Process for preparation of catalytic articles

Abstract

Aspects of the present disclosure relate to apparatuses, systems, and methods of making catalytic articles. A method of making a catalytic article can include supporting a mixture comprising a dry catalyst precursor and a dry support material on a porous substrate, covering the porous substrate to form a covering mixture, and calcining the covering mixture to form a catalytic article having supported catalyst particles embedded within the porous substrate.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Provisional Application No. 63 / 447,148, filed February 21, 2023, which is incorporated herein by reference in its entirety for all purposes. Technical Field

[0003] The present disclosure relates generally to catalytic articles and methods of making catalytic articles. More particularly, the present disclosure relates to catalytic articles and methods of making catalytic articles on porous substrates. Background Art

[0004] Conventional methods for producing catalytic composites involve using active catalyst powders and combining them with a binder to form the catalytic composite. Forming such catalytic composites can require several steps, which can be time-consuming and costly. Therefore, there is a need for catalytic products that offer higher efficiency than composite materials. Summary of the Invention

[0005] The present disclosure generally relates to a method for preparing a catalytic article, comprising supporting supported catalyst particles on a porous substrate and coating the porous substrate to form the catalytic article. In some embodiments, the method may further comprise laminating a porous fibrillated polymer film to the porous substrate to form the catalytic article, wherein the catalytic article comprises supported catalyst particles embedded in the porous substrate. Surprisingly, the catalytic article comprising catalyst powder embedded in the porous substrate exhibits higher catalytic activity than a catalyst composite comprising a binder.

[0006] According to a first embodiment ("Embodiment 1"), a method of preparing a catalytic article comprises loading a mixture comprising a dry catalyst precursor and a dry support material onto a porous substrate; covering the porous substrate to form a covered mixture; and calcining the covered mixture to form a catalytic article having supported catalyst particles embedded within the porous substrate.

[0007] Embodiment 2 is the method of embodiment 1, wherein the porous substrate is covered with a porous fibrillated polymer film.

[0008] Embodiment 3 is the method of embodiment 2, wherein the porous substrate is covered with a second porous substrate.

[0009] According to another embodiment ("Embodiment 4"), a method of preparing a catalytic article includes supporting a plurality of supported catalyst particles on a porous substrate; and covering the porous substrate to form a catalytic article, the catalytic article having the supported catalyst article embedded in the porous substrate.

[0010] Embodiment 5 is the method of embodiment 4, further comprising calcining the supported catalyst particles after covering the porous substrate.

[0011] Embodiment 6 is the method of any one of embodiments 1 to 5, wherein the calcining is performed at a temperature of 100°C to 500°C.

[0012] According to another embodiment ("Embodiment 7"), a method for preparing a catalytic article comprises loading a plurality of supported catalyst particles on a porous substrate; covering the supported catalyst particles with a porous fibrillated polymer membrane; and laminating the porous fibrillated polymer membrane to the porous substrate to form a catalytic article, wherein the catalytic article has supported catalyst particles embedded in the porous substrate and the porous fibrillated polymer membrane.

[0013] Embodiment 8 is the method of embodiment 7, wherein the laminating comprises heating and pressing the porous fibrillated polymer membrane, the plurality of supported catalyst particles, and the porous substrate.

[0014] Embodiment 9 is the method of embodiment 8, wherein the laminating includes heating at a temperature of 250°C to 400°C.

[0015] Embodiment 10 is the method of any one of embodiments 1 to 9, wherein the porous substrate is a polymeric support material comprising at least one of a woven fabric, a nonwoven fabric, a membrane, an open-cell foam, a fiber / particle network, and combinations thereof.

[0016] Embodiment 11 is the method of any one of embodiments 1 to 9, wherein the porous substrate is an inorganic support material comprising sintered particles, glass fiber mat, or basalt needle mat.

[0017] Embodiment 12 is the method of any one of embodiments 1 to 11, wherein the supported catalyst particles have a particle size distribution defined by a D90 value of at least 1 μm.

[0018] Embodiment 13 is the method of any one of embodiments 1 to 12, wherein the supported catalyst particles comprise at least one metal or metal oxide catalyst dispersed on the porous substrate.

[0019] Embodiment 14 is the method of any one of embodiments 1 to 13, wherein the porous substrate comprises supported catalyst particles in a weight range of 1 wt% to 30 wt% supported catalyst particles.

[0020] Embodiment 15 is the method of any one of embodiments 1 to 14, wherein the catalytic article has a porosity of 25% to 90%.

[0021] Embodiment 16 is the method of any one of embodiments 1 to 15, wherein the porous substrate has a porosity of 25% to 90%.

[0022] Embodiment 17 is a method as described in any one of embodiments 1 to 16, wherein the porous substrate comprises a porous felt, and the porous felt comprises polytetrafluoroethylene (PTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), polyparaxylene (PPX), polyester (PE), polypropylene (PP), polyphenylene sulfide (PPS), P-84, nylon, acrylic, aramid, or any combination or blend thereof.

[0023] Embodiment 18 is the method of any one of embodiments 1 to 17, wherein the porous fibrillated polymer membrane has a porosity of 20% to 97%.

[0024] Embodiment 19 is a method as described in any one of embodiments 1 to 18, wherein the porous fibrillated polymer membrane comprises polytetrafluoroethylene (PTFE), expanded PTFE, poly(ethylene-co-tetrafluoroethylene) (ETFE), polyethylene (PE), polyparaxylene (PPX), or any combination or blend thereof.

[0025] Embodiment 20 is the method of any one of embodiments 1 to 19, wherein the catalytic article is in the form of a filter bag, a honeycomb, a monolith, or any other suitable geometric structure.

[0026] Embodiment 21 is the method of any one of embodiments 1 to 20, wherein the catalytic article is used in a flow-through or flow-by configuration.

[0027] Embodiment 22 is the method of any one of embodiments 1 to 21, wherein the supported catalyst particles are located at a depth within the porous substrate that is from 5% to 95% of the total thickness of the porous substrate.

[0028] Embodiment 23 is a catalytic article prepared according to the method of any one of embodiments 1 to 22.

