Monolithic substrate

Abstract

The monomeric substrate comprises a dried and / or cured product of the extruded extrudable paste. The extrudable paste comprises a hollow and / or porous material. The extrudable paste also includes a binder. The monolithic substrate has a bulk density of 60 g / L to 170 g / L.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 417,725, filed Oct. 20, 2022, the content of which is incorporated herein by reference in its entirety. Background of the Invention

[0003] Climate change is a growing consideration. Globally, there is a need to reduce the CO 2 footprint, either by finding alternatives to processes that generate CO 2 , or by capturing the CO 2 released at point sources or in ambient air. Negative emission technologies for removing CO 2 include: afforestation, reforestation, direct air capture (e.g., removing CO 2 from ambient air), and bioenergy with carbon capture and storage (BECCS).

[0004] One method for removing CO 2 from point sources or from ambient air involves flowing a stream loaded with CO 2 through a monolithic piece containing an adsorbent that adsorbs CO 2 . The CO 2 can then be desorbed for removal (e.g., by heating the monolithic piece). However, CO 2 removal by conventional monolithic pieces is limited by the volumetric density (heat capacity) of the monolithic piece, requiring more energy to heat for CO 2 desorption. CO 2 removal efficiency is further limited, which limits the amount of adsorbent that can be added to the monolithic piece. The mechanical strength of the monolithic piece material also plays a role in the ability of the monolithic piece to survive subsequent processing steps, including applying the adsorbent, installing the monolithic piece into a system, and regeneration processes that involve removing spent adsorbent from the monolith and reapplying new adsorbent. The mechanical strength of the monolithic piece depends on characteristics such as the number and thickness of the walls of the structure, all of which are factors that affect the resulting density or heat capacity of the monolithic piece. Summary of the Invention

[0005] In various aspects, the present invention provides a monolithic substrate comprising a dried and / or cured product of an extrudable paste. The extrudable paste comprises hollow and / or porous materials. The extrudable paste further comprises a binder. The monolithic substrate has a bulk density of from 60 g / L to 170 g / L.

[0006] In various aspects, the present invention provides a monolithic substrate comprising a dried and cured product of an extrudable paste. The extrudable paste comprises hollow and / or porous materials, including: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, other hollow or porous particles, or combinations thereof. The extrudable paste further comprises a binder, including polymers, inorganic binders, thermosetting resins, or combinations thereof. The monolithic substrate has a bulk density of from 60 g / L to 170 g / L and an open frontal area of 80 - 95%.

[0007] In various aspects, the present invention provides a method of forming the monolithic substrate of the present invention. The method includes extruding an extrudable paste. The method further includes drying and / or curing the extruded extrudable paste.

[0008] In various aspects, the present invention provides a method of using the monolithic substrate of the present invention. The method includes exposing the monolithic substrate to a gas stream comprising CO 2 such that at least a portion of the CO 2 from the gas stream is adsorbed into a coating on the monolithic substrate, the coating comprising a material that adsorbs and desorbs CO 2 . The method further includes desorbing the CO 2 from the coating on the monolithic substrate.

[0009] In various aspects, the present invention provides a carbonized monolithic substrate comprising a carbonized product of the monolithic substrate of the present invention.

[0010] In various aspects, the present invention provides a carbonized monolithic substrate comprising a dried, cured, and carbonized product of an extrudable paste. The extrudable paste comprises hollow and / or porous materials, including: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or combinations thereof. The extrudable paste further comprises a binder, including polymers, inorganic binders, thermosetting resins, or combinations thereof. The carbonized monolithic substrate has a bulk density of from 60 g / L to 170 g / L and an open frontal area of 80 - 95%.

[0011] In various aspects, the present invention provides a method of forming the carbonized monolithic substrate of the present invention. The method includes carbonizing the monolithic substrate of the present invention. In various aspects, the carbonized monolithic substrate can be conductive.

[0012] In various aspects, the present invention provides methods of using the carbonized monolithic substrates of the present invention. The methods include exposing the carbonized monolithic substrates to a gas stream comprising CO 2 such that at least a portion of the CO from the gas stream is adsorbed into a coating on the carbonized monolithic substrate, the coating comprising a material that adsorbs and desorbs CO 2 . The methods further include desorbing CO 2 from the coating on the carbonized monolithic substrate. 2 .

[0013] In various aspects, the present invention provides carbonized and activated monolithic substrates comprising a carbonized and activated product of the monolithic substrates of the present invention.

[0014] In various aspects, the present invention provides carbonized and activated monolithic substrates comprising a dried and cured carbonized and activated product of an extrudable paste. The extrudable paste comprises hollow and / or porous materials including: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or combinations thereof. The extrudable paste comprises a binder including polymers, inorganic binders, thermosetting resins, or combinations thereof. The extrudable paste further comprises: an adsorbent, an adsorbent aid, an adsorbent precursor, and / or an adsorbent aid precursor, the adsorbent aid including Al 2 O 3 , TiO 2 , SiO 2 or combinations thereof, the adsorbent including zeolites, sodium carbonate, activated carbon, carbon nanotubes, metal-organic frameworks (MOFs), amines, or combinations thereof, and the adsorbent precursor and / or adsorbent aid precursor including Al 2 O 3 precursors, TiO 2 precursors, SiO 2 precursors, or combinations thereof. The carbonized and activated monolithic substrates have a bulk density of from 60 g / L to 170 g / L and an open frontal area of 80 - 95%.

[0015] In various aspects, the present invention provides methods of forming the carbonized and activated monolithic substrates of the present invention. The methods include activating the carbonized monolithic substrates of the present invention.

[0016] In various aspects, the present invention provides methods of using the carbonized and activated monolithic substrates of the present invention. The methods include exposing the carbonized and activated monolithic substrates to a gas stream comprising CO 2 such that at least a portion of the CO from the gas stream is adsorbed into a coating on the carbonized and activated monolithic substrate, the coating comprising a material that adsorbs and desorbs CO 2At least partially adsorbed onto a carbonized and activated monolithic substrate, the coating comprising a material for adsorbing and desorbing CO 2 The method further includes desorbing CO from the coating on the carbonized and activated monolithic substrate 2 .

[0017] In various aspects, the monolithic articles (e.g., monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles) of the present invention and methods for their manufacture and use have certain advantages compared to other monolithic articles and methods for their manufacture and use. For example, in various aspects, compared to other monolithic articles for CO 2 removal, the monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles of the present invention can have a lower mass per unit area (e.g., from thinner walls and / or higher porosity) and / or a lower thermal mass (i.e., less energy is required per unit mass to heat). In various aspects, the monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles of the present invention can have an extruded shape that cannot be produced by other monolithic articles (e.g., cordierite monolithic articles) (e.g., a geometric morphology with thinner walls and / or greater porosity), which is due to, for example, enhanced mechanical strength and / or reduced density before or after hardening. In various aspects, compared to other monolithic articles (e.g., compared to monolithic articles made of cordierite material), the monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles of the present invention can have a higher surface area per unit volume, enabling more efficient CO 2 capture. In various aspects, the higher surface area per unit volume enables a greater adsorbent coating surface area per unit volume on the monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles of the present invention, enabling more efficient CO 2 removal.

[0018] In various aspects, the monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles of the present invention can include adsorbents, adsorbent aids, adsorbent precursors, and / or adsorbent aid precursors incorporated therein and / or coated thereon, such that the monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles of the present invention have a high surface area, greater adsorptivity, or a combination thereof. In various aspects, compared to other monolithic articles (e.g., compared to monolithic articles made of cordierite material), the monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles of the present invention can have a lower pressure drop. In various aspects, the monolithic articles, carbonized monolithic articles, and / or carbonized and activated monolithic articles of the present invention can be produced at a lower cost compared to other monolithic articles of similar size (e.g., compared to monolithic articles made of cordierite material). BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Accompanying Figure 1The various aspects of the present invention are generally shown by way of example and not limitation.

[0020] Figure 1 Photographs show two pastes made with various formulations according to various aspects.

[0021] Figure 2 are photographs of two sheets of different thicknesses roll-formed and cured from the two pastes according to various aspects.

[0022] Figure 3 are photographs of sheets floating in water roll-formed and cured from the two pastes according to various aspects.

[0023] Figure 4 SEM images of show cross-sections of roll-formed and cured sheets according to various aspects.

[0024] Figure 5 Photographs of show side and top views of an extruded honeycomb monolithic part according to various aspects.

