Semi-liquid Alumina Paste for 3D Printing Catalysts

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Solution Overview

Problem

Existing 3D printing methods for alumina catalysts and catalyst supports face challenges such as limited processability of acidic peptized alumina pastes, rapid viscosity changes due to ongoing peptization, and excessive shrinkage during drying and calcination, which affect the printability and quality of the final products.

Innovation Solution

A semi-liquid paste composition for 3D printing is developed, comprising alumina, water, and a specific acid (carboxylic or mineral acid) with a controlled pH between 4-7 and an acid:Al2O3 weight ratio of 0.005-0.05. This composition ensures stable rheological properties over time, allowing for long-term processability and storage without significant viscosity changes.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of operation

If acidic peptized alumina paste is used for 3D printing, then the paste can be extruded through a nozzle, but the viscosity changes rapidly over time due to ongoing peptization

Engineering Contradiction:
ImproveprintabilityVSAvoidviscosity stability
Core Design Contradiction:
Ease of operationVSStability of the object's composition

Solution Approach 1:

The paste is pre-peptized with acid before 3D printing to achieve the desired viscosity and flow properties. This preliminary action ensures the paste is ready for printing with optimal extrusion characteristics, while the printing process is completed within the window before excessive peptization causes viscosity changes.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The 3D printing process is performed rapidly after paste preparation to complete the printing before significant viscosity changes occur due to ongoing peptization. This rushing through the printing process ensures that the paste maintains its printability throughout the operation.

Inventive Principle:
Principle #21Skipping (Rushing through)

2Manufacturing precision

If conventional 3D printing methods are used with alumina paste, then catalyst structures can be created, but excessive shrinkage occurs during drying and calcination

Engineering Contradiction:
Improvestructural accuracyVSAvoidshrinkage
Core Design Contradiction:
Manufacturing precisionVSVolume of moving object

Solution Approach 1:

The paste composition is optimized by adjusting the acid:Al2O3 weight ratio to 0.005-0.05 and controlling pH to 4-7, which modifies the rheological properties and shrinkage behavior. This parameter optimization reduces excessive shrinkage during drying and calcination while maintaining the ability to create precise catalyst structures.

Inventive Principle:
Principle #35Parameter changes

3Ease of operation

If the acid:Al2O3 weight ratio is increased to improve paste flow, then printability is enhanced, but the paste becomes unstable over time

Engineering Contradiction:
Improveextrusion flowVSAvoidstorage stability
Core Design Contradiction:
Ease of operationVSDuration of action of stationary object

Solution Approach 1:

The acid:Al2O3 weight ratio is precisely controlled within the range of 0.005-0.05, which provides an optimal balance between paste flow characteristics for extrusion and stability during storage. This parameter optimization ensures sufficient fluidity for printing while preventing excessive peptization that would cause instability over time.

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 provides a stable and long-term processable paste that maintains its printability for days to months, reduces shrinkage and cracking during processing, and produces catalysts or catalyst supports with consistent quality and desired structural characteristics.

Implementation Method 1

a frequently used method of 3D printing for alumina ceramics production is stereolithography. Sintering temperatures above 1200 ° C are used to achieve high density and mechanical strength.

Methodology Applied
Scientific EffectPeptization:

Implementation Method 2

The paste containing 51% of solids was extruded through a nozzle with a diameter of 410 μm.

Methodology Applied
Scientific EffectExtrusion: Extrusion

Implementation Method 3

The formed structure (10 x 12 mm) was air dried at room temperature for 24 hours

Methodology Applied
Scientific EffectEvaporation: Evaporation

Implementation Method 4

Sintering temperatures above 1200 ° C are used to achieve high density and mechanical strength.

Methodology Applied
Scientific EffectSintering: Sintering

Implementation Method 5

A high calcination temperature 1300°C was also used to anchor the BaMn 2 Al 10 O 19 layer to the support.

Methodology Applied
Scientific EffectCalcination: Heat Treatment

Data Source

PatentEP4497500A1Semi-liquid paste composition for 3D printing and method for preparing a 3D printed catalyst or catalyst support
Publication Date: 2025.01.29 ORLEN SPÓŁKA AKCYJNA
  • EP4497500A1 patent drawingFigure 1~3
  • EP4497500A1 patent drawingFigure 4
  • EP4497500A1 patent drawing

AI summary

A semi-liquid paste composition for 3D printing comprising at least three following components: one source of alumina or a mixture of aluminas, water, at least one acid from a group including carboxylic acid and mineral acid, wherein the pH value of the paste composition is between 4-7, wherein the acid:Al2O3 weight ratio is in the range 0.005 - 0.05.