[0029] Embodiment 24 is a method for a catalytic reaction, which includes contacting a reactant flow with a catalytic product as described in embodiment 22, wherein the reaction is selected from the group consisting of selective catalytic reduction of NOx (SCR), nitrous oxide (N2O) reduction, volatile organic compound (VOC) oxidation, partial oxidation, oxidation, reduction, hydrogenation, dehydrogenation, isomerization, coupling reaction, intramolecular Heck reaction, conjugate addition, nucleophilic addition, α-substitution reaction, methane dry reforming, reverse water gas shift, methanation and ring opening reaction.

[0030] Embodiment 25 is the catalytic article of any one of embodiments 1 to 24, wherein the catalytic article has a catalyst area density of 10 g / m 2 Up to 300g / m 2 .

[0031] Embodiment 26 is the catalytic article of any one of embodiments 1 to 25, wherein the porous substrate is a porous felt comprising polytetrafluoroethylene (PTFE), and the porous fibrillated polymer membrane comprises expanded PTFE (ePTFE).

[0032] Embodiment 27 is the catalytic article of any one of embodiments 1 to 24, wherein the porous substrate and the porous fibrillated polymer membrane both comprise PTFE.

[0033] The above embodiments are intended to be limiting and should not be construed as limiting or otherwise narrowing the scope of any inventive concepts otherwise provided herein. Although multiple embodiments are disclosed, other embodiments will be readily apparent to those skilled in the art from the following detailed description, which illustrates and describes exemplary embodiments. Accordingly, the drawings and detailed description should be construed as illustrative in nature and not restrictive. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The accompanying drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification. They illustrate embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.

[0035] Figure 1 is a flow chart illustrating a method of making a catalytic article according to one embodiment.

[0036] Figure 2 is a flow chart illustrating a method of making a catalytic article according to one embodiment.

[0037] Figure 3 is a flow chart illustrating a method of making a catalytic article according to one embodiment.

[0038] Figure 4Schematic diagram of a sample preparation method 200 of a laminated catalytic article-1 according to one embodiment.

[0039] Figure 5 is a cross-sectional view of a laminated catalytic article-1 according to one embodiment.

[0040] Figure 6 The NOx removal efficiencies of laminated catalytic articles and catalytic composites prepared according to the present disclosure are shown.

[0041] Figure 7 Schematic diagram of a sample preparation method of a laminated catalytic article-3 according to one embodiment.

[0042] Figure 8 Schematic diagram of a sample preparation method of a sandwiched catalytic article-1 according to one embodiment.

[0043] Figure 9 1 is a cross-sectional view of a sandwich catalytic article-1 according to one embodiment.

[0044] Figure 10 Schematic diagram of a sample preparation method of a sandwich catalytic article-2 according to one embodiment. DETAILED DESCRIPTION

[0045] Definitions and Terminology

[0046] The present disclosure is not intended to be interpreted in a limiting sense. For example, the terms used in this application should be interpreted broadly in the context of the meanings given to such terms in the art.

[0047] For imprecise terms, the terms "about" and "approximately" are used interchangeably to indicate that a measurement value includes the stated measurement value and also includes any measurement value that is reasonably close to the stated measurement value. As understood and readily determined by a person of ordinary skill in the relevant art, a measurement value that is reasonably close to the stated measurement value has a relatively small deviation from the stated measurement value. Such deviations may be due to measurement errors, differences in calibration of measurement and / or manufacturing equipment, human errors in reading and / or setting measurements, fine-tuning to optimize performance and / or structural parameters to account for measurement differences associated with other components, specific implementation scenarios, imprecise adjustment and / or operation of an object by a person or machine, etc. If it is determined that a person of ordinary skill in the relevant art cannot readily determine the value of such a reasonably small difference, the terms "about" and "approximately" may be understood to mean plus or minus 10% of the stated value.

[0048] As used herein, the term "activated carbon" may include any carbon having a relatively high surface area, for example, from about 50 to about 3000 m 2 / g, or about 100 to about 2000 m 2 / g (e.g., about 200 to about 1500 m 2 / g, or about 300 to about 1000m 2 / g). Activated carbon can be derived from any carbonaceous material, such as coal (e.g., charcoal), nut shells (e.g., coconut), and wood. Activated carbon can be used in any form, such as powdered, granular, extruded, or pelletized.

[0049] Description of each embodiment

[0050] Those skilled in the art will understand that various aspects of the present disclosure may be implemented by any number of methods and devices configured to perform the desired effects. It should also be noted that the drawings referenced herein are not necessarily drawn to scale, but may be exaggerated to illustrate various aspects of the present disclosure, and in this regard, the drawings should not be considered limiting.

[0051] Figure 1 1 is a flow chart illustrating a method 100 for preparing a catalytic article according to one embodiment. One or more steps of the method 100 may be optional and / or may be modified from one or more steps of other embodiments described herein. In addition, one or more steps of other embodiments described herein may be added to the method.

[0052] In step 102, the method 100 of preparing a catalytic article may include supporting a mixture comprising a dry catalyst precursor and a dry support material on a porous substrate. In some embodiments, the catalyst precursor does not contain any aqueous liquid or any organic liquid, and the support material does not contain any aqueous liquid or any organic liquid.

[0053] In some embodiments, the porous substrate is a polymeric support material selected from the group consisting of a woven fabric, a nonwoven fabric, a membrane, an open-cell foam, a fiber / particle network, and combinations thereof. In certain embodiments, the porous substrate comprises a porous felt comprising polytetrafluoroethylene (PTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), polyparaxylene (PPX), or any combination or blend thereof. In yet other embodiments, the porous substrate is an inorganic support material comprising sintered particles, glass fiber mat, or basalt needled mat.

[0054] In some embodiments, the porous substrate has a porosity of about 25% to about 90%, or about 27.5% to about 88%, or about 30% to about 86%, or about 32.5% to about 84%, or about 35% to about 82%, or about 37.5% to about 80%, or about 40% to about 78%, or about 42.5% to about 76%, or about 45% to about 74%, or about 47.5% to about 72%, or about 50% to about 70%, or porosities encompassed by these ranges.

[0055] In some embodiments, the catalytic article has a porosity of about 25% to about 90%, or about 27.5% to about 88%, or about 30% to about 86%, or about 32.5% to about 84%, or about 35% to about 82%, or about 37.5% to about 80%, or about 40% to about 78%, or about 42.5% to about 76%, or about 45% to about 74%, or about 47.5% to about 72%, or about 50% to about 70%, or porosities encompassed by these ranges.

