Continuous HFO 1234yf Synthesis via Selective Fluorination

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Solution Overview

Problem

Current processes for producing 2,3,3-tetrafluoro-1-propene (HFO 1234yf) often result in low selectivity and yield, and there is a need for a more efficient and continuous method using easily accessible starting materials.

Innovation Solution

A continuous gas-phase process involving hydrogenation and dehydrofluorination steps, with specific molar ratios of hydrogen and catalysts, to produce 2,3,3-tetrafluoro-1-propene, utilizing hexafluoropropylene as a starting material and recycling unreacted intermediates to enhance selectivity and yield.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional processes (pyrolysis or catalytic conversion of HFC 245eb) are used to produce HFO 1234yf, then production is achieved, but selectivity is low and substantial amounts of unwanted isomer HFO 1234ze are formed

Engineering Contradiction:
ImproveselectivityVSAvoidunwanted byproducts
Core Design Contradiction:
Manufacturing precisionVSObject-generated harmful factors

Solution Approach 1:

The process is divided into four sequential reaction steps with distinct functions: hydrogenation of HFP to HFC 236ea, dehydrofluorination to HFO 1225ye, hydrogenation to HFC 245eb, and final dehydrofluorination to HFO 1234yf. Each step is optimized independently to maximize selectivity and minimize unwanted isomers at each stage.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The process performs preliminary hydrogenation and dehydrofluorination steps before the final product formation. By pre-forming specific intermediates (HFC 236ea, HFO 1225ye, HFC 245eb) with controlled fluorine positioning, the final dehydrofluorination step achieves high selectivity for HFO 1234yf over unwanted isomers.

Inventive Principle:
Principle #10Preliminary action

2Productivity

If conventional processes are used, then HFO 1234yf is produced, but yield is low due to formation of unwanted isomers and byproducts

Engineering Contradiction:
ImproveyieldVSAvoidunreacted intermediates
Core Design Contradiction:
ProductivityVSLoss of substance

Solution Approach 1:

The process operates continuously with unreacted intermediates (HFC 236ea, HFO 1225ye, HFC 245eb) being recycled back to the appropriate reaction steps. This eliminates idle time and ensures that all feedstock is eventually converted to product, maximizing overall yield.

Inventive Principle:
Principle #20Continuity of useful action

Solution Approach 2:

The process incorporates feedback loops where reaction products are analyzed and unreacted intermediates are identified and recycled. This closed-loop system continuously optimizes conversion efficiency and minimizes material loss by redirecting unreacted species back into the production stream.

Inventive Principle:
Principle #23Feedback

3Manufacturing precision

If multiple reaction steps are implemented, then selectivity is improved, but process complexity increases

Engineering Contradiction:
ImproveselectivityVSAvoidprocess complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

Multiple reaction steps (hydrogenation, dehydrofluorination, hydrogenation, dehydrofluorination) are merged into a single continuous process flow with integrated recycling. This consolidation achieves high selectivity through sequential optimization while managing complexity through unified process control and intermediate recycling.

Inventive Principle:
Principle #5Merging (Combining)

Data Source

PatentEP2271604B1Method for preparing 2,3,3,3-tetrafluoro-1-propene
Publication Date: 2018.06.27 ARKEMA FRANCE SA

AI summary

The invention relates to a gas phase continuous method for preparing 2,3,3,3-tetrafluoro-1-propene, said method comprising the following steps: (i) hydrogenation of hexafluoropropylene to form 1,1,1,2,3,3 -hexafluoropropane; (ii) dehydrofluorination of the 1,1,1,2,3,3-hexafluoropropane obtained in the previous step, to form 1,2,3,3,3-pentafluoropropene-1; (iii) hydrogenation of the 1,2,3,3,3-pentafluoropropene-1 obtained in the previous step, to form 1,1,1,2,3-pentafluoropropane; and (iv) dehydrofluorination of the 1,1,1,2,3-pentafluoropropane obtained in the previous step, to form 2,3,3,3-tetrafluoro-1-propene.