Oxidative Dehydrogenation Catalyst Preparation via Solvothermal Synthesis

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Solution Overview

Problem

Current methods for producing 1,3-butadiene, such as naphtha cracking and direct butene dehydrogenation, are inefficient due to high energy consumption and side product formation, while existing metal oxide catalysts for oxidative dehydrogenation suffer from poor uniformity and low surface area, leading to reduced catalytic activity and increased catalyst usage.

Innovation Solution

A method involving the preparation of nano-scale metal oxide nanoparticles with a spinel structure, specifically ZnFe2O4, and supporting them on a substrate to enhance surface area and reactivity, using a mixed solution of non-chloride precursors, organic solvent, unsaturated fatty acid, and surfactant, and heating to control particle diameter and dispersion.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If coprecipitation method is used to synthesize metal oxide catalyst, then catalyst can be produced in bulk, but uniformity is poor and surface area per unit volume is small

Engineering Contradiction:
Improvecatalyst production volumeVSAvoidcatalyst uniformity
Core Design Contradiction:
Quantity of substanceVSManufacturing precision

Solution Approach 1:

The patent changes the fundamental synthesis parameters from aqueous coprecipitation to organic solvent-based solvothermal method. This involves using non-aqueous solvents (alcohols, esters, ethers), changing temperature ranges (100-300°C), and modifying pH conditions, which collectively enable precise control over nanoparticle formation while maintaining bulk production capability

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite catalyst systems by combining metal oxides (ZnO, Fe2O3, CuO, MnO2) with organic modifiers (fatty acids, surfactants) during synthesis. These organic components act as structure-directing agents and size-controlling agents, resulting in composite nanoparticle structures with enhanced uniformity and controlled surface area

Inventive Principle:
Principle #40Composite materials

2Quantity of substance

If coprecipitation method is used to synthesize metal oxide catalyst, then catalyst can be produced in bulk, but surface area per unit volume is small

Engineering Contradiction:
Improvecatalyst production volumeVSAvoidcatalyst surface area
Core Design Contradiction:
Quantity of substanceVSArea of stationary object

Solution Approach 1:

The patent employs solvothermal synthesis parameters including elevated temperatures (100-300°C), controlled pressure conditions, and extended reaction times (1-24 hours) to produce nanoparticles with diameters of 1-30 nm. These parameter changes enable high surface area per unit volume while maintaining scalability for bulk production

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces organic intermediaries including fatty acids (oleic acid, stearic acid) and surfactants (CTAB, SDS) that act as capping agents during nanoparticle formation. These intermediaries control particle growth kinetics and prevent aggregation, resulting in dispersed nanoparticles with high surface area that can be produced in bulk quantities

Inventive Principle:
Principle #24Intermediary (Mediator)

3Quantity of substance

If conventional catalyst is used for oxidative dehydrogenation, then catalyst amount can be reduced, but side reaction inhibition is insufficient and catalytic activity is low

Engineering Contradiction:
Improvecatalyst usage amountVSAvoidside reaction occurrence
Core Design Contradiction:
Quantity of substanceVSObject-generated harmful factors

Solution Approach 1:

The patent creates catalysts with non-uniform surface properties by controlling nanoparticle morphology and surface composition. The solvothermal method produces particles with specific crystal facets and surface terminations that have enhanced selectivity for the desired dehydrogenation reaction while suppressing side reactions, allowing reduced catalyst dosage

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The patent develops composite metal oxide catalysts (ZnO-Fe2O3, CuO-ZnO, MnO2-ZnO) where synergistic interactions between different metal oxides enhance both catalytic activity and selectivity. The organic modifiers incorporated during synthesis further tune the electronic and geometric properties of the catalyst surface, improving side reaction inhibition

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

This approach results in a catalyst with high butene conversion rates, superior side reaction inhibition, and increased selectivity for 1,3-butadiene production, reducing catalyst usage and byproduct formation.

Implementation Method 1

a method of preparing a catalyst for oxidative dehydrogenation, wherein the method is performed by supporting or coating a nano-scale metal oxide on a support and comprises a step of obtaining a mixed solution by mixing a non-chloride precursor of Zn, a non-chloride precursor of Fe(III), an organic solvent having a boiling point of 250°C or more, unsaturated fatty acid, and a surfactant and then heating the mixed solution at 100 to 350 °C to prepare a metal oxide

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 2

heating the mixed solution at 100 to 350 °C to prepare a metal oxide having a composition represented by Formula 1 below and an average particle diameter of 1 to 30 nm

Methodology Applied
Scientific EffectHeating: Heating

Data Source

PatentEP3345677B1Method for preparing an oxidative dehydrogenation catalyst
Publication Date: 2023.04.19 LG CHEM LTD
  • EP3345677B1 patent drawingFigure 1~2
  • EP3345677B1 patent drawingFigure 3~4
  • EP3345677B1 patent drawing

AI summary

Disclosed are a catalyst for oxidative dehydrogenation and a method of preparing the same. More particularly, a catalyst for oxidative dehydrogenation of butene having a high butene conversion rate and superior side reaction inhibition effect and thus having high reactivity and high selectivity for a product by preparing metal oxide nanoparticles and then fixing the prepared metal oxide nanoparticles to a support, and a method of preparing the same are provided.