Direct Copper Exchange into Na+-Form Chabazite for SCR Catalysts

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Solution Overview

Problem

The existing processes for preparing copper-containing Chabazite molecular sieves with the CHA structure face challenges in achieving optimal catalytic performance and stability for the selective catalytic reduction (SCR) of nitrogen oxides, particularly under harsh hydrothermal conditions, due to residual Na+ ions and excess CuO, which degrade the zeolite structure and reduce activity.

Innovation Solution

A novel process involving direct copper exchange into the Na+-form of Chabazite using a liquid copper solution with a concentration of 0.05 to 0.3 molar, conducted once without multiple ion-exchange steps, and calcination in the 400 °C to 850 °C range, which eliminates the need for NH4+ ion exchange and reduces residual alkali metals, thereby enhancing stability and catalytic activity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If multiple ion-exchange steps (NH4+ exchange followed by Cu2+ exchange) are used to prepare copper-containing Chabazite, then copper loading is achieved, but residual Na+ ions remain and multiple processing steps increase complexity

Engineering Contradiction:
Improvecopper loadingVSAvoidprocess complexity
Core Design Contradiction:
Quantity of substanceVSDevice complexity

Solution Approach 1:

The patent combines the NH4+ exchange and Cu2+ exchange steps into a single direct copper exchange process. The Cu2+ solution directly replaces Na+ ions in the Chabazite structure, eliminating the intermediate NH4+ exchange step and reducing process complexity while achieving the desired copper loading.

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The patent extracts and eliminates the unnecessary NH4+ exchange intermediate step from the traditional multi-step process. By directly exchanging Cu2+ into the Na+-form Chabazite, the process removes redundant operations while maintaining effective copper incorporation.

Inventive Principle:
Principle #2Taking out (Extraction)

2Quantity of substance

If traditional multi-step ion exchange is used, then copper is introduced into the zeolite, but residual Na+ ions degrade the zeolite structure under hydrothermal conditions

Engineering Contradiction:
Improvecopper contentVSAvoidzeolite stability
Core Design Contradiction:
Quantity of substanceVSStability of the object's composition

Solution Approach 1:

The patent converts the traditionally harmful residual Na+ ions into a beneficial element by using them as the direct target for Cu2+ exchange. The Na+-form Chabazite serves as the starting material for direct copper exchange, allowing complete replacement of Na+ with Cu2+ in a single step, thereby eliminating the harmful effect of residual sodium while enhancing zeolite stability.

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

3Quantity of substance

If excess CuO is present in the catalyst, then copper loading is high, but catalytic activity decreases due to degradation of zeolite structure

Engineering Contradiction:
Improvecopper loadingVSAvoidcatalytic activity
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent optimizes the copper solution concentration parameter (0.05 to 0.3 molar) and liquid-to-solid ratio (2 to 15) to achieve optimal copper loading without excess CuO. By precisely controlling these parameters in the direct exchange process, the method achieves high copper content while maintaining zeolite structure integrity and catalytic activity.

Inventive Principle:
Principle #35Parameter changes

4Quantity of substance

If multiple ion-exchange steps are performed, then thorough metal exchange is achieved, but processing time and operational costs increase

Engineering Contradiction:
Improvemetal exchange completenessVSAvoidprocessing time
Core Design Contradiction:
Quantity of substanceVSLoss of time

Solution Approach 1:

The patent skips the intermediate NH4+ exchange step and rushes directly from Na+-form Chabazite to Cu2+ exchange. This single-step direct exchange process achieves complete metal exchange while significantly reducing processing time and operational costs compared to traditional multi-step methods.

Inventive Principle:
Principle #21Skipping (Rushing through)

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

This process results in copper-containing molecular sieves with high NOx conversion rates (>50% at 200°C and >70% at 450°C) under steady-state conditions, improving catalytic performance and reducing operational costs while maintaining environmental benefits.

Implementation Method 1

direct copper exchange into the Na+-form of Chabazite molecular sieve

Methodology Applied
Scientific EffectIon exchange: Ion Exchange

Implementation Method 2

liquid to solid ratio which is defined as the weight of water and copper salt used to prepare the Cu solution relative to the dry weight of the starting zeolite

Methodology Applied
Scientific EffectDiffusion: Diffusion

Data Source

PatentEP2512669B1Process of direct copper exchange into na+-form of chabazite molecular sieve
Publication Date: 2023.05.03 BASF CORPORATON
  • EP2512669B1 patent drawingFigure 1
  • EP2512669B1 patent drawingFigure 2
  • EP2512669B1 patent drawingFigure 3

AI summary

Disclosed are processes for the preparation of copper containing molecular sieves with the CHA structure wherein the copper is exchanged into the Na+-form of the Chabazite, using a liquid copper solution wherein the concentration of copper is in the range of about 0.001 to about 0.4 molar. Also described are copper containing molecular sieves with the CHA structure, catalysts incorporating molecular sieves, systems and methods for their use.