EP4669459A1

EP4669459A1 - METHOD FOR THE MANUFACTURE OF CATALYTIC ARTICLES

Info

Publication number: EP4669459A1
Application number: EP24711348.3A
Authority: EP
Inventors: Vladimiros NIKOLAKIS; Zhuonan Song; Stephen Stark
Original assignee: WL Gore and Associates Inc
Current assignee: WL Gore and Associates Inc
Priority date: 2023-02-21
Filing date: 2024-02-02
Publication date: 2025-12-31
Also published as: WO2024177797A1; CN120712142A

Abstract

Various aspects of the present disclosure are directed towards apparatuses, systems, and methods of preparing catalytic articles. The method for preparing a catalytic article may include loading a mixture including a dry catalyst precursor and a dry support material on a porous substrate, covering the porous substrate to form a covered mixture, and calcining the covered mixture to form the catalytic article having supported catalyst articles enmeshed within the porous substrate.

Description

PREPARATION METHOD OF CATALYTIC ARTICLES

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of Provisional Application No. 63/447148, filed February 21 , 2023, which is incorporated herein by reference in its entirety for all purposes.

FIELD

[0002] The present disclosure relates generally to catalytic articles, and methods of preparing catalytic articles. More specifically, the present disclosure relates to catalytic articles and methods of preparing catalytic on a porous substrate.

BACKGROUND

[0003] Conventional methods for producing a catalytic composite include the use of active catalyst powders, and combining the active catalysts with binders to form catalytic composite. Forming such catalytic composites may take several steps over a long duration of time, and may be costly. Thus, a need exists for forming a catalytic article with improved efficiency compared to the composites.

SUMMARY

[0004] The present disclosure generally relates to methods for preparing a catalytic article including loading supported catalyst particles on a porous substrate, and covering the porous substrate to form the catalytic article. In some embodiments, the method may further include laminating a porous fibrillated polymer membrane to the porous substrate to form the catalytic article having supported catalyst particles enmeshed within the porous substrate. Surprisingly, the catalytic article with catalyst powder enmeshed within the porous substrate showed a higher catalytic activity compared to the catalyst composite with binders.

[0005] According to a first embodiment (“Embodiment 1”), a method of making a catalytic article includes loading a mixture comprising a dry catalyst precursor and a dry support material on a porous substrate; covering the porous substrate to form a covered mixture; and calcining the covered mixture to form the catalytic article having supported catalyst articles enmeshed within the porous substrate. [0006] Embodiment 2 is the method of Embodiment 1 , wherein the porous substrate is covered with a porous fibrillated polymer membrane.

[0007] Embodiment 3 is the method of Embodiment 2, wherein the porous substrate is covered with a second porous substrate.

[0008] According to another embodiment (“Embodiment 4”), a method of making a catalytic article includes loading a plurality of supported catalyst particles on a porous substrate; and covering the porous substrate to form the catalytic article having the supported catalyst articles enmeshed within the porous substrate.

[0009] Embodiment 5 is the method of Embodiment 4, further including calcining the supported catalyst particles after covering the porous substrate.

[00010] Embodiment 6 is the method of any of Embodiments 1 to 5, wherein the calcining is conducted at a temperature of from 100°C to 500°C.

[00011] According to yet another embodiment (“Embodiment 7”), a method of making a catalytic article includes 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 the catalytic article having supported catalyst particles enmeshed within the porous substrate and the porous fibrillated polymer membrane.

[00012] 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.

[00013] Embodiment 9 is the method of Embodiment 8, wherein the laminating comprises heating conducted at a temperature of from 250°C to 400°C.

[00014] Embodiment 10 is the method of any of Embodiments 1 to 9, wherein the porous substrate is a polymeric support material comprising at least one of a woven fabric, a non-woven fabric, a membrane, an open-celled foam, a fibrous/particulate network, and combinations thereof.

[00015] Embodiment 11 is the method of any of Embodiments 1 to 9, wherein the porous substrate is an inorganic support material comprising sintered particulates, fiberglass felt, or basalt needlefelt.

[00016] Embodiment 12 is the method of any of Embodiments 1 to 11 , wherein the supported catalyst particles have a particle size distribution defined by a D90 value of at least 1 urn. [00017] Embodiment 13 is the method of any of Embodiments 1 to 12, wherein the supported catalyst particles comprise at least one metal or metal oxide catalyst dispersed on the porous substrate.

[00018] Embodiment 14 is the method of any of Embodiments 1 to 13, wherein the porous substrate includes supported catalyst particles in a range from 1 % to 30% by weight of the supported catalyst particles.

[00019] Embodiment 15 is the method of any of Embodiments 1 to 14, wherein the catalytic article has a porosity of from 25% to 90%.

[00020] Embodiment 16 is the method of any of Embodiments 1 to 15, wherein the porous substrate has a porosity of from 25% to 90%.

[00021] Embodiment 17 is the method of any of Embodiments 1 to 16, wherein the porous substrate comprises a porous felt comprising polytetrafluorethylene (PTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), polyparaxylylene (PPX), polyester (PE), polypropylene (PP), polyphenylene sulfide (PPS), P-84, nylon, acrylic, aramid or any combination or blend thereof.

[00022] Embodiment 18 is the method of any of Embodiments 1 to 17, wherein the porous fibrillated polymer membrane has a porosity of from 20% to 97%.

[00023] Embodiment 19 is the method of any of Embodiments 1 to 18, wherein the porous fibrillated polymer membrane comprises polytetrafluorethylene (PTFE), expanded PTFE, poly(ethylene-co-tetrafluoroethylene) (ETFE), polyethylene (PE), polyparaxylylene (PPX), or any combination or blend thereof.