[0025] Figure 6 Photographs of show side and top views of a carbonized extruded honeycomb monolithic part according to various aspects.

[0026] Figure 7 Photographs of show side and top views of a carbonized extruded honeycomb monolithic part according to various aspects. DETAILED DESCRIPTION

[0027] Reference will now be made specifically to certain aspects of the disclosed subject matter. Although the disclosed subject matter will be described in connection with the enumerated claims, it is to be noted that the exemplary subject matter is not intended to limit the claims to the disclosed subject matter.

[0028] Throughout this document, numerical values presented in range format should be construed in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also all the individual numerical values or sub-ranges within that range as if each numerical value and sub-range were explicitly recited. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be construed to include not only about 0.1% to about 5%, but also the individual numerical values (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. Unless otherwise stated, the recited "about X to Y" has the same meaning as "about X to about Y". Similarly, unless otherwise stated, the recited "about X, Y or about Z" has the same meaning as "about X, about Y or about Z".

[0029] In this document, unless the context clearly dictates otherwise, the terms "a", "an", or "the" are used to include one or more than one. Unless otherwise specified, the term "or" is used to mean a non-exclusive "or". The statement "at least one of A and B" or "at least one of A or B" has the same meaning as "A, B, or both A and B". Additionally, it is to be understood that the phrases and terms used herein and not otherwise defined are for descriptive purposes only and not limiting. The use of any section headings is intended to aid in reading the document and not to be construed as limiting; information related to a section heading may appear within or outside of that particular section.

[0030] In the methods described herein, acts may be performed in the specific order stated herein. Alternatively, in any aspect disclosed herein, specific acts may be performed in any order without departing from the principles of the invention, unless a time or order of operation is explicitly stated. Additionally, specific acts may be performed simultaneously, unless the language of the claims explicitly states that they are to be performed separately or the clear meaning of the claims requires it. For example, the act of performing X in a claim and the act of performing Y in a claim may be performed simultaneously in a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0031] As used herein, the term "about" permits a degree of variability in a numerical value or range, e.g., within 10%, within 5%, or within 1% of the stated numerical value or the stated range limit, and includes the exact numerical value or range stated.

[0032] As used herein, the term "substantially" means mostly or mainly, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or greater, or 100%. As used herein, the term "substantially free of" may mean not having or having a negligible amount such that the amount of the material present does not affect the properties of the composition containing the material, such that from about 0 wt% to about 5 wt% of the composition is the material, or from about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.

[0033] Monolithic substrate

[0034] In various aspects, the present invention provides a monolithic substrate. The monolithic substrate comprises the dried and / or cured product of an extrudable paste. The extrudable paste may comprise hollow and / or porous materials. The extrudable paste may further comprise a binder. The monolithic substrate may have a bulk density of 60 g / L to 170 g / L.

[0035] The extrudable paste may be a homogeneous composition. The binder may include any suitable binder. The binder may include an inorganic binder, a polymer (e.g., a crosslinkable polymer), a thermosetting resin, a carbon precursor (e.g., any suitable carbonizable binder), or a combination thereof. The binder may include a phenolic resin. The binder may be present in any suitable proportion of the extrudable paste. For example, the binder may be 10 wt% to 80 wt% of the paste, or 30 wt% to 50 wt% of the paste, or less than or equal to 80 wt% and greater than or equal to 10 wt%, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 wt% of the paste.

[0036] The hollow and / or porous materials may include any suitable materials that are hollow, porous, or a combination thereof. The hollow and / or porous materials may be particulate materials. The hollow and / or porous materials may include organic and / or inorganic materials. The hollow and / or porous materials may include paper, polymers, glass, glass ceramics, ceramics, or a combination thereof. The hollow and / or porous materials may include: hollow glass beads, hollow plastic beads (e.g., polystyrene or polypropylene), hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or a combination thereof. The hollow and / or porous materials may be particulate materials having a particle size (e.g., number average particle mean) of 0.1 microns to 500 microns, or 0.1 microns to 100 microns, or 10 microns to 200 microns, or less than or equal to 500 microns and greater than or equal to 0.1 microns, 0.5, 1, 2, 4, 6, 8, 10, 20, 30, 40, 50, 60, 80, 100, 120, 140, 160, 180, 200, 250, 300, 350, 400, or 450 microns. The hollow and / or porous materials may be present in any suitable proportion of the extrudable paste, such as: 5 wt% to 70 wt%, 10 wt% to 50 wt%, 25 wt% to 35 wt%, or less than or equal to 70 wt% and greater than or equal to 5 wt%, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65 wt% of the paste.

[0037] In various aspects, the monolithic substrate includes an adsorbent and / or an adsorbent aid. The adsorbent and / or the adsorbent aid can be included as part of an extrudable paste prior to its extrusion, and / or can be added to the monolithic piece after extrusion of the extrudable paste, such as before and / or after curing and / or drying. The adsorbent aid can enable the monolithic substrate and / or the carbonized monolithic substrate and / or the carbonized activated monolithic substrate derived therefrom to have a higher surface area. The adsorbent can enable the monolithic substrate and / or the carbonized monolithic substrate and / or the carbonized activated monolithic substrate derived therefrom to have enhanced adsorbability. The adsorbent aid can include Al 2 O 3 、TiO 2 、SiO 2 , or a combination thereof. The adsorbent can include zeolite, sodium carbonate, activated carbon, carbon nanotubes, metal-organic frameworks (MOF), amines, or a combination thereof.

[0038] In various aspects, the monolithic substrate includes an adsorbent precursor and / or an adsorbent aid precursor. The adsorbent precursor and / or the adsorbent aid precursor can be included as part of an extrudable paste prior to its extrusion, and / or can be added to the monolithic piece after extrusion of the extrudable paste, such as before and / or after curing and / or drying. The adsorbent precursor and / or the adsorbent aid precursor can enable the carbonized monolithic substrate and / or the carbonized activated monolithic substrate derived therefrom to have a high surface area. The adsorbent precursor and / or the adsorbent aid precursor can be converted into an adsorbent or an adsorbent aid during the carbonization and / or subsequent activation process of the monolithic piece. The adsorbent precursor and / or the adsorbent aid precursor can include Al 2 O 3 precursor, TiO 2 precursor, SiO 2 precursor, or a combination thereof. The adsorbent precursor and / or the adsorbent aid precursor can include aluminum isopropoxide, titanium isopropoxide, titanium butoxide, tetraethoxysilane, tetrabutoxysilane, or a combination thereof.

[0039] The monolithic substrate can comprise an adsorbent, an adsorbent aid, an adsorbent precursor, an adsorbent aid precursor, or a combination thereof. The weight ratio of the adsorbent, adsorbent aid, adsorbent precursor, adsorbent aid precursor, or a combination thereof to the hollow and / or porous material can be any suitable ratio, such as: 0.01:1 to 2:1, or 0.1:1 to 1:1, or less than or equal to 2:1 and greater than or equal to 0.01:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1 or 0.9:1. The adsorbent, adsorbent aid, adsorbent precursor, adsorbent aid precursor, or a combination thereof can be 0.001 wt% to 10 wt%, or 0.01 wt% to 5 wt%, or less than or equal to 10 wt% and greater than or equal to 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6 or 8 wt% of the extrudable composition.

[0040] The extrudable paste can optionally comprise a viscosity modifier, such as a cellulose derivative. The cellulose derivative can be a methylcellulose derivative, such as methylcellulose and / or hydroxypropylmethylcellulose polymer. The viscosity modifier can be 1 wt% to 15 wt% or 3 wt% to 10 wt% of the extrudable paste.

[0041] The extrudable paste can optionally comprise sodium stearate. Sodium stearate can be 0.1 - 3 wt% or 0.1 - 1 wt% of the extrudable paste.

[0042] The extrudable paste comprises a solvent. The solvent can be any suitable solvent, such as an organic solvent or an aqueous solvent. The liquid can be water. The solvent can form any suitable proportion of the extrudable paste, such as: 5 wt% to 50 wt%, or 10 wt% to 40 wt%, or less than or equal to 50 wt% and greater than or equal to 5 wt%, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46 or 48 wt%.

