeneous combination of the phenol containing molecules and the CO 2 binding molecules) and the support.
  • the support includes a surface (e.g., a surface that can be exposed to a gas including CO 2 during regular use and/or that can interact with the CO 2 -philic phase).
  • the surface can be the surface of pores and/or other surfaces that the CO 2 -philic phase contacts or interacts with.
  • the CO 2 -philic phase e.g., homogeneous or heterogeneous combination of the phenol containing molecules and the CO 2 binding molecules
  • the CO 2 -philic phase can be disposed on the surface of the support, and/or within pores of the support, and/or on exterior surface of a support or any combination thereof.
  • the CO 2 -philic phase can be a coating on the surface of the porous material, a monolayer on the surface of the porous material, a self-assembled monolayer on the surface of the porous material, a bulk phase within the pores of the porous material, a coating on the exterior surface of the porous material, and the like.
  • the support can be made of one or more types of materials such as ceramic, metal, metal oxide, plastic, cellulose, carbon, a zeolite, a metal organic framework (MOF), a porous organic framework (POF), a covenant organic framework (COF), a polymer of intrinsic microporosity (PIM), a polymer, a fibrous cellulose, fiberglass, boron-nitride fiber, and the like.
  • the support can be made of materials that also include the CO 2 - philic phase.
  • the metal oxide support can be selected from cordierite, alumina (e.g., y-alumina, 0- alumina, 6-alumina), cordierite-o-alumina, silica, aluminosilicates, zirconia, germania, magnesia, titania, hafnia, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate, sillimanite, magnesium silicates, zircon, petalite, and combinations thereof.
  • alumina e.g., y-alumina, 0- alumina, 6-alumina
  • cordierite-o-alumina silica, aluminosilicates, zirconia, germania, magnesia, titania, hafnia, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate
  • the charge can be balanced by appropriate counter-ions, such as cations of NR 4 , Na, K, Ca, Mg, Li, H, Rb, Sr, Ba, Cs or anions including phosphate, phosphite, sulfate, sulfate, nitrate, nitrite, chloride, bromide and the like.
  • the metal oxide can contain dopants such as zirconium, iron, tin, silicon, titanium, magnesium, and combinations thereof. It is known that metal oxides can contain acid, base, and neutral sites on their surfaces and that dopants can alter the amount and strength of acid and base sites on the surfaces.
  • the polymer support can be a polymer and/or copolymer of polyolefin(s), polyester(s), polyurethane(s), polycarbonate(s), polyetheretherketone(s), polyphenylene oxide(s), polyether sulfone(s), melamine(s), polyamide(s), polyvinylbenzene, polystyrene- divinylbenzene, polyurethane, polyacrylates, polystyrenes, polyacrylonitriles, polyimides, polyfurfural alcohol, phenol furfuryl alcohol, melamine formaldehydes, resorcinol formaldehydes, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurates, polyacrylamides, various epoxies, agar, and agarose, or combinations thereof.
  • the support can be porous (e.g., macroporous, mesoporous, microporous, or mixtures thereof (e.g., where a macroporous surface can include mesopores, and/or micropores, within one or more of the macropores, where a mesoporous surface can include micropores, and so on)).
  • the porous structure is mesoporous.
  • the pores can extend through the porous structure or porous layer or only extend to a certain depth.
  • the macropores of the porous structure can have pores having a diameter of about 100 nm to 10,000 nm, a length of about 500 nm to 100,000 nm and a volume of 0.2-1 cc/g.
  • the mesopores of the porous structure can have pores having a diameter of about 5 nm to 100 nm, a length of about 10 nm to 10,000 nm, and a volume of 0.1-2 cc/g.
  • the micropores of the porous structure can have pores having a diameter of about 0.5 to 5 nm, a length of about 0.5 nm to 1000 nm and a volume of about 0.1-1 cc/g.
  • the support can be porous and have a porosity of at least 90%, at least 85%, at least 80%, at least 75%, at least 70%, at least 65%, at least 60%, or about 60 to 90%.
  • the support can have a surface area of 1 m 2 /g or more, 10 m 2 /g or more, 100 m 2 /g or more, 150 m 2 /g or more, 200 m 2 /g or more, or 250 m 2 /g or more, 500 m 2 /g or more, 1000 m 2 /g or more.
  • the CO2-philic phase e.g., homogeneous or heterogeneous combination of the phenol containing molecules and the CO 2 binding molecules
  • the CO2-philic phase can be physically impregnated in the internal volume pores of the porous structure and not covalently bonded to the internal surface of the pores of the porous structure, can be grafted (e.g., covalently bonded directly or indirectly) to the internal surface of the pores of the porous structure, or a combination thereof.