[00024] Embodiment 20 is the method of any of Embodiments 1 to 19, wherein the catalytic article is in a form of a filter bag, a honeycomb, a monolith, or any other suitable geometrically structured forms.

[00025] Embodiment 21 is the method of any of Embodiments 1 to 20, wherein the catalytic article is used in a flow-through or flow-by configuration.

[00026] Embodiment 22 is the method of any of Embodiments 1 to 21 , wherein the supported catalyst particles are located at a depth of the porous substrate of from 5% to 95% of a total thickness of the porous substrate.

[00027] Embodiment 23 is a catalytic article prepared by the method of any of Embodiments 1 to 22.

[00028] Embodiment 24 is a method for catalyzing a reaction including contacting a reactant stream with the catalytic article of Embodiment 22, wherein the reaction is selected from the group consisting of selective catalytic reduction of NOx (SCR), nitrous oxide (N2O) reduction, volatile organic compounds (VOCs) oxidation, partial oxidation, oxidation, reduction, hydrogenation, dehydrogenation, isomerization, a coupling reaction, an intramolecular Heck reaction, conjugate addition, a nucleophilic addition, an a-substitution reaction, dry reforming of methane, reverse water gas shift, methanation, and a ring-opening reaction.

[00029] Embodiment 25 is the catalytic article of any of Embodiments 1 to 24, wherein the catalytic article has a catalyst area density of from 10 g/m² to 300 g/m².

[00030] Embodiment 26 is the catalytic article of any of Embodiments 1 to 25, wherein the porous substrate is a porous felt comprising polytetrafluorethylene (PTFE), and the porous fibrillated polymer membrane comprises expanded PTFE (ePTFE).

[00031] Embodiment 27 is the catalytic article of any of Embodiments 1 to 24, wherein the porous substrate and the porous fibrillated polymer membrane both comprise PTFE.

[00032] The foregoing Embodiments are just that, and should not be read to limit or otherwise narrow the scope of any of the inventive concepts otherwise provided by the instant disclosure. While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature rather than restrictive in nature.

BRIEF DESCRIPTION OF THE DRAWINGS

[00033] The accompanying drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments, and together with the description serve to explain the principles of the disclosure.

[00034] FIG. 1 is a flowchart illustrating a method for preparing a catalytic article, in accordance with an embodiment.

[00035] FIG. 2 is a flowchart illustrating a method for preparing a catalytic article, in accordance with an embodiment.

[00036] FIG. 3 is a flowchart illustrating a method for preparing a catalytic article, in accordance with an embodiment.

[00037] FIG. 4 is a schematic depiction of the sample preparation method 200 for a laminated catalytic article-1 , in accordance with an embodiment.

[00038] FIG. 5 depicts a cross-sectional view of a laminated catalytic article-1 , in accordance with an embodiment.

[00039] FIG. 6 depicts the NOx removal efficiency of laminated catalytic article prepared according to the present disclosure and catalytic composites.

[00040] FIG. 7 is a schematic depiction of the sample preparation method for laminated catalytic article-3, in accordance with an embodiment.

[00041] FIG. 8 is a schematic depiction of the sample preparation method for sandwiched catalytic article-1 , in accordance with an embodiment.

[00042] FIG. 9 is a cross-sectional image of sandwiched catalytic article-1 , in accordance with an embodiment.

[00043] FIG. 10 is a schematic depiction of the sample preparation method for sandwiched catalytic article-2, in accordance with an embodiment.

DETAILED DESCRIPTION

Definitions and Terminology

[00044] This disclosure is not meant to be read in a restrictive manner. For example, the terminology used in the application should be read broadly in the context of the meaning those in the field would attribute such terminology.

[00045] With respect to terminology of inexactitude, the terms “about” and “approximately” may be used, interchangeably, to refer to a measurement that includes the stated measurement and that also includes any measurements that are reasonably close to the stated measurement. Measurements that are reasonably close to the stated measurement deviate from the stated measurement by a reasonably small amount as understood and readily ascertained by individuals having ordinary skill in the relevant arts. Such deviations may be attributable to measurement error, differences in measurement and/or manufacturing equipment calibration, human error in reading and/or setting measurements, minor adjustments made to optimize performance and/or structural parameters in view of differences in measurements associated with other components, particular implementation scenarios, imprecise adjustment and/or manipulation of objects by a person or machine, and/or the like, for example. In the event it is determined that individuals having ordinary skill in the relevant arts would not readily ascertain values for such reasonably small differences, the terms “about” and “approximately” can be understood to mean plus or minus 10% of the stated value.

[00046] As used herein, the term “activated carbon” may include any carbon with a relatively high surface area such as from about 50 to about 3000 m²/g or from about 100 to about 2000 m²/g (e.g., from about 200 to about 1500 m²/g or about 300 to about 1000 m²/g). The activated carbon may be derived from any carbonaceous material, such as coal (e.g., charcoal), nutshells (e.g., coconut) and wood. Any form of activated carbon may be used, such as powdered, granulated, extruded or pelleted activated carbon.

Description of Various Embodiments

[00047] Persons skilled in the art will readily appreciate that various aspects of the present disclosure can be realized by any number of methods and apparatuses configured to perform the intended functions. It should also be noted that the accompanying drawing figures referred to herein are not necessarily drawn to scale, but may be exaggerated to illustrate various aspects of the present disclosure, and in that regard, the drawing figures should not be construed as limiting.

[00048] FIG. 1 is a flowchart illustrating a method 100 for preparing a catalytic article in accordance with an embodiment. One or more steps of method 100 may be optional and/or may be modified by one or more steps of other embodiments described herein. Additionally, one or more steps of other embodiments described herein may be added to the method.

