2DCOR-GC:  An Application of the Generalized Two-Dimensional Correlation Analysis as a Route To Optimization of Continuous Flow Supercritical Fluid Reactions

Abstract

A new approach for optimization and monitoring of continuous reactions has been developed using 2D correlation methods for the analysis of GC data (2DCOR-GC). 2DCOR-GC maps are obtained following perturbation of the system that allow the effect of changing reaction parameters such as time, temperature, pressure, or concentration to be both monitored and sequenced with regard to changes in the raw GC data. In this paper, we describe the application of the 2DCOR-GC technique to monitoring the reverse water-gas shift reaction in scCO(2). 2DCOR-GC is combined with FT-IR data to validate the methodology. We also report the application of 2DCOR-GC to probe the mechanism of the alkylation of m-cresol with isopropyl alcohol in scCO(2) using Nafion SAC-13 as the catalyst. These results identify coeluting peaks that could easily be missed without exhaustive method development.

Two-Dimensional Correlation Analysis Useful for Spectroscopy, Chromatography, and Other Analytical Measurements

“…25,26 Izawa et al first proposed the concept of two-dimensional correlation gel permeation chromatography (2D GPC), applied to the study of reaction dynamics in a silane coupling agent sol-gel polymerization process monitored by a time-resolved GPC technique. 25 A series of GPC traces were collected as a function of the reaction time during the course of the polymerization process, and the time-resolved GPC traces were converted to a set of 2D correlation spectra.…”

Design and additive manufacture for flow chemistry

“…Friedel-Crafts alkylation in supercritical CO2. 169 Automated optimisation was demonstrated by the same group, using the Super Modified Simplex Algorithm (SMSIM) to locate an optimum set of reaction conditions for the methylation of alcohols with dimethyl carbonate. 170 Each set of new reaction conditions were determined from the online analysis, and an optimising feedback procedure set the flow system up and ran the next experiment starting from an initial tetrahedron of conditions.…”

Two-dimensional correlation analysis of the reproducibility of high-performance liquid chromatography columns

“…Another milestone was the application in gas chromatography (GC) published by Hyde at al. [7]. They used hetero-correlation analysis with GC-IR spectroscopy.…”