[0043] The dried and / or cured product of the extrudable paste can be the dried product of the extrudable paste, the cured product of the extrudable paste, or the product of both drying and curing the extrudable paste. The drying and / or curing can be any suitable drying or curing. Drying can include heat drying and / or natural drying. Curing can include heating. Drying and curing can be carried out in a single-step process or can be carried out as discrete heating steps. In various aspects, the drying and / or curing can include heating in the temperature range of 50 °C to 400 °C (e.g., less than or equal to 400 °C and greater than or equal to 50 °C, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, or 380 °C) for a duration of 1 minute to 2 h (e.g., less than or equal to 2 h and greater than or equal to 1 minute, 10, 20, 30, 40, 50 minutes, 1 h, 1.2, 1.4, 1.6, or 1.8 h).

[0044] The monolithic substrate can have any suitable bulk density. The bulk density is the mass of the substrate divided by the total volume occupied by the substrate, where the total volume occupied by the substrate includes the particle volume, the inter-particle void volume, and the internal pore volume. For example, the monolithic substrate can have a bulk density as follows: 60 g / L to 170 g / L, 80 g / L to 140 g / L, 80 g / L to 120 g / L, or less than or equal to 170 g / L and greater than or equal to 60 g / L, 65, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120, 122, 124, 126, 128, 130, or 135 g / L.

[0045] Before curing and drying, the extrudable paste can have any suitable bulk density, such as a density less than 1000 g / L, for example: less than 1000 g / L and greater than or equal to 200 g / L, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 820, 840, 860, 880, 900, 920, 940, 960, 980, or 990 g / L.

[0046] When the horizontal extrusion assumes the shape of a monolithic substrate, the extrudable paste can span the gap without collapse or deformation without support, where the gap spacing ranges from 0.1 m to 10 m, or less than or equal to 10 m and greater than or equal to 0.1 m, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, or 9 m.

[0047] In various aspects, the dried and / or cured product of the extruded extrudable paste can be conductive, such that the monolithic substrate is conductive. The conductivity of the monolithic substrate can be sufficient to effect resistive heating of the monolithic substrate by causing current to flow therethrough. In various aspects, such resistive heating can be used to heat the monolithic substrate to carbonize and / or activate the monolithic substrate, as described below.

[0048] The monolithic substrate, carbonized monolithic substrate, and carbonized activated monolithic substrate can include any suitable physical form. In various aspects, the physical form is a tubular form having a plurality of channels therein, the channels including parallel channels longitudinally through the tubular form. The tubular form can have any suitable perimeter profile, such as: circular, oval, square, rectangular, polygonal, or irregular. When viewed from the end of the tubular form, the channels can have any suitable shape, such as a honeycomb shape. The tubular form can include any suitable number of channels per square inch (e.g., measured when viewed from the end), such as: 50 to 400 channels per square inch, or 80 to 220, or less than or equal to 400 channels per square inch and greater than or equal to 50 channels per square inch, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, or 380 channels per square inch. The channels in the tubular form have any suitable wall thickness, such as the following wall thicknesses: 0.001 inches to 0.02 inches, or 0.002 inches to 0.02 inches, 0.003 inches to 0.01 inches, or less than or equal to 0.02 inches or less than or equal to 0.01 inches and greater than or equal to 0.001 inches, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, or 0.019 inches. In various aspects, the channels in the tubular form can include a geometric morphology of 100 / 9.5, 100 / 7.5, 100 / 5.5, or 200 / 4 channels per square inch / 0.001” wall thickness.

[0049] The monolithic substrate can have any suitable open frontal area. The open frontal area is the percentage cross-sectional surface area through which gas can flow. For example, the monolithic substrate can have an open frontal area of: 80 - 95%, 80 - 90%, 90 - 95%, 85 - 95%, or less than 95% and greater than or equal to 80%, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, or 94%.

[0050] The monolithic substrate, carbonized monolithic substrate, and / or carbonized and activated monolithic substrate can have any suitable geometric surface area. The geometric surface area is the total channel surface area per unit volume of the substrate. The monolithic substrate, carbonized monolithic substrate, and / or carbonized and activated monolithic substrate can have a geometric surface area of: 1.3 m 2 / L to 3 m 2 / L, 1.4 m 2 / L to 2.2 m 2 / L, or less than or equal to 3 m 2 / L and greater than or equal to 1.3 m 2 / L, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, or 2.9 m 2 / L.

[0051] The monolithic substrate, carbonized monolithic substrate, and / or carbonized and activated monolithic substrate can have any suitable porosity, such as the following open porosities: 0% to 5%, or 0% to 1%, or 40% to 90%, or 50% to 80%, or less than or equal to 90% and greater than or equal to 0%, 0.01, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, or 88%. As used herein, open porosity refers to the percentage void space excluding the internal pore volume and refers to the total percentage volume available in the substrate for contact with gas. Intact porous / hollow materials result in low open porosity, while fractured or broken porous and / or hollow materials or highly porous materials result in high open porosity. In various aspects, porous and / or hollow materials (e.g., hollow glass beads or hollow plastic beads) can be fractured or broken via heating (e.g., heating during the carbonization and / or activation steps).

[0052] The monolithic substrate, carbonized monolithic substrate, and / or carbonized and activated monolithic substrate can have any suitable maximum matrix volume heat capacity at 25 °C to 100 °C, such as: less than 140 kJ / kgK, or less than 100 kJ / kg / K, or equal to 50 kJ / kgK to 140 kJ / kgK, or 50 kJ / kgK to 100 kJ / kgK, or less than or equal to 140 kJ / kgK and greater than or equal to 50 kJ / kgK, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, or 135 kJ / kgK.

[0053] In various aspects, the monolithic substrate includes a high surface area material on its surface. The high surface area material can be added to the monolithic substrate after drying and / or curing of the extrudable paste, before drying and / or curing of the extrudable paste, or a combination thereof. The high surface area material can be produced on the surface of the monolithic substrate via heating and / or via a chemical reaction thereon.

[0054] In various aspects, the monolithic substrate includes a coating thereon, wherein the coating contains a material for adsorbing and desorbing CO 2 The material can be any suitable material for adsorbing and desorbing CO 2 For example, the material can include: amine-based adsorbents (e.g., poly(ethyleneimine)), metal-organic frameworks (MOF), carbon-based adsorbents, silica-based adsorbents, alumina-based adsorbents, zeolite-based adsorbents, porous crystalline solid adsorbents, metal oxide adsorbents, or a combination thereof.

[0055] Method for manufacturing the monolithic substrate

[0056] Various aspects of the present invention provide a method for forming the monolithic substrate of the present invention. The method can include extruding the extrudable paste described herein, which contains hollow and / or porous materials and a binder, and optionally contains an adsorbent, an adsorbent aid, an adsorbent precursor, and / or an adsorbent aid precursor. The method can also include drying and / or curing the extruded extrudable paste.

[0057] Drying and / or curing can be any suitable drying or curing. Drying can include heat drying and / or natural drying. Curing can include heating. Drying and curing can be carried out in a single-step process or can be carried out as discrete heating steps. In various aspects, drying and / or curing includes heating in a temperature range of 50 °C to 400 °C (e.g., less than or equal to 400 °C and greater than or equal to 50 °C, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, or 380 °C) for a duration of 1 minute to 2 h (e.g., less than or equal to 2 h and greater than or equal to 1 minute, 10, 20, 30, 40, 50 minutes, 1 h, 1.2, 1.4, 1.6, or 1.8 h).

[0058] The method can include coating an adsorbent precursor, an adsorbent, or a combination thereof on the outer surface of the extruded extrudable paste before drying and / or curing.

[0059] The method can optionally include removing water-soluble components (e.g., optional cellulose derivatives such as methylcellulose and / or hydroxypropylmethylcellulose polymers), for example, during drying and / or curing or as a separate processing step.

[0060] Method of using a monolithic substrate

[0061] Various aspects of the present invention provide a method of using the monolithic substrate of the present invention. The method can include exposing the monolithic substrate to a gas stream containing CO 2 so as to adsorb at least a portion of the CO 2 from the gas stream into a coating on the monolithic substrate. The coating can contain a material that adsorbs and desorbs CO 2 . The method can further include desorbing CO 2 from the coating on the monolithic substrate. 2 In various aspects, desorbing CO

[0062] from the coating on the monolithic substrate includes heating the monolithic substrate, for example, by energizing the monolithic substrate to cause resistive heating.