[0056] In some embodiments, the active catalyst powder may include a metal selected from the group consisting of vanadium, copper, platinum, palladium, nickel, iron, cobalt, molybdenum, rhodium, ruthenium, rhenium, or mixtures thereof.

[0057] In some embodiments, the dry catalyst precursor may include a metal and a ligand. In some embodiments, the metal may be selected from one or more of a transition metal, a lanthanide, an alkali metal or an alkaline earth metal or a salt thereof. In some embodiments, the metal may be selected from the 3rd to 14th families (such as 38 transition metals, or the metal of the 13th to 14th families, such as B, Al, Ga, In, Tl, Nh, Si, Ge, Sn or Pb) of the periodic table of the elements. The example of a suitable metal includes one or more compounds (such as halides, hydroxides, carbonates) in Na, K, Cr, Mn, Au, Fe, Cu, Zn, Sn, Ta, Ti, Sb, Al, Co, Ni, Mo, Ru, Rh, Pd and / or Pt and / or these metals. In other embodiments, an alkali metal (such as Na or K) salt may be used as an additive for activated carbon, such as a halide, hydroxide or carbonate of an alkali metal salt. The hydroxide or carbonate of an alkali metal salt is a base. Any other suitable base may be used, including acid amides (such as sodium amide).

[0058] In an exemplary embodiment, the metal is selected from the group consisting of vanadium, copper, platinum, palladium, nickel, iron, cobalt, molybdenum, rhodium, ruthenium, rhenium, or mixtures thereof.

[0059] In some embodiments, the ligand can be a carbonyl, oxalate, ammonium, dimethylamino, bromide, chloride, cyclopentadienyl, diketonate, or a ligand of formula (I):

[0060]

[0061] wherein R1 and R2 are independently alkyl, substituted alkyl, aryl, substituted aryl, acyl and substituted acyl.

[0062] In an exemplary embodiment, the catalyst precursor may include a metal and an acetylacetonate group or a ketone group. For example, the precursor may be selected from the exemplary catalyst precursors listed in Table 1.

[0063] Table 1

[0064]

[0065]

[0066]

[0067] In one embodiment, the catalyst precursor is selected from the group consisting of vanadyl acetylacetonate, vanadium (III) acetylacetonate, platinum (II) acetylacetonate, palladium (II) acetylacetonate, bis(acetylacetonato)dioxomolybdenum (VI) and copper (II) acetylacetonate.

[0068] The support material is not particularly limited as long as it does not affect the final use of the catalytic composite material. In some embodiments, the support material can be porous. Examples of support materials may include, but are not limited to, metals, metal oxides (e.g., titanium dioxide, aluminum oxide, etc.), zeolites, carbon, clays, and combinations thereof.

[0069] In some embodiments, the dry support material may be selected from the group consisting of metal oxides, zeolites, carbon, clays, metal organic frameworks, and combinations thereof. In an exemplary embodiment, the dry support material may be selected from one or more of TiO2, SiO2, Al2O3, zeolites, aluminosilicates, or activated carbon.

[0070] The surface area of ​​the support material may be about 10 m 2 / g to about 3000m 2 / g, about 15m 2 / g to about 2500m 2 / g, about 20m 2 / g to about 2000m 2 / g, about 25m 2 / g to about 1500m 2 / g, about 30m 2 / g to about 1000m 2 / g, about 35m 2 / g to about 800m 2 / g, about 40m 2 / g to about 600m 2 / g, about 45m 2 / g to about 500m 2 / g, about 50m 2 / g to about 400m 2 / g, about 55m 2 / g to about 350m 2 / g, or the surface area encompassed by these ranges. In some embodiments, the surface area of ​​the support material may be about 60 m 2 / g to about 340m 2 / g, about 65m 2 / g to about 330m 2 / g, about 70m 2 / g to about 320m 2 / g, or about 75m 2 / g to about 310m 2 In an exemplary embodiment, the surface area of ​​the support material may be about 80 m 2 / g to about 305m 2 / g.

[0071] The support material may include particles having an average diameter of about 0.5 μm to about 1000 μm, about 0.6 μm to about 900 μm, about 0.7 μm to about 800 μm, about 0.8 μm to about 700 μm, about 0.9 μm to about 600 μm, about 1.0 μm to about 500 μm, about 1.1 μm to about 400 μm, about 1.2 μm to about 300 μm, about 1.3 μm to about 200 μm, about 1.4 μm to about 100 μm, or may include particles having an average diameter within these ranges. In some embodiments, the support material may include particles having an average diameter of about 1.5 μm to about 90 μm, about 1.6 μm to about 80 μm, about 1.7 μm to about 70 μm, about 1.8 μm to about 60 μm, about 1.9 μm to about 55 μm, or about 1.95 μm to about 54 μm. In an exemplary embodiment, the support material may include particles having an average diameter of about 2.0 μm to about 52 μm.

[0072] In some embodiments, the mixture comprising the dry catalyst precursor and the dry support material may be mixed using a vortex mixer, an oscillating mixer, a double cone mixer, or any other suitable mixing device before being loaded onto the porous substrate.

[0073] In step 104, method 100 may include covering the porous substrate to form a covered mixture. In certain embodiments, the porous substrate is covered with a porous fibrillated polymer film. In certain embodiments, the porous substrate is covered with a second porous substrate. In further embodiments, the porous substrate can be folded so that both sides of the mixture are covered by the same porous substrate.

[0074] At step 106 , method 100 may include calcining the blanket mixture to form a catalytic article having supported catalyst particles embedded within a porous substrate.

[0075] According to some embodiments, the calcining step 106 can be performed using a rapid heating method (e.g., heating the blanket mixture on a preheated hot plate). In some embodiments, the calcining step 106 can be performed using a slow heating method (e.g., slowly heating the blanket mixture in a muffle furnace starting at room temperature). In some embodiments, the heating can be performed by placing the mixture in a preheated oven. In yet other embodiments, the mixture can be heated in a furnace.