[00049] At step 102, the method 100 of making a catalytic article may include loading a mixture including a dry catalyst precursor and a dry support material on a porous substrate. In some embodiments, the catalyst precursor is free from any aqueous liquid or any organic liquid, and the support material is free from any aqueous liquid or any organic liquid.

[00050] In some embodiments, the porous substrate is a polymeric support material selected from a woven fabric, a non-woven fabric, a membrane, an open- celled foam, a fibrous/particulate network, and combinations thereof. In certain embodiments, the porous substrate includes a porous felt comprising polytetrafluorethylene (PTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), polyparaxylylene (PPX), or any combination or blend thereof. In yet some embodiments, the porous substrate is an inorganic support material including sintered particulates, fiberglass felt, or basalt needlefelt. [00051] In some embodiments, the porous substrate has a porosity of from about 25% to about 90%, or from about 27.5% to about 88%, or from about 30% to about 86%, or from about 32.5% to about 84%, or from about 35% to about 82%, or from about 37.5% to about 80%, or from about 40% to about 78%, or from about 42.5% to about 76%, or from about 45% to about 74%, or from about 47.5% to about 72%, or from about 50% to about 70%, or may have a porosity encompassed within these ranges.

[00052] In some embodiments, the catalytic article has a porosity of from about 25% to about 90%, or from about 27.5% to about 88%, or from about 30% to about 86%, or from about 32.5% to about 84%, or from about 35% to about 82%, or from about 37.5% to about 80%, or from about 40% to about 78%, or from about 42.5% to about 76%, or from about 45% to about 74%, or from about 47.5% to about 72%, or from about 50% to about 70%, or may have a porosity encompassed within these ranges.

[00053] 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.

[00054] 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 transition metals, lanthanides, alkali or alkaline earth metals, or salts thereof. In some embodiments, the metal may be selected from Groups 3 to 14 of the Periodic Table of Elements (e.g., the 38 transition metals, or metals from Groups 13 to 14 such as B, Al, Ga, In, Tl, Nh, Si, Ge, Sn, or Pb). Examples of suitable metals include Na, K, Or, Mn, Au, Fe, Cu, Zn, Sn, Ta, Ti, Sb, Al, Co, Ni, Mo, Ru, Rh, Pd and/or Pt and/or a compound (e.g., a halide, hydroxide, carbonate) of one or more of these metals. In yet other embodiments, alkali metal (e.g., Na or K) salts may be used as additives for the activated carbon, such as halide, hydroxide, or carbonate salts of alkali metals salts. Hydroxide or carbonate salts of alkali metals salts are bases. Any other suitable bases can be used, including amides (e.g., sodium amide).

[00055] 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.

[00056] In some embodiments, the ligand may be a carbonyl, oxalate, ammonium, dimethylamino, bromide, chloride, cyclopentadienyl, diketonate or a ligand of Formula (I): Formula (I)

[00057] wherein R1 and R2 are independently alkyl, substituted alkyl, aryl, substituted aryl, acyl and substituted acyl.

[00058] 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 exemplary catalyst precursors listed in Table 1.

Table 1

[00059] In an embodiment, the catalyst precursor is selected from the group consisting of vanadyl acetylacetonate, vanadium (III) acetylacetonate, platinum (II) acetylacetonate, palladium(ll) acetylacetonate, bis(acetylacetonato)dioxomolybdenum (VI), and copper (II) acetylacetonate.

[00060] The support material is not particularly limiting so long as it does not affect the end use of the catalytic composite. In some embodiments, the support material may be porous. Examples of the support material may include, but are not limited to, metals, metal oxides (e.g., titanium dioxide, aluminum oxide, etc.), zeolites, carbons, clays, and combinations thereof.

[00061] In some embodiments, the dry support material may be selected from the group consisting of metal oxides, zeolites, carbons, clays, metal organic frameworks, and combinations thereof. In an exemplary embodiment, the dry support material may be selected from one or more of TiC , SiC>2, AI2O3, zeolite, aluminosilicate or activated carbon.

[00062] The support material may have a surface area from about 10 m²/g to about 3000 m²/g, from about 15 m²/g to about 2500 m²/g, from about 20 m²/g to about 2000 m²/g, from about 25 m²/g to about 1500 m²/g, from about 30 m²/g to about 1000 m²/g, from about 35 m²/g to about 800 m²/g, from about 40 m²/g to about 600 m²/g, from about 45 m²/g to about 500 m²/g, from about 50 m²/g to about 400 m²/g, from about 55 m²/g to about 350 m²/g, or may have a surface area encompassed within these ranges. In some embodiments, the support material may have a surface area from about 60 m²/g to about 340 m²/g, from about 65 m²/g to about 330 m²/g, from about 70 m²/g to about 320 m²/g, or from about 75 m²/g to about 310 m²/g. In an exemplary embodiment, the support material may have a surface area from about 80 m²/g to about 305 m²/g.

[00063] The support material may include particles having a mean diameter of from about 0.5 pm to about 1000 pm, from about 0.6 pm to about 900 pm, from about 0.7 pm to about 800 pm, from about 0.8 pm to about 700 pm, from about 0.9 pm to about 600 pm, from about 1 .0 pm to about 500 pm, from about 1.1 pm to about 400 pm, from about 1 .2 pm to about 300 pm, from about 1.3 pm to about 200 pm, from about 1.4 pm to about 100 pm, or may include particles having a mean diameter encompassed within these ranges. In some embodiments, the support material may include particles having a mean diameter of from about 1 .5 pm to about 90 pm, from about 1 .6 pm to about 80 pm, from about 1 .7 pm to about 70 pm, from about 1 .8 pm to about 60 pm, from about 1 .9 pm to about 55 pm, or from about 1 .95 pm to about 54 pm. In an exemplary embodiment, the support material may include particles having a mean diameter of from about 2.0 pm to about 52 pm.

