Pd Membrane with Ceramic Protective Layer for Fluidized Bed Reactors

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Solution Overview

Problem

Hydrogen production in fluidized bed membrane reactors is hindered by the limited mechanical strength of metallic supported membranes at high temperatures and the permeability issues of thin Pd-based membranes, which result in low hydrogen purity and attrition resistance against particles.

Innovation Solution

A hydrogen permeable membrane device featuring a thin Pd or Pd-alloy film coated with a nanoporous ceramic protective layer, including materials like zirconia, YSZ, and silicon carbide, which enhances permeability and attrition resistance, integrated into a reactor with a housing that can be tubular or planar.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If thin Pd-based membranes are used to increase hydrogen flux, then hydrogen permeance is improved, but mechanical strength and attrition resistance deteriorate

Engineering Contradiction:
Improvehydrogen fluxVSAvoidmechanical strength
Core Design Contradiction:
ProductivityVSStrength

Solution Approach 1:

The patent applies composite materials by combining a thin Pd-based selective layer with a porous support layer and an outer protective layer. This composite structure allows the thin Pd layer to provide high hydrogen flux while the support and protective layers provide mechanical strength and attrition resistance, resolving the contradiction between productivity and strength.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent applies local quality by giving different regions of the membrane different functions: the inner Pd-based layer provides hydrogen selectivity and high flux, the porous support layer provides mechanical strength, and the outer protective layer provides attrition resistance. Each layer is optimized for its specific local function, allowing the overall membrane to achieve both high productivity and strength.

Inventive Principle:
Principle #3Local quality

2Productivity

If thin Pd-based membranes are used to increase hydrogen flux, then permeability is improved, but perm-selectivity and purity deteriorate

Engineering Contradiction:
Improvehydrogen fluxVSAvoidperm-selectivity
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The composite membrane structure with multiple layers allows the thin Pd-based selective layer to provide high hydrogen flux while the combination with porous support and protective layers maintains perm-selectivity and hydrogen purity, preventing the deterioration that would occur with a standalone thin membrane.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The Pd-based selective layer is specifically designed with local quality to provide both high permeability and perm-selectivity, while the other layers are optimized for structural support and protection, allowing the membrane as a whole to achieve high productivity without sacrificing purity.

Inventive Principle:
Principle #3Local quality

3Strength

If metallic supported membranes are used to provide mechanical strength, then strength is improved, but stability at high temperatures deteriorates

Engineering Contradiction:
Improvemechanical strengthVSAvoidstability
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The patent uses a composite structure where the porous support layer is made of temperature-stable materials like ceramics or metal oxides rather than simple metallic supports. This allows the membrane to maintain both mechanical strength and thermal stability at high temperatures, resolving the contradiction between strength and reliability.

Inventive Principle:
Principle #40Composite materials

4Device complexity

If self-supported membranes are used to simplify structure, then device complexity is reduced, but the number of membranes required increases

Engineering Contradiction:
ImprovestructureVSAvoidhydrogen production capacity
Core Design Contradiction:
Device complexityVSProductivity

Solution Approach 1:

The composite membrane structure with integrated selective layer, porous support, and protective layer creates a single self-supported unit that is both mechanically strong and highly productive. This eliminates the need for multiple separate membranes while maintaining high hydrogen production capacity, resolving the contradiction between device complexity and productivity.

Inventive Principle:
Principle #40Composite materials

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 membrane achieves high hydrogen permeance and perm-selectivity while maintaining stability under fluidization conditions, significantly reducing attrition and maintaining high selectivity over long-term use, even with harder catalyst particles.

Implementation Method 1

Palladium-based membranes are well known for their use as hydrogen separation devices with high purity hydrogen as product

Methodology Applied
Scientific EffectPermeation: Permeation

Implementation Method 2

The membrane achieves high hydrogen permeance and perm-selectivity

Methodology Applied
Scientific EffectPerm-selectivity:

Implementation Method 3

a nanoporous protective layer of ceramic... which enhances permeability and attrition resistance

Methodology Applied
Scientific EffectAttrition resistance:

Implementation Method 4

a nanoporous protective layer of ceramic, including materials like zirconia, YSZ, and silicon carbide

Methodology Applied
Scientific EffectPorosity: Porosity

Implementation Method 5

the increase in conversion of the feedstock to hydrogen due to the continuous removal of one of the products thereby shifting the equilibrium according to Le Chatelier's principle

Methodology Applied
Scientific EffectLe Chatelier's principle:

Data Source

PatentEP4046704A1Advanced double skin membranes for membrane reactors
Publication Date: 2022.08.24 HYDROGEN ONSITE SL
  • EP4046704A1 patent drawingFigure 1A
  • EP4046704A1 patent drawingFigure 1B
  • EP4046704A1 patent drawingFigure 2A~2C

AI summary

A hydrogen permeable membrane device is provided that includes a porous ceramic layer having a material that includes zirconia, Yttria-stabilized zirconia (YSZ), γ/Al2O3, and/or YSZ- γ/Al2O3, and a porous Pd film or porous Pd-alloy film deposited on the a mesoporous ceramic layer.