[0076] In certain embodiments, the covered mixture may be calcined at a temperature of about 100° C. to about 500° C., about 105° C. to about 480° C., about 110° C. to about 460° C., about 115° C. to about 440° C., about 120° C. to about 430° C., about 125° C. to about 420° C., about 130° C. to about 410° C., about 135° C. to about 400° C., about 140° C. to about 390° C., about 145° C. to about 380° C., or at a temperature encompassed by these ranges. In some embodiments, the dry mixture may be calcined at a temperature of about 146° C. to about 375° C., about 147° C. to about 370° C., or about 148° C. to about 365° C.

[0077] In certain embodiments, such as when the porous substrate is a polymeric support material, the dry mixture can be calcined at a temperature of about 100° C. to about 350° C. The polymeric support material (e.g., porous felt) can include polytetrafluoroethylene (PTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), polyparaxylene (PPX), polyester (PE), polypropylene (PP), polyphenylene sulfide (PPS), P-84, nylon, acrylic, aramid, or any combination or blend thereof.

[0078] In some cases, such as when the porous substrate is PE, the dry mixture can be calcined at a temperature of about 100° C. to about 135° C. In some cases, such as when the porous substrate is polypropylene (PP), the dry mixture can be calcined at a temperature of about 100° C. to about 120° C. In some cases, such as when the porous substrate is polyphenylene sulfide (PPS), the dry mixture can be calcined at a temperature of about 100° C. to about 190° C. In some cases, such as when the porous substrate is nylon, the dry mixture can be calcined at a temperature of about 100° C. to about 121° C. In some cases, such as when the porous substrate is acrylic, the dry mixture can be calcined at a temperature of about 100° C. to about 135° C. In some cases, such as when the porous substrate is aramid, the dry mixture can be calcined at a temperature of about 100° C. to about 220° C.

[0079] In yet other embodiments, such as when the porous substrate is an inorganic support material, the dry mixture may be calcined at a temperature of about 100°C to about 500°C.

[0080] In some embodiments, the covered mixture can be calcined at a rate of about 1°C / min to about 50°C / min, about 1.25°C / min to about 45°C / min, about 1.5°C / min to about 40°C / min, about 1.75°C / min to about 35°C / min, about 2°C / min to about 30°C / min, about 2.25°C / min to about 25°C / min, about 2.5°C / min to about 20°C / min, about 2.75°C / min to about 15°C / min, about 3°C / min to about 10°C / min, or a rate encompassed by these ranges. In some embodiments, the dry mixture can be calcined at a rate of about 3.2°C / min to about 9°C / min, about 3.4°C / min to about 8°C / min, about 3.6°C / min to about 7°C / min, or about 3.8°C / min to about 6°C / min. In an exemplary embodiment, the dry mixture can be calcined at a rate of about 4°C / min to about 5°C / min.

[0081] In some embodiments, the overlay mixture is calcined in an atmosphere containing about 1 to about 100% oxygen by volume, about 2 to about 20% oxygen by volume, about 3 to about 15% oxygen by volume, about 3.5 to about 10% oxygen by volume, about 4 to about 9% oxygen by volume, about 4.5 to about 8% oxygen by volume, about 5 to about 7% oxygen by volume, about 5.5 to about 6.5% oxygen by volume, or oxygen by volume ranges encompassed by these ranges. In one exemplary embodiment, the dry mixture is calcined in an atmosphere containing about 6% oxygen by volume.

[0082] The catalytic article formed in step 106 can be in the form of a filter bag, a honeycomb, a monolith, or any other suitable geometric structure. In certain embodiments, the catalytic article is used in a flow-through configuration, wherein the gas or liquid flows transversely (e.g., perpendicularly) to the cross-section of the catalytic article, such that the gas or liquid passes through the layer of catalyst particles in the catalytic article. In other embodiments, the catalytic article is used in a flow-through configuration, wherein the gas or liquid flows parallel to the cross-section of the catalytic article, such that the gas or liquid flows parallel to and diffuses to the catalyst particles in the catalytic layer and does not pass through the cross-section of the catalytic article.

[0083] In some embodiments, the catalyst area density of the formed catalytic article is about 10 g / m 2 About 300g / m 2 , or about 15g / m 2 About 280g / m 2 , or about 20g / m 2 About 260g / m 2 , or about 25g / m 2 to about 240g / m 2 , or about 30g / m2 About 220g / m 2 , or about 35g / m 2 About 200g / m 2 , or about 40g / m 2 About 200g / m 2 , or about 45g / m 2 About 180g / m 2 , or about 50g / m 2 About 160g / m 2 , or about 55g / m 2 About 140g / m 2 , or about 60g / m 2 About 120g / m 2 .

[0084] In step 108, method 100 may include contacting the reactant stream with the catalytic article. In some embodiments, the reaction may be selected from the group consisting of: DeNOx, selective catalytic reduction of NOx (SCR), nitrous oxide (NO) reduction, volatile organic compound (VOC) oxidation, partial oxidation, oxidation, reduction, hydrogenation, dehydrogenation, isomerization, coupling reaction, intramolecular Heck reaction, conjugate addition, nucleophilic addition, α-substitution reaction, methane dry reforming, reverse water gas shift, methanation, and ring opening reaction.

[0085] In some embodiments, the catalytic article has a NOx removal efficiency of about 1% to about 99%, about 5% to about 90%, about 10% to about 80%, about 15% to about 70%, about 20% to about 60%, or a NOx removal efficiency encompassed by these ranges.

[0086] In some embodiments, the catalytic article has an NH3 oxidation efficiency of about 20% to about 99%, about 25% to about 90%, about 30% to about 80%, about 35% to about 75%, about 40% to about 70%, about 40% to about 65%, or an NH3 oxidation efficiency encompassed by these ranges.

[0087] Figure 2 1 is a flow chart illustrating a method 200 for preparing a catalytic article according to one embodiment. One or more steps of method 200 may be optional and / or may be modified from one or more steps of other embodiments described herein. In addition, one or more steps of other embodiments described herein may be added to the method.

[0088] In some embodiments, method 200 may include loading a plurality of supported catalyst particles onto a porous substrate in step 202, and covering the porous substrate to form a catalytic article in step 204. In certain embodiments, the porous substrate is covered with a porous fibrillated polymer film. In certain embodiments, the porous substrate is covered with a second porous substrate. In yet other embodiments, the porous substrate may be folded so that both sides of the mixture are covered by the same porous substrate.

