Macroporous Calcium Hydroxide Adsorbent for Emergency SO2 Retention

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Solution Overview

Problem

Existing adsorbent materials are inadequate for efficiently retaining high concentrations of sulfur dioxide (SO2) in emergency emissions from copper smelters, particularly during power outages, due to limitations in mechanical strength, diffusional limitations, and retention capacity under high-flow, high-temperature conditions.

Innovation Solution

A shaped adsorbent material composed of calcium hydroxide, sodium bicarbonate, potassium bicarbonate, and sepiolite, optimized for high mechanical strength and macroporosity, is used in a fixed bed system to capture SO2 efficiently under emergency conditions, forming CaSO3 on the surface and minimizing diffusional limitations.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If conventional adsorbent materials are used for SO2 retention, then the system can operate under normal conditions, but the retention capacity is insufficient for high-concentration emergency emissions

Engineering Contradiction:
ImproveSO2 retention capacityVSAvoidperformance under emergency conditions
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent uses a composite material consisting of calcium hydroxide (active component for SO2 reaction), sepiolite (porous structure provider), and sodium bicarbonate (mechanical strength enhancer). This composite structure combines the high reactivity of calcium hydroxide with the macroporous architecture of sepiolite, achieving both high retention capacity and reliable performance under emergency high-flow conditions

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention utilizes sepiolite, a natural porous clay mineral, to create a macroporous structure with pore sizes of 0.03-10 μm. This porous architecture provides high surface area for SO2 adsorption and facilitates rapid gas diffusion, enabling the material to handle high-concentration emergency emissions effectively

Inventive Principle:
Principle #31Porous materials

2Productivity

If the adsorbent material has high porosity to reduce diffusional limitations, then gas diffusion improves, but mechanical strength decreases

Engineering Contradiction:
Improvegas diffusion rateVSAvoidmechanical strength
Core Design Contradiction:
ProductivityVSStrength

Solution Approach 1:

The patent creates a composite where sepiolite provides the macroporous structure for rapid gas diffusion, while sodium bicarbonate acts as a binding agent to maintain mechanical integrity. The synergistic combination allows the material to simultaneously achieve high porosity (0.2-2.0 mL/g) and adequate mechanical strength for industrial application

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention optimizes the pore size parameter to 0.03-10 μm range, which balances diffusional efficiency with structural stability. This specific pore size range allows rapid SO2 diffusion while maintaining sufficient mechanical strength, resolving the contradiction between productivity and strength

Inventive Principle:
Principle #35Parameter changes

3Quantity of substance

If calcium hydroxide is used as the primary adsorbent, then SO2 reaction capacity increases, but the material lacks mechanical consistency

Engineering Contradiction:
ImproveSO2 reaction capacityVSAvoidmechanical consistency
Core Design Contradiction:
Quantity of substanceVSStability of the object's composition

Solution Approach 1:

The patent formulates a composite where calcium hydroxide (5-50 wt%) provides high SO2 reaction capacity, sepiolite (40-80 wt%) provides structural consistency and porosity, and sodium bicarbonate (5-20 wt%) enhances mechanical strength. This multi-component composite resolves the mechanical weakness of pure calcium hydroxide while preserving its high reactivity

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

Sepiolite acts as an intermediary material that provides structural framework and mechanical consistency to the calcium hydroxide particles. The sepiolite network holds the calcium hydroxide in place, preventing particle disintegration while allowing SO2 to access the reactive calcium hydroxide surfaces

Inventive Principle:
Principle #24Intermediary (Mediator)

4Loss of time

If the emergency system activates immediately, then SO2 release is prevented, but the system requires rapid response capability that conventional systems lack

Engineering Contradiction:
Improveresponse timeVSAvoidretention efficiency
Core Design Contradiction:
Loss of timeVSProductivity

Solution Approach 1:

The macroporous structure of sepiolite with pore sizes of 0.03-10 μm enables rapid gas diffusion and immediate SO2 uptake upon system activation. The high porosity (0.2-2.0 mL/g) ensures that SO2 molecules can quickly penetrate the adsorbent bed, achieving effective retention within seconds of emergency activation

Inventive Principle:
Principle #31Porous materials

Solution Approach 2:

The invention optimizes the particle size and pore distribution parameters to maximize diffusion rates. The specific surface area is maintained between 1-20 m²/g, and pore sizes are controlled at 0.03-10 μm, creating optimal conditions for rapid gas-phase SO2 diffusion and reaction, enabling immediate response capability

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 material achieves greater than 99% SO2 retention for extended periods, reducing emissions below 1000 mg/Nm3 and minimizing air quality issues, with a retention capacity exceeding 300 mg SO2 per gram of adsorbent.

Implementation Method 1

calcium hydroxide, which reacts with SO2 to form CaSO3

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 2

which is adsorbed with high efficiency on the surface due to the existence of a macroporous structure

Methodology Applied
Scientific EffectAdsorption: Adsorption

Data Source

PatentEP4474044B1Macroporous materials containing calcium hydroxide and their use in processes of retention of so2
Publication Date: 2025.10.22 CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS (CSIC)
  • EP4474044B1 patent drawingFigure 1A~1C
  • EP4474044B1 patent drawingFigure 2~4
  • EP4474044B1 patent drawingFigure 5A~5B

AI summary

The present invention relates to an adsorbent material with high capacity for retaining SO2 present in high concentrations in high flow gaseous streams, and its particular use in the elimination of SO2 in emergency point emissions of copper factories. This material comprises calcium hydroxide as an acidic gas adsorbent element, together with sepiolite as a binding agent and sodium and potassium bicarbonates as basifying elements and may be obtained by an easy process which requires mainly a dry treatment at temperatures below 60ºC.