Department of Chemical & Biological Engineering , Korea University , 145 Anam-ro , Seongbuk-gu, Seoul 02841 , Republic of Korea.
Dongwon Heavy Industries Company, Limited , Jeongoksandan 7-gil , Seosin-myeon, Hwaseong 18554 , Republic of Korea.
Environ Sci Technol. 2019 Dec 3;53(23):14041-14053. doi: 10.1021/acs.est.9b04273. Epub 2019 Oct 25.
Hydrogen production from renewable resources, such as lignocellulosic biomass, is highly desired, under the most sustainable and mildest reaction conditions. In this study, a new sustainable three-step process for the production of hydrogen has been proposed. In the first step, a crude formic acid (CF) solution, which included typical reaction byproducts, in particular, acetic acid, levulinic acid, saccharides, 5-hydroxymethylfurfural, furfural, and lignin, was obtained through the combined hydrolysis/oxidation of the biomass, in the presence of diluted sulfuric acid/hydrogen peroxide, as homogeneous catalysts. In the second one, the distilled formic acid (DF) solution was obtained by distillation of the CF solution, for example, by isolating liquid byproducts, or the lignin-free CF (LCF) solution was recovered by CF filtration for the elimination of only solid lignin particles. In the final step, hydrogen was produced from the DF or LCF solutions through formic acid dehydrogenation over Pd supported on amine-functionalized mesoporous silica catalysts, in the presence of sodium formate, as an additive. The clean hydrogen, which is produced from biomass passing through formic acid, could be applied as an energy source of fuel cells. This new hydrogen production process is smart, allowing the hydrogen production with mild reaction conditions, eventually starting from different lignocellulosic feedstocks, and it could be integrated within the existing hydrothermal technology for levulinic acid production, which has been already recognized as efficient and sustainable. In addition to the production of hydrogen as an energy source of fuel cells, formic acid derived from biomass could be utilized as a platform chemical for chemical, agricultural, textile, leather, pharmaceutical, and rubber industries.
从可再生资源（如木质纤维素生物质）中生产氢气，在最可持续和最温和的反应条件下是非常理想的。在这项研究中，提出了一种新的可持续的三步法生产氢气的方法。在第一步中，在稀释硫酸/过氧化氢作为均相催化剂的存在下，通过生物质的联合水解/氧化作用，得到一种包含典型反应副产物的粗甲酸（CF）溶液，特别是乙酸、乙酰丙酸、糖、5-羟甲基糠醛、糠醛和木质素。在第二步中，通过蒸馏CF 溶液获得蒸馏甲酸（DF）溶液，例如通过分离液体副产物，或者通过 CF 过滤回收无木质素 CF（LCF）溶液，以去除仅有的固体木质素颗粒。在最后一步，通过钯负载在胺功能化介孔硅催化剂上的甲酸脱氢作用，从 DF 或 LCF 溶液中生产氢气，在添加甲酸钠的情况下作为添加剂。从通过甲酸的生物质生产的清洁氢气可以用作燃料电池的能源。这种新的氢气生产工艺很智能，允许在温和的反应条件下进行氢气生产，最终可以从不同的木质纤维素原料开始，并且可以与已经被认为是高效和可持续的已有的水热技术中的乙酰丙酸生产工艺集成。除了作为燃料电池的能源生产氢气外，生物质衍生的甲酸还可以用作化学、农业、纺织、皮革、制药和橡胶工业的平台化学品。
