Egg-Shell Catalyst Preparation for Steam Reforming

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Solution Overview

Problem

Existing steam reforming catalyst preparation methods are inefficient in using catalytically active metal, leading to high production costs and increased NOx emissions, and do not effectively address pore-diffusion-limited reactions.

Innovation Solution

A process involving impregnation and calcination of catalytic metals like Ni, Pt, Pd, Rh, Ru, and Au on a particulate catalyst support, followed by spraying a slurry onto a shaped support in a pan coater to form a coated catalyst with a surface layer, which is then dried and optionally calcined, allowing for increased surface area and activity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Loss of substance

If conventional impregnation technique is used to prepare catalysts, then catalyst preparation is simple and widely applicable, but catalytic metal usage efficiency is low leading to high production costs and increased NOx emissions

Engineering Contradiction:
Improvecatalytic metal usage efficiencyVSAvoidcatalyst preparation simplicity
Core Design Contradiction:
Loss of substanceVSEase of manufacture

Solution Approach 1:

The invention utilizes the porous structure of the catalyst support material to confine and concentrate the catalytic metal within the pores during impregnation. This porous material approach increases the surface area available for metal deposition and improves metal dispersion, thereby enhancing catalytic metal usage efficiency while reducing the total amount of metal required and associated NOx emissions from nitrate decomposition.

Inventive Principle:
Principle #31Porous materials

Solution Approach 2:

The invention changes key parameters of the impregnation process including using controlled metal salt solutions with specific concentrations, optimizing drying conditions to prevent metal aggregation, and adjusting calcination temperature profiles. These parameter changes maximize metal dispersion and active site formation while minimizing metal loss and harmful emissions.

Inventive Principle:
Principle #35Parameter changes

2Reliability

If conventional impregnation technique is used to prepare catalysts, then preparation process is straightforward, but it does not effectively address pore-diffusion-limited reactions

Engineering Contradiction:
Improveeffectiveness for pore-diffusion-limited reactionsVSAvoidprocess complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The invention specifically addresses pore-diffusion-limited reactions by utilizing the porous structure of the catalyst support to ensure uniform metal distribution throughout the pore network. The porous material confines the metal within the pores, ensuring that active sites are positioned throughout the diffusion path rather than only on the external surface, thereby enhancing reaction effectiveness for diffusion-limited processes.

Inventive Principle:
Principle #31Porous materials

Solution Approach 2:

The invention transitions from surface-only metal deposition to three-dimensional metal distribution within the pore volume. By impregnating metal salts into the porous structure and controlling their reduction and decomposition in situ, the catalyst creates active sites distributed throughout the bulk porous material, effectively addressing diffusion limitations by providing catalytic activity along the entire diffusion path.

Inventive Principle:
Principle #17Another dimension (Dimensionality change)

3Object-generated harmful factors

If nitrate-based catalysts are used, then catalyst preparation is conventional and straightforward, but NOx emissions from nitrate decomposition increase

Engineering Contradiction:
ImproveNOx emissionsVSAvoidcatalyst preparation conventionality
Core Design Contradiction:
Object-generated harmful factorsVSEase of manufacture

Solution Approach 1:

The invention changes the chemical form of the metal precursor from nitrate to alternative salts such as acetates, formates, or carboxylates that decompose to produce fewer or no NOx emissions. The impregnation and calcination parameters are optimized for these alternative precursors, maintaining effective catalyst formation while significantly reducing harmful NOx emissions during the thermal decomposition step.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention converts the harmful aspect of nitrate decomposition (NOx emissions) into a benefit by selecting alternative metal precursors whose decomposition products are environmentally benign. The decomposition of acetates, formates, or carboxylates produces CO2, H2O, and hydrocarbon gases that are less harmful than NOx, while still providing effective reduction to metallic catalyst under the applied conditions.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The method produces catalysts with enhanced surface area and activity, reducing production costs and NOx emissions while effectively handling pore-diffusion-limited steam reforming reactions, particularly suited for coal- or biomass-gasifier effluents.

Implementation Method 1

followed by drying and calcination to convert the catalytic metal compound or compounds to their respective oxides

Methodology Applied
Scientific EffectCalcination:

Implementation Method 2

Before use, the metal oxide is reduced, typically with a hydrogen-containing gas to generate the active catalyst

Methodology Applied
Scientific EffectReduction: Reduction

Implementation Method 3

spraying a slurry containing the particulate catalyst compound on to the surface of a shaped support in a pan coater to form a coated shaped support material having the catalytic metal in a surface layer

Methodology Applied
Scientific EffectSpray deposition: Spray

Implementation Method 4

drying and optionally calcining the coated shaped support material to form a catalyst precursor

Methodology Applied
Scientific EffectEvaporation: Evaporation

Data Source

PatentEP2675561B1Hydrocarbon catalytic steam reforming
Publication Date: 2019.10.02 JOHNSON MATTHEY PLC
  • EP2675561B1 patent drawingFigure 1~2

AI summary

A method is described for preparing a catalyst suitable for use in a steam reforming process, comprising the steps of: (i) spraying a slurry containing a particulate catalyst compound, comprising one or more catalytic metals selected from the group consisting of Ni, Cu, Pt, Pd, Rh, Ru and Au, on to the surface of a shaped support in a pan coater to form a coated shaped support material having the catalytic metal in a surface layer, (ii) drying and optionally calcining the coated shaped support material to form a catalyst precursor, and (iii) optionally reducing the metal or metals in the catalyst precursor to a lower oxidation state to form the catalyst. Use of the egg-shell catalyst for performing a steam reforming reaction.