  • the CO2-philic phase e.g., homogeneous or heterogeneous combination of the phenol containing molecules and the CO 2 binding molecules
  • the covalent bonding can be achieved using known techniques in the art for bonding sorbents.
  • the CO2-philic phase e.g., homogeneous or heterogeneous combination of the phenol containing molecules and the CO 2 binding molecules
  • the CO2-philic phase can be confined within the pores of the support, but not bonded to the surface.
  • the CO2-philic phase (e.g., homogeneous or heterogeneous combination of the phenol containing molecules and the CO 2 binding molecules) is present in a plurality of pores (internal volume) of the porous structure
  • porous structure can include a structure having pores in its surface or a structure having a porous layer or coating on the surface of the structure (where the structure itself may or may not be porous)), where the CO2-philic phase has a loading of about 10% to 75% by weight of the support.
  • the loading is determined by thermogravimetric analysis (TGA).
  • the support can include a surface layer on the surface of the pores of the support that can bond with the CO 2 -philic phase.
  • the surface layer can include organically modified moieties (e.g., alkyl groups, amines, thiols, phosphines, and the like) on the surface (e.g., outside and/or inside surfaces of pores) of the material.
  • the surface layer can include surface alkyl groups, amines, thiols, phosphines, and the like, that the CO 2 -philic phase can directly covalently bond and/or indirectly covalently bond (e.g., covalently bond to a linker covalently bonded to the material).
  • the surface layer can include an organic polymer having one or more of the following groups: alkyl groups, amines, thiols, phosphines, and the like.
  • the structure can be a carbon support, where the carbon support can include one or more of the following groups: alkyl groups, amines, thiols, phosphines, and the like.
  • the CO 2 -philic phase can occupy about 10 to 100% of the mesopore volume of the support, or can occupy about 30 to 90% of the mesopore volume of the support, or can occupy about 40 to 80% of the mesopore volume of the support, or can occupy about 50 to 70% of the mesopore volume of the support.
  • the process of making a formed support or structure described above and herein can be used to create any of the structures listed in this paragraph and those in the following paragraphs.
  • the sorbent comprising the CO 2 -philic phase and the support, can be formed into or applied to a structure.
  • the CO 2 -philic phase and the support can form 100% of the structure or less than 100% (e.g., each combination of ranges between about 10%, about 20%, about 30%, about 40%, about 50% and about 60%, about 70%, about 80%, about 90%, about 99% such as about 10-99%, about 10 to 80%, about 10 to 50%, about 50 to 99%, about 50 to 90%, about 50 to 80%), where a sufficient amount of sorbent is on the surface of the structure to absorb the desired amount of CO 2 .
  • the structure can be a honeycomb, a laminate sheet, a foam, fibers, minimal surface solids, powder trays, pellets, powder, and the like or a combination of two or more of the foregoing.
  • the structure can be porous and have a porosity of at least 90%, at least 85%, at least 80%, at least 75%, at least 70%, at least 65%, at least 60%, or about 60 to 90%.
  • the porosity of the structure can be comprised of macropores, mesopores, and/or micropores.
  • the CO 2 -philic phase is predominantly (e.g., about 40 to 100% or about 50 to 90%, or about 60 to 80%) located within the mesopores of the structure.
  • the structure can be comprised entirely of sorbent or can contain another substrate material such as ceramic, metal, metal oxide, plastic or another material.
  • the structure can be a porous substrate and can also include a porous coating on some or all parts of the porous substrate, where the CO 2 -philic phase can be present in the pores of one or both of the porous substrate and the porous coating.
  • the structure is comprised entirely of sorbent (e.g., homogeneous or heterogeneous combination of the phenol containing molecules and the CO 2 binding molecules), it can be formed by extrusion, molding, 3D printing, and the like, for example.
  • the structure can be formed using support material without the CO 2 -philic phase or using the support with the CO2-philic phase already incorporated.
  • the CO 2 -philic phase can be incorporated into the structure through an impregnation, grafting, or other functionalization technique.
  • the support material can be applied to a substrate as a porous coating (also referred to as a “washcoat”) on the surface of the substrate.
  • the porous coating can be a foam such as a polymeric foam (e.g., polyurethane foam, a polypropylene foam, a polyester foam, and the like), a metal foam, or a ceramic foam.
  • the porous coating can include a metal-oxide layer (e.g., such as a foam).
  • the metal-oxide layer can be silica or alumina on the surface of the substrate, for example.
  • the porous coating can be present on the surface of the substrate, within the pores or voids of the substrate, or a combination thereof.
  • the porous coating can be about 50 pm to 1500 pm thick and the pores can be of the dimension described above and herein.
