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    富磷生物质气化过程中不同形态磷的迁移转化行为

    Migration and transformation behavior of different phosphorus fractions during the gasification of phosphorus-rich biomass

    • 摘要: 玉米秸秆、牛粪、蓝藻等生物质由于富含磷而被称为富磷生物质,因其储量丰富且易引发环境问题,将其单独气化或与其他原料共气化有望实现其资源化利用,认识富磷生物质中含磷组分在高温气化过程中的迁移转化行为至关重要。研究选用玉米秸秆、牛粪和蓝藻3种不同类型的富磷生物质,采用欧盟组织提出的连续提取总磷和4种形态磷元素(有机磷、无机磷、非磷灰石态无机磷和磷灰石态无机磷)溶液的方法,结合电感耦合等离子体发射光谱仪定量分析3种原料在气化前后磷元素形态的迁移转化规律。借助傅里叶红外光谱检测气化灰渣中赋存的磷酸根离子、硅氧键等无机化合物和官能团吸收振动峰的变化,借助X射线衍射光谱和FactSage热力学模拟探究熔渣中相态和磷酸盐矿物的变化,揭示磷与其他元素之间的作用机理。结果表明:气化有助于富磷生物质中磷元素迁移到灰渣固体中,促进富磷生物质中有机磷或非磷灰石态无机磷向生物可利用性强的磷灰石态无机磷转化。玉米秸秆在气化前磷元素的形态主要以非磷灰石态无机磷和有机磷为主,牛粪以非磷灰石态无机磷和磷灰石态无机磷为主,玉米秸秆和牛粪的气化灰渣中磷的主要形态为磷灰石态无机磷,且磷灰石态无机磷与总磷的比值m(AP)∶m(TP)高达90%,而蓝藻气化前后m(AP)∶m(TP)值由1.17%升至43.28%。磷通过结合碱和碱土金属生成磷酸钾、磷酸钙、白磷酸钙等碱/碱土−磷酸盐矿物质赋存于灰渣中导致磷灰石态无机磷含量较高。气化可促进富磷生物质中磷元素向灰渣固体中迁移转化,为开发气化处理富磷生物质技术提供一定的理论支撑。

       

      Abstract: Biomasses such as corn straw, cow dung, and blue-green algae, which are rich in phosphorus, are referred to as phosphorus-rich biomasses. Due to their abundant reserves and potential environmental issues, their individual gasification or co-gasification with other feedstocks holds promise for resource utilization. Understanding the migration and transformation behavior of phosphorus components in phosphorus-rich biomass during high-temperature gasification is crucial. The study selects corn straw, cow dung, and blue-green algae uses the continuous extraction method proposed by the European Union to extract total phosphorus and four forms of phosphorus elements(organic phosphorus, inorganic phosphorus, non-apatite inorganic phosphorus, and apatite inorganic phosphorus). The migration and transformation of phosphorus species in these three materials before and after gasification are quantitatively analyzed using inductively coupled plasma-optical emission spectrometry. Fourier transform infrared spectroscopy was used to detect changes in phosphate ions, silicon-oxygen bonds, and other inorganic compounds and functional group peaks in the phosphorus-rich biomass ash and gasification residues. By utilizing X-ray diffraction spectroscopy and FactSage thermodynamic simulations, the changes in the phases and phosphate minerals in the slag are investigated, revealing the interaction mechanisms between phosphorus and other elements. The results show that gasification helps the migration of phosphorus elements from phosphorus-rich biomass into the solid ash, where they exist in the form of inorganic phosphates. It also promotes the transformation of organic phosphorus or non-apatite inorganic phosphorus in phosphorus-rich biomass into the more bioavailable form of available phosphorus. Before gasification, the phosphorus fractions in corn straw were mainly in the forms of non-apatite inorganic phosphorus and organic phosphorus, while in cow dung, they were primarily in the forms of non-apatite inorganic phosphorus and apatite inorganic phosphorus. After gasification, the main phosphorus fraction in the gasification residues of corn straw and cow dung is apatite inorganic phosphorus, with the ratio of apatite inorganic phosphorus to total phosphorus m(AP)∶m(TP) reaching as high as 90%. In contrast, for blue-green algae, the m(AP)∶m(TP) ratio increased from 1.17% before gasification to 43.28% after gasification. Phosphorus can exist in the ash as alkali/alkaline earth-phosphate minerals such as potassium phosphate, calcium phosphate, and whitlockite, formed by combining with alkali and alkaline earth metals, leading to a higher content of apatite inorganic phosphorus. Gasification can promote the migration and transformation of phosphorus from phosphorus-rich biomass to the solid ash, providing theoretical support for the development of gasification-based technologies for the synergistic treatment of phosphorus-rich biomass.

       

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