Investigation of the elution behavior of dissociating itaconic acid on a hydrophobic polymeric adsorbent using in-line Raman spectroscopy

Abstract

The use of adsorption for the purification of dicarboxylic acids is rather limited and currently predominantly confined to ion-exchange chromatography. A promising, but less regarded alternative is the use of hydrophobic adsorbents. Regarding hydrophobic absorbents, the literature focuses on screenings of adsorbents for purification of (di)carboxylic acids with regard to adsorption equilibria. The investigation of dynamic phenomena in the column received only minor attention. In this contribution, this knowledge gap is addressed. First, the adsorption behavior of itaconic acid species on the hydrophobic, highly-crosslinked polymeric adsorbent Chromalite™ PCG1200C is investigated. For this purpose, adsorption isotherms are determined via frontal analysis at pH values of 2, 3, 4.5, 6.5, and 8 to evaluate the dependency of the adsorption capacity on the dissociation state. Capacities above 150 g L_ads^-1 at liquid phase concentrations of 70 g L^-1 are observed at a pH of 2. A strong decrease of capacity with increasing pH value, i.e., with increasing fraction of dissociated negatively charged acid species, is observed. Second, pulse experiments at aforementioned pH values are performed. Thereby, in-line Raman spectra are recorded at the column outlet, which allows the direct differentiation of the acid species state of dissociation. The spectral information is evaluated for quantitative concentration profiles of itaconic acid species using Indirect Hard Modeling with mixture hard models that are calibrated subject to ideal as well as non-ideal thermodynamics. In-line measurement errors of ≤ 3.5 g L^-1 are achieved for the itaconic acid species. In dependency of the pH of the feed solution, a separation of the individual acid species within the pulse experiments is observed. It is conjectured that the process is dominated by a superposition of species-dependent adsorption characteristics and dissociation reactions.

Keywords: Dicarboxylic acid; Hydrophobic adsorbent; Process analytical technology; Raman spectroscopy; Species adsorption.