EP-4739430-A1 - SORBENT MATERIALS FOR CO2 CAPTURE, USES THEREOF AND METHODS FOR MAKING SAME

EP4739430A1EP 4739430 A1EP4739430 A1EP 4739430A1EP-4739430-A1

Abstract

A method for preparing a sorbent material (3) for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air (1), flue gas and biogas, containing said gaseous carbon dioxide as well as further gases different from gaseous carbon dioxide, by cyclic adsorption/desorption using a sorbent material (3) capable of reversibly binding carbon dioxide and adsorbing said gaseous carbon dioxide in a unit (8), wherein the sorbent material (3) comprises: primary amine moieties as well as at least one of secondary amine, and tertiary amine moieties immobilized on a solid support, and is made using an amination pathway avoiding cross-linking.

Inventors

GROPP, Cornelius
ALBANI, DAVIDE
DURRER, Julian
LIMONE, Claudio
YOSHIDA, TOMOHIDE
SCHNEIDER, PATRICK
LAGOMARSINO, Giacomo
NAHI, Ouassef

Assignees

Climeworks AG

Dates

Publication Date: 20260513
Application Date: 20240702

Claims (15)

1. A method for preparing a sorbent material (3) for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air (1), flue gas and biogas, containing said gaseous carbon dioxide as well as further gases different from gaseous carbon dioxide, by cyclic adsorption/desorption using a sorbent material (3) capable of reversibly binding carbon dioxide and adsorbing said gaseous carbon dioxide in a unit (8), wherein the sorbent material (3) comprises: primary amine moieties as well as at least one of secondary amine, and tertiary amine moieties, immobilized on a solid support, wherein a solid support precursor is provided, having at least one of a primary amine, and secondary amine functionality, and wherein this solid support precursor is reacted with at least one reactant selected from the following group: wherein PG is a protecting group, with the proviso that PG may also be a cyclic group with one branch of the cycle replacing the hydrogen bound to the protected secondary amine moiety of the reactant, X is a leaving group, i is in the range of 1-6 for structure (I) and in the range of 0-5 for structure (II), and in both cases includes substituted or unsubstituted moieties selected from the group consisting of: -CH2- , -CH(CH3)-, and wherein the resulting material is converted into said sorbent material (3) by removing said protecting group.
2. Method according to claim 1 , wherein the protecting group is selected from the group consisting of: hydrogenhalogenide, including HCI, HBr, HI, phthalimide, pyrazole, including pyrazole hydrochloride, tert-butyloxycarbonyl, para-toluenesulfone, benzylidene, acetate/acetamide or trifluoroacetate/trifluoroacetamide, wherein preferably for systems of the type (I), in which the protecting group is selected as hydrogenhalogenide, including HCI, HBr, HI, the reactant is provided for the reaction by starting from a respective alkanolamine and reacting this with a organohalogenating reagent, including thionylchloride, and subsequently contacting this with said solid support precursor.
3. Method according to any of the preceding claims, wherein the conversion into said sorbent material (3) takes place by removing said protecting group using an organic base or an inorganic base or combination thereof, wherein preferably organic bases are selected from the group of alkylamines, including triethylamine, pyridine, imidazole, tetramethylammonium hydroxide and wherein inorganic bases are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, and a combination thereof.
4. Method according to any of the preceding claims, wherein the reaction with the reactant and/or the step of removal of said protecting group is carried out in an organic or an inorganic solvent or a combination thereof, wherein preferably the solvent is selected from the group consisting of water, methanol, tetrahydrofurane, ethanol, di-methoxy methane, dimethylformamide, or a combination thereof, wherein preferably the solvent is water.
5. Method according to any of the preceding claims, wherein the reactant is added to the solid support precursor in an equivalent ratio of 0.1-10, preferably 0.1 -1.0, relative to the primary/secondary amine content of the solid support precursor.
6. Method according to any of the preceding claims, wherein the solid support precursor is at least one of a structured and/or porous polymer, silica, class II or class III MOF, in particular the solid support precursor is polystyrene based, preferably a polystyrene based benzyl amine, preferably it is an amine functionalized styrene-divinylbenzene support, preferably functionalised by primary benzylamine or primary a-methylbenzylamine, or a styrene allylamine solid support precursor and/or wherein the solid support precursor is a solid styrene-divinylbenzene support functionalised by primary benzylamine or primary a-methylbenzylamine groups, preferably as the result of a reaction of halogenmethylated styrene-divinylbenzene, preferably chloromethylated styrene-divinylbenzene, with hexamethylenetetramine or, alternatively or through amidomethylation of styrene-divinylbenzene and subsequent hydrolysis, or a styrene allylamine solid support precursor and/or wherein the method is a method of regeneration and wherein the solid support precursor is a solid support capable of reversibly binding carbon dioxide and adsorbing said gaseous carbon dioxide in a unit, which has been used for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air (1), flue gas and biogas, containing said gaseous carbon dioxide as well as further gases different from gaseous carbon dioxide, by cyclic adsorption/desorption, wherein preferably such regeneration is carried out if the carbon dioxide capture capacity has dropped by more than 30%, preferably by more than 20%, more preferably by more than 15% compared with the carbon dioxide capture capacity of pristine sorbent material, or regeneration of the sorbent material is carried out after having cycled the sequence of adsorption/desorption steps at least 500 times, preferably at least 1000 times, more preferably at least 10,000 times, but preferably before having cycled the sequence of steps 50,000 times, preferably before having cycled the sequence of steps 25,000 times.
