Copper-ZSM-34 Zeolite SCR Catalyst Hydrothermal Stability

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Solution Overview

Problem

Current catalysts for the selective catalytic reduction (SCR) of nitrogen oxides with ammonia face challenges in maintaining hydrothermal stability and cost-effectiveness, particularly under harsh conditions encountered during the regeneration of soot filters, where many metal-promoted zeolites experience dealumination and loss of activity.

Innovation Solution

A copper-containing ZSM-34, OFF, or ERI zeolitic material with a silica to alumina mole ratio of 10 to 15 and copper content of 1 to 10 wt.-%, and an alkali metal content of less than 0.7 wt.-% is developed, which undergoes ammonium exchange and calcination followed by copper exchange, offering improved stability and cost reduction.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional metal-promoted zeolites are used for SCR, then catalytic activity is achieved, but hydrothermal stability deteriorates under harsh conditions

Engineering Contradiction:
Improvehydrothermal stabilityVSAvoiddealumination resistance
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent changes the chemical composition parameters of the zeolite by严格控制 the silica to alumina ratio within 2.5 to 4.0 and limiting alkali metal content to less than 0.7 wt.-%. This parameter optimization prevents dealumination under hydrothermal conditions while maintaining SCR catalytic activity, resolving the contradiction between catalytic performance and hydrothermal stability.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite catalyst system combining copper ions with optimized ZSM-34 zeolite structure. The copper content is controlled at 1 to 10 wt.-% CuO, forming a composite material where copper provides SCR activity while the stabilized zeolite framework provides hydrothermal resistance, achieving both catalytic function and structural stability.

Inventive Principle:
Principle #40Composite materials

2Reliability

If alkali metal content is reduced to improve stability, then hydrothermal stability is improved, but manufacturing complexity increases

Engineering Contradiction:
Improvehydrothermal stabilityVSAvoidmanufacturing process simplicity
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent applies preliminary ammonium exchange treatment before copper loading to remove alkali metals from the zeolite structure. This preliminary action reduces alkali metal content to less than 0.7 wt.-%, preventing dealumination and improving hydrothermal stability. The exchange process is integrated into the manufacturing workflow, making the additional step manageable while achieving the stability benefit.

Inventive Principle:
Principle #10Preliminary action

3Productivity

If copper content is increased to enhance SCR performance, then catalytic activity is improved, but cost increases

Engineering Contradiction:
ImproveSCR performanceVSAvoidcopper content
Core Design Contradiction:
ProductivityVSQuantity of substance

Solution Approach 1:

The patent optimizes the copper content parameter within the range of 1 to 10 wt.-% CuO, finding the optimal balance between SCR catalytic activity and material cost. The controlled copper loading on the stabilized ZSM-34 framework provides sufficient catalytic performance while avoiding excessive copper consumption, resolving the contradiction between productivity and quantity of substance.

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 copper-containing ZSM-34, OFF, or ERI zeolitic material exhibits high hydrothermal stability and SCR performance, retaining surface area and activity even after severe aging, providing a cost-effective solution for SCR applications.

Implementation Method 1

copper-containing ZSM-34, OFF, or ERI zeolitic material exhibits high hydrothermal stability and SCR performance

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

undergoes ammonium exchange and calcination followed by copper exchange

Methodology Applied
Scientific EffectIon Exchange: Ion Exchange

Data Source

PatentEP2593212B2Copper containing ZSM-34, off and/or ERI zeolitic material for selective reduction of NOX
Publication Date: 2021.06.02 BASF SE

AI summary

A copper containing ZSM-34, OFF and /or ERI zeolitic material is provided, which has a silica to alumina mole ratio ranging from about 4 to about 50 and a copper content, reported as CuO, ranging from about 1 to about 10wt.%, based on the total weight of the calcined zeolitic material, and an alkali metal content, reported as the metal oxide, of less than about 0.7wt.%.