酸环境对沼渣水热炭形成过程中氮形态及转化规律的影响

    Regulation of nitrogen forms and transformation in hydrothermal carbonization of biogas residue by acid types in biogas slurry environment

    • 摘要: 为实现生物质资源的高效转化与氮元素的定向调控,该研究以畜禽粪便沼渣为原料,沼液为介质,探究不同酸环境(柠檬酸、乙酸、硝酸、磷酸)对水热炭化(hydrothermal carbonization, HTC)过程中N形态及迁移规律的影响。结果表明,酸的添加促进了N元素的迁移,提高了水热炭中的含氮量。硝酸和磷酸通过促进缩合、曼尼希反应及吡咯氮环化,提高了水热炭中吡啶氮和季氮的相对含量,但是其强酸性和强氧化性也促进了氮氧化物及沉淀的生成,导致部分氮源的挥发与损失。在有机酸环境下,水热炭化过程可以通过温和水解及络合作用稳定氮源,抑制氮挥发,有利于N在水热炭中的固定。柠檬酸环境在提高水热炭中N元素的富集度和稳定性方面具有最佳效果,使水热炭中N含量大幅提高至2.42%,与原始沼液对照组相比,提高了55.13%。该研究为掺氮碳材料的可控制备及沼气工程副产物的资源化利用提供了理论支撑。

       

      Abstract: A Biogas project can often lead to a large amount of residues and slurry production. Fortunately, hydrothermal carbonization (HTC) can be expected to treat the high-humidity solid wastes. Biogas residues and slurry are rich in nitrogen. During HTC, the speciation and migration of nitrogen are closely linked to the combustion of hydrochar, the preparation of nitrogen-doped carbon-based materials, and the recovery of nutrients. This study aims to realize the efficient conversion of biogas residues and the directional regulation of nitrogen elements. A systematic investigation was made to explore the influence of the different acid environments (citric acid, acetic acid, nitric acid, and phosphoric acid) on the nitrogen speciation and migration regulation during HTC. The livestock manure digestates were taken as the medium using biogas slurry. The products of HTC were separated into the hydrochar and aqueous phase. The morphology and distribution of the nitrogen species were characterized by CHNS/O, XRF, FTIR, XPS, pH, NH4+-N, and TKN. The yield was finally evaluated after measurement. Results showed that the acid addition significantly reduced the hydrochar yields, whereas the nitrogen migration enhanced the nitrogen content in hydrochar. However, various acid environments shared significant influences on the nitrogen migration and transformation during HTC. The distribution was regulated among the solid, aqueous, and gaseous phases, while its enrichment level and speciation were altered in hydrochar. Different acidic additives were determined to regulate the morphology and content of N in hydrochar using the hydrolysis, cyclization, condensation, oxidation, and crosslinking with the carbon backbone. Inorganic acids (nitric and phosphoric) markedly reduced the relative content of protein-N in hydrochar to 24.59 % and 24.71 %, respectively. Protonation was intensified to enhance the catalytic activity, condensation, and Mannich reactions. Nevertheless, the strong acidity and oxidation also drove C–N bond conversion into C=N, leading to the part of the nitrogen to be lost as nitrogen oxides. In addition, the nitric acid mainly promoted the N migration toward the aqueous phase, whereas phosphoric acid simultaneously promoted the N transfer into both the aqueous and gaseous phases. The divalent alkaline-earth metals, such as Ca2+ and Mg2+, were co-precipitated with NH4+-N and PO43− in the biogas slurry, in order to form struvite (MgNH4PO4·6H2O) or calcium phosphate minerals. Thereby, the organic nitrogen was retained in the digestate-derived hydrochar under phosphoric acid conditions. Moreover, the high concentrations of Na+ and K+ in the solid phase were promoted the volatilization or solubilization of nitrogen as NH3 or NH4+, leading to the decreasing nitrogen retention in the solid product. Especially in an organic-acid environment, the citric acid was used to stabilize the nitrogen sources by mild hydrolysis and the chelating of tricarboxylic structure. The volatilization and excessive migration were curbed in the aqueous phase. Organic acids enhanced the Maillard reactions to promote the yield and stability of pyrrolic-N and pyridinic-N. The nitrogen content of HC-M reached 2.42 %, indicating a 55.13 % increase over the raw-slurry control. Although the acetic acid was less effective than citric acid for the solid-phase N enrichment, it still outperformed the inorganic acids. In summary, the citric-acid environment can provide the best performance for the stable nitrogen in hydrochar, which is the most favorable condition for the nitrogen fixation in the solid phase. This finding can provide the theoretical support for the controllable synthesis of N-doped carbon materials and the valorization of byproducts of biogas engineering.

       

    /

    返回文章
    返回