Pd-Bi-Sb Catalyst for Oxidative Esterification Selectivity

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Solution Overview

Problem

Existing catalysts for oxidative esterification, such as those using Pd-Bi catalysts or Pd-Bi-X intermetallics on ZnO or CaCO3 supports, suffer from low MMA selectivity and mechanical instability, making them unsuitable for efficient production of methyl methacrylate (MMA).

Innovation Solution

A catalyst comprising palladium, bismuth, and antimony supported on alumina is used for oxidative esterification of methacrolein and methanol, with optimized ratios and preparation methods to enhance MMA selectivity and catalyst stability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If Pd-Bi catalyst is used for oxidative esterification, then the reaction can proceed, but MMA selectivity is low

Engineering Contradiction:
ImproveMMA selectivityVSAvoidreaction efficiency
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent changes the chemical composition parameters of the catalyst by introducing antimony (Sb) in addition to palladium (Pd) and bismuth (Bi), and optimizes their atomic ratios (Pd: 1-10 wt%, Bi: 1-20 wt%, Sb: 1-30 wt%). This parameter modification significantly improves MMA selectivity while maintaining reaction efficiency.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite catalyst system combining Pd-Bi-Sb metals supported on alumina. This composite structure leverages the synergistic effects of different metals to achieve high MMA selectivity (above 90%) while maintaining catalytic activity, resolving the contradiction between selectivity and productivity.

Inventive Principle:
Principle #40Composite materials

2Reliability

If ZnO or CaCO3 support is used for Pd-Bi-X intermetallics, then catalyst activity is achieved, but mechanical stability and acid resistance are poor

Engineering Contradiction:
Improvecatalyst activityVSAvoidmechanical stability and acid resistance
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent replaces expensive and unstable supports (ZnO, CaCO3) with alumina, which provides superior mechanical stability, acid resistance, and thermal stability. This substitution maintains catalyst activity while dramatically improving the structural integrity and longevity of the catalyst system.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The patent changes the support material parameter from carbonate or oxide supports to alumina support, which has higher surface area, better mechanical strength, and superior chemical stability. This parameter change resolves the contradiction between catalyst activity and structural stability.

Inventive Principle:
Principle #35Parameter changes

3Device complexity

If conventional catalysts are used, then the process is simple, but long-term catalyst life is limited

Engineering Contradiction:
Improveprocess simplicityVSAvoidcatalyst life
Core Design Contradiction:
Device complexityVSDuration of action of stationary object

Solution Approach 1:

The patent develops a composite Pd-Bi-Sb/alumina catalyst that combines multiple metal components with a stable alumina support. This composite structure enhances catalyst durability and resistance to deactivation, extending catalyst life while maintaining process simplicity through a single-step catalytic system.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent optimizes the metal composition parameters (Pd: 1-10 wt%, Bi: 1-20 wt%, Sb: 1-30 wt%) and support properties to achieve long-term stability. The alumina support provides thermal and mechanical stability, while the optimized metal ratios prevent sintering and deactivation, extending catalyst operational life.

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 process achieves high selectivity to MMA, with selectivity rates of at least 90% and yield calculations confirming the effectiveness of the catalyst system in producing methyl methacrylate efficiently.

Implementation Method 1

contacting MAL, methanol, and an oxygen-containing gas in a reaction zone in the presence of a catalyst comprising palladium, bismuth, and antimony under reaction conditions sufficient to produce MMA

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

a catalyst comprising at least palladium and X, X representing bismuth and/or lead, supported on a carrier

Methodology Applied
Scientific EffectAdsorption: Adsorption

Data Source

PatentEP3212608B1Oxidative esterification process for making methyl methacrylate
Publication Date: 2020.12.30 ROHM & HAAS CO

AI summary

A process for the preparation of MMA via oxidative esterification in the presence of a catalyst comprising palladium, bismuth, and antimony.