[0089] The catalytic article can have supported catalyst particles embedded within a porous substrate. In certain embodiments, at step 206, method 200 can optionally include calcining the supported catalyst particles after coating the porous substrate at step 204.

[0090] Figure 3 1 is a flow chart illustrating a method 300 for preparing a catalytic article according to one embodiment. One or more steps of the method 300 may be optional and / or may be modified from one or more steps of other embodiments described herein. In addition, one or more steps of other embodiments described herein may be added to the method.

[0091] In step 302, method 300 may include supporting a plurality of supported catalyst particles on a porous substrate. In some embodiments, the supported catalyst particles have a particle size distribution defined by a D90 value of at least 1 μm.

[0092] The porous substrate can include supported catalyst particles in a weight range of from about 1 wt % to about 30 wt % supported catalyst particles, or from about 1.5 wt % to about 25 wt %, or from about 2 wt % to about 20 wt %, or from about 2.5 wt % to about 15 wt %, or from about 3 wt % to about 10 wt % supported catalyst particles, or can include supported catalyst particles within these ranges.

[0093] In certain embodiments, the supported catalyst particles include at least one metal or metal oxide catalyst dispersed on a porous substrate. The supported catalyst particles used in step 302 may include those described, for example, in U.S. Patent Application No. 20220212181A1 to Gore.

[0094] In step 304, method 300 may include covering the supported catalyst particles with a porous fibrillated polymer membrane. The porous fibrillated polymer membrane may have a porosity of about 20% to about 97%, or about 20% to about 95%, or about 20% to about 90%, or about 21% to about 85%, or about 22% to about 80%, or about 23% to about 75%, or about 24% to about 70%, or about 25% to about 65%, or about 26% to about 60%, or about 27% to about 55%, or about 28% to about 50%, or about 29% to about 45%, or about 30% to about 40%, or porosities encompassed by these ranges.

[0095] In certain embodiments, the supported catalyst particles are located at a depth within the porous substrate of from about 5% to about 95% of the total thickness of the porous substrate, or from about 10% to about 90% of the total thickness of the porous substrate, or from about 15% to about 85% of the total thickness of the porous substrate, or from about 20% to about 80% of the total thickness of the porous substrate, or from about 25% to about 75% of the total thickness of the porous substrate, or from about 30% to about 70% of the total thickness of the porous substrate, or from about 35% to about 65% of the total thickness of the porous substrate, or from about 40% to about 60% of the total thickness of the porous substrate, or from about 45% to about 55% of the total thickness of the porous substrate, or may be located at a depth within the substrate encompassed within these ranges.

[0096] In some embodiments, the porous fibrillated polymer membrane comprises polytetrafluoroethylene (PTFE), expanded PTFE, poly(ethylene-co-tetrafluoroethylene) (ETFE), ultra-high molecular weight polyethylene (UHMWPE), polyparaxylene (PPX), polylactic acid, or any combination or blend thereof. In an exemplary embodiment, the porous substrate is a porous felt, the porous felt comprises polytetrafluoroethylene (PTFE), and the porous fibrillated polymer membrane comprises expanded PTFE (ePTFE).

[0097] In step 306, method 300 may include laminating a porous fibrillated polymer membrane to a porous substrate to form a catalytic article having supported catalyst particles embedded in the porous substrate and the porous fibrillated polymer membrane. In certain embodiments (not shown), the method may include covering the porous substrate with a second porous substrate and laminating the second porous substrate to the porous substrate. In some cases, laminating the second porous substrate to the porous substrate may also include using an adhesive.

[0098] In some embodiments, the lamination comprises heating and pressing a porous fibrillated polymer film, a plurality of supported catalyst particles, and a porous substrate. In certain embodiments, wherein the porous substrate is a polymer support material selected from the group consisting of a woven fabric, a nonwoven fabric, a membrane, an open-cell foam, a fiber / particle network, and combinations thereof, the lamination heating may be performed at a temperature of about 250° C. to 400° C., or about 260° C. to 390° C., or about 270° C. to 380° C., or about 280° C. to 370° C., or about 290° C. to 360° C., or about 300° C. to about 350° C., or at a temperature encompassed within these ranges.

[0099] In yet other embodiments, wherein the porous substrate is an inorganic support material comprising sintered particles, glass fiber felt, or basalt needle felt, the lamination heating may be carried out at a temperature of about 200°C to about 450°C, or about 210°C to about 440°C, or about 220°C to about 430°C, or about 230°C to about 420°C, or about 240°C to about 410°C, or about 250°C to about 400°C, or about 260°C to about 390°C, or about 270°C to about 380°C, or about 280°C to about 370°C, or about 290°C to about 360°C, or may be carried out at a temperature encompassed within these ranges.

[0100] In an alternative embodiment ( Figure 3 (not shown), a method for preparing a catalytic product, which may include loading a plurality of supported catalyst particles on a first porous substrate, covering the supported catalyst particles with a second porous substrate, and laminating the second porous substrate to the first porous substrate to form a catalytic product having supported catalyst particles embedded in two porous substrates. In some embodiments, laminating the second porous substrate to the first porous substrate may include heating and pressing the two porous substrates having the plurality of supported catalyst particles in the middle. In certain embodiments, an adhesive may be added between the two porous substrates for lamination. In an exemplary embodiment, the first and second porous substrates may include PTFE felt.

[0101] Test Method

[0102] It should be understood that although certain methods and apparatus are described below, other methods or apparatuses determined suitable by one of ordinary skill in the art may alternatively be employed.

[0103] Particle size analysis

[0104] The particle size of the vanadium pentoxide-supported titanium dioxide catalyst was measured using a Horiba particle analyzer. The mean diameter (MV) of the vanadium pentoxide-supported titanium dioxide catalyst was 1.24 μm, and the D90 was 3.41 μm. The D90 describes the diameter where 90% of the distribution has a smaller particle size and 10% has a larger particle size. The particle size distribution data is shown in Table 2.

[0105] Table 2. Particle size distribution of vanadium pentoxide-supported titanium dioxide catalysts.

