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    熔融碳酸盐辅助螺旋藻催化热解研究

    Experimental study on catalytic pyrolysis of spirulina assisted by molten carbonate

    • 摘要: 针对藻类生物质催化热解技术中生物油氮氧含量高和催化剂易失活的问题,研究了熔融盐耦合分子筛/铈基催化剂催化螺旋藻热解特性,探究了耦合体系对螺旋藻热解生物油的脱氮脱氧效果,并深入考察了熔融碳酸盐抑制催化剂失活的作用机制。结果表明:熔融碳酸盐能有效将生物油中氮、氧元素产率降低25.90%、28.53%,相较于催化热解,熔融碳酸盐耦合H-β(Si/Al=26)分子筛和NiCe/Al2O3分别使生物油中含氧/含氮化合物的含量下降了71.49%/31.20%与53.14%/39.50%,但仅将单次热解时的芳香族化合物含量提升4.02%与11.02%。熔融碳酸盐耦合后,单次热解后H-β(Si/Al=26)的积碳质量降低了31.60%,而NiCe/Al2O3的积碳质量降低了20.97%。熔融碳酸盐通过脱除挥发分中含氧化合物和含氮杂环类等物质抑制积碳生成,同时其与碱性酰胺类/胺类物质间的反应避免了活性位点的失活。此外熔融盐抑制了与碳双键和氨基相关的缩合反应,提高了重质组分饱和度,抑制其进一步聚合形成积碳。由于熔融碳酸盐对催化剂稳定性的提升,循环5次后耦合体系获得的生物油中芳香族化合物的含量相较催化热解都提升超过48%。

       

      Abstract: To address the high nitrogen and oxygen content in bio-oil and catalyst deactivation during catalytic pyrolysis of algal biomass, this study investigated the pyrolysis characteristics of spirulina catalyzed by a molten salt-coupled zeolite/cerium-based catalyst system. The denitrification and deoxygenation effects of the coupled system on Spirulina pyrolysis bio-oil were examined, and the mechanism by which molten carbonate inhibits catalyst deactivation was thoroughly investigated. The results demonstrate that molten carbonate effectively reduces the yield of nitrogen and oxygen elements in bio-oil by 25.90% and 28.53%, respectively. Compared with catalytic pyrolysis alone, the molten carbonate coupled with H-β(Si/Al=26) and NiCe/Al2O3 reduced the content of oxygen/nitrogen-containing compounds in bio-oil by 71.49%/31.20% and 53.14%/39.50%, respectively, while increasing aromatic compound content during single pyrolysis by only 4.02% and 11.02%. After coupling with molten carbonate, the coke deposition mass on H-β(Si/Al=26) decreased by 31.60%, and that on NiCe/Al2O3 decreased by 20.97% after single pyrolysis. Molten carbonate inhibits coke formation by removing oxygen-containing compounds and nitrogen-containing heterocycles from volatiles, while its reaction with basic amides/amines prevents deactivation of active sites. Additionally, molten salt suppresses condensation reactions related to carbon double bonds and amino groups, enhances the saturation of heavy components, and inhibits their further polymerization into coke. Owing to the improved catalyst stability from molten carbonate, the aromatic compound content in bio-oil obtained after 5 cycles using the coupled system increased by over 48% compared to conventional catalytic pyrolysis.

       

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