# US 11,998,900 B2 · Immobilizing metal catalysts in a porous support via additive manufacturing and chemical vapor transformation

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- Number: US 11,998,900 B2
- Document ID: US11998900B2
- Status: Granted
- Kind: B2
- Application number: 17/863,719
- Filed: 2022-07-13
- Published: 2024-01-18
- Granted: 2024-06-04
- Earliest claimed: 2022-07-13
- Assignees: Baker Hughes Oilfield Operations LLC
- Applicants: Alexander John Cruz; Navin Sakthivel; Jayesh Jain; Michelangelo Bellacci
- Inventors: Alexander John Cruz; Navin Sakthivel; Jayesh Jain; Michelangelo Bellacci
- Web page: https://patentgrep.com/patent/US11998900B2

## CPC

- B01J 31/1625: {immobilised by covalent linkages, i.e. pendant complexes with optional linking groups}
- B01J 23/40: of the platinum group metals
- B01J 23/48: Silver or gold
- B01J 23/74: Iron group metals
- B01J 31/1616: {Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00)}
- B01J 31/1691: {Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- B01J 31/1815: {with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine}
- B01J 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- B01J 35/393: {Metal or metal oxide crystallite size}
- B01J 35/45: Nanoparticles
- B01J 35/50: characterised by their shape or configuration
- B01J 35/647: {2-50 nm}
- B01J 35/651: {50-500 nm}
- B01J 35/653: {500-1000 nm}
- B01J 35/657: {larger than 1000 nm}
- B01J 35/695: {polymodal}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/0219: {the coating containing organic compounds}
- B01J 37/0228: {in several steps}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B33Y 40/20: Post-treatment, e.g. curing, coating or polishing
- B33Y 80/00: Products made by additive manufacturing
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/30: Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- 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 2231/625: of CO2
- B01J 2531/0216: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/26: Zinc
- B01J 2531/48: Zirconium
- B01J 2531/84: Metals of the iron group
- B33Y 10/00: Processes of additive manufacturing
- C10G 2/50: {from carbon dioxide with hydrogen}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## Abstract

A method of immobilizing a metal catalyst in a porous support includes additively forming a precursor structure on a substrate from a metal catalyst and at least one of a metal oxide or a metal cluster compound; exposing the precursor structure to a vapor of an organic linker; and reacting the at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker to form a porous support that immobilizes the metal catalyst.

## Claims

### Claim 1

A method of immobilizing a metal catalyst in a porous support, the method comprising:
additively forming a precursor structure on a substrate from a metal catalyst and at least one of metal oxides or metal cluster compounds;
exposing the precursor structure to a vapor of an organic linker; and
reacting the at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker to form a porous support that immobilizes the metal catalyst.

### Claim 2 (depends on 1)

The method of claim 1, comprising additively forming the precursor structure via an aerosol jetting process, a binder jetting process, or a material jetting process.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metal catalyst comprises nanoparticles of a precious metal catalyst.

### Claim 4 (depends on 1)

The method of claim 1, wherein the metal catalyst comprises at least one of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, platinum, chromium, tungsten, molybdenum, iron, or cobalt.

### Claim 5 (depends on 1)

The method of claim 1, wherein the metal catalyst has an average particle size of about 1 nm to about 20 nm.

### Claim 6 (depends on 1)

The method of claim 1, wherein the metal catalyst is present in an amount of about 1 to about 5% based on a total weight of the porous support.

### Claim 7 (depends on 1)

The method of claim 1, wherein the precursor structure is formed from the metal catalyst and the metal oxide, and the metal oxide comprises at least one of zinc oxide, aluminum oxide, magnesium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, calcium oxide, barium oxide, cerium oxide, manganese oxide, gallium oxide, cadmium oxide, titanium oxide, zirconium oxide, or magnesium aluminum oxide.

### Claim 8 (depends on 1)

The method of claim 1, wherein the precursor structure is formed from the metal catalyst and the metal cluster compound, and the metal cluster compound comprises at least one of a titanium-based cluster compound or a zirconium-based cluster compound.