[0106]

[0107] Example

[0108] Example 1 - Laminated Catalytic Article for NOx Removal-1 (Laminated between PTFE Felt and ePTFE Membrane 28g / m 2 V2O5 / TiO2 catalyst)

[0109] Sample preparation: Figure 4 Schematic diagram of sample preparation method 400 for catalytic article 408 (i.e., laminated catalytic article-1). As shown in the figure, in step 402, 0.2 g of vanadium pentoxide-loaded titanium dioxide particles obtained from CRI Catalysts were ground and loaded onto the surface of a porous PTFE felt using a polypropylene scraper. The average particle size of the vanadium pentoxide-loaded titanium dioxide was approximately 1.24 μm. The area density of the PTFE felt was approximately 860 g / m 2 The catalyst particles (vanadium pentoxide-loaded titanium dioxide) were evenly scraped onto the PTFE felt using a scraper, covering an area of ​​71 cm 2 .

[0110] In step 404 of method 400, the air permeability is 35 cfm / ft at 0.5 inch water level. 2 The catalyst particles and PTFE felt are covered with a porous expanded PTFE membrane. In step 406, the resulting sample is placed in an aluminum foil envelope, which is then placed in a heated hydraulic press. The top plate is heated to 635°F, while the bottom plate is maintained at ambient temperature. The plates are closed and pressurized to 5000 psi. The dwell time under these conditions is 3 seconds, after which the plates are opened. The result is a catalytic article 408.

[0111] The catalyst area density of the obtained catalytic product 408 (i.e., laminated catalytic product-1) is 28.2 g / m 2 The total area density of the laminated catalytic product-1 is 888g / m 2 At 0.5 inches of water level, the air permeability of the laminated catalytic article-1 was 0.89 cfm / ft 2 .

[0112] The total porosity within the laminated catalytic article is the void volume of the sample divided by the total volume of the sample, which is calculated using the following formula:

[0113] % Porosity = (1-bulk density / skeleton density)*100%

[0114] The bulk density is calculated using the following formula:

[0115] Bulk density = sample weight / sample volume, g / cm 3

[0116] Skeletal density was calculated using the following formula:

[0117] Skeletal density (g / cm 3 ) = 1 / (catalyst weight ratio / catalyst density+PTFE felt weight ratio / PTFE felt density), wherein:

[0118] Catalyst density = 4.0 g / cm 3 ,

[0119] PTFE felt density = 2.35g / cm 3

[0120] The bulk density of the laminated catalytic product-1 is calculated to be 0.87 g / cm 3 , skeleton density is 2.38g / cm 3 The calculated total porosity is 63.4%.

[0121] The total porosity of the porous PTFE felt was calculated using the same method. The bulk density of the porous PTFE felt was 0.61 g / cm 3 , skeleton density is 2.35g / cm 3 The calculated total porosity of the porous PTFE felt was 74.0%. Figure 5 A cross-sectional view of a laminated catalytic article 500 (e.g., catalytic article 408 formed in Example 1) is shown. As shown, catalyst particles 502 are embedded within a porous substrate 504, with a membrane layer 506 laminated on top. The total thickness of the laminated catalytic article 500 was measured to be 890 μm. The penetration depth of the catalyst particles was 322 μm.

[0122] Example 2 - Laminated Catalytic Article for NOx Removal-2 (Laminated between PTFE Felt and ePTFE Membrane 70g / m 2 V2O5 / TiO2 catalyst)

[0123] Sample preparation: 0.45 g of vanadium pentoxide-loaded titanium dioxide particles (CRI Catalysts, a division of Royal Dutch Shell, The Hague, The Netherlands) were loaded onto the surface of a porous PTFE felt using a polypropylene scraper. The area density of the PTFE felt was 860 g / m 2 The catalyst particles (vanadium pentoxide-loaded titanium dioxide) were evenly scraped onto the PTFE felt using a scraper, covering an area of ​​64 cm2 .

[0124] Air permeability is 35 cfm / ft at 0.5 inch water level 2 The catalyst particles and PTFE felt were covered with a porous expanded PTFE membrane. The resulting sample was placed in an aluminum foil envelope, which was then placed in a heated hydraulic press. The top plate was heated to 635°F and the bottom plate was kept at ambient temperature. The plates were closed and pressurized to 5000 pounds. The residence time under this condition was 3 seconds, and then the plates were opened. The catalyst area density of the resulting laminated catalytic product-2 was 70.3 g / m 2 The total area density of the laminated catalytic product-1 is 930 g / m 2 At 0.5 inches of water level, the air permeability of the laminated catalytic article-2 was 0.33 cfm / ft 2 The bulk density of the laminated catalytic product-2 is 1.07 g / cm 3 , skeleton density is 2.42g / cm 3 The calculated total porosity of the laminated catalytic article-2 was 55.8%.

[0125] Example 3 - NOx removal efficiency of catalytic composite materials

[0126] Composite Sample Preparation: Two catalytic composites comprising vanadium pentoxide-loaded titanium dioxide particles [CRI Catalysts, a division of Royal Dutch Shell, The Hague, The Netherlands] were prepared using the general dry mixing method taught in U.S. Patent No. 7,791,861 B2 to Zhong et al. to form composite tapes, which were then uniaxially expanded according to the teachings of U.S. Patent No. 3,953,566 to Gore. The average particle size of the vanadium pentoxide-loaded titanium dioxide was approximately 1.24 μm. The catalyst area densities of the two catalytic composites were 46.7 and 101.8 g / m 2 Catalytic composite sample preparation is also described in Gore's U.S. patent application number US 20220212181 A1.

[0127] NOx reaction efficiency: The catalytic NOx removal efficiency from simulated flue gas was tested on laminated catalytic product-1 and laminated catalytic product-2 (i.e., samples prepared according to Examples 1 and 2 of this article) and catalytic composite materials (i.e., composite material samples prepared according to Example 3).

[0128] A 4.5 inch x 4.5 inch square of each catalytic sample was placed in a sample holder located in the reaction chamber. The samples were exposed to a simulated flue gas balanced with N2 at 200°C. The simulated flue gas contained 360 ppm NO, 340 ppm NH3, 6 vol% O2, and a total flow rate of 4.2 liters / minute. In order to determine the NOx Removal efficiency, using MKS MULTI-GAS TM A 2030D FTIR analyzer (MKS Instruments, Andover, MA) monitored the upstream and downstream concentrations of NO and NO 3 (ie, relative to the catalytic membrane).