  • the support material, the substrate, and/or the structure can be made of a ceramic substrate such as cordierite, alumina (e.g., ⁇ -alumina, ⁇ -alumina, ⁇ -alumina), cordierite- a-alumina, silica, aluminosilicates, zirconia, germania, magnesia, titania, hafnia, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate, sillimanite, magnesium silicates, zircon, petalite, and combinations thereof.
  • a ceramic substrate such as cordierite, alumina (e.g., ⁇ -alumina, ⁇ -alumina, ⁇ -alumina), cordierite- a-alumina, silica, aluminosilicates, zirconia, germania, magnesia, titania, hafnia, silicon nitride,
  • the metal or metal oxide structure can be aluminum, titanium, stainless steel, a Fe-Cr alloy, or a Cr-AI-Fe alloy.
  • the charge can be balanced by appropriate counter-ions, such as cations of NR 4 , Na, K, Ca, Mg, Li, H, Rb, Sr, Ba, Cs, or anions including phosphate, phosphite, sulfate, sulfate, nitrate, nitrite, chloride, bromide and the like.
  • the support material, the substrate, and/or the structure can be made of a plastic substrate that can be made of a polymer and/or copolymer of polyolefin(s), polyester(s), polyurethane(s), polycarbonate(s), polyetheretherketone(s), polyphenylene oxide(s), polyether sulfone(s), melamine(s), polyamide(s), polyvinylbenzene, polystyrene-divinylbenzene, polyurethane, polyacrylates, polystyrenes, polyacrylonitriles, polyimides, polyfurfural alcohol, phenol furfuryl alcohol, melamine formaldehydes, resorcinol formaldehydes, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurates, polyacrylamides, various epoxies, agar, and agarose, or combinations thereof.
  • the structure can be a honeycomb structure such as a honeycomb monolith structure that includes channels.
  • the honeycomb structure can have a regular, corrugated structure.
  • the honeycomb monolith structure can have a length and width on the order of centimeters to meters while the thickness can be on the order of millimeters to centimeters or more.
  • the honeycomb monolith structure does not have fibrous dimensions.
  • the honeycomb structure can be a flow-through substrate comprising open channels defined by walls of the channels.
  • the channels can have about 50 to about 900 cells per square inch.
  • the channels can be polygonal (e.g... square, triangular, hexagonal, octagonal) sinusoidal, circular, or the like, in cross-section.
  • the channel length can have a configuration that is straight, zig-zag, skewed, or herringbone in shape.
  • the length of the channel can be 1 mm to 10s or 100s of cm or more.
  • the channels can have walls that are perforated or louvered.
  • the sorbent can be disposed in the pores of the honeycomb structure and/or in the pores of a porous layer on the surface of the honeycomb structure.
  • the honeycomb structure can have a geometric void fraction, otherwise known as the open face area, of between 0.3 to 0.95 or about 0.5 to 0.9.
  • the honeycomb structure can comprise an inlet end, an outlet end, and inner channels extending from the inlet end to the outlet end.
  • the honeycomb comprises a multiplicity of cells extending from the inlet end to the outlet end, the cells being defined by intersecting cell or channel walls.
  • the honeycomb structure and/or substrate can be ceramic (e.g., of a type produced by Corning under the trademark Celcor®) that can be used with the sorbent in accordance with the principles of the present disclosure.
  • the sorbent can be coated or otherwise immobilized on the inside of the pores of the ceramic honeycomb structure and/or within a porous layer on the surface of the ceramic honeycomb structure.
  • the porous coating can include a metal-oxide layer such as silica or alumina on the surface of the substrate.
  • the metal-oxide layer can be mesoporous and macroporous.
  • the honeycomb monolith may have a depth of 3 inches to 10 feet or about 3 and 24 inches.
  • the structure can be laminate sheets. Laminate sheets are structures containing a one-dimensional wall structure, whereby sheets are stacked upon one and other with space in between each sheet such that gas can flow between the sheets.
  • the structure can be a foam. Foams are structures with an irregular channel structure surrounded by an irregular solid structure. The solid structure is interconnected such that the foam material is self-standing.
  • the structure can be a plurality of fibers.
  • Fibers are structures with high aspect ratio, and in gas contacting applications can be arranged in a regular array amongst one another when supported at least on one end of the fiber.
  • the fibers can be solid or hollow.
  • the structure can be a minimal surface solid.
  • Minimal surface solids are structures often used in packing for distillation and absorption systems to increase contact area with a material and a fluid.
  • Minimal surface area solids are geometries that have zero mean surface area and include shapes such as gyroids. Gyroids can be sinusoidal, for example.
