Solid-State Ion Exchange for Copper-Exchanged SAPO Catalysts

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Solution Overview

Problem

Conventional methods for introducing copper ions into crystalline microporous silicoaluminophosphates require high temperatures, which can cause material damage and are not very effective, especially for achieving sufficient activity in selective catalytic reduction (SCR) reactions.

Innovation Solution

A solid state ion exchange method involving a physical mixture of copper oxide and a microporous silicoaluminophosphate in an ammonia-containing atmosphere at temperatures between 100°C and 250°C, allowing for effective copper ion exchange and catalyst activation at lower temperatures.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional methods (contacting with metal ion solution followed by calcination) are used to introduce copper ions into crystalline microporous silicoaluminophosphates, then copper ions can be introduced into the material, but high temperatures (>750°C) are required which causes material damage and is not very effective for achieving sufficient activity in SCR reactions

Engineering Contradiction:
Improvecatalyst activity for SCR reactionVSAvoidactivation temperature
Core Design Contradiction:
ReliabilityVSTemperature

Solution Approach 1:

Ammonia serves as an intermediary substance that facilitates copper ion exchange at lower temperatures. The ammonia atmosphere enables the introduction of copper ions into the silicoaluminophosphate framework without requiring high temperature calcination, thus resolving the contradiction between achieving sufficient catalyst activity and avoiding material damage from high temperature processing

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention changes the chemical environment parameters by introducing an ammonia-containing atmosphere during the ion exchange process. This parameter change allows the ion exchange to proceed at lower temperatures (below 750°C) while still achieving effective copper ion incorporation and sufficient SCR reaction activity, eliminating the need for high temperature activation

Inventive Principle:
Principle #35Parameter changes

2Reliability

If high temperature heating (>750°C) is applied to activate Cu-SAPO-34 material, then sufficient activity for selective catalytic reduction is achieved, but the high temperature causes redistribution of Cu throughout the SAPO-34 crystals and potential material damage

Engineering Contradiction:
Improvecatalyst activityVSAvoidcopper distribution stability
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

Ammonia acts as a mediating agent that enables copper ion exchange and activation at lower temperatures without causing excessive copper redistribution. The ammonia atmosphere facilitates controlled ion exchange that maintains stable copper distribution within the crystal structure while still achieving sufficient catalytic activity for SCR reactions

Inventive Principle:
Principle #24Intermediary (Mediator)

3Productivity

If solid state ion exchange is performed without ammonia atmosphere, then copper oxide and microporous silicoaluminophosphate can be mixed, but the ion exchange requires high temperatures and long heating times (12-72 hours)

Engineering Contradiction:
Improveion exchange efficiencyVSAvoidheating time
Core Design Contradiction:
ProductivityVSLoss of time

Solution Approach 1:

Ammonia serves as a catalytic intermediary that dramatically accelerates the solid state ion exchange process. By introducing ammonia into the system, the heating time is reduced from 12-72 hours to much shorter durations, while still achieving complete copper ion exchange. This resolves the contradiction between achieving thorough ion exchange and minimizing processing time

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention changes the chemical atmosphere parameter from inert to ammonia-containing, which fundamentally alters the ion exchange kinetics. This parameter change enables the exchange process to proceed rapidly at lower temperatures without requiring extended heating periods, thus resolving the time efficiency contradiction

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

This method enables the production of SCR-active copper-exchanged microporous silicoaluminophosphate materials at significantly lower temperatures, reducing the risk of material damage and improving catalyst efficiency for nitrogen oxide reduction in exhaust gases.

Implementation Method 1

a solid state ion exchange method involving a physical mixture of copper oxide and a microporous silicoaluminophosphate in an ammonia-containing atmosphere at temperatures between 100°C and 250°C, allowing for effective copper ion exchange

Methodology Applied
Scientific EffectIon exchange: Ion Exchange

Implementation Method 2

Metalloaluminophosphates materials exchanged with Fe or Cu are effective catalysts for the catalytic reduction of NO x , e.g in the exhaust of power plants, or in the exhaust of diesel engines

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 3

The catalytic reduction of NO x is referred to as SCR (selective catalytic reduction)

Methodology Applied
Scientific EffectSelective catalytic reduction: Catalysis

Data Source

PatentEP3129141B1Method for producing metal exchanged metallo-aluminophosphates by solid-state ion exchange at low temperatures
Publication Date: 2020.04.15 HALDOR TOPSOE AS

AI summary

Method for the preparation of a metal exchanged crystalline microporous metalloaluminophosphate or mixtures containing metal exchanged microporous metalloaluminophosphates materials comprising the steps of providing a dry mixture containing a) one or more metalloaluminophosphates starting materials that exhibit ion exchange capacity, and b) one or more metal compounds; heating the mixture in a gaseous atmosphere containing ammonia to a temperature and for a time sufficient to initiate and perform a solid state ion exchange of ions of the metal compound and ions of the crystalline microporous material; and obtaining the metal-exchanged microporous metalloaluminophosphate material or mixtures containing the metal-exchanged microporous metalloaluminophosphate material.