基于组分协同效应的造纸厂固体废弃物热解特性研究

doi:10.11949/0438-1157.20211428

摘要/Abstract

摘要：

为了明晰真实组分比例下实际造纸固废的热解特性以及组分间协同效应对热解行为的影响，通过人工分拣确定实际造纸固废的真实组分比例，进行了TG-FTIR和Py-GC/MS实验，并结合DG-DAEM动力学分析，系统地研究了组分协同效应对造纸固废热解行为及其主要热解产物分布的影响机制。结果表明，组分协同效应对实际造纸固废热解过程具有显著影响。组分协同效应不仅有利于造纸固废热解过程中挥发分的释放，还可以有效促进CH₄小分子的生成。进一步的动力学分析表明，造纸固废混合样品热解过程中降解反应更占优势。此外，在不同温度下，混合样品主要液态热解产物分布中碳氢化合物相对含量的实验值总是高于其理论值，而总的含氧组分的相对含量的实验值总是低于其理论值，混合样品组分间的协同效应有利于热解产物中含氧组分的脱氧以及向烃类产物的转化。

关键词: 组分, 协同效应, 热解, 废物处理, TG-FTIR, Py-GC/MS, DG-DAEM

Abstract:

In order to clarify the pyrolysis characteristics of actual paper mill solid waste under the real component ratio and the influence of the synergistic effects between the components on its pyrolysis behavior, the real ratio of the components of the actual paper mill solid waste was determined by manual sorting. Besides, combined with DG-DAEM kinetic analysis, TG-FTIR and Py-GC/MS experiment were performed to systematically investigate the influence mechanism of the synergistic effects between the components on its pyrolysis behavior and the distribution of main pyrolysis products of paper mill solid waste. The results showed that the synergistic effects of its components had a significant impact on the pyrolysis process of actual paper mill solid waste. The synergistic effects of the components were not only conducive to the release of volatiles in the pyrolysis process of paper mill solid waste, but also could effectively promote the generation of small molecules like CH₄. Further kinetic analysis showed that the degradation reaction was dominant during the pyrolysis process of mixture sample of paper mill solid waste. In addition, at different temperatures, the experimental value of the relative content of hydrocarbons in the main liquid pyrolysis product distribution of the mixture sample was always higher than its theoretical value, while the experimental value of the relative content of the total oxygen-containing components was always lower than its theoretical value. The synergistic effect between the components of the mixed sample is beneficial to the deoxygenation of oxygen-containing components in the pyrolysis product and the conversion to hydrocarbon products.

Key words: components, synergistic effects, pyrolysis, waste treatment, TG-FTIR, Py-GC/MS, DG-DAEM

中图分类号:

X 705

王冠宇, 朱玲君, 周劲松, 王树荣. 基于组分协同效应的造纸厂固体废弃物热解特性研究[J]. 化工学报, 2022, 73(1): 393-401.

Guanyu WANG, Lingjun ZHU, Jinsong ZHOU, Shurong WANG. Study on pyrolysis characteristics of paper mill solid waste based on synergistic effects of its components[J]. CIESC Journal, 2022, 73(1): 393-401.

图/表 9

表1 纸类样品、塑料样品和混合样品的工业分析和元素分析结果

Table 1 Results of proximate and ultimate analysis of paper sample， plastic sample and mixture sample

样品	工业分析/%				元素分析/%
样品	M_ad	A_ad	V_ad	FC_ad	C_ad	H_ad	N_ad	St_ad	O_ad^①
纸类样品	9.80	6.65	69.82	13.73	38.62	4.84	0.25	0.95	38.89
塑料样品	2.93	12.12	78.71	6.24	55.59	8.18	0.13	1.48	19.57
混合样品	4.97	10.24	75.80	8.99	48.54	8.45	0.18	0.91	26.71

图1 20℃/min时纸类样品、塑料样品和混合样品的TG和DTG曲线

Fig.1 TG and DTG curves of paper sample, plastic sample and mixture sample at heating rate of 20℃/min

