Copper Zeolite Catalyst Hydrothermal Stability Identification

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Solution Overview

Problem

Current catalytic materials used in SCR processes for nitrogen oxides (NOx) reduction in internal combustion engine exhausts face challenges in maintaining catalytic activity and hydrothermal stability at high temperatures, particularly during aging conditions up to 800°C, which affects their performance and durability.

Innovation Solution

A method for identifying catalytic materials that involves copper-containing molecular sieves with a CHA framework, using DRIFT spectroscopy to evaluate perturbed vibrational peaks, selecting samples with a specific ratio of Cu+2 to Cu(OH)+1 cations, and aging them at 800°C for 16 hours in 10% H2O/air to ensure stability and NOx conversion efficiency.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If copper-containing molecular sieves are used for SCR catalysis, then NOx conversion activity is improved, but hydrothermal stability deteriorates at high temperatures above 400°C

Engineering Contradiction:
ImproveNOx conversion activityVSAvoidhydrothermal stability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent applies parameter changes by controlling the oxidation state of copper (Cu+2 vs Cu+1) and the Si/Al ratio of the molecular sieve framework. Specifically, maintaining a high proportion of Cu+2 cations and optimizing the Si/Al ratio between 2.5:1 and 5:1 creates a catalyst that achieves both high NOx conversion activity and improved hydrothermal stability at temperatures above 400°C, resolving the contradiction between activity and stability.

Inventive Principle:
Principle #35Parameter changes

2Duration of action of stationary object

If catalysts are subjected to high temperature aging conditions, then durability is improved, but catalytic activity deteriorates

Engineering Contradiction:
ImprovedurabilityVSAvoidcatalytic activity
Core Design Contradiction:
Duration of action of stationary objectVSProductivity

Solution Approach 1:

The patent applies preliminary action by pre-oxidizing the copper-containing molecular sieve to ensure a high proportion of Cu+2 cations before the catalyst is deployed. This preliminary oxidation treatment, combined with optimizing the Si/Al ratio, prepares the catalyst structure to resist degradation during subsequent high-temperature aging, thereby maintaining both durability and catalytic activity over time.

Inventive Principle:
Principle #10Preliminary action

3Reliability

If the proportion of Cu+2 cations is increased, then hydrothermal stability is improved, but the complexity of controlling cation ratio increases

Engineering Contradiction:
Improvehydrothermal stabilityVSAvoidcation ratio control
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent simplifies the control of cation ratio by establishing specific parameter ranges: maintaining the Si/Al ratio between 2.5:1 and 5:1 and ensuring Cu+2 cations constitute at least 60% (preferably 70-90%) of total copper. These defined parameter ranges provide a clear, controllable approach to achieving hydrothermal stability without excessive complexity in the manufacturing process.

Inventive Principle:
Principle #35Parameter changes

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 effectively identifies catalytic materials with enhanced hydrothermal stability and NOx conversion activity, maintaining a stable ratio of Cu+2 cations post-aging, thus improving the durability and performance of catalytic materials in high-temperature hydrothermal conditions.

Implementation Method 1

subjecting the plurality of samples to Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy so as to evaluate perturbed T-O-T vibrational peaks corresponding to the Cu +2

Methodology Applied
Scientific EffectVibrational spectroscopy (DRIFT): Absorption Spectroscopy

Implementation Method 2

Molecular sieves such as zeolites are employed in the catalysis of certain chemical reactions for example the selective catalytic reduction (SCR) of nitrogen oxides with a reductant such as ammonia, urea or hydrocarbons

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 3

providing a plurality of samples, each comprising particles of a copper-containing molecular sieve containing ion-exchanged copper as Cu +2

Methodology Applied
Scientific EffectIon exchange: Ion Exchange

Data Source

PatentEP3600655B1Method to identify a catalytic material stable toward hydrothermal aging
Publication Date: 2024.01.24 BASF MOBILE EMISSIONS CATALYSTS LLC
  • EP3600655B1 patent drawingFigure 1
  • EP3600655B1 patent drawingFigure 2
  • EP3600655B1 patent drawingFigure 3

AI summary

The present disclosure relates to copper-containing molecular sieve catalysts that are highly suitable for the treatment of exhaust containing NOx pollutants. The copper-containing molecular sieve catalysts contain ion-exchanged copper as Cu+2 and Cu(OH)+1, and DRIFT spectroscopy of the catalyst exhibits perturbed T-O-T vibrational peaks corresponding to the Cu+2 and Cu(OH)+1. In spectra taken of the catalytic materials, a ratio of the Cu+2 to the Cu(OH)+1 peak integration areas preferably can be ≥ 1. The copper-containing molecular sieve catalysts are aging stable such that the peak integration area percentage of the Cu+2 peak (area Cu+2/(area Cu+2 + area Cu(OH)+1)) increases by ≤ 20% upon aging at 800oC for 16 hours in the presence of 10% H2O/air, compared to the fresh state.