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    钙基材料增强生物质气化制氢及氮硫转化特性模拟

    Simulation of hydrogen production and nitrogen sulfur transformation characteristics of sortion-enhanced steam gasification of biomass using Calcium-based materials

    • 摘要: 生物质作为一种丰富的可再生及碳中性能源,在热化学制氢领域具有巨大潜力,但传统蒸汽气化过程普遍存在氢气产率不高、CO2排放较大以及含氮含硫污染物难控制等问题。钙基材料CO2捕集增强生物质气化制氢技术利用钙基材料的原位脱碳,可有效提高氢气浓度及产量。为提升生物质气化制氢并揭示该过程中的氮硫转化特性,本研究以高氮高硫海洋生物质浒苔为原料,基于Aspen Plus模拟平台,构建了耦合CaO碳酸化—煅烧循环的热力学模型,考察了CaO吸收剂对气化过程中CO2捕集及其对水气变换反应平衡的调控作用。系统分析了反应温度、蒸汽/生物质质量比(m(S)∶m(B))和钙/碳物质的量比(n(Ca)∶n(C))对气体产物组成、碳转化率、合成气热值及氮硫转化特性的影响。结果表明,通过参数优化,在气化温度为800~850 ℃、蒸汽/生物质质量比(m(S)∶m(B))为0.6~0.8、钙/碳物质的量比(n(Ca)∶n(C))为1.5~2.0最佳工况下,可实现H2/CO物质的量比超过3.5,碳转化率高于94%,合成气低位热值达11.8~12.1 MJ/m3的多目标平衡,同时钙基材料通过化学吸附与催化转化双重机制,有效调控氮硫迁移路径NH3和HCN总量低于35×10−5,N2选择性超85%,H2S脱除率达96%以上,硫主要以CaS形式固化,污染物排放大幅降低。该研究为高氮高硫海洋生物质气化制氢的工业应用提供了理论基础和工艺优化路径,推动低碳制氢与高效碳捕集技术的发展。

       

      Abstract: Biomass, as an abundant renewable and carbon-neutral energy source, holds significant potential in the field of thermochemical hydrogen production. However, conventional steam gasification processes commonly suffer from low hydrogen yield, substantial CO2 emissions, and challenges in controlling nitrogen and sulfur pollutants. The sorption-enhanced steam gasification of biomass using Calcium-based materials can improve hydrogen concentration and yield, with in-situ CO2 capture by Calcium-based materials. To enhance biomass gasification for hydrogen production and elucidate nitrogen-sulfur transformation characteristics during this process, t high-sulfur marine biomass (Sargassum) was utilized as feedstock. Based on the Aspen us simulation platform, a thermodynamic model coupling CaO carbonation-calcination cycles was developed to investigate the role of CaO absorbent in CO2 capture during gasification and its regulation of steam reforming reaction equilibrium. Systematic analysis was conducted on the effects of reaction temperature, mass ratio of steam to biomass (m(S)∶m(B)), and calcium-to-carbon molar ratio (n(Ca)∶n(C)) on gas product composition, carbon conversion rate, syngas calorific value, and nitrogen-sulfur conversion characteristics. Results indicate that through parameter optimization, optimal conditions of gasification temperature (800-850 ℃), mass ratio of steam to biomass (m(S)∶m(B)) (0.6−0.8), and calcium-to-carbon molar ratio (n(Ca)∶n(C)) (1.5−2.0), a molar ratio of H2/CO exceeding 3.5 can be achieved, achieve a carbon conversion rate exceeding 94% and a low-heat-value syngas of 11.8−12.1 MJ/m3. with a low calorific value of 11.8−12.1 MJ/m3. Simultaneously, calcium-based materials effectively regulate nitrogen and sulfur migration pathways through dual mechanisms of chemical adsorption and catalytic conversion, keeping total NH3 and HCN below 35×10−5, achieving N2 selectivity exceeding 85%, and H2S removal rates surpassing 96%. Sulfur is primarily solidified as CaS, significantly reducing pollutant emissions. This research provides a theoretical foundation and process optimization pathway for the industrial application of hydrogen production via gasification of high-nitrogen, high-sulfur marine biomass, advancing the development of low-carbon hydrogen production and efficient carbon capture technologies.

       

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