图2 混合样品的实验失重曲线和理论失重曲线的比较

Fig.2 Comparison of experimental and theoretical TG curves of mixture sample

表 2 三种样品基于DG-DAEM拟合的动力学参数

Table 2 Kinetic parameters of three samples based on DG-DAEM fitting

样品	E₀₁/(kJ/mol)	σ₁/(kJ/mol)	lgA/s^-1	E₀₂/(kJ/mol)	σ₂/(kJ/mol)	ω
纸类样品	167.59	4.32	12.03	200.02	58.81	0.75
塑料样品	170.86	14.76	12.20	210.52	6.38	0.55
混合样品	170.25	10.94	12.32	211.00	9.13	0.58

图3 三种样品基于DG-GAEM的实验曲线与拟合曲线的比较

Fig.3 Comparison of the experimental curves and fitting curves of three samples based on DG-DAEM

图4 三种样品在其最大失重峰处的FTIR谱图

Fig.4 FTIR spectra of three samples at their maximum absorption peaks

图5 典型气态产物释放随温度的变化规律

Fig.5 Variation of release of typical gaseous products with temperature

图6 单组分样品在不同温度下的主要热解产物分布

Fig.6 Distribution of main pyrolysis products of single component samples at different temperatures

图7 混合样品在不同温度下主要热解产物实验分布和理论分布的比较

Fig.7 Comparison of experimental and theoretical distribution of main pyrolysis products of mixture sample at different temperatures

