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    硝酸辅助碱木质素水热过程特性及机理

    Characteristics and mechanism of nitric acid-assisted hydrothermal process of alkali lignin

    • 摘要: 硝酸可使木质素快速解聚,具有使造纸黑液水热液化(Hydtrothermal Liquefaction, HTL)高值利用的潜力。以碱木质素(Alkaline Lignin, AL)为原料,分别研究了在硝酸作用下,不同反应时间、反应温度、反应初始压力下木质素水热过程特性,并探究了反应过程中碳元素的迁徙过程及水热反应过程机制。研究发现硝酸辅助AL水热反应过程由脱支链(10%~15%)、酸析聚集(65%~70%)和解聚(15%~20%)组成。水热产物主要受温度和初始压力的影响,对反应时间敏感程度较低。水热温度增加会促进水热炭的脱支链反应、抑制AL酸析聚集形成水热炭,使固体产物碳质量分数从77.0%减少至51.6%,气体产物碳质量分数从0.6%提高到14.2%;而增大初始反应压力会抑制AL解聚、促进AL酸析聚集形成水热炭,使液体产物碳质量分数从17.6%下降至4.1%,而固体产物质量分数则从50.8%增大至64.9%。木质素水热分解气体产物主要为CO2和少量的CO,主要来自水热过程羰基、羧基及醚键的断裂;液体产物主要为AL解聚后的单体、二聚体以及酚类低聚物,主要来自酸催化AL的部分解聚和解聚产物的再聚合;水热炭主要由AL在酸性环境下软化、粘连成的疏水无定型中间体,吸附部分解聚的木质素碎片通过交联碳化过程形成。结合三态产物碳分布,反应时间为4 h、反应温度为180 ℃、初始反应压力为0 MPa是最适宜的工况,此时固体碳质量分数为50.8%,液体产物碳质量分数为17.6%。

       

      Abstract: Nitric acid demonstrates the ability to rapidly depolymerize lignin, thereby facilitating the value-added utilization of papermaking black liquor via hydrothermal liquefaction (HTL). Using alkaline lignin (AL) as the raw material, the characteristics of the lignin hydrothermal process under different reaction times, temperatures and initial pressures in the presence of nitric acid were investigated. Additionally, the migration process of carbon elements and the reaction mechanism of hydrothermal process were explored. The study indicates that the nitric acid-assisted AL hydrothermal reaction process consists of debranching reactions (10%−15%), acid-induced precipitation aggregation (65%−70%), and depolymerization (15%−20%). Hydrothermal products are predominantly influenced by temperature and initial pressure, exhibiting relatively low sensitivity to reaction time. An increase in hydrothermal temperature can promote debranching reactions of hydrothermal carbon and inhabit the acid-induced precipitation aggregation of AL to form hydrothermal carbon, reducing the proportion of carbon in solid products from 77.0% to 51.6%, and increasing the proportion of carbon in gaseous products from 0.6% to 14.2%. Elevating the initial reaction pressure can inhaibit depolymerization and promote the acid-induced precipitation aggregation of AL to form hydrothermal carbon, leading to a decrease in the proportion of carbon in liquid products from 17.6% to 4.1%, whereas the proportion of carbon in solid products increases from 50.8% to 64.9%. The primary gaseous products of lignin hydrothermal decomposition are CO2 and a minor amount of CO, which originate from the cleavage of carbonyl, carboxyl, and ether bonds during the hydrothermal process. Liquid products primarily consist of monomers, dimers, and phenolic oligomers derived from the depolymerization of AL, resulting from partial depolymerization catalyzed by acid and subsequent repolymerization of the depolymerization products. Hydrothermal carbon is mainly composed of hydrophobic amorphous intermediates formed through the softening and adhesion of AL in an acidic environment, which adsorb partially depolymerized lignin fragments and undergo cross-linking carbonization. According to the carbon distribution among the three-phase products, the optimal operational parameters are determined as a reaction time of 4 hours, a reaction temperature of 180  °C and an initial pressure of 0 MPa. Under these conditions, the solid products accounts for 50.8% of the total carbon content and the liquid products contributes 17.6%.

       

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