Thermo-kinetic and reactivity analysis of rice husk and its macromolecular constituents during thermochemical conversion for sustainable valorization

Hamado Ouedraogo, Yohan Richardson, María González Martínez, Sayon dit Sadio Sidibe, Ange Nzihou
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Abstract

Rice husk (RH), an abundant agricultural by-product, offers significant potential for sustainable energy generation and material recovery due to its lignocellulosic composition and high silica content. We conducted a detailed thermo-kinetic analysis of RH under inert and oxidative atmospheres. Initial characterization showed that RH is primarily composed of cellulose (56.6%, mass fraction), lignin (30.3%), and hemicellulose (7.5%), with a high ash content (25.2%) dominated by silica (SiO2: 254086.65 mg/kg). This makes RH a valuable source of amorphous silica, though it may cause slagging, fouling, and maintenance challenges in high-temperature thermochemical systems. Under combustion, oxygen accelerated devolatilization, resulting in higher mass loss, lower activation energies (99.09–114.95 kJ/mol), and faster kinetics compared to pyrolysis (hemicellulose: 4.06–29.17 kJ/mol; cellulose: 158.80–188.71 kJ/mol; lignin: 61.43–79.81 kJ/mol). Thermodynamic analysis indicated that oxidation promoted more ordered transition states and reduced energy barriers, enhancing the conversion efficiency. Performance indices were introduced to evaluate combustibility, ignition, and reactor safety. During pyrolysis, RH components transitioned from diffusion- or nucleation-controlled kinetics at low conversions to reaction-order control at higher conversions. Combustion initially followed chemical control, shifted to diffusion-limited kinetics as char and ash accumulated, and reverted to chemical control during residual carbon oxidation. Lignin displayed complex, multi-step kinetics under both conditions. These results provide a comprehensive understanding of RH thermal behavior, supporting the design of more efficient and safer thermochemical systems and valorization strategies, including energy recovery, biochar, syngas generation, and amorphous silica extraction for sustainable bio-based industries.

Graphical abstract

稻壳及其大分子成分在热化学转化过程中的热动力学和反应性分析
稻壳是一种丰富的农业副产品,由于其木质纤维素成分和高硅含量,稻壳在可持续能源生产和材料回收方面具有巨大的潜力。我们在惰性气氛和氧化气氛下对RH进行了详细的热动力学分析。初步表征表明,RH主要由纤维素(56.6%,质量分数)、木质素(30.3%)和半纤维素(7.5%)组成,以二氧化硅(SiO2: 254086.65 mg/kg)为主,灰分含量高(25.2%)。这使得RH成为无定形二氧化硅的宝贵来源,尽管它可能在高温热化学系统中导致结渣、结垢和维护挑战。在燃烧过程中,氧气加速了脱挥发过程,与热解过程(半纤维素:4.06-29.17 kJ/mol;纤维素:158.80-188.71 kJ/mol;木质素:61.43-79.81 kJ/mol)相比,其质量损失更高,活化能更低(99.09-114.95 kJ/mol),动力学更快。热力学分析表明,氧化促进了更有序的过渡态,降低了能垒,提高了转化效率。引入了性能指标来评价可燃性、点火性和反应堆安全性。在热解过程中,RH组分从低转化率时的扩散或成核控制动力学转变为高转化率时的反应顺序控制动力学。燃烧最初遵循化学控制,随着炭和灰分的积累转向扩散限制动力学,并在残余碳氧化期间恢复到化学控制。两种条件下木质素均表现出复杂的多步动力学。这些结果提供了对RH热行为的全面理解,支持设计更高效、更安全的热化学系统和增值策略,包括能源回收、生物炭、合成气生成和无定形二氧化硅萃取,用于可持续的生物基工业。图形抽象
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