### Claim 9 (depends on 1)

The method of claim 1, wherein the metal oxide and the metal cluster compound have an average particle size of about 10 nm to about 100 μm.

### Claim 10 (depends on 1)

The method of claim 1, wherein the precursor structure comprises the metal catalyst disposed in a matrix formed from at least one of the metal oxide or the metal cluster compound, and the matrix has pores with a pore size of about 200 nm to about 1 mm.

### Claim 11 (depends on 1)

The method of claim 1, further comprising controlling the pore size of the matrix by dispensing a porous particle as a dispersed phase through one deposition head and dispensing the metal catalyst and at least one of the metal oxide or the metal cluster compound through another deposition head.

### Claim 12 (depends on 1)

The method of claim 1, further comprising statistically characterizing pores' variability within an additive manufacturing process and dependency on additive manufacturing parameters, and stochastically or parametrically optimizing the additive manufacturing parameters to provide a selected pore size, morphology, distribution, or a combination thereof of the precursor structure.

### Claim 13 (depends on 1)

The method of claim 1, wherein the organic linker comprises at least one of a carboxylate or an imidazolate.

### Claim 14 (depends on 1)

The method of claim 1, wherein the substrate is an electrode or an internal packing material.

### Claim 15 (depends on 1)

The method of claim 1, comprising reacting the at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker at a temperature of about 80° C. to about 100° C. to form the porous support.

### Claim 16 (depends on 1)

The method of claim 1, comprising reacting the at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker at a pressure of about 0.001 bar to about 1 bar to form the porous support.

### Claim 17 (depends on 1)

The method of claim 1, wherein the additively forming, the exposing, and the reacting occur in a single reactor chamber.

### Claim 18 (depends on 1)

The method of claim 1, further comprising exposing the porous support to a temperature of about 120° C. to about 150° C. at a subatmospheric pressure of about 0.0001 bar to about 0.001 bar to activate the porous support.

### Claim 19 (depends on 1)

The method of claim 1, wherein
the porous support is a metal-organic framework, and
the metal-organic framework is a crystalline network comprising inorganic nodes linked by organic moieties, the inorganic nodes formed from the at least one of the metal oxide or the metal cluster compound, and the organic moieties formed from the organic linker.

### Claim 20 (depends on 19)

The method of claim 19, wherein the porous support comprises pores having a pore size of about 5 to about 20 angstroms; and at least a portion of the metal catalyst is disposed in the pores.

### Claim 21 (depends on 1)

The method of claim 1, wherein the porous support has a multimodal pore size distribution comprising first pore sizes from about 5 to about 20 angstroms, attributed to intrinsic porosity of the porous support, second pore sizes from about 1 nm to about 200 nm, and third pore sizes from about 200 nm to about 1 mm.

### Claim 22 (depends on 1)

The method of claim 1, wherein the porous support is discontinuous and has a predetermined pattern.

### Claim 23 (depends on 1)

The method of claim 1, wherein the porous support has a first portion and a second portion, and the first portion and the second portion have at least one of a different thickness; a different shape; a different metal catalyst; or a porous support.

### Claim 24 (depends on 1)

The method of claim 1, comprising:
additively forming the precursor structure on the substrate via an aerosol jetting process, a binder jetting process, or a material jetting process from the metal catalyst and at least one of the metal oxides or the metal cluster compounds in a reactor chamber equipped with a heater, the metal catalyst comprising nanoparticles of a precious metal;
introducing the vapor of the organic linker into the reactor chamber;
exposing the precursor structure to the vapor of the organic linker in the reactor chamber;
reacting the at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker in the reactor chamber at a temperature of about 80° C. to about 100° C. to form the porous support; and
exposing the porous support to a temperature of about 120° C. to about 150° C. at a subatmospheric pressure of about 0.0001 bar to about 0.001 bar to activate the porous support forming a supported catalyst, the supported catalyst comprising a metal-organic framework having pores with a pore size of from about 5 to about 20 angstroms and at least a portion of the metal catalyst disposed in the pores.