Synergistic oxidation-reforming of biomass for high quality syngas production based on a bifunctional catalyst

Tao He , Dan Zhang , Wenqing Chen , Zeng Liu , Ruidong Zhao , Jianqing Li , Jingli Wu , Zhiqi Wang , Jinhu Wu
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Abstract

Conventional O2 gasification for low-rank biomass/sludge conversion is prone to high CO2 concentrations in the syngas because of its high O content and low calorific value. This study establishes a synergistic oxidation-reforming reaction route for the conversion of low-rank carbon-containing resources into high-quality syngas. The efficient oxidation-reforming reaction is based on the bifunctional catalyst NiO–Fe2O3/Al2O3, which includes Fe2O3 oxidation sites and NiO reforming sites. Hydrogen temperature-programmed reduction, together with X-ray diffraction and X-ray photoelectron spectroscopy experiments, demonstrated that the two functional active sites have strong interactions with the support, leading to efficient cooperation between the oxidation reaction and reforming reaction with regards to both the reaction sequence and C/H/O element balance. Syngas produced from biomass/sludge based on oxidation-reforming reactions has an extremely low CO2 concentration of approximately 3%, and the valid gas (CO, H2) concentration exceeds 95%. The valid gas yield of walnut shell reached 1452.9 mL/g, the total gas yield was 1507.2 mL/g, and the H2/CO ratio was 1.02, which are all very close to the theoretical maximum values of 1553.1 mL/g and 1.01, respectively, demonstrating that the inherent CO2/H2O along with CH4/tar species were efficiently converted to H2 and CO through oxidation-reforming reactions. During a 60-cycle test, NiO-Fe2O3/Al2O3 exhibited good redox stability.

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基于双功能催化剂的生物质协同氧化-转化技术,用于生产优质合成气
用于低级生物质/污泥转化的传统 O2 气化技术由于 O 含量高、热值低,容易导致合成气中 CO2 浓度过高。本研究建立了一条将低级含碳资源转化为高质量合成气的协同氧化-重整反应路线。高效氧化-重整反应基于双功能催化剂 NiO-Fe2O3/Al2O3,其中包括 Fe2O3 氧化位点和 NiO 重整位点。氢气温度编程还原以及 X 射线衍射和 X 射线光电子能谱实验表明,这两个功能活性位点与载体之间具有很强的相互作用,导致氧化反应和重整反应在反应顺序和 C/H/O 元素平衡方面的高效合作。基于氧化-重整反应从生物质/污泥中产生的合成气的二氧化碳浓度极低,约为 3%,有效气体(CO、H2)浓度超过 95%。核桃壳的有效产气量达到 1452.9 mL/g,总产气量为 1507.2 mL/g,H2/CO 比率为 1.02,均非常接近理论最大值 1553.1 mL/g 和 1.01,表明固有的 CO2/H2O 和 CH4/tar 物种通过氧化还原反应被有效地转化为 H2 和 CO。在 60 个循环测试中,NiO-Fe2O3/Al2O3 表现出良好的氧化还原稳定性。
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