[00064] In some embodiments, the mixture including the dry catalyst precursor and the dry support material may have been mixed using a vortex mixer, a shaking mixer, a double cone mixer, or any other suitable mixing device prior to being loaded on the porous substrate.

[00065] At step 104, the 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 membrane. In certain embodiments, the porous substrate is covered with a second porous substrate. In yet certain embodiments, the porous substrate may be folded such that the mixture is covered on both sides by the same piece of porous substrate.

[00066] At step 106, the method 100 may include calcining the covered mixture to form a catalytic article having supported catalyst articles enmeshed within the porous substrate.

[00067] According to some embodiments, the calcining step 106 may be performed using a fast-heating method (e.g., heating the covered mixture on a pre- heated hot plate). In some embodiments, the calcining step 106 may be performed using a slowing-heating method (e.g., slowly heating the covered mixture in a muffle oven starting at room temperature). In some embodiments, the mixture may be heated by being placed in a preheated oven. In yet some embodiments, the mixture may be heated in a furnace.

[00068] In certain embodiments, the covered mixture may be calcined at a temperature of from about 100°C to about 500°C, from about 105°C to about 480°C, from about 110°C to about 460°C, from about 115°C to about 440°C, from about 120°C to about 430°C, from about 125°C to about 420°C, from about 130°C to about 410°C, from about 135°C to about 400°C, from about 140°C to about 390°C, from about 145°C to about 380°C, or at a temperature encompassed within these ranges. In some embodiments, the dry mixture may be calcined at a temperature of from about 146°C to about 375°C, from about 147°C to about 370°C, or from about 148°C to about 365°C.

[00069] In certain embodiments, for example when the porous substrate is a polymeric support material, the dry mixture may be calcined at a temperature of from about 100°C to about 350°C. The polymeric support material (e.g., a porous felt) may include polytetrafluorethylene (PTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), polyparaxylylene (PPX), polyester (PE), polypropylene (PP), polyphenylene sulfide (PPS), P-84, nylon, acrylic, aramid or any combination or blend thereof.

[00070] In some instances, for example when the porous substrate is PE, the dry mixture may be calcined at a temperature of from about 100°C to about 135°C. In some instances, for example when the porous substrate is polypropylene (PP), the dry mixture may be calcined at a temperature of from about 100°C to about 120°C. In some instances, for example when the porous substrate is polyphenylene sulfide (PPS), the dry mixture may be calcined at a temperature of from about 100°C to about 190°C. In some instances, for example when the porous substrate is nylon, the dry mixture may be calcined at a temperature of from about 100°C to about 121°C. In some instances, for example when the porous substrate is acrylic, the dry mixture may be calcined at a temperature of from about 100°C to about 135°C. In some instances, for example when the porous substrate is aramid, the dry mixture may be calcined at a temperature of from about 100°C to about 220°C.

[00071] In yet certain embodiments, for example when the porous substrate is an inorganic support material, the dry mixture may be calcined at a temperature of from about 100°C to about 500°C.

[00072] In some embodiments, the covered mixture may be calcined at a rate of from about 1 °C/min to about 50°C/min, from about 1 25°C/min to about 45°C/min, from about 1.5°C/min to about 40°C/min, from about 1.75°C/min to about 35°C/min, from about 2°C/min to about 30°C/min, from about 2.25°C/min to about 25°C/min, from about 2.5°C/min to about 20°C/min, from about 2.75°C/min to about 15°C/min, from about 3°C/min to about 10°C/min, or at a rate encompassed within these ranges. In some embodiments, the dry mixture may be calcined at a rate of from about 3.2°C/min to about 9°C/min, from about 3.4°C/min to about 8°C/min, from about 3.6°C/min to about 7°C/min, or from about 3.8°C/min to about 6°C/min. In an exemplary embodiment, the dry mixture may be calcined at a rate of from about 4°C/min to about 5°C/min.

[00073] In some embodiments, the covered mixture is calcined in an atmosphere containing from about 1 to about 100 vol.% oxygen, from about 2 to about 20 vol.% oxygen, from about 3 to about 15 vol.% oxygen, from about 3.5 to about 10 vol.% oxygen, from about 4 to about 9 vol.% oxygen, from about 4.5 to about 8 vol.% oxygen, from about 5 to about 7 vol.% oxygen, from about 5.5 to about 6.5 vol.% oxygen, or containing a vol.% oxygen encompassed within these ranges. In an exemplary embodiment, the dry mixture is calcined in an atmosphere containing about 6 vol.% oxygen.

[00074] The catalytic article formed in step 106 may be in a form of a filter bag, a honeycomb, a monolith, or any other suitable geometrically structured forms. In certain embodiments, the catalytic article is used in a flow-through configuration, where gas or liquid is flowing transverse to (e.g., perpendicular to) a cross section of the catalytic article, such that the gas or liquid passes through the catalyst particle layer in the catalytic article. In yet certain embodiments, the catalytic article is used in a flow-by configuration, where gas or liquid is flowing parallel to the cross-section of the catalytic article, such that the gas or liquid is flowing parallel and diffuse to the catalyst particle in the catalytic layer, and does not pass through the cross section of the catalytic article.

[00075] In some embodiments, the catalytic article formed has a catalyst area density of from about 10 g/m² to about 300 g/m², or from about 15 g/m² to about 280 g/m², or from about 20 g/m² to about 260 g/m², or from about 25 g/m² to about 240 g/m², or from about 30 g/m² to about 220 g/m², or from about 35 g/m² to about 200 g/m², or from about 40 g/m² to about 200 g/m², or from about 45 g/m² to about 180 g/m², or from about 50 g/m² to about 160 g/m², or from about 55 g/m² to about 140 g/m², or from about 60 g/m² to about 120 g/m².