[0063] Various aspects of the present invention provide a carbonized monolithic substrate that includes a carbonized product of the monolithic substrate of the present invention. The carbonized monolithic substrate includes a carbonized product of the monolithic substrate. The monolithic substrate includes a dried and / or cured product of an extruded extrudable paste. The extrudable paste can include hollow and / or porous materials. The extrudable paste can further include a binder. The monolithic substrate can have a bulk density of 60 g / L to 170 g / L.

[0064] The carbonized product can be the product of heat treatment of the monolithic substrate, such as the product of heat treatment in an inert atmosphere. The carbonized product can be the product of heat treatment of the monolithic substrate in an inert atmosphere at 400°C to 2000°C, 400°C to 1200°C, or less than or equal to 2000°C and greater than or equal to 400°C, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800 or 1900°C.

[0065] In various aspects, the carbonized monolithic substrate can be conductive. The carbonized monolithic substrate can be conductive so that current can flow through the carbonized monolithic substrate to resistively heat the carbonized monolithic substrate.

[0066] The carbonized monolithic substrate can also include a coating containing a material that adsorbs and desorbs CO 2 gas. The material that adsorbs and desorbs CO 2 gas can be any suitable material; for example, the material can include: amine adsorbents (e.g., poly(ethyleneimine)), metal-organic frameworks (MOF), carbon-based adsorbents, silica-based adsorbents, alumina-based adsorbents, zeolite-based adsorbents, porous crystalline solid adsorbents, metal oxide adsorbents, or combinations thereof.

[0067] The carbonized monolithic substrate can have any suitable bulk density. For example, the carbonized monolithic substrate can have a bulk density of: 60 g / L to 170 g / L, 80 g / L to 140 g / L, 80 g / L to 120 g / L, or less than or equal to 170 g / L and greater than or equal to 60 g / L, 65, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120, 122, 124, 126, 128, 130 or 135 g / L.

[0068] The carbonized monolithic substrate can have any suitable open frontal area. For example, the carbonized monolithic substrate can have an open frontal area of: 80 - 95%, 80 - 90%, 90 - 95%, 85 - 95%, or less than 95% and greater than or equal to 80%, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93 or 94%.

[0069] Unless otherwise specified, other properties of the carbonized monolithic substrate can be the same as those of the monolithic substrate disclosed herein.

[0070] Method for manufacturing a carbonized monolithic substrate

[0071] In various aspects, the present invention provides a method for forming the carbonized monolithic substrate of the present invention. The method may include carbonizing the monolithic substrate of the present invention.

[0072] Carbonization may include heat treatment at a suitable temperature, for example, carried out under an inert atmosphere (e.g., argon). Carbonization may include heating to a temperature range of: 400 °C to 2000 °C, 400 °C to 1200 °C, or less than or equal to 2000 °C and greater than or equal to 400 °C, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, or 1900 °C under an inert atmosphere.

[0073] Method for using a carbonized monolithic substrate

[0074] Various aspects of the present invention provide a method for using the carbonized monolithic substrate of the present invention. The method may include exposing the carbonized monolithic substrate to a gas stream containing CO 2 so as to adsorb at least part of the CO 2 from the gas stream onto a coating on the carbonized monolithic substrate. The coating may contain a material that adsorbs and desorbs CO 2 The method may include desorbing CO 2 from the coating on the carbonized monolithic substrate. In various aspects, desorbing CO 2 from the coating on the carbonized monolithic substrate includes heating the carbonized monolithic substrate, for example, by energizing the carbonized monolithic substrate to cause resistive heating.

[0075] Carbonized and activated monolithic substrate

[0076] Various aspects of the present invention provide a carbonized and activated monolithic substrate, which comprises a carbonized and activated product of the monolithic substrate of the present invention. The carbonized and activated monolithic substrate includes a carbonized and activated product of the monolithic substrate. The monolithic substrate comprises a dried and / or cured product of an extrudable paste. The extrudable paste may comprise hollow and / or porous materials. The extrudable paste may further comprise a binder. The monolithic substrate may have a bulk density of 60 g / L to 170 g / L.

[0077] The carbonized and activated product may be a product of heat treatment of the monolithic substrate or the carbonized monolithic substrate, for example, under an inert atmosphere and / or in the presence of steam and / or CO 2The product of heat treatment in the case of. The carbonized and activated product can be a product obtained by heat-treating a monolithic substrate in an inert atmosphere at 400°C to 2000°C or 400°C to 1200°C, and then in the presence of steam and / or CO 2 Heat treatment is carried out at a temperature of 500°C to 1500°C or 500°C to 1200°C. The carbonized and activated product can be a product obtained by heat-treating a monolithic substrate in an inert atmosphere at 700°C to 1000°C, and then in the presence of steam and / or CO 2 Heat treatment is carried out at a temperature of 700°C to 900°C.

[0078] The carbonized and activated monolithic substrate can have any suitable open porosity. For example, the carbonized and activated monolithic substrate can have an open porosity of 0% to 90%, or 0% to 1%, or 1% to 90%, or less than or equal to 90% and greater than or equal to 0%, 0.001, 0.005, 0.01, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.8, 2, 4, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86 or 88%. In various aspects, a high open porosity can be achieved by causing hollow and / or porous materials to burst or break during carbonization and / or activation, and / or by using a porous material as the hollow and / or porous material.

[0079] The carbonized and activated monolithic substrate can have any suitable surface area, for example: 50 m 2 / g or greater surface area, or a surface area of 50 m 2 / g to 400 m 2 / g, or less than or equal to 400 m 2 / g and greater than or equal to 50 m 2 / g, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380 m 2 / g.

[0080] The carbonized and activated monolithic substrate can also include a coating containing a material that adsorbs and desorbs CO 2 gas. For CO 2The material for gas adsorption and desorption can be any suitable material; for example, the material can include: amine-based adsorbents (e.g., poly(ethyleneimine)), metal-organic frameworks (MOFs), carbon-based adsorbents, silica-based adsorbents, alumina-based adsorbents, zeolite-based adsorbents, porous crystalline solid adsorbents, metal oxide adsorbents, or combinations thereof.

[0081] The carbonized and activated monolithic substrate can have any suitable bulk density. For example, the carbonized and activated monolithic substrate can have a bulk density as follows: 60 g / L to 170 g / L, 80 g / L to 140 g / L, 80 g / L to 120 g / L, or less than or equal to 170 g / L and greater than or equal to 60 g / L, 65, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120, 122, 124, 126, 128, 130 or 135 g / L.

[0082] The carbonized and activated monolithic substrate can have any suitable open frontal area. For example, the carbonized and activated monolithic substrate can have an open frontal area as follows: 80 - 95%, 80 - 90%, 90 - 95%, 85 - 95%, or less than 95% and greater than or equal to 80%, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93 or 94%.

[0083] Unless otherwise specified, other properties of the carbonized and activated monolithic substrate can be the same as those of the carbonized monolithic substrate and the monolithic substrate disclosed herein.

[0084] Method for manufacturing the carbonized and activated monolithic substrate

[0085] In various aspects, the present invention provides a method for forming the carbonized and activated monolithic substrate of the present invention. The method can include activating the carbonized monolithic substrate of the present invention.

[0086] Activation can include heat treatment at a suitable temperature, for example, in the presence of a gas stream (such as steam and / or CO 2 ) that can activate the carbonized monolithic substrate or generate additional surface area on the carbonized monolithic substrate. Activation can include in the presence of a gas stream (such as steam and / or CO 2) is heated to the following temperature ranges: 500 °C to 1500 °C, or 700 °C to 900 °C, or less than or equal to 1500 °C and greater than or equal to 500 °C, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400 or 1450 °C. In various aspects, the heat treatment can include resistively heating the carbonized monolithic substrate by passing an electric current through it.

[0087] The method of forming a carbonized and activated monolithic substrate can further include adding a coating to the activated carbonized monolithic substrate, wherein the coating comprises a material that adsorbs and desorbs CO 2 gas. The coating can comprise any suitable material that adsorbs and desorbs CO 2 gas; for example: amine adsorbents (e.g., poly(ethyleneimine)), metal-organic frameworks (MOF), carbon-based adsorbents, silica-based adsorbents, alumina-based adsorbents, zeolite-based adsorbents, porous crystalline solid adsorbents, metal oxide adsorbents, or combinations thereof.