7. Method according to any of the preceding claims, wherein the reactant has i= 1 -5, preferably i= 1 -4 or i= 1 -3 for structure (I) and i= 1 -4, preferably i= 1 -3 for structure (II).
8. Method according to any of the preceding claims, wherein the solid support material, preferably in the form of a styrene-divinylbenzene based support material or a styrene allylamine support material, is in the form of at least one of monolith, layer or sheet, hollow or solid fibres, preferably in woven or nonwoven structures, hollow or solid particles, or extrudates, wherein preferably it takes the form of preferably essentially spherical beads,
9. Method according to any of the preceding claims, wherein the solid support material, preferably in the form of a styrene-divinylbenzene based support material or a styrene allylamine support material, is in the form of solid particles embedded in a porous or non-porous matrix.
10. Method according to any of the preceding claims, wherein the sorbent material takes the form of preferably essentially spherical beads with a particle size (D50) in the range of 0.002 - 4 mm, 0.005 - 2 mm, 0.002 - 1.5 mm, 0.005 - 1.6 mm or 0.01-1 .5 mm, preferably in the range of 0.30-1.25 mm.
11. Method according to any of the preceding claims, wherein X of the reactant is selected from the group consisting of halogen, tosylate, mesylate, ester, imide, carbodiimide, pyrazole.
12. Sorbent material capable of reversibly binding carbon dioxide, for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air (1), flue gas and biogas, preferably for direct air capture, in particular using a temperature, vacuum, or temperature/vacuum swing process, wherein said sorbent material (3) is obtainable or obtained using a method according to any of the preceding claims.
13. Use of a sorbent material (3) according to claim 12 for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air (1), flue gas and biogas, preferably for direct air capture, in particular using a temperature, vacuum, or temperature/vacuum swing process, wherein said sorbent material (3), wherein the sorbent material (3) comprises: primary amine moieties as well as at least one of secondary amine, and tertiary amine moieties immobilized on a solid support.
14. Use according to claim 13, wherein for separating gaseous carbon dioxide a method is used, which comprises at least the following sequential and in this sequence repeating steps (a) - (e): (a) contacting said gas mixture (1) with the sorbent material (3) to allow at least said gaseous carbon dioxide to adsorb on the sorbent material (3) by flow-through through said unit (8) essentially under ambient atmospheric pressure conditions and ambient atmospheric temperature conditions in an adsorption step; (b) isolating said sorbent material (3) with adsorbed carbon dioxide in said unit (8) from said flow-through; (c) inducing an increase of the temperature of the sorbent material (3) to a temperature starting the desorption of carbon dioxide; (d) extracting at least the desorbed gaseous carbon dioxide from the unit (8) and separating gaseous carbon dioxide in or downstream of the unit (8); (e) bringing the sorbent material (3) essentially to ambient atmospheric temperature conditions and ambient atmospheric pressure conditions.
15. Unit for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air (1), flue gas and biogas, preferably direct air capture unit, comprising at least one reactor unit (8) containing sorbent material (3) according to claim 12 in a form suitable and adapted for flow-through of said gas mixture (1), wherein the reactor unit comprises an inlet for said gas mixture, preferably for ambient air (1), and an outlet (2) for said gas mixture, preferably for ambient air during adsorption, wherein the reactor unit is heatable to a temperature of at least 60°C for the desorption of at least said gaseous carbon dioxide and the reactor unit being openable to flow-through of the gas mixture, preferably of the ambient atmospheric air, and for contacting it with the sorbent material for an adsorption step, wherein preferably the reactor unit is further evacuable to a vacuum pressure of 400 mbar(abs) or less, wherein the sorbent material (3) preferably takes the form of at least part of an adsorber structure comprising an array of individual adsorber elements, each adsorber element preferably comprising at least one support layer and at least one sorbent material layer comprising or consisting of at least one sorbent material, wherein preferably the adsorber elements in the array are arranged essentially parallel to each other and spaced apart from each other forming parallel fluid passages for flow-through of said gas mixture, preferably of ambient atmospheric air and/or steam, at least one device, preferably a condenser, for separating carbon dioxide from water, wherein preferably at the gas outlet side of said device for separating carbon dioxide from water, preferably said condenser, there is at least one of, preferably both of a carbon dioxide concentration sensor and a gas flow sensor for controlling the desorption process.