[00076] At step 108, the method 100 may include contacting a reactant stream with the catalytic article. In some embodiments, the reaction may be selected from a group consisting of DeNOx, selective catalytic reduction of NOx (SCR), nitrous oxide (N2O) reduction, volatile organic compounds (VOCs) oxidation, partial oxidation, oxidation, reduction, hydrogenation, dehydrogenation, isomerization, a coupling reaction, an intramolecular Heck reaction, conjugate addition, a nucleophilic addition, an a-substitution reaction, dry reforming of methane, reverse water gas shift, methanation, and a ring-opening reaction.

[00077] In some embodiments, the catalytic article has an NOx removal efficiency of from about 1 % to about 99%, from about 5% to about 90%, from about 10% to about 80%, from about 15% to about 70%, from about 20% to about 60%, or has an NOx removal encompassed within these ranges.

[00078] In some embodiments, the catalytic article has an NH3 oxidation efficiency of from about 20% to about 99%, from about 25% to about 90%, from about 30% to about 80%, from about 35% to about 75%, from about 40% to about 70%, from about 40% to about 65%, or has an NH3 oxidation efficiency encompassed within these ranges.

[00079] FIG. 2 is a flowchart illustrating a method 200 for preparing a catalytic article in accordance with an embodiment. One or more steps of method 200 are optional and/or can be modified by one or more steps of other embodiments described herein. Additionally, one or more steps of other embodiments described herein may be added to the method.

[00080] In some embodiments, the method 200 may include loading a plurality of supported catalyst particles on a porous substrate at step 202, and covering the porous substrate to form a catalytic article at step 204. In certain embodiments, the porous substrate is covered with a porous fibril lated polymer membrane. In certain embodiments, the porous substrate is covered with a second porous substrate. In yet certain embodiments, the porous substrate may be folded such that the mixture is covered on both sides by the same piece of porous substrate.

[00081] The catalytic article may have the supported catalyst articles enmeshed within the porous substrate. In certain embodiments, at step 206, the method 200 may optionally include calcining the supported catalyst particles after covering the porous substrate in step 204.

[00082] FIG. 3 is a flowchart illustrating a method 300 for preparing a catalytic article in accordance with an embodiment. One or more steps of method 300 are optional and/or can be modified by one or more steps of other embodiments described herein. Additionally, one or more steps of other embodiments described herein may be added to the method.

[00083] At step 302, the method 300 may include loading 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 urn.

[00084] The porous substrate may include supported catalyst particles in a range from about 1 % to about 30% by weight of the supported catalyst particles, or from about 1 .5% to about 25%, or from about 2% to about 20%, or from about 2.5% to about 15%, or from about 3% to about 10% by weight of the supported catalyst particles, or may include supported catalyst particles encompassed within these ranges.

[00085] In certain embodiments, the supported catalyst particles include at least one metal or metal oxide catalyst dispersed on the porous substrate. The supported catalyst particles used at step 302 may include those described in, for example, U.S. Patent App. 20220212181 A1 to Gore.

[00086] At step 304, the method 300 may include covering the supported catalyst particles with a porous fibrillated polymer membrane. The porous fibril lated polymer membrane may have a porosity of from about 20% to about 97%, or from about 20% to about 95%, or from about 20% to about 90%, or from about 21 % to about 85%, or from about 22% to about 80%, or from about 23% to about 75%, or from about 24% to about 70%, or from about 25% to about 65%, or from about 26% to about 60%, or from about 27% to about 55%, or from about 28% to about 50%, or from about 29% to about 45%, or from about 30% to about 40%, or may have a porosity encompassed within these ranges.

[00087] In certain embodiments, the supported catalyst particles are located at a depth of the porous substrate of from about 5% to about 95% of a total thickness of the porous substrate, or from about 10% to about 90%, or from about 15% to about 85%, or from about 20% to about 80%, or from about 25% to about 75%, or from about 30% to about 70%, or from about 35% to about 65%, or from about 40% to about 60%, or from about 45% to about 55% of a total thickness of the porous substrate, or may be located at a depth of the substrate encompassed within these ranges.

[00088] In some embodiments, the porous fibrillated polymer membrane includes polytetrafluorethylene (PTFE), expanded PTFE, poly(ethylene-co- tetrafluoroethylene) (ETFE), ultra-high molecular weight polyethylene (UHMWPE), polyparaxylylene (PPX), polylactic acid, or any combination or blend thereof. In an exemplary embodiment, the porous substrate is a porous felt including polytetrafluorethylene (PTFE), and the porous fibrillated polymer membrane includes expanded PTFE (ePTFE).

[00089] At step 306, the method 300 may include laminating the porous fibrillated polymer membrane to the porous substrate to form a catalytic article having supported catalyst particles enmeshed within 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 certain instances, laminating a second porous substrate to a porous substrate may further include use of an adhesive.

[00090] In some embodiments, the laminating includes heating and pressing the porous fibrillated polymer membrane, the plurality of supported catalyst particles, and the porous substrate. In certain embodiments, where the porous substrate is a polymeric support material selected from a woven fabric, a non-woven fabric, a membrane, an open-celled foam, a fibrous/particulate network, and combinations thereof, the heating for lamination may be conducted at a temperature of from about 250°C to 400°C, or from about 260°C to 390°C, or from about 270°C to 380°C, or from about 280°C to 370°C, or from about 290°C to 360°C, or from about 300°C to about 350°C, or may be conducted at a temperature encompassed within these ranges.

