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<p>In this study, two novel methanesulfonic acid (MSA)-based deep eutectic solvents (DESs) were developed, namely (MSA)/tetraoctylammonium bromide (MSA/TOAB) and MSA/choline chloride (MSA/ChCl), offering a breakthrough in green catalysis for biodiesel production. These DESs demonstrated exceptional catalytic activity, achieving over 99% free fatty acid (FFA) conversion under optimized conditions: a methanol-to-oleic acid (M/O) molar ratio of 12:1, a DES dosage of 2 wt.%, a reaction temperature of 70°C, and a reaction time of 100 min for MSA/TOAB and 60 min for MSA/ChCl. Their industrial applicability was validated by processing high-acid value feedstocks (e.g., grease trap waste and palm acid oil), effectively reducing acid values to below 1 mg KOH/g with minimal pretreatment. Kinetic analysis revealed low activation energies (10.85 kJ/mol for MSA/TOAB and 6.59 kJ/mol for MSA/ChCl), demonstrating their superior energy efficiency. The recyclability of both DESs was also evaluated, with MSA/ChCl retaining over 99% efficiency after three cycles, highlighting its superior stability. Following the esterification, transesterification was successfully conducted using KOH as a catalyst, achieving fatty acid methyl ester (FAME) yields between 87.71 and 96.70%. The highest yield (96.70%) was obtained from soybean oil/oleic acid treated with MSA/ChCl, demonstrating the effectiveness of DESs in ensuring high biodiesel conversion by minimizing FFAs and reducing soap formation. These MSA-based DESs present highly efficient, greener alternatives to conventional acid catalysts, offering advantages such as lower corrosiveness, easy separation, and milder reaction conditions. This study introduces a novel, scalable, and sustainable approach to biodiesel production, emphasizing the potential of MSA-based DESs as next-generation catalysts for industrial applications.</p>

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Introducing Two Novel Methanesulfonic Acid-Based Deep Eutectic Solvents as Efficient Green Catalysts for Enhanced Esterification Reaction: Insights into Kinetics and Industrial Feasibility

  • 期刊论文

  • 发表日期：

    2025年6月10日

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  • Akram Ali Nasser Mansoor Al-Haimi,
  • Fatma Yehia,
  • Fen Liu,
  • Chen Yang,
  • Shunni Zhu,
  • Zhongming Wang

摘要

In this study, two novel methanesulfonic acid (MSA)-based deep eutectic solvents (DESs) were developed, namely (MSA)/tetraoctylammonium bromide (MSA/TOAB) and MSA/choline chloride (MSA/ChCl), offering a breakthrough in green catalysis for biodiesel production. These DESs demonstrated exceptional catalytic activity, achieving over 99% free fatty acid (FFA) conversion under optimized conditions: a methanol-to-oleic acid (M/O) molar ratio of 12:1, a DES dosage of 2 wt.%, a reaction temperature of 70°C, and a reaction time of 100 min for MSA/TOAB and 60 min for MSA/ChCl. Their industrial applicability was validated by processing high-acid value feedstocks (e.g., grease trap waste and palm acid oil), effectively reducing acid values to below 1 mg KOH/g with minimal pretreatment. Kinetic analysis revealed low activation energies (10.85 kJ/mol for MSA/TOAB and 6.59 kJ/mol for MSA/ChCl), demonstrating their superior energy efficiency. The recyclability of both DESs was also evaluated, with MSA/ChCl retaining over 99% efficiency after three cycles, highlighting its superior stability. Following the esterification, transesterification was successfully conducted using KOH as a catalyst, achieving fatty acid methyl ester (FAME) yields between 87.71 and 96.70%. The highest yield (96.70%) was obtained from soybean oil/oleic acid treated with MSA/ChCl, demonstrating the effectiveness of DESs in ensuring high biodiesel conversion by minimizing FFAs and reducing soap formation. These MSA-based DESs present highly efficient, greener alternatives to conventional acid catalysts, offering advantages such as lower corrosiveness, easy separation, and milder reaction conditions. This study introduces a novel, scalable, and sustainable approach to biodiesel production, emphasizing the potential of MSA-based DESs as next-generation catalysts for industrial applications.