参考文献 27

1	Minelgaitė A, Liobikienė G. Waste problem in European Union and its influence on waste management behaviours[J]. Science of the Total Environment, 2019, 667: 86-93.
2	Nanda S, Berruti F. Municipal solid waste management and landfilling technologies: a review[J]. Environmental Chemistry Letters, 2021, 19(2): 1433-1456.
3	Chen Y C. Evaluating greenhouse gas emissions and energy recovery from municipal and industrial solid waste using waste-to-energy technology[J]. Journal of Cleaner Production, 2018, 192: 262-269.
4	Cai W, Liu C H, Zhang C X, et al. Developing the ecological compensation criterion of industrial solid waste based on emergy for sustainable development[J]. Energy, 2018, 157: 940-948.
5	中华人民共和国国家统计局. 中国统计年鉴2020 [M]. 北京:中国统计出版社, 2020.
	National Bureau of Statistics of China. Chinese Statistical Yearbook 2020[M]. Beijing: China Statistics Press, 2020.
6	朱君. 制浆造纸行业固废物资源化利用探索[J]. 化工管理, 2014, 21: 175-176.
	Zhu J. Exploration on resource utilization of solid waste in pulp and paper industry[J]. Chemical Enterprise Management, 2014, 21:175-176.
7	Veluchamy C, Kalamdhad A S. Influence of pretreatment techniques on anaerobic digestion of pulp and paper mill sludge: a review[J]. Bioresource Technology, 2017, 245: 1206-1219.
8	宋艳培, 庄修政, 詹昊, 等. 城市污泥/褐煤共水热碳化产物的热化学转化特性及规律研究[J]. 化工学报, 2020, 71(5): 2320-2332.
	Song Y P, Zhuang X Z, Zhan H, et al. Investigation on thermochemical conversion characteristics and regularity of co-hydrothermal carbonization solid fuel from sewage sludge and lignite[J]. CIESC Journal, 2020, 71(5): 2320-2332.
9	Fang S W, Yu Z S, Lin Y, et al. A study on experimental characteristic of co-pyrolysis of municipal solid waste and paper mill sludge with additives[J]. Applied Thermal Engineering, 2017, 111: 292-300.
10	Das S, Lee S H, Kumar P, et al. Solid waste management: scope and the challenge of sustainability[J]. Journal of Cleaner Production, 2019, 228: 658-678.
11	Wang G Y, Dai Y J, Yang H P, et al. A review of recent advances in biomass pyrolysis[J]. Energy & Fuels, 2020, 34(12): 15557-15578.
12	Czajczyńska D, Anguilano L, Ghazal H, et al. Potential of pyrolysis processes in the waste management sector[J]. Thermal Science and Engineering Progress, 2017, 3: 171-197.
13	Song Q, Zhao H Y, Xing W L, et al. Effects of various additives on the pyrolysis characteristics of municipal solid waste[J]. Waste Management, 2018, 78: 621-629.
14	Ma W C, Rajput G, Pan M H, et al. Pyrolysis of typical MSW components by Py-GC/MS and TG-FTIR[J]. Fuel, 2019, 251: 693-708.
15	Chen H P, Xie Y P, Chen W, et al. Investigation on co-pyrolysis of lignocellulosic biomass and amino acids using TG-FTIR and Py-GC/MS[J]. Energy Conversion and Management, 2019, 196: 320-329.
16	Chen L, Yu Z S, Liang J Y, et al. Co-pyrolysis of chlorella vulgaris and kitchen waste with different additives using TG-FTIR and Py-GC/MS[J]. Energy Conversion and Management, 2018, 177: 582-591.
17	Sun C, Li C X, Tan H Y, et al. Synergistic effects of wood fiber and polylactic acid during co-pyrolysis using TG-FTIR-MS and Py-GC/MS[J]. Energy Conversion and Management, 2019, 202: 112212.
18	陈强, 王艳, 翟华敏. 基于TG-FTIR和Py-GC-MS分析的椰壳热解特性研究[J]. 林产化学与工业, 2020, 40(1): 45-52.
	Chen Q, Wang Y, Zhai H M. Pyrolysis characteristics of coconut shell based on TG-FTIR and Py-GC-MS analysis[J]. Chemistry and Industry of Forest Products, 2020, 40(1):45-52.
19	Yang H P, Yan R, Chen H P, et al. Characteristics of hemicellulose, cellulose and lignin pyrolysis[J]. Fuel, 2007, 86(12/13): 1781-1788.
20	Dai G X, Wang S R, Zou Q, et al. Improvement of aromatics production from catalytic pyrolysis of cellulose over metal-modified hierarchical HZSM-5[J]. Fuel Processing Technology, 2018, 179: 319-323.
21	宋飞跃, 丁浩植, 张立强, 等. 生物质三组分混合热解耦合作用研究[J]. 太阳能学报, 2019, 40(1): 149-156.
	Song F Y, Ding H Z, Zhang L Q, et al. Research on pyrolysis of mixture of biomass components[J]. Acta Energiae Solaris Sinica, 2019, 40(1): 149-156.
22	Dai G X, Wang K G, Wang G Y, et al. Initial pyrolysis mechanism of cellulose revealed by in situ DRIFT analysis and theoretical calculation[J]. Combustion and Flame, 2019, 208: 273-280.
23	Singh R K, Ruj B, Sadhukhan A K, et al. A TG-FTIR investigation on the co-pyrolysis of the waste HDPE, PP, PS and PET under high heating conditions[J]. Journal of the Energy Institute, 2020, 93(3): 1020-1035.
24	Alam M, Rammohan D, Peela N R. Catalytic co-pyrolysis of wet-torrefied bamboo sawdust and plastic over the zeolite H-ZSM-5: synergistic effects and kinetics[J]. Renewable Energy, 2021, 178: 608-619.
25	Alam M, Bhavanam A, Jana A, et al. Co-pyrolysis of bamboo sawdust and plastic: synergistic effects and kinetics[J]. Renewable Energy, 2020, 149: 1133-1145.
26	Wang S R, Dai G X, Ru B, et al. Effects of torrefaction on hemicellulose structural characteristics and pyrolysis behaviors [J]. Bioresource Technology, 2016, 218: 1106-1114.
27	Dai G X, Zou Q, Wang S R, et al. Effect of torrefaction on the structure and pyrolysis behavior of lignin[J]. Energy & Fuels, 2018, 32(4): 4160-4166.

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