Description

TITLE SORBENT MATERIALS FOR CO2 CAPTURE, USES THEREOF AND METHODS FOR MAKING SAME TECHNICAL FIELD The present invention relates to carbon dioxide capture materials with primary and/or secondary amine carbon dioxide capture moieties with good capture and swelling properties, as well as methods for preparing such capture materials, uses of such capture materials and carbon dioxide capture methods involving such materials. PRIOR ART According to the OECD report of 2017 [Global Energy & CO2 Status Report 2017, OECD/IEA March 2018] the yearly emissions of CO2 to the atmosphere are ca 32.5 Gt (Gigatons, or 32.5x10E9 tons). As of February 2020 all but two of the 196 states that in 2016 have negotiated the Paris Agreement within the United Nations Framework Convention on Climate Change (UFCCC) have ratified it. The meaning of this figure is that a consensus is reached regarding the threat of climate change and regarding the need of a global response to keep the rise of global temperature well below 2 degrees Celsius above pre-industrial levels. The technical and scientific community engaged in the challenge of proposing solutions to meet the target of limiting CO2 emissions to the atmosphere and to remove greenhouse gases from the atmosphere through or with a number of technologies. Flue gas capture, or the capture of CO2 from point sources, such as specific industrial processes and specific CO2 emitters, deals with a wide range of relatively high concentrations of CO2 (3-100 vol %) depending on the process that produces the flue gas. High concentrations make the separation of the CO2 from other gases thermodynamically more favorable and consequently economically favorable as compared to the separation of CO2 from sources with lower concentrations, such as ambient air, where the concentration is in the order of 400 ppm. Nonetheless, the very concept of capturing CO2 from point sources has strong limitations: it is specifically suitable to target such point sources, but is inherently linked to specific locations where the point sources are located and can at best limit emissions and support reaching carbon neutrality, while as a technical solution it will not be able to contribute to negative emissions (i.e., permanent removal of carbon dioxide from the atmosphere) and to remove historic emission. In order to achieve negative emissions (i.e., permanent removal carbon dioxide from the atmosphere), the two most notable solutions currently applied, albeit being at an early stage of development, are the capturing of CO2 by means of vegetation (i.e., trees and plants, but not truly permanent removal) using natural photosynthesis, and by means of DAC technologies, which is the only truly permanent removal. Forestation has broad resonance with the public opinion. However, the scope and feasibility of re-forestation projects is debated and is likely to be less simple an approach as believed because it requires a large footprint in terms of occupied surface to captured CO2 ratio. On the other hand, DAC has lower land footprint and therefore it does not compete with the production of crops, can permanently remove CO2 from the atmosphere and can be deployed everywhere on the planet. The above-described strategies to mitigate climate change all have potential and are considered as a potential part of the overall solution. The most likely future scenario is the deployment of multiple or a variety of different approaches, after undergoing further development. Several DAC technologies were described, such as for example, the utilization of alkaline earth oxides to form calcium carbonate as described in US-A-2010034724. Different approaches comprise the utilization of solid CO2 adsorbents, hereafter named sorbents, in the form of packed beds of typically sorbent particles and where CO2 is captured at the gassolid interface. Such sorbents can contain different types of amino functionalisation and polymers, such as immobilized aminosilane-based sorbents as reported in US-B-8834822, and amine-functionalised cellulose as disclosed in WO-A-2012/168346. WO-A-2011/049759 describes the utilization of an ion exchange material comprising an aminoalkylated bead polymer for the removal of carbon dioxide from industrial applications. WO-A-2016/037668 describes a sorbent for reversibly adsorbing CO2 from a gas mixture, where the sorbent is composed of a polymeric adsorbent having a primary amino functionality. The materials can be regenerated by applying pressure or humidity swing. Several academic publications, such as Alesi et al. in Industrial & Engineering Chemistry Research 2012, 51 , 6907-6915; Veneman et al. in Energy Procedia 2014, 63, 2336; Yu et al. in Industrial & Engineering Chemistry Research 2017, 56, 3259-3269, also investigated in detail the use of cross-linked polystyrene resins functionalised with primary benzylamines as solid sorbents for DAC applications. Polystyrene-divinylbenzene resins have also been used as a support to