[0129] The NOx removal efficiency (i.e., "DeNOx efficiency (%)") was calculated according to the following formula:

[0130]

[0131] Where NOx = total concentration of NO and NO2 in the gas stream

[0132] NOx inlet = upstream concentration of NOx

[0133] NOx output = downstream concentration of NOx

[0134] Figure 6 The NOx removal efficiency of a laminated catalytic article and a catalytic composite material is shown. As shown, the laminated catalytic article achieves similar NOx removal efficiency performance compared to the catalytic composite material using a lower amount of catalyst. At 45% NOx removal efficiency, the laminated catalytic article uses approximately 30% less catalyst than the catalytic composite material.

[0135] Example 4 - Laminated Catalytic Article 3 for NH3 Oxidation (Laminated between PTFE Felt and ePTFE Membrane) 30g / m 2 Pd / Al2O3 catalyst)

[0136] Sample preparation: Figure 7 Schematic diagram of the sample preparation method of the laminated catalytic article-3. As shown in the figure, 0.055g of acetylacetonate palladium (II) [STREM Chemical Inc.] was added to 0.36g of Al2O3 [Sigma Aldrich-199966, surface area 155m 2 3.6 wt% palladium / AlO catalyst particles were prepared in scintillation vials (data provided by Sigma Aldrich). The two dry powders were mixed by shaking on a vortex mixer (Cole-Parmer) for several minutes. The powder mixture was then transferred to an aluminum weight pan and placed on a hot plate set to 250°C for 15 minutes.

[0137] 0.164 g of the prepared Pd / Al2O3 catalyst particles were loaded onto the surface of the PTFE felt using a polypropylene scraper. The catalyst particles (Pd / Al2O3) were evenly scraped onto the PTFE felt using a scraper, covering an area of ​​54 cm 2The air permeability is 35 cfm / ft at 0.5 inch water level. 2 The catalyst particles and PTFE felt were covered with a porous expanded PTFE membrane. The resulting sample was placed in an aluminum foil envelope, which was then placed in a heated hydraulic press. The top plate was heated to 635°F and the bottom plate was kept at ambient temperature. The plates were closed and pressurized to 5000 pounds. The residence time under this condition was 3 seconds, and then the plates were opened. The resulting catalyst area density of the laminated catalytic product-3 was 30.4 g / m 2 .

[0138] NH3 Oxidation: The performance of the laminated catalytic article-3 prepared according to Example 4 for NH3 oxidation was tested using the following procedure. A 26 mm diameter laminated catalytic article-3 was placed in a sample holder. The catalytic strip was first treated with 115 ppm NH3 in N2 at a total flow rate of 0.45 L / min for 2 hours at 200°C. After the 2-hour treatment, 6 vol% O2 was introduced into the gas mixture while maintaining the NH3 concentration and total flow rate constant. NH3 oxidation was measured using 115 ppm NH3, 6 vol% O2 in N2 at a total flow rate of 0.45 L / min at 200°C. To determine the NH3 oxidation efficiency, the upstream (i.e., NH3 concentration entering the chamber before exposure to the catalytic strip) and downstream NH3 concentrations were monitored using an MKS MULTI-GASTM 2030 DFTIR analyzer (MKS Instruments, Andover, MA).

[0139] The NH3 oxidation efficiency (i.e., "NH3 oxidation efficiency (%)") was calculated according to the following formula:

[0140]

[0141] Where NH3 = the concentration of NH3 in the corresponding stream

[0142] NH3 in = upstream concentration of NH3

[0143] NH3 output = downstream concentration of NH3

[0144] At 200 ° C, the laminated catalytic product-3 (laminated between PTFE felt and ePTFE membrane 30g / m 2 The NH3 oxidation efficiency measured over the Pd / Al2O3 catalyst was 69.2%.

[0145] Example 5 - Sandwich catalytic article for NOx removal-1 (97g / sandwiched between PTFE felt and PTFE felt) m 2 V2O5 / TiO2 catalyst)

[0146] Sample preparation: Figure 8Schematic diagram of the sample preparation method of sandwich catalytic product-1. As shown in the figure, 0.58 g of vanadium acetylacetonate (Sigma Aldrich) was added to 0.8 g of TiO2 (Hombikat 8602, with a surface area of ​​about 340 m 2 The powder mixture was shaken on a vortex mixer (Cole-Parmer) for 15 minutes. 0.8 g of the powder mixture was loaded onto the surface of the porous PTFE felt using a polypropylene scraper. The area density of the PTFE felt was 860 g / m 2 The powder mixture was evenly scraped onto the PTFE felt using a scraper, covering an area of ​​82 cm 2 .

[0147] A second layer of PTFE felt was used to cover the powder mixture and PTFE felt. The resulting sample was transferred to a furnace and heat-treated in air at 230°C for 2 hours, with an initial temperature ramp rate of 5°C / min. Before calcination, the powder mixture was white. After the calcination process, the powder mixture transformed into a V2O5 / TiO2 catalyst, changing its color from white to yellow and becoming embedded within the porous PTFE felt substrate.

[0148] NOx removal efficiency: NOx removal efficiency was measured as described in Example 3 above. The NOx removal efficiency of the sandwich catalytic article-1 (97 g / m2 sandwiched between PTFE felt and PTFE felt) was measured at 200°C. 2 The NOx removal efficiency of the V2O5 / TiO2 catalyst is 74.5%.

[0149] Figure 9 The figure shows a cross-sectional view of the sandwich catalytic article 1. As shown in the figure, the total thickness of the sandwich catalytic article 1 (bottom) is 1460.3 μm. The penetration depth of the embedded catalyst powder is 1284.8 μm. The catalyst area density of the resulting sandwich catalytic article 1 is 97.5 g / m 2 The total area density of the sandwich catalytic product-1 is 1817.5g / m 2 .

