Integrated HFO-1234yf Synthesis with Fluorination and Dehydrochlorination

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Solution Overview

Problem

Existing methods for producing hydrofluoroolefins like HFO-1234yf are either hazardous, economically costly, or result in low yields with significant byproduct formation, necessitating a more efficient and economical production process.

Innovation Solution

An integrated manufacturing process involving three separate reaction steps, including vapor and liquid phase reactions, utilizing specific catalysts and reactors, with optional purification processes, which maximizes raw material utilization and product yields, and includes the ability to isolate by-products that are commercially valuable. The process includes the ability to recycle unreacted starting materials to maximize raw material utilization and product yields, and includes the ability to isolate by-products that are commercially valuable.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If hydrogen gas is used to contact fluorinated alcohols for producing HFOs, then the process achieves relatively high yield, but the process becomes hazardous due to commercial scale handling of hydrogen gas at high temperature and economically costly due to the need for on-site hydrogen plants

Engineering Contradiction:
ImproveyieldVSAvoidhazard
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

The patent extracts the hazardous hydrogen gas handling step from the process by using alternative fluorinating agents (such as sulfur tetrafluoride or gaseous fluorine) that can be delivered without requiring on-site hydrogen production facilities, thereby eliminating the associated hazards and infrastructure costs while maintaining high yields

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent introduces intermediate compounds (fluorinated alcohols as starting materials) that can be converted to HFOs through fluorination reactions using safer, more manageable fluorinating agents, serving as intermediaries that avoid direct hydrogen gas handling while achieving the desired product

Inventive Principle:
Principle #24Intermediary (Mediator)

2Ease of manufacture

If pyrolysis of methyl chloride and tetrafluoroethylene is used to make fluorine containing olefins, then the process can be performed with available materials, but the process results in relatively low yield and significant formation of unwanted byproducts including carbon black that deactivates the catalyst

Engineering Contradiction:
Improveavailability of starting materialsVSAvoidyield
Core Design Contradiction:
Ease of manufactureVSProductivity

Solution Approach 1:

The patent performs preliminary fluorination of chlorinated hydrocarbons to create pre-fluorinated intermediates before the final olefin formation step, ensuring that fluorine atoms are already in place on the molecular structure, which directs the reaction toward the desired HFO product and prevents formation of carbon black and other unwanted byproducts

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent changes the reaction parameters by using controlled fluorination conditions with specific fluorinating agents and catalysts, transitioning from uncontrolled pyrolysis conditions to a more selective chemical reaction environment that achieves high yields while minimizing byproduct formation

Inventive Principle:
Principle #35Parameter changes

3Ease of manufacture

If pyrolysis process is used for producing fluorine containing olefins, then the process can proceed with available starting materials, but a very large percentage of organic starting material is converted to unwanted and unimportant byproducts

Engineering Contradiction:
Improveprocess feasibilityVSAvoidstarting material conversion to byproducts
Core Design Contradiction:
Ease of manufactureVSLoss of substance

Solution Approach 1:

The patent converts the potential harm of excessive reactivity in pyrolysis processes into benefit by using controlled fluorination reactions where the high reactivity of fluorinating agents is directed toward specific positions on the chlorinated hydrocarbon molecules, ensuring that starting material is converted to desired HFO products rather than unwanted byproducts

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

The process achieves high yields and maximizes raw material utilization and product yields, and includes the ability to isolate by-products that are commercially valuable, thereby achieving high yields and reducing production costs.

Implementation Method 1

contacting said starting composition with a first fluorinating agent to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene

Methodology Applied
Scientific EffectNucleophilic substitution: Chemical Bonding

Implementation Method 2

contacting said first intermediate composition with a second fluorinating agent to produce a second intermediate composition comprising 2-chloro-1,1,1,2- tetrafluoropropane

Methodology Applied
Scientific EffectNucleophilic substitution: Chemical Bonding

Implementation Method 3

catalytically dehydrochlorinating at least a portion of said 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product comprising 2,3,3,3-tetrafluoroprop-1-ene

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP3722273B1Integrated process to produce 2,3,3,3-tetrafluoropropene
Publication Date: 2026.04.29 SOLSTICE ADVANCED MATERIALS US INC
  • EP3722273B1 patent drawingFigure 1
  • EP3722273B1 patent drawingFigure 2
  • EP3722273B1 patent drawingFigure 3

AI summary

A method for preparing 2,3,3,3-tetrafluoroprop-1-ene comprising (a) providing a starting composition comprising at least one compound having a structure selected from Formulae I, II and III:          CX2=CCl-CH2X     (Formula I)          CX3-CCl=CH2     (Formula II)          CX3-CHCl-CH2X     (Formula III) wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine; (b) contacting said starting composition with a first fluorinating agent to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene and a first chlorine-containing byproduct; (c) contacting said first intermediate composition with a second fluorinating agent to produce a second intermediate composition comprising 2-chloro-1,1,1,2-tetrafluoropropane and a second chlorine-containing byproduct; and (d) catalytically dehydrochlorinating at least a portion of said 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product comprising 2,3,3,3-tetrafluoroprop-1-ene.