Cerium-Promoted Skeletal Catalysts for Low-Butanol BDO Hydrogenation

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Solution Overview

Problem

Current catalysts for producing 1,4-butanediol from 1,4-butynediol suffer from predictable limited lifetime and produce significant amounts of n-butanol and other byproducts, which are difficult to suppress despite optimized operating conditions.

Innovation Solution

Incorporating cerium as a promoter in a skeletal metal catalyst, such as nickel-aluminum, and activating the catalyst with an alkali solution to form an alloy, which reduces the formation of n-butanol and other byproducts during the hydrogenation process.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If conventional promoters (Mo, Cr, or Fe) are added to skeletal metal catalysts, then catalyst activity is improved, but butanol byproduct formation increases due to increased surface acidity

Engineering Contradiction:
Improvecatalyst activityVSAvoidbutanol byproduct formation
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The patent changes the chemical parameter of the promoter from conventional elements (Mo, Cr, Fe) to rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). This parameter change fundamentally alters the catalyst's acid-base properties, reducing surface acidity while maintaining or enhancing catalytic activity for hydrogenation, thereby suppressing butanol byproduct formation.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite catalyst system combining skeletal metal (Ni, Co, or Cu) with rare earth promoters and optionally with alumina. This composite structure leverages the synergistic effects of different materials: the skeletal metal provides hydrogenation activity, while the rare earth components regulate surface acidity and improve selectivity, achieving both high activity and low byproduct formation.

Inventive Principle:
Principle #40Composite materials

2Object-generated harmful factors

If optimized operating conditions (low temperature, high pressure, controlled feed pH) are used, then butanol formation is reduced, but the reduction is insufficient to meet impurity limits

Engineering Contradiction:
Improvebutanol byproduct formationVSAvoidimpurity limit compliance
Core Design Contradiction:
Object-generated harmful factorsVSReliability

Solution Approach 1:

The patent extracts and eliminates the root cause of butanol formation by removing acidic Al species from the catalyst through selective leaching with碱 solutions. This extraction process selectively removes the harmful acidic components while retaining the beneficial catalytic metal structures, achieving fundamental suppression of butanol byproduct formation beyond what operating condition optimization can accomplish.

Inventive Principle:
Principle #2Taking out (Extraction)

3Stability of the object's composition

If acidic Al species are present in the skeletal metal catalyst, then catalyst structure is maintained, but byproduct formation including butanol increases

Engineering Contradiction:
Improvecatalyst structureVSAvoidbyproduct formation
Core Design Contradiction:
Stability of the object's compositionVSObject-generated harmful factors

Solution Approach 1:

The patent applies local quality modification by selectively removing acidic Al species from specific regions of the catalyst while preserving the skeletal metal structure. The selective leaching process creates a catalyst with localized properties: areas with reduced acidity for high selectivity while maintaining the overall structural integrity and catalytic functionality through the preserved metal framework.

Inventive Principle:
Principle #3Local quality

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 significantly lowers the production of n-butanol to less than 3.0% by weight, improving the catalyst's selectivity and stability, thereby reducing downstream purification costs.

Implementation Method 1

reacting a solution comprising 1,4-butynediol with hydrogen in a presence of a catalyst

Methodology Applied
Scientific EffectHydrogenation: Hydrogenation

Implementation Method 2

The catalyst may be a skeletal metal catalyst, which includes cerium as a promoter

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 3

The activation process may include selectively removing aluminum from the alloy

Methodology Applied
Scientific EffectSelective leaching:

Data Source

PatentUS12479782B2Catalysts, preparation method thereof, and selective hydrogenation processes
Publication Date: 2025.11.25 WR GRACE & CO CONN

AI summary

The present invention relates to a process for making 1,4 butanediol. The process may include reacting a solution comprising 1,4-butynediol with hydrogen in a presence of a catalyst. The catalyst may include cerium.