[0150] Example 6 - Sandwich catalytic article for NOx removal-2 (80g / sandwiched between PTFE felt and PTFE felt) m 2 V2O5 / TiO2 catalyst)

[0151] Sample preparation: Figure 10Schematic diagram of the sample preparation method for Sandwich Catalyst Product-2. As shown in the figure, 0.7 g of vanadium pentoxide-loaded titanium dioxide particles (CRI Catalysts, a division of Royal Dutch Shell, The Hague, The Netherlands) were loaded onto the surface of a PTFE felt using a polypropylene scraper. The catalyst powder (vanadium pentoxide-loaded titanium dioxide) was evenly spread over the PTFE felt using the scraper, covering an area of ​​87 cm. 2 A second layer of PTFE felt was used to cover the catalyst and PTFE felt. The resulting sample was transferred to a furnace and heat treated in air at 230°C for 2 hours with an initial temperature increase rate of 5°C / min. The catalyst area density of the resulting sandwich catalytic product-2 was 80.2 g / m 2 The total area density of the sandwich catalytic product-2 is 1800g / m 2 .

[0152] NOx removal efficiency: NOx removal efficiency was measured as described in Example 3 above. The NOx removal efficiency of sandwich catalytic article-2 (80 g / m2 sandwiched between PTFE felt and PTFE felt) was measured at 200°C. 2 The NOx removal efficiency of the V2O5 / TiO2 catalyst is 58%.

[0153] The invention of this application has been described above generally and with reference to specific embodiments. It will be apparent to those skilled in the art that various modifications and variations may be made to the embodiments described herein without departing from the scope of the invention. Therefore, the embodiments are intended to cover such modifications and variations of the invention as come within the scope of the appended claims and their equivalents.

Claims

1. A method for preparing a catalytic product, the method comprising: supporting a mixture comprising a dry catalyst precursor and a dry support material on a porous substrate; covering the porous substrate to form a covering mixture; and The blanket mixture is calcined to form a catalytic article having supported catalyst particles embedded within the porous substrate.

2. The method of claim 1, wherein the porous substrate is covered with a porous fibrillated polymer film. The method of claim 1 , wherein the porous substrate is covered with a second porous substrate.

4. A method for preparing a catalytic product, the method comprising: supporting a plurality of supported catalyst particles on a porous substrate; and The porous substrate is coated to form a catalytic article having supported catalyst particles embedded within the porous substrate.

5. The method of claim 4, further comprising calcining the supported catalyst particles after coating the porous substrate.

6. The method of any one of claims 1 to 5, wherein the calcining is performed at a temperature of 100 to 500°C.

7. A method for preparing a catalytic article, the method comprising: supporting a plurality of supported catalyst particles on a porous substrate; covering the supported catalyst particles with a porous fibrillated polymer membrane; and The porous fibrillated polymer membrane is laminated to the porous substrate to form a catalytic article having supported catalyst particles embedded within the porous substrate and the porous fibrillated polymer membrane.

8. The method of claim 7, wherein the laminating comprises heating and pressing the porous fibrillated polymer membrane, the plurality of supported catalyst particles, and the porous substrate.

9. The method of claim 8, wherein the laminating comprises heating at a temperature of 250°C to 400°C.

10. The method of any one of claims 1-9, wherein the porous substrate is a polymeric support material comprising at least one of a woven fabric, a nonwoven fabric, a membrane, an open-cell foam, a fiber / particle network, and combinations thereof.

11. The method of any one of claims 1 to 9, wherein the porous substrate is an inorganic support material comprising sintered particles, glass fiber mat, or basalt needle mat.

12. The process of any one of claims 1 to 11, wherein the supported catalyst particles have a particle size distribution defined by a D90 value of at least 1 μm.

13. The method of any one of claims 1-12, wherein the supported catalyst particles comprise at least one metal or metal oxide catalyst dispersed on the porous substrate.

14. The method of any one of claims 1-13, wherein the porous substrate comprises supported catalyst particles in an amount ranging from 1 wt% to 30 wt% supported catalyst particles.

15. The method of any one of claims 1 to 14, wherein the catalytic article has a porosity of 25% to 90%.

16. The method of any one of claims 1 to 15, wherein the porous substrate has a porosity of 25% to 90%.

17. The method of any one of claims 1 to 16, wherein the porous substrate comprises a porous felt comprising polytetrafluoroethylene (PTFE), poly(ethylene-co-tetrafluoroethylene), (ETFE), polyparaxylene (PPX), polyester (PE), polypropylene (PP), polyphenylene sulfide (PPS), P-84, nylon, acrylic, aramid, or any combination or blend thereof.

18. The method of any one of claims 1 to 17, wherein the porous fibrillated polymer membrane has a porosity of 20% to 97%.

19. The method of any one of claims 1 to 18, wherein the porous fibrillated polymer membrane comprises polytetrafluoroethylene (PTFE), expanded PTFE, poly(ethylene-co-tetrafluoroethylene) (ETFE), polyethylene (PE), polyparaxylene (PPX), or any combination or blend thereof.

20. The method of any one of claims 1 to 19, wherein the catalytic article is in the form of a filter bag, a honeycomb, a monolith, or any other suitable geometric structure.

21. The method of any one of claims 1-20, wherein the catalytic article is used in a flow-through or flow-through configuration.

22. The method of any one of claims 1-21, wherein the supported catalyst particles are located at a depth within the porous substrate that is from 5% to 95% of the total thickness of the porous substrate.

23. A catalytic article prepared by the method of any one of claims 1 to 22.

24. A method for a catalytic reaction comprising contacting a reactant stream with a catalytic article as described in claim 22, wherein the reaction is selected from the group consisting of selective catalytic reduction of NOx (SCR), nitrous oxide (N2O) reduction, volatile organic compound (VOC) oxidation, partial oxidation, oxidation, reduction, hydrogenation, dehydrogenation, isomerization, coupling reaction, intramolecular Heck reaction, conjugate addition, nucleophilic addition, α-substitution reaction, methane dry reforming, reverse water gas shift, methanation and ring opening reaction.

25. The catalytic article of any one of claims 1 to 24, wherein the catalyst area density of the catalytic article is 10 g / m 2 Up to 300g / m 2 .

26. The catalytic article of any one of claims 1-25, wherein the porous substrate is a porous felt comprising polytetrafluoroethylene (PTFE) and the porous fibrillated polymer membrane comprises expanded PTFE (ePTFE).

27. The catalytic article of any one of claims 1-24, wherein the porous substrate and the porous fibrillated polymeric membrane both comprise PTFE.

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