[00091] In yet certain embodiments, where the porous substrate is an inorganic support material including sintered particulates, fiberglass felt, or basalt needlefelt , the heating for lamination may be conducted at a temperature of from about 200°C to about 450°C, or from about 210°C to about 440°C, or from about 220°C to about 430°C, or from about 230°C to about 420°C, or from about 240°C to about 410°C, or from about 250°C to about 400°C, or from about 260°C to about 390°C, or from about 270°C to about 380°C, or from about 280°C to about 370°C, or from about 290°C to about 360°C, or may be conducted at a temperature encompassed within these ranges.

[00092] In an alternative embodiment (not shown in FIG. 3), a method for preparing a catalytic article 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 article having supported catalyst particles enmeshed within two pieces of porous substrates. In some embodiments, the laminating of a second porous substrate to a first porous substrate may include heating and pressing the two porous substrates with the plurality of supported catalyst particles in the middle. In certain embodiments, the laminating may be done with addition of adhesives in between the two porous substrates. In an exemplary embodiment, the first and second porous substrate may include a PTFE felt.

TEST METHODS

[00093] It should be understood that although certain methods and equipment are described below, other methods or equipment determined suitable by one of ordinary skill in the art may be alternatively utilized.

Particle Size Analysis

[00094] Particle size of vanadium pentoxide on titanium dioxide catalyst was measured by Horiba Particle Analyzer. The mean diameter (“MV”) of vanadium pentoxide on titanium dioxide catalyst is 1.24 urn, and D90 is 3.41 urn. D90 describes the diameter where ninety percent of the distribution has a smaller particle size and ten percent of the distribution has a larger particle size. Particle size distribution data is shown in Tables 2.

Table 2. Particle size distribution of vanadium pentoxide on titanium dioxide catalyst.

EXAMPLES

Example 1 - Laminated catalytic article-1 for NOx removal (28 gram/m² V2O5/TiO2 catalyst laminated between PTFE felt and ePTFE membrane)

[00095] Sample preparation: FIG. 4 is a schematic depiction of the sample preparation method 400 for a catalytic article 408 (i.e. laminated catalytic article-1). As shown, at step 402, 0.2 gram of vanadium pentoxide on titanium dioxide particles obtained from CRI catalyst Company was milled and loaded on the surface of a porous PTFE felt by a polypropylene spatula. The mean particle size for the vanadium pentoxide on titanium dioxide was approximately 1.24 pm. The area density of the PTFE felt is about 860 gram/m². The catalyst particles (vanadium pentoxide on titanium dioxide) were rubbed uniformly by the spatula on the PTFE felt to cover an area of 71 cm².

[00096] At step 404 of the method 400, a porous expanded PTFE membrane having an air permeability of 35 cfm/ft² at 0.5 inches water gauge was used to cover the catalyst particle and PTFE felt. At step 406, the resulting swatch was placed in an aluminum foil envelope, then placed in a heated hydraulic press. The top plate was heated to 635 °F and bottom remained at ambient temperature. The plates were closed and pressurized to 5000 pounds. Dwell time at this condition was 3 seconds and the plates were then opened. A catalytic article 408 is formed as a result.

[00097] The resulting catalytic article 408 (i.e. laminated catalytic article-1 ) has a catalyst area density of 28.2 gr/m², the total area density of the laminated catalytic article-1 is 888 gram/m². The air permeability of laminated catalytic article-1 is 0.89 cfm/ft² at 0.5 inches water gauge.

[00098] The total porosity within the laminated catalytic article is the void volume of the sample divided by the total volume of the sample, which was calculated with the below formula:

%Porosity = (1 -bulk density/skeletal density)*100%

[00099] Bulk density was calculated with the below formula:

Bulk density = weight of sample/volume of the sample, gram/cm³

[000100] Skeletal density was calculated with the below formula:

Skeletal density (gram/cm³) = 1 /(catalyst weight ratio/catalyst density + PTFE felt weight ratio/PTFE felt density), wherein: catalyst density = 4.0 gram/cm³,

PTFE felt density = 2.35 gram/cm³

[000101] As calculated, the bulk density of laminated catalytic article-1 was 0.87 gram/cm³, skeletal density was 2.38 gram/cm³. Calculated total porosity was 63.4%.

[000102] 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 gram/cm3, skeletal density was 2.35 gram/cm³. The calculated total porosity of the porous PTFE felt was 74.0%. FIG. 5 depicts a cross-sectional view of a laminated catalytic article 500 (e.g., the catalytic article 408 formed in Example 1 ). As shown, the catalyst particles 502 are enmeshed within the porous substrate 504 with a membrane layer 506 laminated on top. The total thickness of the laminated catalytic article 500 is measured to be 890 urn. The penetration depth of the catalyst particle is 322 urn. Example 2 - Laminated catalytic article-2 for NOx removal (70 gram/m² V2O5/TiO2 catalyst laminated between PTFE felt and ePTFE membrane)

[000103] Sample preparation: 0.45 gram of vanadium pentoxide on titanium dioxide particles (CRI catalyst Company, a division of Royal Dutch Shell, The Hague, Netherlands) was loaded on the surface of a porous PTFE felt by polypropylene spatula. The area density of the PTFE felt is 860 gr/m². The catalyst particles (vanadium pentoxide on titanium dioxide) were rubbed uniformly by the spatula on the PTFE felt to cover an area of 64 cm².

[000104] A porous expanded PTFE membrane having an air permeability of 35 cfm/ft² at 0.5 inches water gauge was used to cover the catalyst particle and PTFE felt. The resulting swatch was placed in an aluminum foil envelope, then placed in a heated hydraulic press. The top plate was heated to 635 °F and bottom remained at ambient temperature. The plates were closed and pressurized to 5000 pounds. Dwell time at this condition was 3 seconds and the plates were then opened. The resulting laminated catalytic article-2 has a catalyst area density of 70.3 gram/m², the total area density of the laminated catalytic article-1 is 930 gram/m². The air permeability of laminated catalytic article-2 is 0.33 cfm/ft² at 0.5 inches water gauge. The bulk density of laminated catalytic article-2 was 1 .07 gram/ cm³, skeletal density was 2.42 gram/ cm³. The calculated total porosity of the laminated catalytic article-2 was 55.8%.

