Catalytic Selective Oxidation of β-O-4 Bond in Phenethoxybenzene as a Lignin Model Using (TBA)5[PMo10V2O40] Nanocatalyst: Optimization of Operational Conditions

Author:

Díaz Juan12,Pizzio Luis R.3,Pecchi Gina12ORCID,Campos Cristian H.1ORCID,Azócar Laura4,Briones Rodrigo5,Romero Romina1ORCID,Troncoso Eduardo12ORCID,Méndez-Rivas Camila1,Melín Victoria1,Murillo-Sierra Juan C.1,Contreras David12ORCID

Affiliation:

1. Facultad de Ciencias Químicas, Universidad de Concepción, Concepción 4070386, Chile

2. ANID—Millennium Science Initiative Program—Millennium Nuclei on Catalytic Process towards Sustainable Chemistry (CSC), Santiago 8970117, Chile

3. Centro de Investigación y Desarrollo en Ciencias Aplicadas Dr. Jorge J. Ronco, Universidad de La Plata, La Plata B1900AJK, Argentina

4. Centro de Energía, Departamento de Química Ambiental, Facultad de Ciencias, Universidad Católica de la Santísima Concepción, Concepción 4090541, Chile

5. Centro de Investigación de Polímeros Avanzados (CIPA), Concepción 4051381, Chile

Abstract

The catalytic oxidation of phenethoxybenzene as a lignin model compound with a β-O-4 bond was conducted using the Keggin-type polyoxometalate nanocatalyst (TBA)5[PMo10V2O40]. The optimization of the process’s operational conditions was carried out using response surface methodology. The statistically significant variables in the process were determined using a fractional factorial design. Based on this selection, a central circumscribed composite experimental design was used to maximize the phenethoxybenzene conversion, varying temperature, reaction time, and catalyst load. The optimal conditions that maximized the phenethoxybenzene conversion were 137 °C, 3.5 h, and 200 mg of catalyst. In addition, under the optimized conditions, the Kraft lignin catalytic depolymerization was carried out to validate the effectiveness of the process. The depolymerization degree was assessed by gel permeation chromatography from which a significant decrease in the molar mass distribution Mw from 7.34 kDa to 1.97 kDa and a reduction in the polydispersity index PDI from 6 to 3 were observed. Furthermore, the successful cleavage of the β-O-4 bond in the Kraft lignin was verified by gas chromatography–mass spectrometry analysis of the reaction products. These results offer a sustainable alternative to efficiently converting lignin into valuable products.

Funder

Millennium Science Initiative

Project National Agency for Research and Development

Chilean ANID Doctorate

Doctoral Thesis in Productive Area

FONDAP SERC-CHILE

Publisher

MDPI AG

Subject

Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science

Reference43 articles.

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4. Oxidative Upgrade of Lignin—Recent Routes Reviewed;Lange;Eur. Polym. J.,2013

5. Joungerius, A.L. (2013). Catalytic Conversion of Lignin for the Production of Aromatics. [Ph.D. Thesis, University of Utrecht].

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