TBHP Distillation for High Purity Epoxidation

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Solution Overview

Problem

Previous processes for forming tert-butyl hydroperoxide (TBHP) solutions in tert-butyl alcohol (TBA) suffer from yield-lowering impurities and inefficient TBHP loss in distillation overhead streams, leading to lower propylene oxide yields and operational risks due to exothermic reactions during epoxidation.

Innovation Solution

A distillation process that increases TBHP concentration to 65 wt% or higher with a reflux ratio of at least 2:1, reducing impurities to 0.4-1 wt%, followed by controlled introduction of the concentrated TBHP solution into an epoxidation reactor with a molybdenum catalyst for efficient propylene oxide production.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If vacuum distillation process is used to increase TBHP concentration to 65 wt% or higher, then TBHP concentration is improved, but impurity levels increase and TBHP loss in overhead streams occurs

Engineering Contradiction:
ImproveTBHP concentrationVSAvoidimpurity levels
Core Design Contradiction:
Quantity of substanceVSManufacturing precision

Solution Approach 1:

The distillation process is divided into multiple sequential stages: first a debutanizer removes light ends (isobutane, water, methanol, acetone), then a TBA stripper removes heavy ends (TBA, di-TBA ether, water). This segmentation allows each stage to target specific impurities, achieving high TBHP concentration (65 wt% or higher) while maintaining low impurity levels (less than 1 wt%), resolving the contradiction between concentration and purity.

Inventive Principle:
Principle #1Segmentation

2Productivity

If TBHP concentration is increased to 65 wt% or higher, then epoxidation efficiency is improved, but operational risks increase due to highly exothermic reactions

Engineering Contradiction:
Improveepoxidation efficiencyVSAvoidoperational safety
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent performs preliminary purification actions before the epoxidation reaction by removing light ends in the debutanizer and heavy ends in the TBA stripper. This preliminary removal of impurities that could cause unwanted side reactions or safety issues enables the subsequent use of high concentration TBHP (65 wt% or higher) in epoxidation to proceed safely and efficiently, resolving the contradiction between productivity and reliability.

Inventive Principle:
Principle #10Preliminary action

3Productivity

If impurity levels are reduced to less than 1 wt%, then propylene oxide yield is improved, but distillation process complexity increases

Engineering Contradiction:
Improvepropylene oxide yieldVSAvoiddistillation process complexity
Core Design Contradiction:
ProductivityVSDevice complexity

Solution Approach 1:

The distillation system uses a universal solvent (tert-butyl alcohol, TBA) that serves multiple functions: it is the reaction medium for TBHP formation, the extractant for purifying TBHP from light and heavy ends, and the catalyst solvent for the epoxidation reaction. This multi-functionality allows the same solvent to be used throughout the process, achieving low impurity levels (less than 1 wt%) and high propylene oxide yield without requiring complex additional purification equipment.

Inventive Principle:
Principle #6Universality (Multi-functionality)

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 a highly concentrated TBHP solution with low impurities, enabling effective epoxidation catalyst formation and increased propylene oxide production efficiency, while minimizing operational risks and impurity-related issues.

Implementation Method 1

a distillation procedure is employed to form a concentrated TBHP in TBA solution

Methodology Applied
Scientific EffectDistillation: Distillation

Implementation Method 2

The reflux ratio (D/L) employed alternatively is at least 2:1

Methodology Applied
Scientific EffectCondensation: Condensation

Implementation Method 3

an epoxidation catalyst, for a time and under reaction conditions so that a reaction product solution comprised of propylene oxide is formed

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 4

epoxidation reactions carried out by direct injection of solutions with TBHP in TBA concentrations of 65 wt% or higher to an epoxidation reactor are highly exothermic

Methodology Applied
Scientific EffectExothermic Reaction: Exothermic Reaction

Data Source

PatentEP3507273B1Production of tert- butyl hydroperoxide solution and process to form products therefrom
Publication Date: 2021.11.24 LYONDELL CHEMICAL TECHNOLOGY LP
  • EP3507273B1 patent drawingFigure 1
  • EP3507273B1 patent drawing

AI summary

A process for forming a concentrated solution, including distilling in a distillation zone comprised of 10 or more theoretical distillation stages, at a pressure of no greater than 300 mm Hg and a reflux ratio (D/L) of at least 1:1, an amount of an initial solution comprised of tert-butyl hydroperoxide (TBHP) in tert-butyl alcohol (TBA) having a TBHP concentration of up to 60 wt.% and a total impurity content greater than 0.01 wt.%, for a time and under distillation conditions to form a concentrated solution comprised of TBHP in TBA; and separating an overhead distillate from the distillation zone so that the concentrated solution thereafter has a TBHP concentration greater than 60 wt.%, a TBA concentration less than 40 wt.%, a water impurity content no greater than 0.1 wt.% and a total impurity content of no greater than 1 wt.%. Related epoxidation catalyst formation and epoxidation processes are also described.