# US 11,439,996 B2 · Method for producing catalyst monoliths

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- Number: US 11,439,996 B2
- Document ID: US11439996B2
- Status: Granted
- Kind: B2
- Application number: 16/465,019
- Filed: 2017-11-29
- Published: 2019-12-19
- Granted: 2022-09-13
- Earliest claimed: 2016-11-30
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Esther Groeneveld; Peter Berben; Bernard Reesink
- Web page: https://patentgrep.com/patent/US11439996B2

## 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 method for producing a three-dimensional porous catalyst monolith of stacked catalyst fibers, comprising the following steps: a) Preparing a suspension paste in a liquid diluent of metal, metal alloy and/or metal oxide particles of catalytically active metal or metal alloy in which the metals, metal alloy and metal oxide particles can be supported on or mixed with inorganic oxide catalyst support particles, and which suspension can furthermore comprise a binder material, all particles in the suspension having an average particle size in the range of from 0.5 to 500 μm, b) extruding the paste of step a) through one or more nozzles preferably having a maximum diameter of less than 5 mm, more preferably 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, d) if necessary, 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.

## Claims

### Claim 1

A method for producing a three-dimensional porous catalyst monolith of stacked catalyst fibers, 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, 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 optionally further comprises a binder material, all particles of the powders of prefabricated supported catalysts 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 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,
d) 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 method of claim 1, wherein in step b) the nozzles have a maximum diameter of less than 5 mm.

### Claim 3 (depends on 2)

The method of claim 2, wherein the nozzles have a maximum diameter of less than 1 mm.

### Claim 4 (depends on 1)

The method of claim 1, wherein the monolith of stacked catalyst fibers is three-dimensionally structured by depositing the extruded fibers in a regular, recurring stacking pattern to form a three-dimensionally structured porous catalyst monolith precursor.

### Claim 5 (depends on 1)

The method of claim 1, wherein the monolith is formed from one continuous extruded fiber or from multiple individual extruded fibers.

### Claim 6 (depends on 1)

The method of claim 1, wherein the regular, recurring stacking pattern is composed of stacked layers of extruded fibers, wherein in each layer at least 50 wt % of the extruded fibers are deposited parallel to each other and spatially separated from each other, or in a cobweb pattern.

### Claim 7 (depends on 6)

The method according to claim 6, wherein at least 50 wt % of the extruded fibers are deposited 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 8 (depends on 1)

The method according to claim 1, wherein the inorganic oxide catalyst support is 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 9 (depends on 8)

The method according to claim 8, wherein nickel oxide nanoparticles having a number average particle size of less than 100 nm, measured by sieving the particles or by photographic techniques, are supported on the inorganic oxide catalyst support particles.

### Claim 10 (depends on 8)

The method according to claim 8, wherein the inorganic oxide catalyst support is silica, having a number average particle size in the range of from 1 to 200 μm, measured by sieving the particles or by photographic techniques.

### Claim 11 (depends on 8)

The method according to claim 8, wherein nickel oxide nanoparticles having a number average particle size of less than 100 nm, measured by sieving the particles or 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.

### Claim 12 (depends on 1)

The method according to claim 1, wherein the catalytically active metal is selected from the group consisting of Na, K, Mg, Ca, Ba, Al, 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 13 (depends on 1)

The method according to claim 1, wherein a binder material is employed, selected from the group consisting of inorganic binders.

### Claim 14 (depends on 1)

The method of claim 1, wherein no organic binder material is present in the suspension.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the drying is performed at a temperature in the range of from −100 to 1000° C.

### Claim 16 (depends on 1)

The method according to claim 1, wherein the monolith has a porosity of at least 20%, determined by Hg-PV or He-density.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the three-dimensional porous catalyst monolith of stacked catalyst fibers has a side crushing strength of at least 60 N.

### Claim 18 (depends on 1)

The method according to claim 1, wherein the three-dimensional porous catalyst monolith of stacked catalyst fibers is for use in oxidation, hydrogenation, dehydration, desulphurization, amination or dehydrogenation reactions.

### Claim 19 (depends on 1)

The method according to claim 1, wherein a binder material is employed, selected from the group consisting of clays, alumina, silica and mixtures thereof.