Oxalic Acid Dissolution of Mixed Oxide Dehydrogenation Catalysts

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Solution Overview

Problem

Current methods for removing mixed oxide catalysts from reactors and piping in oxidative dehydrogenation processes are inefficient and can result in the formation of harmful catalyst dust, with limited use of oxalic acid for solubilization and no effective means to disperse alumina supports.

Innovation Solution

Contacting the catalysts, comprising specific metal oxide compositions, with an oxalic acid solution at elevated temperatures to dissolve and remove them, along with agitation to enhance the process, allowing for the separation of valuable metals and alumina supports.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If physical treatment methods are used to remove catalysts and residues, then removal can be achieved, but harmful catalyst dust is formed

Engineering Contradiction:
Improvecatalyst removal efficiencyVSAvoidcatalyst dust formation
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The invention changes the chemical state of the catalyst from solid particulate form to dissolved ionic form by treating it with oxalic acid solution. This parameter change from solid to dissolved state eliminates dust formation while maintaining effective catalyst removal, as the catalyst components (Mo, V, Nb, Te oxides) dissolve into the acid solution rather than becoming airborne particles.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention replaces mechanical/physical removal methods with a chemical dissolution process. Instead of using physical treatment that generates dust, the catalyst is chemically dissolved in oxalic acid solution, substituting a mechanical system with a chemical system that achieves the same removal goal without harmful byproducts.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

2Productivity

If conventional cleaning methods are used, then catalyst removal is achieved, but the process is inefficient and time-consuming

Engineering Contradiction:
Improvecleaning efficiencyVSAvoidcleaning time
Core Design Contradiction:
ProductivityVSLoss of time

Solution Approach 1:

The invention optimizes the chemical parameters of the cleaning process by using oxalic acid at specific concentrations (0.5-5 M) and temperatures (20-100°C), which dramatically accelerates the dissolution rate of the catalyst components. This parameter optimization enables complete catalyst removal in significantly reduced time compared to conventional methods, improving cleaning efficiency while minimizing time loss.

Inventive Principle:
Principle #35Parameter changes

3Productivity

If strong acids are used to dissolve catalysts, then complete removal is achieved, but damage to reactor components occurs

Engineering Contradiction:
Improvecatalyst dissolution completenessVSAvoidreactor component integrity
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The invention selects oxalic acid as the dissolving agent, which has optimal parameters for selectively dissolving catalyst components (Mo, V, Nb, Te oxides) while being sufficiently mild to avoid damaging reactor components. The acid concentration is controlled at 0.5-5 M, and temperature at 20-100°C, creating a parameter window that achieves complete catalyst removal while preserving reactor integrity.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

Oxalic acid acts as an intermediary substance that facilitates the removal of catalyst components without directly attacking the reactor structure. It selectively interacts with the metal oxide catalyst components, forming soluble complexes, while its mild nature prevents harmful reactions with stainless steel or other reactor materials, thus protecting component integrity.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Productivity

If oxalic acid is used to dissolve catalysts, then catalyst removal is achieved, but alumina support dissolution may occur

Engineering Contradiction:
Improvecatalyst active component removalVSAvoidalumina support loss
Core Design Contradiction:
ProductivityVSLoss of substance

Solution Approach 1:

The invention carefully controls the parameters of oxalic acid treatment (concentration 0.5-5 M, temperature 20-100°C, time sufficient for catalyst dissolution) to create selective dissolution conditions. Under these parameters, the catalyst active components (Mo, V, Nb, Te oxides) dissolve rapidly, while alumina support remains largely intact due to its lower reactivity with oxalic acid under these controlled conditions, minimizing support loss.

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

Effectively dissolves the catalysts and supports in oxalic acid solutions, preventing dust formation and enabling efficient cleaning of reactors and piping, while maintaining the integrity of stainless steel components and allowing for the recovery of valuable metals.

Implementation Method 1

contacting the catalyst with from 10 to 100 mL of not less than a 0.5 molar solution typically not less than 1 M up to the solubility limit of oxalic acid in an aqueous solution at the temperature of treatment per g of catalyst at a temperature from 20°C up to the boiling temperature of a saturated solution preferably greater than 60°C most preferably greater than 80°C for a period of time for at least 1 hour in some cases 20 or more hours; wherein contacting the catalyst comprises dissolving the catalyst in the solution of oxalic acid

Methodology Applied
Scientific EffectChemical Bonding: Chemical Bonding

Data Source

PatentEP3806990B1Removing and cleaning dehydrogenation catalysts
Publication Date: 2023.12.06 NOVA CHEM (INT) SA
  • EP3806990B1 patent drawingFigure 1
  • EP3806990B1 patent drawingFigure 2
  • EP3806990B1 patent drawingFigure 3

AI summary

Oxidative dehydrogenation catalysts comprising mixed oxides of Mo, V, Nb, Te and optionally a promoter may be dissolved in aqueous solutions of oxalic acid. This permits the removal of catalyst and catalyst residues from reactors for the oxidative dehydrogenation of paraffins and particularly ethane.