# US 11,439,995 B2 · Three-dimensionally structured porous catalyst monolith of stacked catalyst fibers

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- Number: US 11,439,995 B2
- Document ID: US11439995B2
- Status: Granted
- Kind: B2
- Application number: 16/464,998
- Filed: 2017-11-29
- Published: 2020-01-16
- Granted: 2022-09-13
- Earliest claimed: 2016-11-30
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Esther Groeneveld; Peter Berben; Bernard Reesink; Bart Michielsen; Jasper Lefevere
- Web page: https://patentgrep.com/patent/US11439995B2

## CPC

- B01J 37/038: {to form slurries or suspensions, e.g. a washcoat}
- B01J 21/08: Silica
- B01J 23/755: Nickel
- B01J 35/393: {Metal or metal oxide crystallite size}
- B01J 35/45: Nanoparticles
- B01J 35/56: Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths
- B01J 35/58: Fabrics or filaments
- B01J 35/60: characterised by their surface properties or porosity
- B01J 35/77: Compounds characterised by their crystallite size
- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- B01J 37/03: Precipitation; Co-precipitation
- B01J 37/18: with gases containing free hydrogen
- B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C 64/165: using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
- B33Y 10/00: Processes of additive manufacturing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- B33Y 80/00: Products made by additive manufacturing
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING

## Abstract

A three-dimensionally structured porous catalyst monolith of stacked catalyst fibers with a fiber diameter of less than 1 mm made from one or more continuous fibers or stacked individual fibers, wherein the stacked catalyst fibers are arranged in a regular, recurring stacking pattern of fiber layers to form the three-dimensionally structured monolith, and wherein in each of the stacked fiber layers at least 50 wt % of the fibers are arranged parallel to each other and spatially separated from each other, or in a cobweb pattern, and wherein the side crushing strength of the monolith is at least 60 N.

## Claims

### Claim 1

A three-dimensionally structured porous catalyst monolith of stacked catalyst fibers with a fiber diameter of less than 1 mm made from one or more continuous fibers or stacked individual fibers, wherein the stacked catalyst fibers are arranged in a regular, recurring stacking pattern of fiber layers to form the three-dimensionally structured monolith, and wherein in each of the stacked fiber layers at least 50 wt % of the fibers are arranged parallel to each other and spatially separated from each other, or in a cobweb pattern, and wherein the side crushing strength of the monolith is at least 60 N, in which the monolith is formed of catalytically active metal or metal alloy supported on inorganic oxide catalyst support particles, starting from powders of prefabricated catalysts, obtained by a method comprising the following steps:
a) preparing a suspension paste in a liquid diluent of powders of prefabricated supported catalysts, in which metal, metal alloy and/or metal oxide particles of the catalytically active metal or metal alloy are supported on inorganic oxide catalyst support particles, and which suspension can furthermore comprise a binder material, all particles in the suspension having a number average particle size in the range of from 0.5 to 500 μm, measured by sieving the particles or by photographic techniques,
b) extruding the paste of step a) through one or more nozzles having a maximum diameter of less than 1 mm to form fibers, and depositing the extruded fibers to form a three-dimensional porous catalyst monolith precursor,
c) drying the porous catalyst monolith precursor to remove the liquid diluent, optionally reducing the metal oxide(s) in the porous catalyst monolith precursor to form the catalytically active metal or metal alloy,
wherein no temperature treatment of the porous catalyst monolith precursor or porous catalyst monolith at temperatures above 1000° C. is performed.

### Claim 2 (depends on 1)

The catalyst monolith of claim 1, wherein the side crushing strength of the catalyst monolith is at least twice the side crushing strength of an individual fiber of which the catalyst monolith is composed.

### Claim 3 (depends on 1)

The catalyst monolith of claim 1, wherein the side crushing strength is at least 100 N.

### Claim 4 (depends on 1)

The catalyst monolith of claim 1, wherein the fiber diameter is in the range of from 0.2 to less than 1.0 mm.

### Claim 5 (depends on 1)

The catalyst monolith of claim 1, wherein the catalyst monolith is in the form of a cylinder with circular or ellipsoidal cross section, a cuboid, a sphere, an ellipsoid, a tablet or a polygon.

