State Key Laboratory of Pulp and Paper Engineering, South China University of Technology

热解技术在制浆造纸厂污泥的无害化、资源化、减量化处置方面具有很大的应用潜力。目前对制浆造纸厂污泥在热解过程的热解行为、热动力学特性和产品组成情况了解仍不全面。采用热重红外联用(TG-FTIR)、快速热解-气质联用(Py-GC/MS)技术,研究了制浆造纸厂污泥在不同加热速率下的热分解行为以及挥发性产物的释放特性,并采用多组分平行反应动力学模型、动力学补偿法以及主图法探究了有机物热解动力学。研究结果表明,制浆造纸污泥中的有机物质主要集中在温度范围为140℃至600℃之间进行热解,热解产物主要包括H2O、CH4、CO2、CO、NH3、酮、醛、羧酸、酚、芳烃、醚和醇类等物质。随着热解温度升高至600~900℃时,制浆造纸污泥中的CaCO3将会分解,产生大量CO2,同时CO2会与热解炭反应生成CO。研究采用的4组分的平行反应动力学模型可以较好地描述制浆造纸污泥中的有机物分解过程。4个假组分的平均表观活化能分别为171.54、179.50、192.05、200.86kJ/mol;指前因子分别为1.74×1011~8.34×1016、1.47×1011~5.55×1013、1.40×1011~1.55×1012、1.67×1010~1.34×1013s-1。不同组分之间遵循不同的反应机理模型,随着转化分数增加反应机理模型也会逐渐发生变化。

Pyrolysis technology holds significant potential for the harmless, resourceful, and reduced disposal of sludge in pulp and paper mills. Currently, the understanding of the thermal behavior, t hermodynamic characteristics, and product composition during the pyrolysis process of sludge from pulp and paper mills remains incomplete. In this study, thermogravimetry-fourier transform infrared (TG-FTIR) technology was employed to investigate the thermal behavior and real-time release char acteristics of volatile products for pulp and paper mill sludge pyrolysis at different heating rates.Addi tionally, a multi-component parallel reaction kinetics model, kinetics compensation effect, and master plot method were used to explore the pyrolysis kinetics of organic compounds. The results indicated that the thermal decomposition of organic matter in pulp and paper sludge was primarily concentrated in the temperature range of 140 ~ 600 ℃. The pyrolysis products mainly included H2 O, CH4, CO2, CO, NH3, ketones, aldehydes, carboxylic acids, phenols, aromatics, ethers, and alcohols. As the pyrolysis temperature increased (600~900 ℃), CaCO3 in the pulp and paper sludge decomposed, producing a large amount of CO2, and simultaneous reactions occurred between CO2 and pyrolytic carbon to generate CO. The parallel reaction kinetics model with four components could effectively describe the organic decomposition process of pulp and paper sludge. The average apparent activation energy for the four pseudo-components were 171.54, 179.50, 192.05, and 200.86 kJ/ mol, with pre-exponential factor ranging from 1.74×1011 ~8.34×1016, 1.47×1011 ~5.55×1013, 1.40×1011 ~1.55×1012, and 1.67× 1010 ~1.34×1013 s-1, respectively. Different reaction mechanism models were followed among the various components, and the reaction mechanism models were changed with increasing conversion fraction.

国家自然科学基金资助项目(22178123,22311530109);华南理工大学国家级大学生创新创业训练计划资助项目(202310561107)

丁蕾,陈方军,任冠龙,等.制浆造纸厂污泥热分解特性及其动力学、热力学分析[J].能源环境保护,2024,38(2):180-189.

DING Lei, CHEN Fangjun, REN Guanlong, et al. Thermal decomposition characteristics, kinetics and thermody⁃namic analysis of pulp and paper mill sludge[J]. Energy Environmental Protection, 2024, 38(2): 180-189.