  • the structure can be a powder tray. Powder trays are structures whereby trays hold loose powder or pellets of the sorbent of the present disclosure to form a structured contactor without the material forming a self-standing structure by itself.
  • Powder trays can be arranged in stacked layers to form sheets thereby forming a structure similar to a laminate. These layers can be created using flexible sheets, stiff sheets, or other flat surface that is mounted on a stiff frame structure. Powders are loose, free flowing solids with small characteristic particle diameter such as to provide a powdery consistency. Pellets are beads, balls, or other compacted structures used to provide structure and surface area to sorbents In an aspect, the structure can be sorbent particle volumes. Sorbent particle volumes can be contained by one or more walls such that gas can pass through them while keeping the sorbent contained. Sorbent particle volumes can be arranged relative to other sorbent particle volumes such as to approximate a honeycomb, fiber, or other structured contactor with a solid body.
  • the sorbent (e.g., structure) in the form of a contactor is an efficient embodiment for an effective method for capturing CO 2 from ambient air or other gas mixtures (e.g., flue gas, exhaust gas, natural gas, or other gasses containing CO 2 ) because a structured contactor, or a contactor, can be engineered to provide high surface area and low pressure drop for the air processing.
  • Gas mixtures e.g., flue gas, exhaust gas, natural gas, or other gasses containing CO 2
  • Contactors can take the forms described of a honeycomb, a laminate sheet, a foam, fibers, minimal surface solids, powder trays, pellets, powder, and the like or a combination of two or more of the foregoing.
  • the modified CO 2 -philic phase (e.g., CO 2 binding molecules and phenol containing molecules) maintains high CO 2 capacities relative to the native CO 2 -philic phase that is not modified.
  • the sorbents lose less of the capacity to capture CO 2 following oxidative exposures compared to sorbents created without the improvement to the CO 2 -philic phase, thereby providing them with longer commercial lifetime.
  • the present disclosure provides for methods of capturing CO 2 from ambient air or other gas mixtures (e.g., flue gas, exhaust gas, natural gas, or other gasses containing CO 2 ).
  • the method includes introducing the ambient air to the sorbent (e.g., structure), heating the sorbent (e.g., about 10 to 200° C above the regular sorbent temperature to absorb the CO 2 ) to at least a first temperature to controllably release the CO 2 ; and collecting the CO 2 in a CO 2 collection device.
  • the sorbent e.g., structure
  • heating the sorbent e.g., about 10 to 200° C above the regular sorbent temperature to absorb the CO 2
  • a first temperature e.g., about 10 to 200° C above the regular sorbent temperature to absorb the CO 2
  • the temperature increase in the sorbent can be performed by contacting the sorbent with a gas at elevated temperature, contacting the sorbent with a fluid at an elevated temperature, contacting the sorbent with a heat exchanger with hot fluid or gas running through it, by heating the walls of the container, vessel, or other containment device that contains the sorbent, or by contacting the sorbent with steam (e.g., the steam may be at a temperature between 60 to 200° C, and be saturated or superheated).
  • the method can be implemented using the system described below.
  • the present disclosure provides for systems and devices for capturing CO 2 from ambient air or other gas mixtures (e.g., flue gas, exhaust gas, natural gas, or other gasses containing CO 2 ) where removal of CO 2 is important.
  • the system includes a first device configured to introduce the ambient air or other gas mixture to the sorbent or contactor, where the sorbent or contactor includes those described herein.
  • the sorbent is exposed to the ambient air or other gas mixture for a period of time (e.g., hours).
  • the sorbent is a honeycomb monolith that has an open face area of between 0.3-0.95.
  • the first device is configured to deliver the ambient air, for example, to the honeycomb monolith at a velocity of between 0.25-10 m/s.
  • a second device configured to heat the sorbent containing bound CO 2 to at least a first temperature (e.g., about 40 to 200° C, about 50 to 200° C, or about 60 to 200° C) to release the CO 2 .
  • the second device of the system can operate to desorb CO 2 by the sorbent.
  • the second device can include components to support temperature swing, pressure swing, steam swing, concentration swing, combinations thereof, or other dynamic processes to desorb the CO 2 .
  • the steam swing process can include exposing the sorbent to steam, where the temperature of the steam is about 60° C to 150° C and the pressure of the steam is about 0.2 bara to 5 bara.
  • a third device is configured to collect the released CO 2 .
  • the system can be operated so that the sorbent absorbs and desorbs the CO 2 in an efficient and cost-effective manner. Aspects of the present disclosure can be described by the following paragraphs.
  • the present disclosure provides for a sorbent comprising: a CO 2 -philic phase and a support, wherein the CO 2 -philic phase includes CO 2 binding molecules and phenol containing molecules.