[0088] Method of using a carbonized and activated monolithic substrate

[0089] Various aspects of the present invention provide methods of using the carbonized and activated monolithic substrates of the present invention. The method can include exposing the carbonized and activated monolithic substrate to a gas stream comprising CO 2 such that at least a portion of the CO from the gas stream is adsorbed 2 into the coating on the carbonized and activated monolithic substrate. The coating can comprise a material that adsorbs and desorbs CO 2 gas. The method can further include desorbing CO 2 from the coating on the carbonized and activated monolithic substrate. In various aspects, desorbing CO 2 from the coating on the carbonized and activated monolithic substrate includes heating the carbonized and activated monolithic substrate, for example by passing an electric current through the carbonized and activated monolithic substrate to cause resistive heating.

[0090] The methods of using the monolithic substrates, carbonized monolithic substrates, and carbonized and activated monolithic substrates described herein can be used for any suitable CO 2 removal method, such as direct air capture (DAC) or CO capture at an effluent source 2The monolithic substrates, carbonized monolithic substrates, and carbonized and activated monolithic substrates described herein can withstand temperatures of 200 °C or higher and a moisture environment. In aspects where the monolithic substrates, carbonized monolithic substrates, and carbonized and activated monolithic substrates include an adsorbent coating thereon, the adsorbent coating may not substantially penetrate into the substrate, such that the adsorbent coating is a wall coating, increasing or maximizing contact with the gas passing therethrough.

[0091] Examples

[0092] The various aspects of the present invention can be better understood by reference to the following examples given in a schematic manner. The present invention is not limited to the examples given herein.

[0093] Part I: Inert Substrate.

[0094] Example 1-1: Hollow Glass Beads with Phenolic Resin.

[0095] Two pastes were prepared using the formulations described in Table 1. The components were mixed together to form the pastes.

[0096] Table 1: Hollow Glass Beads with Phenolic Resin Composition.

[0097] Formulation 1 Formulation 2 <![CDATA[Hollow glass beads (ZKYL H60), D 50 is about 50 microns]]> g 10 10 Culminal 724 (methyl cellulose derivative) g 2 2 Sodium stearate (LIGA) g 0.2 0.2 Water g 7 7 Phenolic resin GP510D50 g 18 9 Estimated resin volume % after curing 33％ 20％

[0098] Figure 1 Photographs showing the pastes made using Formulation 1 (left) and Formulation 2 (right). Both pastes are extrudable.

[0099] Each paste was hand-rolled into sheets having two different thicknesses (about 0.7 mm and about 2 mm), and then cured using the following thermal cycle: 85 °C for 30 minutes, 100 °C for 30 minutes, 150 °C for 30 minutes. Figure 2 Photographs showing the sheets rolled and cured from these two paste formulations having these two different thicknesses, with the left sheet formed from Formulation 1 and the right sheet formed from Formulation 2, the top sheet being about 2 mm thick and the bottom sheet being about 0.7 mm thick. The cured sheets are rigid and mechanically strong. Figure 3 Photographs showing the rolled and cured sheets (floating in water) prepared from Formulation 1 (left) and Formulation 2 (right), indicating that the rolled and cured sheets have a specific gravity less than 1.

[0100] Figure 3 The samples shown were allowed to float in water for 12 days and then removed and dried at 150 °C for 40 minutes. The two samples lost 3.3% of their original cured weight (Formulation 1) and 3.6% of their original cured weight (Formulation 2), which may be due to the leaching of Culminal 724 and / or LIGA. However, they still remained intact and mechanically strong.

[0101] Figure 4 A scanning electron microscope (SEM) image is shown, showing the cross-section of a rolled and cured sheet manufactured using the same formulation as Formulation 1 but without phenolic resin.

[0102] Example 1-2: Hollow polymer beads with phenolic resin.

[0103] Example 1 was repeated, but hollow polymer beads were used instead of hollow glass beads. The resulting paste was extrudable and could be cured and rolled to form a rigid and mechanically strong sheet that floats in water.

[0104] Part II: Substrate for adsorbent to be used.

[0105] Example 2-1: Hollow glass beads with phenolic resin, pyrolyzed and activated.

[0106] The paste of Example 1-1 was extruded into a monolithic honeycomb structure and cured using the same procedure as described in Example 1-1. Then, the extruded and cured paste was carbonized in an inert atmosphere (e.g., N 2 or Ar) at a temperature of 700 °C to 1000 °C for 1 h, and then activated in steam or CO 2 at a temperature of 700 °C to 900 °C for 1 h to obtain a high surface area. The curing, carbonization, and activation steps can be carried out as separate processes or integrated as multiple stages of a single process.

[0107] The mass and thermal mass of the cured, carbonized, and activated monolithic form are less than the same properties of a cordierite honeycomb structure having the same physical form.

[0108] Example 2-2: Hollow glass beads with phenolic resin and Al 2 O 3 precursor, pyrolyzed and activated.

[0109] Example 2-2 was repeated, but the paste also contained an alumina precursor (e.g., an aluminum alkoxide (e.g., aluminum isopropoxide)) and / or alumina particles, and the weight ratio of the alumina precursor and / or alumina to the amount of hollow glass beads was 1:10 to 1:1.

[0110] The mass and thermal mass of the cured, carbonized, and activated monolithic form are less than the same properties of a cordierite honeycomb structure having the same physical form.

[0111] Example 2-3: Hollow glass beads with phenolic resin and TiO 2 precursor, pyrolyzed and activated.

[0112] Example 2-2 was repeated, but the paste for manufacturing the monolithic form further contained a titanium oxide precursor (such as a titanium alkoxide (e.g., aluminum isopropoxide or titanium butoxide)) and / or titanium oxide particles, and the weight ratio of the titanium oxide precursor and / or titanium oxide to the amount of hollow glass beads was 1:10 to 1:1.

[0113] The mass and thermal mass of the cured carbonized activated monolithic form are less than the same properties of a cordierite honeycomb structure having the same physical form.

[0114] Example 2-4: Hollow glass beads having a phenolic resin and SiO 2 precursor, pyrolyzed and activated.

[0115] Example 2-2 was repeated, but the paste for manufacturing the monolithic form further contained SiO 2 precursor (such as an alkoxysilane (e.g., tetraethoxysilane or tetrabutoxysilane)) and / or silica particles, and the weight ratio of the silica precursor and / or silica to the amount of hollow glass beads was 1:10 to 1:1.

[0116] The mass and thermal mass of the cured carbonized activated monolithic form are less than the same properties of a cordierite honeycomb structure having the same physical form.

[0117] Table 2 shows the properties of the reference materials and substrates and the materials and substrates of the present invention. GSA is the geometric surface area, and OFA is the open frontal area (the transparent cross-sectional surface through which flow can occur). Unless otherwise stated, the geometry is 100 / 7.5.

[0118] Table 2: Properties of the reference materials and substrates and the materials and substrates of the present invention.

[0119]

[0120] Example 2-5: Hollow glass beads having a phenolic resin, and extruded into a honeycomb body, which was carbonized at 400 °C, 800 °C, and 970 °C.

[0121] The formulation 1 of Example 1-1 was scaled up 50 times, weighed, and mixed in a ProcessAll mixer. The paste was successfully extruded through a 1” diameter 200 / 12 die on a small plunger extruder. The extruded honeycomb body was cured at 150 °C for 1 hour. The cured honeycomb body became mechanically firm. As Figure 5 shown are photos of the extruded honeycomb body showing the top view and the side view.

[0122] Two cured honeycomb bodies were carbonized at 400 °C in an N 2 atmosphere. As Figure 6Shown are photographs of a side view and a top view of a cured and carbonized honeycomb body. The weight loss due to carbonization is about 11%, and the estimated carbon yield is about 76%.

[0123] Two cured honeycomb bodies were carbonized at 800 °C in an N 2 atmosphere. As Figure 7 shown are photographs of a side view and a top view of a cured and carbonized honeycomb body. The weight loss due to carbonization is about 23.2%, and the estimated carbon yield is about 48.5%. Another cured honeycomb body was also carbonized at 970 °C in an N 2 atmosphere (not shown).

[0124] The honeycomb body is expected to be thermally conductive. The honeycomb bodies carbonized at 800 °C and 970 °C were measured to be electrically conductive.

[0125] The terms and expressions that have been used are used as illustrative rather than restrictive terms, and the use of these terms and expressions does not exclude any equivalent features or parts thereof of the features shown and described, but it should be recognized that various modifications may fall within the scope of the aspects of the present invention. Accordingly, it should be understood that although the present invention has been specifically described by specific aspects and optional features, those skilled in the art can conceive of changes and variations of the content disclosed herein, and such changes and variations should be considered to fall within the scope of the aspects of the present invention.

