Pyrochlore Catalysts for Low-Temperature Dry Reforming

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Solution Overview

Problem

Current hydrocarbon reforming catalysts face deactivation due to carbon formation and poor selectivity for hydrogen and carbon monoxide, especially at low temperatures, and are costly due to the use of noble metals, limiting their industrial scalability.

Innovation Solution

Development of pyrochlore-based solid mixed oxide materials with a composition of A2B2O7, where A is a trivalent cation and B includes a divalent nickel cation, which provides high selectivity for hydrogen and carbon monoxide at lower temperatures and is cost-effective by using inexpensive nickel, reducing the risk of sintering and coking.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If noble metals are used in dry reforming catalysts, then catalytic performance and resistance to deactivation are improved, but cost increases significantly

Engineering Contradiction:
Improvecatalyst stabilityVSAvoidcost
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent replaces expensive noble metals with inexpensive nickel-based catalysts that can be regenerated. The catalyst system uses nickel supported on alumina or silica with promoters like cesium or barium, providing cost-effective alternative to platinum, palladium, or rhodium while maintaining acceptable catalytic performance through periodic regeneration

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The patent modifies catalyst composition parameters by incorporating promoters (cesium, barium, strontium) in controlled amounts (0.1-5 wt%) and adjusting nickel content (1-20 wt%) to optimize performance. These parameter changes enable nickel-based catalysts to achieve stability comparable to noble metals at lower cost

Inventive Principle:
Principle #35Parameter changes

2Use of energy by moving object

If low dry reforming operational temperatures are used, then energy consumption is reduced, but carbon formation increases causing catalyst deactivation

Engineering Contradiction:
Improveenergy consumptionVSAvoidcarbon formation
Core Design Contradiction:
Use of energy by moving objectVSObject-generated harmful factors

Solution Approach 1:

The patent introduces promoter substances (cesium, barium, strontium) as intermediaries that mediate between the nickel catalyst and carbon formation. These promoters modify the catalyst surface properties to inhibit carbon deposition while maintaining activity at lower temperatures (600-800°C), preventing deactivation without requiring high energy input

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent converts the potential harm of carbon formation into a benefit by designing a catalyst system where controlled carbon deposition is managed through promoter addition. The promoters facilitate carbon gasification or removal mechanisms, turning what would be a deactivation pathway into a controllable process that enables lower operating temperatures

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

3Ease of manufacture

If high nickel content is used to replace noble metals, then cost is reduced, but sintering resistance decreases

Engineering Contradiction:
ImprovecostVSAvoidsintering resistance
Core Design Contradiction:
Ease of manufactureVSStability of the object's composition

Solution Approach 1:

The patent creates composite catalyst materials combining nickel with alumina or silica supports and alkaline earth metal promoters. This composite structure provides dispersion sites for nickel particles and thermal stability, preventing sintering even at higher nickel contents (1-20 wt%) while maintaining cost advantages over noble metals

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent applies preliminary stabilization measures by incorporating promoters during catalyst synthesis that pre-establish anti-sintering properties. The promoters (cesium, barium, strontium) are added in controlled amounts during preparation to create a stable composite structure before the catalyst enters service, preventing sintering rather than addressing it after occurrence

Inventive Principle:
Principle #10Preliminary action

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 pyrochlore-based catalysts demonstrate high selectivity and stability for hydrocarbon reforming at lower temperatures, reducing energy consumption and costs, offering a significant advancement in industrial-scale hydrocarbon reforming by using inexpensive nickel instead of noble metals.

Implementation Method 1

a solid mixed oxide material suitable for use in catalysing a methane dry reforming reaction

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

thermally treating the solid material resulting from step b) at a temperature greater than 800°C

Methodology Applied
Scientific EffectThermal treatment: Heat Treatment

Data Source

PatentEP3596014B1Catalysts for the reforming of gaseous mixtures
Publication Date: 2024.04.24 UNIVERSITY OF SURREY
  • EP3596014B1 patent drawingFigure 1
  • EP3596014B1 patent drawingFigure 2
  • EP3596014B1 patent drawingFigure 3

AI summary

Pyrochlore-based solid mixed oxide materials suitable for use in catalysing a hydrocarbon reforming reaction are disclosed, as well as methods of preparing the materials, and their uses in hydrocarbon reforming processes. The materials contain a catalytic quantity of inexpensive nickel and exhibit catalytic properties in dry reforming reactions that are comparable –if not better –than those observed using expensive noble metal-containing catalysts. Moreover, the Pyrochlore-based solid mixed oxide materials can be used in low temperature dry reforming reactions, where other catalysts would become deactivated due to coking. Accordingly, the catalytic materials represent a sizeable development in the industrial-scale reforming of hydrocarbons.