  • the CO 2 binding molecules can include CO 2 binding moieties.
  • the CO 2 -philic phase is an amine.
  • the amine is an amine polymer.
  • the amine polymer is branched, hyperbranched, dendritic, or linear.
  • the amine polymer is one of polyethylenimine, polypropylenimine, polyallylamine, polyvinylamine, polyglycidylamine, or polystyrene- divinylbenzene polymer functionalized with amine, or other amine polymers.
  • the CO 2 -philic phase homogeneous.
  • the CO 2 -philic phase heterogeneous.
  • the phenol containing molecules is selected from: pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (commercial name Irganox 1010), DL- ⁇ -tocopherol, butylhydroxytoluene, 2,6-di-tert-butyl-4- methoxyphenol, tert-butylhydroquinone, 2(3)-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-1,4- dihydroxybenzene, 3-tert-butyl-4-hydroxyanisole, pyrrogallol, n-propyl gallate, 2,2’- methylenebis(6-tert-butyl-4-methylphenol), 2-tert-butyl-4-methylphenol, 2-(4,6-diphenyl-1,3,5- triazin-2-yl)-5-[(hexyl)oxy]-phenol, ethylene
  • the phenol containing molecules is selected from: pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate) (commercial name Irganox 1010), DL-a-tocopherol, butylhydroxytoluene, 2,6-di-tert-butyl-4-methyoxyphenol, tert-butylhydroquinone, 2(3)-tert-butyl- 4-methoxyphenol, 2,2’-methylenebis(6-tert-butyl-4-methylphenol), 2-naphthol, L-ascorbic acid, 4,4’-thiodiphenol, hesperetin, and 4,4’-thiobis-(2-tert-butyl-5-methylphenol).
  • pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate)
  • the phenol containing molecules is selected from: butylhydroxytoluene, 2-naphthol, L-ascorbic acid, tert-butylhydroquinone, and 4,4’-thiobis-(2-tert-butyl-5-methylphenol).
  • the amine is physically impregnated into pores of the support.
  • the amine is physically impregnated onto the surface of the support.
  • the amine is covalently bonded to the surface of the support.
  • the support is ceramic, metal, metal oxide, plastic, cellulose, carbon (e.g., particles), a zeolite, a metal organic framework (MOF), a porous organic framework (POF), a covenant organic framework (COF), a polymer of intrinsic microporosity (PIM), a polymer, a fibrous cellulose, fiberglass, or boronnitride fiber.
  • MOF metal organic framework
  • POF porous organic framework
  • COF covenant organic framework
  • PIM polymer of intrinsic microporosity
  • PIM polymer of intrinsic microporosity
  • the present disclosure provides for a contactor, comprising a structure and the sorbent as described above or herein.
  • the structure is selected from a honeycomb, a laminate sheet, a foam, fibers, a minimal surface solid, powder trays, pellets, or a combination of these.
  • the present disclosure provides for a system for capturing CO 2 from a gas, optionally the gas is ambient air, comprising: a first device configured to introduce the gas to the sorbent or contactor as described above or herein to bind CO 2 to the sorbent; a second device configured to heat the sorbent containing bound CO 2 to at least a first temperature to release the CO 2 ; and a third device configured to collect the released CO 2 . After being heated the sorbent is regenerated so it able to absorb CO 2 from the gas.
  • the sorbent is in the form of a honeycomb, a laminate sheet, a foam, fibers, a minimal surface solid, powder trays, pellets, a combination thereof.
  • the honeycomb has an open face area of between 0.3-0.95.
  • the gas approaches the honeycomb at a velocity of between 0.25-10 m/s.
  • the system is configured to operate to remove CO 2 from ambient air, where the ambient air has a low concentration of CO 2 .
  • the present disclosure provides for a method of capturing CO 2 from gas optionally the gas is ambient air comprising: introducing the ambient air to the sorbent as described above or herein to bind CO 2 to the sorbent; heating the sorbent to at least a first temperature to controllably release the CO 2 ; and collecting the CO 2 in a CO 2 collection device. Heating the sorbent regenerates the sorbent so it is able to absorb CO 2 from ambient air. The sorbent is heated by contacting it with steam.
  • the method is configured to operate to remove CO 2 from ambient air, where the ambient air has a low concentration of CO 2 .
  • the sorbent is in the form of a honeycomb, a laminate sheet, a foam, fibers, a minimal surface solid, powder trays, pellets, a combination thereof.
  • the present disclosure provides for a system for implement the method as described above or herein. Examples
  • the removal of CO 2 from ambient air through engineered chemical processes, otherwise known as Direct Air Capture (DAC), is emerging as an important environment technology for the mitigation of climate change.
