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<p>Current thermochemical methods for hydrogen (H<sub>2</sub>) production, such as coal gasification and steam reforming, inevitably produce anthropogenic CO<sub>2</sub>. In contrast, biomass-derived H<sub>2</sub> offers a carbon–neutral pathway. Despite its high energy density, lignin—accounting for ~ 30% of lignocellulosic biomass—has been underutilized. This study presents an alkaline thermal treatment (ATT) process that efficiently converts lignin into high-purity H<sub>2</sub> while minimizing CO<sub>2</sub> emissions by sequestering carbon as solid carbonate, potentially rendering the process carbon negative. Compared to conventional gasification, the ATT process operates at 170–450&#xa0;°C lower temperature. Under optimized conditions, lignin-ATT produced 116.02&#xa0;mmol H<sub>2</sub>/g lignin (2.6 L H<sub>2</sub>/g lignin), the highest H<sub>2</sub> yield reported for lignocellulosic biomass, far exceeding cellulose-ATT (39.07&#xa0;mmol H<sub>2</sub>/g cellulose), with a maximum H<sub>2</sub> purity of 94.75%. Importantly, this study confirms that stoichiometric NaOH addition enables H<sub>2</sub> production reaching nearly 97% of the theoretical maximum yield at significantly lower temperatures than steam gasification. The reactivity of different alkaline hydroxides is also compared. This study also demonstrates a sustainable approach using black liquor, real waste lignin, and a NaOH recycling system. This strategy reduces the production costs and generates CaCO₃ as a valuable by-product.</p>

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High-Yield Hydrogen Production from Lignin via Optimized Alkaline Thermal Treatment with CO₂ Sequestration

  • 期刊论文

  • 发表日期：

    2025年6月23日

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  • Jieun Park,
  • Hyemin Jung,
  • Do Hee Han,
  • Dayeon Ko,
  • Seung-Eun Lee,
  • Pascal Metivier,
  • Woo-Jae Kim

摘要

Current thermochemical methods for hydrogen (H2) production, such as coal gasification and steam reforming, inevitably produce anthropogenic CO2. In contrast, biomass-derived H2 offers a carbon–neutral pathway. Despite its high energy density, lignin—accounting for ~ 30% of lignocellulosic biomass—has been underutilized. This study presents an alkaline thermal treatment (ATT) process that efficiently converts lignin into high-purity H2 while minimizing CO2 emissions by sequestering carbon as solid carbonate, potentially rendering the process carbon negative. Compared to conventional gasification, the ATT process operates at 170–450 °C lower temperature. Under optimized conditions, lignin-ATT produced 116.02 mmol H2/g lignin (2.6 L H2/g lignin), the highest H2 yield reported for lignocellulosic biomass, far exceeding cellulose-ATT (39.07 mmol H2/g cellulose), with a maximum H2 purity of 94.75%. Importantly, this study confirms that stoichiometric NaOH addition enables H2 production reaching nearly 97% of the theoretical maximum yield at significantly lower temperatures than steam gasification. The reactivity of different alkaline hydroxides is also compared. This study also demonstrates a sustainable approach using black liquor, real waste lignin, and a NaOH recycling system. This strategy reduces the production costs and generates CaCO₃ as a valuable by-product.