| Autor: |
Kojčinović A; Department of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia.; Graduate School, University of Nova Gorica, Vipavska Cesta 13, 5000 Nova Gorica, Slovenia., Likozar B; Department of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia.; Pulp and Paper Institute, Bogišićeva 8, 1000 Ljubljana, Slovenia.; Faculty of Polymer Technology, Ozare 19, SI-2380 Slovenj Gradec, Slovenia., Grilc M; Department of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia.; Graduate School, University of Nova Gorica, Vipavska Cesta 13, 5000 Nova Gorica, Slovenia.; Pulp and Paper Institute, Bogišićeva 8, 1000 Ljubljana, Slovenia. |
| Abstrakt: |
Combining carboxylation reactions using carbon dioxide (CO 2 ) as a reactant with phenol results in creation of new C-C bonds, and represents one of the most promising routes in sustainable utilization of ubiquitous and readily available resources for production of highly valuable products. This study provides a detailed and well-structured investigation of the effect of various reaction conditions (reactant loading, reaction duration, temperature, CO 2 pressure) on the carboxylation of phenol. Sodium phenoxide carboxylation showed well-resolved trends with variation of temperature and time, and resulted in production of salicylic acid (SA) in the range of 11.4 to 47.8%, 4-hydoxybenzoic acid (4HBA) in the range of 2.0 to 8.2%, while the dicarboxylated 4-hydroxyisophthalic acid (4HiPh) was only detected in trace amounts. The effect of the variation of reactant content was shown to be significantly influenced by the reactor size, solid/vessel and gas/solid contact area, as well as the efficiency of the stirring. CO 2 pressure was shown to be a crucial element, where reactions carried out below 2 MPa CO 2 did not show any activity. While investigating the reaction mechanism, it was shown that the salt analogues of potential products could be acidified in situ by the moisture present, and immediately degraded back to phenol, thus lowering yields of potentially obtained products. The experimental results were successfully used to compose a kinetic model, which very well describes the experimentally obtained results. As such, this study provides a valuable dataset for valorization of lignocellulosic aromatic compounds as well as highly abundant and environmentally detrimental carbon dioxide into industrially valuable mono- and dicarboxylic acids. |