  • DAC Direct Air Capture
  • DAC is a technology that can provide negative emissions, removing CO 2 from the atmosphere.
  • the current DAC technology is expensive thereby limiting its deployment. Therefore, improvements to DAC technology are needed.
  • DAC technologies rely on solid sorbent materials as a medium to perform the separation of CO 2 from the air. These sorbents are generally applied in temperature swing processes, where at low temperature CO 2 from the air binds to the sites within them, and then at high temperature the CO 2 is released into a concentrated product that can be sequestered or sold as a product. Many DAC sorbents utilize amines to bind CO 2 in this manner. Certain amine types can be effective at binding CO 2 from low concentrations such as that found in the air (400 ppm). While some amine types are effective at binding CO 2 from ambient air, they slowly oxidize in air from ambient oxygen.
  • Some sorbents used in DAC processes are composite materials, containing a CO2-philic phase (e.g., CO 2 binding molecules and phenol containing molecules) that is distributed in or within a solid material that provides it with surface area.
  • the CO 2 -philic phase can be grafted to the solid surface, physically impregnated into the pores of the solid material, or physically supported on the surface of the solid material.
  • the CO 2 -philic phase of these sorbents can be amines or other molecules that can bind CO 2 .
  • the amines can be polymeric amines such as polyethylenimine, polypropylenimine, polyallylamine, polyvinylamine, polybutylamine or others. These polymeric amines can be linear, branched, hyperbranched, dendritic, or take the form some other macromolecule.
  • the amines can be small molecules such as TEPA, TPTA or others.
  • the amines can be aminosilanes.
  • the solid support material can be a metal oxide, carbon, metal, or other structure that can provide ample surface area for the CO 2 -philic phase to be deposited to allow for useful CO 2 adsorption and desorption capacities and kinetics. In this way, the solid support material is functionalized with the CO 2 -philic phase to create a composite sorbent.
  • the sorbents can be formed or incorporated into macrostructures, or contactors, to provide advantages in applications such as DAC.
  • Such structures can be honeycomb monoliths, laminate sheets, pellets, or other structures that can provide a high geometric surface area for air or CO 2 containing gasses to efficiently contact the sorbent such that the CO 2 can bind to the sorbent.
  • the sorbents can be utilized in processes to capture CO 2 from air or a variety of other gas stream such as flue gas, natural gas and others. These processes are known as “CO 2 Capture Processes”. CO 2 capture processes can utilize temperature swing, concentration swing, pressure swing, steam stripping or other swing techniques to remove CO 2 that has been bound the surface of the sorbent. There has been relatively little development of improved CO 2 sorbents utilizing polyethylenimine, and especially for DAC applications. Now having described the embodiments of the present disclosure, in general, the following examples describes some additional embodiments of the present disclosure. While embodiments of the present disclosure are described in connection with these examples and the corresponding text and figures, there is no intent to limit embodiments of the present disclosure to these descriptions.
  • Figure 1B shows the primary components of the sorbent system.
  • the sorbent system is comprised of a support material and a CO 2 -philic phase.
  • a single CO 2 - philic phase is shown incorporated into a single support.
  • the CO 2 -philic phase shown is polyethylenimine (PEI).
  • PEI polyethylenimine
  • One known adsorption product of CO 2 and PEI is ammonium carbamate.
  • Mesoporous alumina is shown as a support.
  • Figure 2 shows one embodiment of a honeycomb monolith contactor. The figure shows the primary geometrical features of a honeycomb monolith, having straight, flowthrough channels surrounded on all sides by walls. The figure schematically shows a washcoat applied to the walls, where the washcoat is comprised of sorbent.
  • the sorbent is comprised of a support material and a CO 2 -philic phase, such as PEI.
  • Phenol containing molecules evaluated as additives to polyethylenimine (PEI) A variety of additive molecules were evaluated to assess their ability to reduce the oxidation rate of PEI in sorbents. The additives tested were phenol containing molecules, which can be primary antioxidants.
  • Example 3 Preparation of improved CO 2 sorbents containing polyethylenimine (PEI) and phenol containing molecules Branched polyethylenimine (PEI), MW 800 is available from Sigma Aldrich.
  • the phenol containing compounds used are listed in the table below.
  • the PEI was dissolved in a solution of methanol, after which the phenol was added in a ratio corresponding to 0.1 mol phenol per mol of N present in PEI and stirred until homogenous. Then, a mesoporous alumina was dispersed in the mixture. After stirring for >4h, the solvent was removed using rotary evaporation and subsequent drying in a vacuum oven at 100° C.