[0126] Exemplary aspects.

[0127] The following exemplary aspects are provided, and the numbers are not to be construed as indicating a level of importance:

[0128] Aspect 1 provides a monolithic substrate comprising:

[0129] a dried and / or cured product of an extrudable paste, the extrudable paste comprising:

[0130] a hollow and / or porous material, and

[0131] a binder;

[0132] wherein the monolithic substrate has a bulk density of 60 g / L to 170 g / L.

[0133] Aspect 2 provides the monolithic substrate of Aspect 1, wherein the dried and / or cured product of the extrudable paste is a dried product of the extrudable paste.

[0134] Aspect 3 provides the monolithic substrate of any one of Aspects 1-2, wherein the dried and / or cured product of the extrudable paste is a cured product of the extrudable paste.

[0135] Aspect 4 provides a monolithic substrate according to any one of Aspects 1 - 3, wherein the dried and / or cured product of the extrudable paste is the dried and cured product of the extrudable paste.

[0136] Aspect 5 provides a monolithic substrate according to any one of Aspects 1 - 4, wherein the monolithic substrate has a bulk density of 80 g / L to 140 g / L.

[0137] Aspect 6 provides a monolithic substrate according to any one of Aspects 1 - 5, wherein the monolithic substrate has a bulk density of 80 g / L to 120 g / L.

[0138] Aspect 7 provides a monolithic substrate according to any one of Aspects 1 - 6, wherein the monolithic substrate has a bulk density of less than 1000 g / L.

[0139] Aspect 8 provides a monolithic substrate according to any one of Aspects 1 - 7, wherein when horizontally extruded into the shape of the monolithic substrate, the extrudable paste spans a gap in the range of 0.1 m to 10 m without collapsing or deforming.

[0140] Aspect 9 provides a monolithic substrate according to any one of Aspects 1 - 8, wherein the dried and / or cured product of the extrudable paste is conductive.

[0141] Aspect 10 provides a monolithic substrate according to any one of Aspects 1 - 9, wherein the hollow and / or porous material includes paper, polymer, glass, glass - ceramic, ceramic, or a combination thereof.

[0142] Aspect 11 provides a monolithic substrate according to any one of Aspects 1 - 10, wherein the hollow and / or porous material is particulate material having a particle size of 0.1 micrometer to 500 micrometers or 0.1 micrometer to 100 micrometers.

[0143] Aspect 12 provides the monolithic substrate of Aspect 11, wherein the particulate material has a particle size of 10 micrometers to 200 micrometers.

[0144] Aspect 13 provides a monolithic substrate according to any one of Aspects 1 - 12, wherein the hollow and / or porous material is: hollow glass beads, hollow plastic beads, hollow glass - ceramic beads, hollow ceramic beads, cenospheres, fly - ash - based hollow beads, or a combination thereof.

[0145] Aspect 14 provides a monolithic substrate according to any one of Aspects 1 - 13, further comprising an adsorbent and / or an adsorbent aid.

[0146] Aspect 15 provides the monolithic substrate of Aspect 14, wherein the extrudable paste comprises the adsorbent and / or the adsorbent aid as a homogeneous mixture.

[0147] Aspect 16 provides a monolithic substrate according to any one of aspects 14 - 15, wherein an adsorbent and / or an adsorbent aid is added after curing and / or drying of the extruded extrudable paste.

[0148] Aspect 17 provides a monolithic substrate according to any one of aspects 14 - 16, wherein the adsorbent aid includes Al 2 O 3 , TiO 2 , SiO 2 or a combination thereof, and wherein the adsorbent includes zeolite, sodium carbonate, activated carbon, carbon nanotubes, metal - organic framework (MOF), amine or a combination thereof.

[0149] Aspect 18 provides a monolithic substrate according to any one of aspects 1 - 17, further comprising an adsorbent precursor and / or an adsorbent aid precursor.

[0150] Aspect 19 provides the monolithic substrate of aspect 18, wherein the extrudable paste comprises an adsorbent precursor and / or an adsorbent aid precursor as a homogeneous mixture thereof.

[0151] Aspect 20 provides a monolithic substrate according to any one of aspects 18 - 19, wherein the adsorbent precursor and / or the adsorbent aid precursor is added after curing and / or drying of the extruded extrudable paste.

[0152] Aspect 21 provides a monolithic substrate according to any one of aspects 18 - 20, wherein the adsorbent precursor and / or the adsorbent aid precursor includes Al 2 O 3 precursor, TiO 2 precursor, SiO 2 precursor or a combination thereof.

[0153] Aspect 22 provides a monolithic substrate according to any one of aspects 18 - 21, wherein the adsorbent precursor and / or the adsorbent aid precursor includes an aluminum alkoxide, a titanium alkoxide, an alkoxysilane or a combination thereof.

[0154] Aspect 23 provides a monolithic substrate according to any one of aspects 18 - 22, wherein the adsorbent precursor and / or the adsorbent aid precursor includes aluminum isopropoxide, titanium isopropoxide, titanium butoxide, tetraethyl orthosilicate, tetrabutyl orthosilicate or a combination thereof.

[0155] Aspect 24 provides a monolithic substrate according to any one of aspects 18 - 23, wherein the mass ratio of the adsorbent precursor and / or the adsorbent aid precursor to the hollow and / or porous material is from 0.01:1 to 2:1, by weight.

[0156] Aspect 25 provides a monolithic substrate of any one of aspects 18 - 24, wherein the mass ratio of the adsorbent precursor and / or the adsorbent promoter precursor to the hollow and / or porous material is 0.1:1 to 1:1, by weight.

[0157] Aspect 26 provides a monolithic substrate of any one of aspects 1 - 25, wherein the binder comprises an inorganic binder, a polymer, a thermosetting resin, or a combination thereof.

[0158] Aspect 27 provides a monolithic substrate of any one of aspects 1 - 26, wherein the binder further comprises a phenolic resin.

[0159] Aspect 28 provides a monolithic substrate of any one of aspects 1 - 27, wherein the monolithic substrate comprises a honeycomb shape.

[0160] Aspect 29 provides the monolithic substrate of aspect 28, wherein the honeycomb shape comprises 50 to 400 channels per square inch.

[0161] Aspect 30 provides a monolithic substrate of any one of aspects 28 - 29, wherein the honeycomb shape comprises 80 to 220 channels per square inch.

[0162] Aspect 31 provides a monolithic substrate of any one of aspects 28 - 30, wherein the honeycomb shape comprises a wall thickness of 0.001 inches to 0.02 inches.

[0163] Aspect 32 provides a monolithic substrate of any one of aspects 28 - 31, wherein the honeycomb shape comprises a wall thickness of 0.003 inches to 0.01 inches.

[0164] Aspect 33 provides a monolithic substrate of any one of aspects 28 - 32, wherein the honeycomb shape comprises the following geometric morphologies: 100 / 9.5, 100 / 7.5, 100 / 5.5, or 200 / 4 channels per square inch / 0.001” wall thickness.

[0165] Aspect 34 provides a monolithic substrate of any one of aspects 1 - 33, wherein the monolithic substrate has an open frontal area of 80 - 95%.

[0166] Aspect 35 provides a monolithic substrate of any one of aspects 1 - 34, wherein the monolithic substrate has a geometric surface area of 1.3 m 2 / L to 3 m 2 / L.

[0167] Aspect 36 provides a monolithic substrate of any one of aspects 1 - 35, wherein the monolithic substrate has a geometric surface area of 1.4 m 2 / L to 2.2 m 2 / L.

[0168] Aspect 37 provides a monolithic substrate according to any one of Aspects 1-36, wherein the monolithic substrate has an open porosity of 0% to 5%.

[0169] Aspect 38 provides a monolithic substrate according to any one of Aspects 1-37, wherein the monolithic substrate has an open porosity of 0% to 1%.

[0170] Aspect 39 provides a monolithic substrate according to any one of Aspects 1-38, wherein the monolithic substrate has an open porosity of 40% to 90%.

[0171] Aspect 40 provides a monolithic substrate according to any one of Aspects 1-39, wherein the monolithic substrate has an open porosity of 50% to 80%.

[0172] Aspect 41 provides a monolithic substrate according to any one of Aspects 1-40, wherein the dried and / or cured product of the extrudable paste is a product of heat treatment at 50 °C to 400 °C for 1 minute to 2 h.

