Dehydration of Alpha-Substituted Carboxylic Acids in High-Pressure Water

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Solution Overview

Problem

Existing dehydration processes for alpha-substituted carboxylic acids, such as alpha-hydroxyisobutyric acid, suffer from low single pass conversions, significant by-product formation, particularly dimeric and oligomeric forms, which require laborious separation and result in energy-intensive recycling, and catalyst-related commercial disadvantages.

Innovation Solution

A catalyst-free process is developed, operating at pressures of 40-1000 bar in the presence of water, achieving high conversions and minimizing by-product formation by maintaining reaction conditions of 280-400°C and residence times of 1-300 seconds, with water concentrations of 10-90% and using alkali metal or alkaline earth metal salts as pH buffers.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If dehydration is carried out at atmospheric pressure and 210-225°C with alkali metal catalysts, then the reaction proceeds with catalyst activity, but by-products (dimeric and oligomeric forms) accumulate and require continuous catalyst addition and partial discharge

Engineering Contradiction:
Improvereaction rateVSAvoidby-product formation
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The invention changes the pressure parameter from atmospheric pressure to high pressure (40-1000 bar) and adjusts temperature to 280-400°C, which fundamentally alters the reaction pathway to achieve high conversion (up to 90%) while suppressing by-product formation through the unique properties of high-pressure water environment

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention removes the catalyst component from the system entirely, replacing catalytic dehydration with direct thermal dehydration in high-pressure water, thereby eliminating the harmful side reactions that catalysts promote while maintaining high reaction efficiency

Inventive Principle:
Principle #2Taking out (Extraction)

2Productivity

If catalysts are used to achieve dehydration, then conversion efficiency improves, but catalyst losses and recovery complexities increase operational costs

Engineering Contradiction:
Improveconversion efficiencyVSAvoidcatalyst loss
Core Design Contradiction:
ProductivityVSLoss of substance

Solution Approach 1:

The invention completely removes catalysts from the dehydration process by utilizing high-pressure water (40-1000 bar) at 280-400°C to directly dehydrate alpha-hydroxyisobutyric acid to methacrylic acid, achieving up to 90% conversion without any catalyst addition, recovery, or disposal requirements

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The high-pressure water environment serves as both the reaction medium and the enabling condition for the reaction itself, where water under high pressure and temperature directly facilitates the dehydration reaction through its unique physical-chemical properties, eliminating the need for external catalyst assistance

Inventive Principle:
Principle #25Self-service

3Device complexity

If low single pass conversion is accepted, then separation and recycling processes can be simpler, but energy consumption increases due to laborious separation and recycling requirements

Engineering Contradiction:
Improveseparation process complexityVSAvoidenergy consumption
Core Design Contradiction:
Device complexityVSUse of energy by moving object

Solution Approach 1:

By changing to high pressure (40-1000 bar) and elevated temperature (280-400°C), the invention achieves high single-pass conversion (up to 90%) that simplifies downstream separation and eliminates the need for energy-intensive recycling operations, as the reaction proceeds to near-completion in a single pass

Inventive Principle:
Principle #35Parameter changes

4Productivity

If halide salts are used as catalysts, then dehydration reaction proceeds, but alpha-halogenated by-products form and corrosive materials are required

Engineering Contradiction:
Improvereaction proceedsVSAvoidalpha-halogenated by-products and corrosion
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The invention removes halide salt catalysts from the system and replaces them with high-pressure water as the reaction medium, which achieves dehydration without generating alpha-halogenated by-products and eliminates the need for corrosion-resistant materials by operating in a non-corrosive water environment

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention converts the typically harmful role of water (which would normally need to be removed in dehydration reactions) into a beneficial high-pressure reaction medium that enables the dehydration to proceed at high conversion while suppressing unwanted side reactions through its unique properties under pressure

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

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 process achieves conversions of up to 90% with by-product formation reduced to less than 2%, primarily eliminating dimeric and oligomeric impurities, thereby improving selectivity to over 96% and reducing energy consumption and catalyst losses.

Implementation Method 1

carrying out the dehydration in the presence of water and at pressures of 40-1000 bar

Methodology Applied
Scientific EffectHigh pressure water reaction medium: Pressure Increase

Implementation Method 2

achieving high conversions and minimizing by-product formation by maintaining reaction conditions of 280-400°C

Methodology Applied
Scientific EffectThermal energy activation: Heating

Implementation Method 3

using alkali metal or alkaline earth metal salts as pH buffers

Methodology Applied
Scientific EffectpH buffering: Electrolyte

Data Source

PatentUS10160713B2Dehydration of alpha-substituted carboxylic acids in the presence of water at high pressures
Publication Date: 2018.12.25 ROHM GMBH
  • US10160713B2 patent drawing
  • US10160713B2 patent drawing
  • US10160713B2 patent drawing

AI summary

The present invention describes a process for dehydrating alpha-substituted carboxylic acids in the presence of water at high pressures while avoiding by-products.