Example 3 - NOx removal rate of catalytic composites

[000105] Composite samples preparation: Two catalytic composites including vanadium pentoxide on titanium dioxide particles (CRI Catalyst Company, a division of Royal Dutch Shell, The Hague, Netherlands) were prepared using the general dry blending methodology taught in U.S. Patent No. 7,791 ,861 B2 to Zhong et al. to form composite tapes that were then uniaxially expanded according to the teachings of U.S. Patent No. 3,953,566 to Gore. The mean particle size of the vanadium pentoxide on titanium dioxide was approximately 1.24 pm. The catalyst area density for the two catalytic composite was 46.7 and 101 .8 gram/m². The catalytic composite sample preparation is also described in U.S. Patent App. No. US 20220212181 A1 to Gore.

[000106] NOx reaction efficiency: The laminated catalytic articles- 1 and laminated catalytic articles-2 (i.e. , samples prepared according to Examples 1 and 2 herein) and catalytic composites (i.e. , composite samples prepared according to Example 3) were tested for catalytic NOx removal efficiency from a simulated flue gas.

[000107] A square of 4.5 inch x 4.5 inch of each catalytic sample was placed in a sample holder located within a reaction chamber. The samples were exposed to an N2 balanced simulated flue gas at 200 °C. The simulated flue gas contained 360 ppm NO, 340 ppm NH3, 6 vol% O2 with a total flowrate of 4.2 L/min. In order to determine NOx removal efficiency, the upstream and downstream concentrations (i.e., relative to the catalytic membrane) of both NO and NH3 were monitored with a MKS MULTI-GAS™ 2030D FTIR analyzer (MKS Instruments, Andover, MA).

[000108] NOx removal efficiency (i.e., “DeNOx efficiency (%)”) was calculated based on the following equation:

NOx in - NOx out DeNOx efficiency (%) = - — — - x 100%

^{J v J} NOx in where NOx = total concentration of NO and NO2 in the stream

NOx in = upstream concentration of NOx

NOx out = downstream concentration of NOx

[000109] FIG. 6 depicts the NOx removal efficiency of laminated catalytic article and catalytic composites. As shown, a similar NOx removal efficiency performance was obtained by utilizing less amount of catalyst for the laminated catalytic articles compared to the NOx removal efficiency performance of the catalytic composites. At 45% NOx removal efficiency, the laminated catalytic article used approximately 30% less amount of the catalyst compared to the catalytic composites.

Example 4 - Laminated catalytic article-3 for NH3 oxidation (30 gram/m² Pd/ALOs catalyst laminated between PTFE felt and ePTFE membrane)

[000110] Sample preparation: FIG. 7 is a schematic depiction of the sample preparation method for laminated catalytic article-3. As shown, 3.6 wt.% palladium/ALOs catalyst particle was prepared by adding 0.055 gram of Palladium ( 11) acetylacetonate (STREM Chemical Inc.) into 0.36 gram of AI2O3 (Sigma Aldrich- 199966, 155 m²/g +/-10% surface area, data provided by Sigma Aldrich) in a scintillation vial. The two dry powders were mixed by shaking on a Vortex Mixer (Cole-Parmer) for a few minutes. The powder mixture was then transferred to an aluminum weight dish and placed on a hotplate with a setpoint temperature at 250 °C for 15 minutes.

[000111 ] 0.164 gram of as prepared Pd/Al2O3 catalyst particles was loaded on the surface of a PTFE felt by polypropylene spatula. The catalyst particles (Pd/A^Os) were rubbed uniformly by the spatula on the PTFE felt to cover an area of 54 cm². A porous expanded PTFE membrane having an air permeability of 35 cfm/ft² at 0.5 inches water gauge was used to cover the catalyst particle and PTFE felt. The resulting swatch was placed in an aluminum foil envelope, then placed in a heated hydraulic press. The top plate was heated to 635 °F and bottom remained at ambient temperature. The plates were closed and pressurized to 5000 pounds. Dwell time at this condition was 3 seconds and the plates were then opened. The resulting laminated catalytic article-3 has a catalyst area density of 30.4 gram/m².

[000112] NH₃ oxidation reaction: The following procedure was used to test performance of the laminated catalytic article-3 prepared according to Example 4 for NH₃ oxidation. A laminated catalytic article-3 with 26 mm diameter was placed in a sample holder. The catalytic tape was first treated with 115 ppm NH3 in N2 with a total flowrate of 0.45 L/min for 2 hours at 200°C. After 2 hours treatment, 6 vol% O2 was introduced to the gas mixture while maintaining the NH₃ concentration and total flowrate constant. The NH₃ oxidation reaction was measured with 115 ppm NH3, 6 vol% O2 in N2 with a total flowrate of 0.45 L/min at 200°C. In order to determine NH₃ oxidation efficiency, the upstream (i.e. , the concentration of NH₃ entering into the chamber before exposure to the catalytic tape) and downstream concentration of NH₃ were monitored with a MKS MULTI-GASTM 2030D FTIR analyzer (MKS Instruments, Andover, MA).

[000113] NH₃ oxidation efficiency (i.e., “NH₃ oxidation efficiency (%)”) was calculated based on the following equation:

NH₃ in - NH₃ out NH₃ oxidation efficiency (%) = - , - x 100%

NH₃ LYl where NH₃ = concentration of NH₃ in the respective stream

NH₃ in = upstream concentration of NH₃

NH₃ out = downstream concentration of NH₃

[000114] The measured NH₃ oxidation efficiency for laminated catalytic article-3 (30 gram/m² Pd/ALOs catalyst laminated between PTFE felt and ePTFE membrane) is 69.2% at 200°C.