[0173] Aspect 42 provides a monolithic substrate according to any one of Aspects 1-41, further comprising a high surface area material on its surface.

[0174] Aspect 43 provides a monolithic substrate according to any one of Aspects 1-42, further comprising a coating thereon, the coating comprising a material for adsorbing and desorbing CO 2 and performing adsorption and desorption.

[0175] Aspect 44 provides a monolithic substrate, comprising:

[0176] a dried and cured product of an extrudable paste, the extrudable paste comprising:

[0177] hollow and / or porous materials, including: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or combinations thereof, and

[0178] a binder, including polymers, inorganic binders, thermosetting resins, or combinations thereof;

[0179] wherein the monolithic substrate has a bulk density of 60 g / L to 170 g / L and an open frontal area of 80 - 95%.

[0180] Aspect 45 provides a carbonized monolithic substrate, comprising a carbonized product of the monolithic substrate according to any one of Aspects 1-44.

[0181] Aspect 46 provides the carbonized monolithic substrate of Aspect 45, wherein the carbonized monolithic substrate is conductive.

[0182] Aspect 47 provides a carbonized monolithic substrate of any one of aspects 45 - 46, further comprising a coating containing a material that adsorbs and desorbs CO 2 from the air.

[0183] Aspect 48 provides a carbonized monolithic substrate of any one of aspects 45 - 47, wherein the carbonized product is a heat treatment product in an inert atmosphere at 400°C to 2000°C.

[0184] Aspect 49 provides a carbonized monolithic substrate of any one of aspects 45 - 48, wherein the carbonized product is a heat treatment product in an inert atmosphere at 400°C to 1200°C.

[0185] Aspect 50 provides a carbonized monolithic substrate, comprising:

[0186] a dried and cured carbonized product of an extrudable paste, the extrudable paste comprising:

[0187] hollow and / or porous materials, including: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or combinations thereof, and

[0188] a binder, including polymers, inorganic binders, thermosetting resins, or combinations thereof;

[0189] wherein the carbonized monolithic substrate has a bulk density of 60 g / L to 170 g / L and an open frontal area of 80 - 95%.

[0190] Aspect 51 provides a carbonized and activated monolithic substrate, comprising a carbonized and activated product of the monolithic substrate of any one of aspects 1 - 44.

[0191] Aspect 52 provides the carbonized and activated monolithic substrate of aspect 51, wherein the carbonized and activated product is: a product heat treated in an inert atmosphere at 400°C to 2000°C and heat treated in the presence of steam and / or CO 2 at a temperature of 500°C to 1500°C, or a product heat treated in an inert atmosphere at 400°C to 1200°C and heat treated in the presence of steam and / or CO 2 at a temperature of 500°C to 1200°C.

[0192] Aspect 53 provides the carbonized and activated product of any one of aspects 51 - 52, wherein the carbonized and activated product is heat treated in an inert atmosphere at 700°C to 1000°C and heat treated in the presence of steam and / or CO at a temperature of 700°C to 900°C2 The product heat-treated therein.

[0193] Aspect 54 provides a carbonized and activated monomeric substrate according to any one of aspects 51 - 53, wherein the carbonized and activated monomeric substrate has an open porosity of 0% to 1%.

[0194] Aspect 55 provides a carbonized and activated monomeric substrate according to any one of aspects 51 - 54, wherein the carbonized and activated monomeric substrate has an open porosity of 1% to 90%.

[0195] Aspect 56 provides a carbonized and activated monomeric substrate according to any one of aspects 51 - 55, further comprising a coating containing a material that adsorbs and desorbs CO 2 and desorbs.

[0196] Aspect 57 provides the carbonized and activated monomeric substrate of aspect 56, wherein the coating contains poly(ethyleneimine).

[0197] Aspect 58 provides a carbonized and activated monomeric substrate according to any one of aspects 51 - 57, wherein the carbonized and activated monomeric substrate has a surface area of 50 m 2 / g to 400 m 2 / g.

[0198] Aspect 59 provides a carbonized and activated monomeric substrate, comprising:

[0199] A dried and cured carbonized and activated product of an extrudable paste, the extrudable paste comprising:

[0200] Hollow and / or porous materials, including: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or combinations thereof,

[0201] Binders, including polymers, inorganic binders, thermosetting resins, or combinations thereof, and

[0202] Adsorbents, adsorbent aids, adsorbent precursors, and / or adsorbent aid precursors, the adsorbent aids including Al 2 O 3 、TiO 2 、SiO 2 or combinations thereof, the adsorbents including zeolites, sodium carbonate, activated carbon, carbon nanotubes, metal-organic frameworks (MOF), amines, or combinations thereof, and the adsorbent precursors and / or adsorbent aid precursors including Al 2 O 3 precursors, TiO 2 precursors, SiO 2 precursors, or combinations thereof;

[0203] Among them, the carbonized and activated monolithic substrate has a bulk density of 60 g / L to 170 g / L and an open frontal area of 80 - 95%.

[0204] Aspect 60 provides a method for forming the monolithic substrate of any one of Aspects 1 - 44, the method comprising:

[0205] extruding an extrudable paste; and

[0206] drying and / or curing the extruded extrudable paste.

[0207] Aspect 61 provides the method of Aspect 60, further comprising coating an adsorbent precursor and / or an adsorbent promoter precursor on the outer surface of the extruded extrudable paste before curing.

[0208] Aspect 62 provides the method of any one of Aspects 60 - 61, further comprising coating an adsorbent and / or an adsorbent promoter on the outer surface of the extruded extrudable paste after curing.

[0209] Aspect 63 provides the method of any one of Aspects 60 - 62, wherein the curing and / or drying comprises heating in a temperature range of 50°C to 400°C for a duration of 1 minute to 2 h.

[0210] Aspect 64 provides a method for forming the carbonized monolithic substrate of any one of Aspects 45 - 50, the method comprising:

[0211] carbonizing the monolithic substrate of any one of Aspects 1 - 44.

[0212] Aspect 65 provides the method of Aspect 64, wherein the carbonization comprises heat treatment in an inert atmosphere at 400°C to 2000°C or 400°C to 1200°C.

[0213] Aspect 66 provides the method of any one of Aspects 64 - 65, wherein the carbonization comprises heat treatment in an inert atmosphere at 400°C to 1200°C.

[0214] Aspect 67 provides a method for forming the carbonized and activated monolithic substrate of any one of Aspects 51 - 59, the method comprising:

[0215] activating the carbonized monolithic substrate of any one of Aspects 45 - 50.

[0216] Aspect 68 provides the method of Aspect 67, wherein the activation comprises heat treatment at a temperature of 500°C to 1500°C in the presence of steam and / or CO 2 and.

[0217] Aspect 69 provides the method of any one of aspects 67 - 68, wherein the activation includes heat treatment at a temperature of 700 °C to 900 °C in the presence of steam and / or CO 2 .

[0218] Aspect 70 provides the method of any one of aspects 67 - 69, wherein the activation includes passing an electric current through the carbonized monolithic substrate to perform resistance heating thereon.

[0219] Aspect 71 provides the monolithic substrate of any one of aspects 67 - 70, further comprising adding a coating to the activated carbonized monolithic structure, the coating comprising a material that adsorbs and desorbs CO 2 .

[0220] Aspect 72 provides the method of aspect 71, wherein the coating comprises poly(ethylene imine).

[0221] Aspect 73 provides a method of using the monolithic substrate of any one of aspects 1 - 44, the method comprising:

[0222] exposing the monolithic substrate to a gas stream comprising CO 2 so as to adsorb at least part of the CO from the gas stream 2 into a coating on the monolithic substrate, the coating comprising a material that adsorbs and desorbs CO 2 ; and

[0223] desorbing CO from the coating on the monolithic substrate 2 .

[0224] Aspect 74 provides a method of using the carbonized monolithic substrate of any one of aspects 45 - 50, the method comprising:

[0225] exposing the carbonized monolithic substrate to a gas stream comprising CO 2 so as to adsorb at least part of the CO from the gas stream 2 into a coating on the carbonized monolithic substrate, the coating comprising a material that adsorbs and desorbs CO 2 ; and

[0226] desorbing CO from the coating on the carbonized monolithic substrate 2 .

