HFO-1234yf Production via Chromium Oxide Catalysis

Resolve Bottlenecks,
Find Innovative Solutions
Generate Solutions

Solution Overview

Problem

Current processes for producing 2,3,3-tetrafluoropropene (HFO-1234yf) are inefficient, requiring expensive reagents, severe reaction conditions, and low yields, making them unsuitable for industrial-scale production.

Innovation Solution

A single-step process using a fluorine-containing propane, such as CF2ClCF2CH3, contacted with chromium oxides or iron fluorides in a gas phase, in the presence of oxygen and hydrogen fluoride, to produce HFO-1234yf with improved selectivity and yield.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If hydrogen fluoride is used in large excess (18 mol per mol of starting material) to prepare HFO-1234yf using chromium oxyfluoride, then the reaction can proceed, but the efficiency deteriorates due to poor atom economy and high reagent consumption

Engineering Contradiction:
Improvereaction efficiencyVSAvoidhydrogen fluoride consumption
Core Design Contradiction:
ProductivityVSLoss of substance

Solution Approach 1:

The patent changes the molar ratio parameter from the conventional 18:1 (HF:starting material) to a much lower ratio, achieving the same reaction efficiency with significantly reduced hydrogen fluoride consumption. This parameter optimization directly resolves the contradiction between productivity and substance loss.

Inventive Principle:
Principle #35Parameter changes

2Ease of manufacture

If zinc is used as reagent in ethanol to produce HFO-1234yf in a single-step process, then the reaction proceeds, but the process becomes unsuitable for industrial-scale production due to high cost and large waste production

Engineering Contradiction:
Improveprocess simplicityVSAvoidindustrial scalability
Core Design Contradiction:
Ease of manufactureVSProductivity

Solution Approach 1:

The patent replaces expensive zinc reagent with a catalyst system that can be used in small amounts and potentially regenerated. This substitution makes the process economically viable for industrial-scale production while maintaining ease of manufacture.

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

Solution Approach 2:

The catalytic system allows for potential recovery and reuse of the catalyst, reducing waste production compared to stoichiometric zinc consumption. This aligns with green chemistry principles for industrial scalability.

Inventive Principle:
Principle #34Discarding and recovering

3Productivity

If palladium catalyst supported on carrier is used for gas phase reduction of HFC-1214ya to produce HFO-1234yf, then the reaction can proceed, but the yield remains unsatisfactory and requires further improvement

Engineering Contradiction:
Improvereaction yieldVSAvoidcatalyst system complexity
Core Design Contradiction:
ProductivityVSDevice complexity

Solution Approach 1:

The patent employs a composite catalyst system combining chromium oxyfluoride with other materials to achieve satisfactory yield. The composite structure enhances catalytic activity and selectivity compared to simple palladium catalysts.

Inventive Principle:
Principle #40Composite materials

4Productivity

If other reported processes (amine reaction, thermal decomposition, Lewis acid catalysis) are used to prepare HFO-1234yf, then the reaction can proceed, but they are not effective for industrial purposes due to difficult starting materials, severe conditions, expensive reagents, or low yield

Engineering Contradiction:
Improveoverall process effectivenessVSAvoidprocess feasibility
Core Design Contradiction:
ProductivityVSEase of manufacture

Solution Approach 1:

The patent optimizes reaction parameters including temperature, pressure, molar ratios, and catalyst composition to achieve a balance between effectiveness and feasibility. The modified conditions make the process suitable for industrial application while maintaining high yield.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent replaces expensive reagents (amines, Lewis acids like SbF5) with more economical chromium-based catalysts, making the process economically viable for industrial production while maintaining effectiveness.

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

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 high yield and selectivity of HFO-1234yf, maintaining catalytic activity over an extended period while reducing catalyst degradation, making it economically viable for industrial production.

Implementation Method 1

contacting a fluorine-containing propane represented by the formula CF2XCFYCH2Z with at least one catalyst selected from the group consisting of chromium oxides, fluorinated chromium oxides, and iron fluorides in a gas phase

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP2318339B1Process for preparing 2,3,3,3-tetrafluoropropene
Publication Date: 2012.09.05 DAIKIN INDUSTRIES LTD

AI summary

The present invention provides a process for producing 2,3,3,3-tetrafluoropropene represented by the formula CF3CF=CH2, comprising contacting a fluorine-containing propane represented by the formula CF2XCFYCH2Z, wherein X is Cl, Br, or I; one of Y and Z is H, and the other is F, Cl, Br, or I, with at least one catalyst selected from the group consisting of chromium oxides, fluorinated chromium oxides, and iron fluorides in a gas phase. According to the process of the invention, 2,3,3,3-tetrafluoropropene can be easily produced under economically advantageous conditions.