### Claim 6 (depends on 1)

The catalyst monolith of claim 1, wherein at least 50 wt % of the fibers are arranged as linear strands parallel to each other and spatially separated from each other, or wherein multiple cobweb patterns are stacked, wherein the direction of the strands in each layer is different from the direction in neighboring layers, so that a porous structure with contact points of strands of neighboring layers results.

### Claim 7 (depends on 1)

The catalyst monolith of claim 1, wherein the catalyst monolith has at least 10 stacked fiber layers.

### Claim 8 (depends on 1)

The catalyst monolith of claim 1, wherein the catalyst monolith has a volume in the range of from 0.027 cm3 to 125 m3.

### Claim 9 (depends on 1)

The catalyst monolith of claim 1, wherein the catalyst monolith has a porosity of at least 20% determined by Hg-PV or HE-density.

### Claim 10 (depends on 1)

The catalyst monolith of claim 1, wherein the catalytically active metal is selected from the group consisting of Na, K, Mg, Ca, Ba, Al, Al2O3, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Sn, Sb, La, Hf, W, Re, Ir, Pt, Au, Pb, and Ce and mixtures or alloys thereof.

### Claim 11 (depends on 1)

The catalyst monolith of claim 1, wherein the catalytically active metal or metal alloy is supported on an inorganic oxide catalyst support selected from the group consisting of silicon dioxide, aluminium oxide, titanium dioxide, zirconium dioxide, magnesium oxide, calcium oxide, mixed metal oxides, hydrotalcites, spinels, perovskites, metal phosphates, silicates, zeolites, steatite, cordierite, carbides, nitrides, and mixtures or blends thereof.

### Claim 12 (depends on 1)

The catalyst monolith of claim 1, wherein the side crushing strength is at least 100 N 300 N.

### Claim 13 (depends on 1)

The catalyst monolith of claim 1, wherein at least 70 wt % of the fibers are arranged as linear strands parallel to each other and spatially separated from each other, or wherein multiple cobweb patterns are stacked, wherein the direction of the strands in each layer is different from the direction in neighboring layers, so that a porous structure with contact points of strands of neighboring layers results.

### Claim 14 (depends on 1)

The catalyst monolith of claim 1, wherein the catalyst monolith has at least 20 stacked fiber layers.

### Claim 15 (depends on 1)

The catalyst monolith of claim 1, wherein the catalyst monolith has a porosity of at least 30% determined by Hg-PV or HE-density.

### Claim 16 (depends on 1)

A method for producing the three-dimensional porous catalyst monolith of stacked catalyst fibers of claim 1, comprising the following steps:
a) preparing a suspension paste in a liquid diluent of powders of prefabricated supported catalysts, in which metal, metal alloy and/or metal oxide particles of the catalytically active metal or metal alloy are supported on inorganic oxide catalyst support particles, and which suspension can furthermore comprise a binder material, all particles in the suspension having a number average particle size in the range of from 0.5 to 500 μm, measured by sieving the particles or by photographic techniques,
b) extruding the paste of step a) through one or more nozzles having a maximum diameter or less than 1 mm to form fibers, and depositing the extruded fibers to form a three-dimensional porous catalyst monolith precursor,
c) drying the porous catalyst monolith precursor to remove the liquid diluent, optionally reducing the metal oxide(s) in the porous catalyst monolith precursor to form the catalytically active metal or metal alloy,
wherein no temperature treatment of the porous catalyst monolith precursor or porous catalyst monolith at temperatures above 1000° C. is performed.

### Claim 17 (depends on 16)

The method according to claim 16, wherein nickel oxide nanoparticles having a number average particle size of less than 100 nm, measured by photographic techniques, are supported on the inorganic oxide catalyst support particles.

### Claim 18 (depends on 16)

The method according to one of claim 16, wherein a binder material is employed, selected from the group consisting of inorganic binders.

### Claim 19 (depends on 16)

The method according to claim 16, wherein nickel oxide nanoparticles having a number average particle size of less than 100 nm, measured by photographic techniques, are supported on the inorganic oxide catalyst support particles in an amount of from 1 to 70 wt %, based on the inorganic oxide catalyst support particles, wherein the inorganic oxide catalyst support is silica, having a number average particle size in the range of from 0.05 to 200 μm, measured by sieving the particles or by photographic techniques.

### Claim 20 (depends on 16)

The method according to one of claim 16, wherein a binder material is employed, selected from the group consisting of clays, alumina, silica and mixtures thereof, and wherein no organic binder material is present in the suspension.