  • Mass ratios of the alumina and PEI/phenol were controlled such as to achieve 40-80% filling of the mesopores of the mesoporous alumina with PEI/phenol mixture.
  • the resultant composite sorbents were of a powdery consistency. Table 1: Details on phenols used for the preparation of phenol containing CO 2 sorbents.
  • the DSC traces reveal different oxidative profiles for the materials during the course of the exposure and also confirm that the phenol molecules have been incorporated into the CO 2 -philic phase.
  • the mass gain of the material corresponds to the adsorption of CO 2 and therefore can be used to measure the total quantity and rate of CO 2 adsorption onto the materials.
  • Various improved sorbents were characterized for CO 2 adsorption using this method, and compared to the baseline PEI based sorbent. Sorbents created using PEI and several phenol containing molecules were evaluated relative to the sorbent with PEI alone. The sorbents were evaluated on two bases, i) CO 2 capacity, mmol of CO 2 adsorbed per mol of sorbent present, and ii) amine efficiency, mmol of CO 2 adsorbed per mol of N in PEI present in sample.
  • the former unit of performance is useful to show bulk sorbent performance
  • the second unit of performance is useful to evaluate the performance of the amine polymer itself and takes into account changes to the bulk composition of the sorbent.
  • Figure 6 shows transient TGA uptake curves under DAC conditions for sorbents created with improved CO 2 -philic phases utilizing PEI combined with phenol additives, each at 0.1 mol additive / mol PEI, compared to that of unmodified PEI.
  • the sorbents are able to adsorb CO 2 at the ultra-dilute conditions of 400 ppm, with varying degrees of amine efficiency.
  • the Phenol 10 and Phenol 11 additives appear to not impact the ability of the material to adsorb CO 2 compared to PEI.
  • the Phenol 12 and Phenol 5 additives reduce the ability to adsorb CO 2 to some extent, followed by Phenol 6 loosing almost all ability to adsorb CO 2 . All of the phenol additives either improve or maintain the initial rate of adsorption of CO 2 as compared to PEI, with the exception of Phenol 6.
  • the initial rate of adsorption follows the trend of PEI + Phenol 5 > PEI + Phenol 11 ⁇ 3(, ⁇ Phenol 12 > PEI + Phenol 10 > PEI > PEI + Phenol 6. This indicates that some of the phenol additives can improve the CO 2 adsorption rate, thereby allowing sorbents to equilibrate more quickly when adsorbing CO 2 from air or other dilute streams.
  • Example: Testing of Oxidative Stability The oxidative stability of materials can be probed in several ways. In this study, the oxidative stability of the sorbents was evaluated by tracking the heat flow evolved from the materials using a DSC during exposure to isothermal oxidative conditions.
  • the sorbents were first treated in inert gas at 100° C to desorb any bound H 2 O and CO 2 before being equilibrated at either 125, 137.5 or 150° C under inert gas for 60 minutes.
  • the gas was then isothermally switched to a 17% O 2 mixture (CO 2 -free air, or air), or a mixture of 17% O 2 and 20% CO 2 , and held until the reaction finished.
  • This isothermal, oxidative environment was maintained for a specific amount of time to measure the heat flow and mass loss.
  • the sample was then cooled under N 2 to room temperature.
  • the DSC measures the incremental heat flux, which increases, levels out, and then decreases to zero.
  • the oxidation was considered complete when the integrated heat flow over 10 min changed less than ⁇ 0.01% of the total integrated heat.
  • DSC data were converted from the base unit of mW/mg sorbent to W/gPEI using the PEI loading measured by TGA burnoff. DSC data were corrected for drift by applying an offset, determined by the heat flow value when the DSC curve approached a horizontal line.
  • the total heat evolved was calculated by integrating heat flow over time.
  • the extent of oxidation from DSC was calculated by dividing the integral heat flow curve by the total heat evolved.
  • Figure 8 shows oxidation curves in the presence of CO 2 for CO 2 sorbents created with a variety of phenols, labeled by their reference in Figure 3, mixed with PEI at a ratio of 0.1 mol additive / mol PEI, and supported in mesoporous alumina.
  • the figure shows two general categories of behavior; some phenols slow the oxidation rate of PEI, and some phenols do not greatly change the oxidation rate of PEI.
  • Phenol 1, Phenol 5, and Phenol 12 slow the oxidation rate of PEI, while Phenol 11 has a comparable rate of oxidation to that of PEI.
  • the differences between the extent of oxidation observed for the different phenol additives in Figure 8 suggest that phenols can be effective antioxidants for the conditions related to regeneration during CO 2 capture processes, but to varying extents.