Example 5 - Sandwiched catalytic article-1 for NOx removal (97 gram/m² 2O5/TiO2 catalyst sandwiched between PTFE felt and PTFE felt)

[000115] Sample preparation: FIG. 8 is a schematic depiction of the sample preparation method for sandwiched catalytic article-1. As shown, 0.58 gram of vanadyl acetylacetonate (Sigma-Aldrich) was added into 0.8 gram of TiO2 (Hombikat 8602, with a surface area of about 340 m²/g) in a scintillation vial. The powder mixture was shaken on a Vortex Mixer (Cole-Parmer) for 15 minutes. 0.8 gram of powder mixture was loaded on the surface of a porous PTFE felt by polypropylene spatula. The area density of the PTFE felt is 860 gram/m². The powder mixture was rubbed uniformly by the spatula on the PTFE felt to cover an area of 82 cm².

[000116] A second layer of PTFE felt was used to cover the powder mixture and PTFE felt. The resulting swatch was transferred to a furnace, thermally 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 in white color. After the calcination process, the powder mixture was converted to V2Os/TiO2 catalyst as the color of the powder mixture changed from white to yellow and enmeshed within the porous PTFE felt substrate.

[000117] NOx removal efficiency: NOx removal efficiency was measured as described above in Example 3. The measured NOx removal efficiency of sandwiched catalytic article-1 (97 gram/m² 2Os/TiO2 catalyst sandwiched between PTFE felt and PTFE felt) was 74.5% at 200°C.

[000118] FIG. 9 is a cross-sectional image of sandwiched catalytic article-1 . As shown, the total thickness of the sandwiched catalytic article-1 (bottom part) is 1460.3 urn. The penetration depth of the enmeshed catalyst powder is 1284.8 urn. The resulting sandwiched catalytic article-1 has a catalyst area density of 97.5 gram/m², the total area density of the sandwiched catalytic article-1 is 1817.5 gram/m².

Example 6 - Sandwiched catalytic article-2 for NOx removal (80 gram/m² 2O5/TiO2 catalyst sandwiched between PTFE felt and PTFE felt)

[000119] Sample preparation: FIG. 10 is a schematic depiction of the sample preparation method for sandwiched catalytic article-2. As shown, 0.7 gram of vanadium pentoxide on titanium dioxide particles (CRI catalyst Company, a division of Royal Dutch Shell, The Hague, Netherlands) was loaded on the surface of a PTFE felt by polypropylene spatula. The catalyst powder (vanadium pentoxide on titanium dioxide) was rubbed uniformly by the spatula on the PTFE felt to cover an area of 87 cm². A second layer of PTFE felt was used to cover the catalyst and PTFE felt. The resulting swatch was transferred to a furnace, thermally treated in air at 230 °C for 2 hours with an initial temperature ramp rate of 5 °C/min. The resulting sandwiched catalytic article-2 has a catalyst area density of 80.2 gram/m², the total area density of the sandwiched catalytic article-2 is 1800 gram/m².

[000120] NOx removal efficiency: NOx removal efficiency was measured as described above in Example 3. The measured NOx removal efficiency of sandwiched catalytic article-2 (80 gram/m² V2Os/TiO2 catalyst sandwiched between PTFE felt and PTFE felt) was 58% at 200 °C.

[000121] The invention of this application has been described above both generically and with regard to specific embodiments. It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments without departing from the scope of the disclosure. Thus, it is intended that the embodiments cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims

WHAT IS CLAIMED IS:

1. A method of making a catalytic article comprising: loading a mixture comprising a dry catalyst precursor and a dry support material on a porous substrate; covering the porous substrate to form a covered mixture; and calcining the covered mixture to form the catalytic article having supported catalyst articles enmeshed within the porous substrate.

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

3. The method of claim 1 , wherein the porous substrate is covered with a second porous substrate.

4. A method of making a catalytic article comprising: loading a plurality of supported catalyst particles on a porous substrate; and covering the porous substrate to form the catalytic article having the supported catalyst articles enmeshed within the porous substrate.

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

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

7. A method of making a catalytic article comprising: 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 the catalytic article having supported catalyst particles enmeshed 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 8, wherein the laminating comprises heating conducted at a temperature of from 250°C to 400°C.

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

11 . The method of any of claims 1 -9, wherein the porous substrate is an inorganic support material comprising sintered particulates, fiberglass felt, or basalt needlefelt.

12. The method of any of claims 1-11 , wherein the supported catalyst particles have a particle size distribution defined by a D90 value of at least 1 urn.

13. The method of any 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 of claims 1-13, wherein the porous substrate includes supported catalyst particles in a range from 1 % to 30% by weight of the supported catalyst particles.

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

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

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

18. The method of any of claims 1 -17, wherein the porous f ibri I lated polymer membrane has a porosity of from 20% to 97%.

19. The method of any of claims 1 -18, wherein the porous f ibri I lated polymer membrane comprises polytetrafluorethylene (PTFE), expanded PTFE, poly(ethylene-co- tetrafluoroethylene) (ETFE), polyethylene (PE), polyparaxylylene (PPX), or any combination or blend thereof.

20. The method of any of claims 1-19, wherein the catalytic article is in a form of a filter bag, a honeycomb, a monolith, or any other suitable geometrically structured forms.

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

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

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

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

25. The catalytic article of any of claims 1 -24, wherein the catalytic article has a catalyst area density of from 10 g/m² to 300 g/m²

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

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