[0227] Aspect 75 provides a method of using the carbonized and activated monolithic substrate of any one of aspects 51 - 59, the method comprising:

[0228] exposing the carbonized and activated monolithic substrate to a gas stream comprising CO 2 so as to adsorb at least part of the CO from the gas stream 2At least partially adsorbed onto a carbonized and activated monolithic substrate, the coating comprising a material for adsorbing and desorbing CO 2 ; and

[0229] Desorbing CO from the coating on the carbonized and activated monolithic substrate 2 .

[0230] Aspect 76 provides a monolithic substrate, a carbonized monolithic substrate, a carbonized and activated monolithic substrate, or a method according to any one or any combination of aspects 1-75, optionally configured such that all of the stated elements and options are available for use or selection.

[0231] Aspect 76 provides a monolithic substrate, a carbonized monolithic substrate, a carbonized and activated monolithic substrate, or a method according to any one or any combination of aspects 1-75, wherein the monolithic substrate, the carbonized monolithic substrate, or the carbonized and activated monolithic substrate has a maximum matrix volume heat capacity of less than 140 kJ / kgK at 25°C to 100°C.

[0232] Aspect 76 provides a monolithic substrate, a carbonized monolithic substrate, a carbonized and activated monolithic substrate, or a method according to any one or any combination of aspects 1-75, wherein the monolithic substrate, the carbonized monolithic substrate, or the carbonized and activated monolithic substrate has a maximum matrix volume heat capacity of less than 100 kJ / kgK at 25°C to 100°C.

Claims

1. A monolithic substrate, which comprises: the dried and / or cured product of an extrudable paste, the extrudable paste comprising: hollow and / or porous materials, and a binder; wherein the monolithic substrate has a bulk density of 60 g / L to 170 g / L and an open front of 80 - 95%.

2. The monolithic substrate according to claim 1, wherein, the hollow and / or porous materials are: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or a combination thereof, wherein the particulate materials have a particle size of 0.1 micron to 100 microns.

3. The monolithic substrate according to any one of claims 1 - 2, further comprising an adsorbent, an adsorbent aid, an adsorbent precursor, an adsorbent aid precursor, or a combination thereof.

4. The monolithic substrate according to claim 3, wherein, the adsorbent comprises zeolite, sodium carbonate, activated carbon, carbon nanotubes, metal-organic frameworks (MOF), amines, or a combination thereof; The adsorbent promoter includes Al 2 O 3 , TiO 2 , SiO 2 , or a combination thereof; and The adsorbent precursor and / or adsorbent promoter precursor includes Al 2 O 3 precursor, TiO 2 precursor, SiO 2 precursor, or a combination thereof.

5. The monolithic substrate according to any one of claims 1 - 4, wherein, the binder comprises an inorganic binder, a polymer, a thermosetting resin, or a combination thereof.

6. The monolithic substrate according to any one of claims 1 - 5, wherein, the monolithic substrate has a honeycomb shape, wherein the honeycomb shape contains 50 to 400 channels per square inch and a wall thickness of 0.001 inch to 0.02 inch.

7. The monolithic substrate according to any one of claims 1-6 further comprises a coating thereon, and the coating comprises a material for adsorbing and desorbing CO 2 therefrom.

8. A carbonized monolithic substrate, which comprises the carbonized product of the monolithic substrate according to any one of claims 1 - 7, wherein, the carbonized product is a heat treatment product in an inert atmosphere at 400 °C to 1200 °C.

9. A carbonized monolithic substrate, which comprises: the dried, cured and carbonized product of an extrudable paste, the extrudable paste comprising: hollow and / or porous materials, which include: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or a combination thereof, and a binder, which includes a polymer, an inorganic binder, a thermosetting resin, or a combination thereof; wherein the carbonized monolithic substrate has a bulk density of 60 g / L to 170 g / L and an open front of 80 - 95%.

10. A carbonized and activated monolithic substrate, which comprises the carbonized and activated product of the monolithic substrate according to any one of claims 1 - 7.

11. The carbonized and activated monolithic substrate according to claim 10, further comprising a coating containing a material that adsorbs and desorbs CO 2 gas.

12. A carbonized and activated monolithic substrate, which comprises: the dried, cured, carbonized and activated product of an extrudable paste, the extrudable paste comprising: hollow and / or porous materials, which include: hollow glass beads, hollow plastic beads, hollow glass ceramic beads, hollow ceramic beads, cenospheres, fly ash-based hollow beads, or a combination thereof, a binder, which includes a polymer, an inorganic binder, a thermosetting resin, or a combination thereof, and An adsorbent, an adsorbent aid, an adsorbent precursor, and / or an adsorbent aid precursor, the adsorbent aid including Al 2 O 3 , TiO 2 , SiO 2 , or a combination thereof, the adsorbent including zeolite, sodium carbonate, activated carbon, carbon nanotubes, metal-organic framework (MOF), amine, or a combination thereof, and the adsorbent precursor and / or the adsorbent aid precursor including an Al 2 O 3 precursor, a TiO 2 precursor, an SiO 2 precursor, or a combination thereof; Among them, the carbonized and activated monolithic substrate has a bulk density of 60 g / L to 170 g / L, an open frontal area of 80-95%, and a surface area of 50 m 2 / g to 400 m 2 / g.

13. The monolithic substrate according to any one of claims 1 - 7, the carbonized monolithic substrate according to any one of claims 8 - 9, or the carbonized and activated monolithic substrate according to any one of claims 10 - 12, wherein, The carbonized monolithic substrate, the carbonized monolithic substrate or the carbonized and activated monolithic substrate has a maximum matrix volume heat capacity of less than 140 kJ / kgK at 25°C to 100°C.

14. The carbonized monolithic substrate according to any one of claims 8-9 or 13, or the carbonized and activated monolithic substrate according to any one of claims 10-13, wherein, the carbonized monolithic substrate or the carbonized and activated monolithic substrate is conductive.

15. A method for forming the monolithic substrate according to any one of claims 1-7 or 13, the method comprises: extruding an extrudable paste; and drying and / or curing the extruded extrudable paste, wherein the drying and / or curing comprises heating for a duration of 1 minute to 2 h in a temperature range of 50°C to 400°C.

16. A method for forming the carbonized monolithic substrate according to any one of claims 8-9 or 13, the method comprises: carbonizing the monolithic substrate according to any one of claims 1-7 or 13, wherein the carbonizing comprises heat treatment in an inert atmosphere at 400°C to 1200°C.

17. A method for forming the carbonized and activated monolithic substrate according to any one of claims 10-13, the method comprises: Activate the carbonized monolithic substrate according to any one of claims 8-9 or 13, wherein the activation comprises heat treatment at a temperature of 500 °C to 1500 °C in the presence of steam and / or CO 2 and the like.

18. The method according to claim 17, wherein, activation comprises passing an electric current through the carbonized monolithic substrate to perform resistance heating thereon.

19. The method according to any one of claims 17-18, further comprising adding a coating to the activated carbon monomer structure, the coating comprising a material for adsorbing and desorbing CO 2 therefrom.

20. A method for using the monolithic substrate according to any one of claims 1-7 or 13, the method comprises: Exposing a monolithic substrate to a gas stream comprising CO 2 such that at least a portion of the CO from the gas stream is adsorbed into a coating on the monolithic substrate, the coating comprising a material that adsorbs and desorbs CO 2 ; 2 ​ and Desorption of CO from the coating on a monolithic substrate 2 。 21. A method for using the carbonized substrate according to any one of claims 8-9 or 13, the method comprises: Exposing a carbonized monolithic substrate to a gas stream comprising CO 2 such that at least a portion of the CO from the gas stream is adsorbed into a coating on the carbonized monolithic substrate, the coating comprising a material that adsorbs and desorbs CO 2 ; 2 ​ and Desorbing CO from a coating on a carbonized monolithic substrate 2 .

22. A method for using the carbonized and activated monolithic substrate according to any one of claims 10-13, the method comprises: Exposing a carbonized and activated monolithic substrate to a gas stream comprising CO 2 such that at least a portion of the CO from the gas stream is adsorbed into a coating on the carbonized and activated monolithic substrate, the coating comprising a material that adsorbs and desorbs CO 2 ; 2 ​ and Desorbing CO from a coating on a carbonized and activated monolithic substrate 2 .

23. The method according to any one of claims 21-22, wherein, The carbonized substrate or the carbonized and activated monomeric substrate is conductive, wherein the desorption of CO 2 includes resistively heating the carbonized substrate or the carbonized and activated monomeric substrate.

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