  • Figure 9 shows oxidation curves in the presence of CO 2 -free air only for CO 2 sorbents created with a variety of phenols, labeled by their reference in Figure 3, mixed with PEI at a ratio of 0.1 mol additive I mol PEI, and supported in mesoporous alumina.
  • the figure shows that all of the phenols tested accelerated the oxidation rate of PEI, to varying extents. Phenol 2, Phenol 11 , and Phenol 12 accelerated oxidation the least, followed by Phenol 5.
  • Figures 8-9 illustrate that phenols are effective antioxidants in conditions when CO 2 is present but not in CO 2 -free (air) conditions. This is an unexpected result, given that phenols are used commercially as antioxidant additives. There are certain use cases where phenols may be useful in reducing oxidative degradation in CO 2 capture processes that have high concentrations of CO 2 . In this regard, materials of the present disclosure can be tuned based on the process in which they are deployed.
  • oxidation-resistant sorbent honeycomb monoliths For the preparation of oxidation-resistant sorbent honeycomb monoliths, a 4,4’-Thiobis- (2-tert-butyl-5-methylphenol) and PEI solution was prepared: MeOH was used to dissolve the PEI and the phenol was added in a ratio corresponding to 0.1 mol phenol per mol of N present in PEI and stirred until fully homogenous. The PEI/phenol mixture was allowed to stir at room temperature for approximately 1 hour prior to impregnation in the monolith.
  • Honeycomb monoliths having a honeycomb channel structure, comprised of porous titania were utilized.
  • honeycomb monolith contains 7 wt% PEI and 6 wt% phenol with a pore fill of 48%.
  • Figure 10 shows the TGA burnoff for the prepared honeycomb monolith with PEI and Phenol 12 additive.
  • ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a concentration range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range.
  • the term “about” can include traditional rounding according to significant figures of the numerical value.
  • the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about ‘y’”.

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Abstract

La présente divulgation concerne des sorbants et des contacteurs, des procédés d'utilisation de sorbants et de contacteurs pour capturer du CO2, des structures comprenant le sorbant, ainsi que des systèmes et des dispositifs utilisant des sorbants et des contacteurs pour capturer du CO2. La présente divulgation concerne des sorbants et des contacteurs qui comprennent une phase CO2-phile et un support. La phase CO2-phile comprend des molécules de liaison au CO2 et des molécules contenant du phénol.
PCT/US2023/066672 2022-05-06 2023-05-05 Sorbants contenant du phénol, systèmes comprenant des sorbants, et procédés utilisant les sorbants WO2023215875A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010029843A1 (en) * 2000-01-31 2001-10-18 Nichias Co., Ltd. Chemical filter and manufacturing method thereof
US20070149398A1 (en) * 2005-12-12 2007-06-28 Jones Christopher W Structures for capturing CO2, methods of making the structures, and methods of capturing CO2
US20130078172A1 (en) * 2011-09-12 2013-03-28 West Virginia University Research Corporation Layered Solid Sorbents For Carbon Dioxide Capture
US20130095996A1 (en) * 2011-10-06 2013-04-18 Basf Corporation Methods of applying a sorbent coating on a substrate, a support, and/or a substrate coated with a support
US20140127119A1 (en) * 2011-06-09 2014-05-08 Asahi Kasei Kabushiki Kaisha Carbon dioxide absorber and carbon dioxide separation/recovery method using the absorber
WO2019059368A1 (fr) * 2017-09-25 2019-03-28 株式会社クラレ Absorbeur de gaz de dioxyde de carbone, accumulateur à électrolyte non aqueux contenant celui-ci, et procédé de séparation et récupération de gaz de dioxyde de carbone

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010029843A1 (en) * 2000-01-31 2001-10-18 Nichias Co., Ltd. Chemical filter and manufacturing method thereof
US20070149398A1 (en) * 2005-12-12 2007-06-28 Jones Christopher W Structures for capturing CO2, methods of making the structures, and methods of capturing CO2
US20140127119A1 (en) * 2011-06-09 2014-05-08 Asahi Kasei Kabushiki Kaisha Carbon dioxide absorber and carbon dioxide separation/recovery method using the absorber
US20130078172A1 (en) * 2011-09-12 2013-03-28 West Virginia University Research Corporation Layered Solid Sorbents For Carbon Dioxide Capture
US20130095996A1 (en) * 2011-10-06 2013-04-18 Basf Corporation Methods of applying a sorbent coating on a substrate, a support, and/or a substrate coated with a support
WO2019059368A1 (fr) * 2017-09-25 2019-03-28 株式会社クラレ Absorbeur de gaz de dioxyde de carbone, accumulateur à électrolyte non aqueux contenant celui-ci, et procédé de séparation et récupération de gaz de dioxyde de carbone

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