Effect of hydrothermal treatment on pyrolysis characteristics and kinetics of oily sludge

doi:10.16085/j.issn.1000-6613.2022-1208

Abstract

Abstract:

This paper used a thermogravimetric analyzer to study the changes in the pyrolysis properties of oily sludge (OS) before and after hydrothermal treatment. At the same time, the apparent activation energies of the samples were calculated by two model-free methods, Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (FWO). The apparent activation energy of oily sludge treated at different hydrothermal temperatures in different pyrolysis stages was determined. The effects of hydrothermal treatment and hydrothermal temperature on the pyrolysis characteristics and kinetic parameters of oily sludge were investigated. The thermal analysis results showed that the temperature range in different pyrolysis stage intervals shifted to a lower level and the weight loss rate increased significantly in the first stage and the third stage due to the change in oil type and content after hydrothermal treatment. At the same conversion rate, the apparent activation energy of OS after hydrothermal treatment at different pyrolysis stages was lower than that of OS. According to the FWO method, as the hydrothermal reaction temperature increased from 160℃ to 240℃, the apparent activation energy of OS in the first-stage and the third-stage pyrolysis increased from 75.20kJ/mol and 171.12kJ/mol to 78.28kJ/mol and 192.59kJ/mol, respectively, and the average apparent activation energy in the second stage of pyrolysis decreased from 151.04kJ/mol to 144.18kJ/mol.

Key words: oily sludge, hydrothermal treatment, pyrolysis, activation energy, kinetics

摘要：

利用热重分析仪研究了水热处理对含油污泥（OS）热解特性的影响，并使用Kissinger-Akahira-Sunose（KAS）和Ozawa-Flynn-Wall（FWO）的方法对其热解动力学进行了分析，确定了经过不同水热温度处理后的含油污泥在不同热解阶段的表观活化能，考察了水热处理及其水热温度对含油污泥热解特性及动力学参数的影响。热分析的结果表明：水热处理使得含油污泥在热解不同阶段的终止温度向较低温度区间移动，在相同的转化率下经过水热处理后的OS在不同热解阶段的表观活化能均低于原样。随着水热反应温度从160℃增加到240℃，根据FWO法估算的OS在热解第一阶段的平均表观活化能从75.20kJ/mol增加到78.28kJ/mol，热解第二阶段的平均表观活化能从151.04kJ/mol降低到144.18kJ/mol，热解第三阶段的平均活化能从171.12kJ/mol增加到了192.59kJ/mol。

关键词: 含油污泥, 水热, 热解, 活化能, 动力学

CLC Number:

DUAN Yihang, GAO Ningbo, QUAN Cui. Effect of hydrothermal treatment on pyrolysis characteristics and kinetics of oily sludge[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 603-613.

段一航, 高宁博, 全翠. 水热处理对含油污泥热解特性及动力学影响[J]. 化工进展, 2023, 42(2): 603-613.

Figures/Tables 11

References 31

1	DUAN Yihang, GAO Ningbo, SIPRA Ayesha Tariq, et al. Characterization of heavy metals and oil components in the products of oily sludge after hydrothermal treatment[J]. Journal of Hazardous Materials, 2022, 424: 127293.
2	ZHOU Lingsheng, JIANG Xiumin, LIU Jianguo. Characteristics of oily sludge combustion in circulating fluidized beds[J]. Journal of Hazardous Materials, 2009, 170(1): 175-179.
3	SILVA L J DA, ALVES F C, DE FRANÇA F P. A review of the technological solutions for the treatment of oily sludges from petroleum refineries[J]. Waste Management & Research, 2012, 30(10): 1016-1030.
4	TANG Siqi, ZHENG Chunmiao, YAN Feng, et al. Product characteristics and kinetics of sewage sludge pyrolysis driven by alkaline earth metals[J]. Energy, 2018, 153: 921-932.
5	ZUBAIDY E A H, ABOUELNASR D M. Fuel recovery from waste oily sludge using solvent extraction[J]. Process Safety and Environmental Protection, 2010, 88(5): 318-326.
6	PUASA S W, ISMAIL K N, MUSMAN M Z A, et al. Enhanced oily sludge dewatering using plant-based surfactant technology[J]. Materials Today: Proceedings, 2019, 19: 1159-1165.
7	MANARA P, ZABANIOTOU A. Towards sewage sludge based biofuels via thermochemical conversion—A review[J]. Renewable and Sustainable Energy Reviews, 2012, 16(5): 2566-2582.
8	GAO Ningbo, DUAN Yihang, LI Zongyang, et al. Hydrothermal treatment combined with in situ mechanical compression for floated oily sludge dewatering[J]. Journal of Hazardous Materials, 2021, 402: 124173.
9	XU Menghan, ZHANG Jie, LIU Haifeng, et al. The resource utilization of oily sludge by co-gasification with c oal[J]. Fuel, 2014, 126: 55-61.
10	董向元, 郭淑青, 杨继涛, 等. 玉米秸秆水热焦热解及动力学特性研究[J]. 林产化学与工业, 2018, 38(3): 83-89.
	DONG Xiangyuan, GUO Shuqing, YANG Jitao, et al. Pyrolysis and kinetic characteristics of corn stalk char from hydrothermal carbonization[J]. Chemistry and Industry of Forest Products, 2018, 38(3): 83-89.
11	邢献军, 杨静, 范方宇, 等. 木屑及其水热炭的热解特性和动力学对比[J]. 农业工程学报, 2017, 33(4): 258-264.
	XING Xianjun, YANG Jing, FAN Fangyu, et al. Comparison of pyrolysis characteristics and kinetics of sawdust and its hydrochar[J]. Transactions of the Chinese Society of Agricultural Engineering, 2017, 33(4): 258-264.
12	WANG Shule, WEN Yuming, SHI Ziyi, et al. Effect of hydrothermal carbonization pretreatment on the pyrolysis behavior of the digestate of agricultural waste: A view on kinetics and thermodynamics[J]. Chemical Engineering Journal, 2022, 431: 133881.
13	ZHANG Jingmiao, XIA Ao, ZHU Xianqing, et al. Co-production of carbon quantum dots and biofuels via hydrothermal conversion of biomass[J]. Fuel Processing Technology, 2022, 232: 107276.
14	高昌胜, 魏茂, 蒋文广, 等. 基于含油污泥热解残渣的路基材料制备与性能评价[J]. 硅酸盐通报, 2019, 38(6): 1895-1900.
	GAO Changsheng, WEI Mao, JIANG Wenguang, et al. Preparation and performance evaluation of roadbed materials based on pyrolysis residue of oily sludge[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(6): 1895-1900.
15	张秀霞, 贾宏宇, 刘炳琨. 超声处理对污泥热解特性及反应动力学影响[J]. 中国石油大学学报(自然科学版), 2022, 46(1): 171-176.
	ZHANG Xiuxia, JIA Hongyu, LIU Bingkun. Effects of ultrasonic treatment on pyrolysis characteristics and reaction kinetics of municipal sludge[J]. Journal of China University of Petroleum (Edition of Natural Science), 2022, 46(1): 171-176.
16	刘承飞, 李江平, 刘大方, 等. 废旧电脑印刷电路板的热解特性及动力学分析[J]. 有色金属科学与工程, 2022, 13(1): 38-43.
	LIU Chengfei, LI Jiangping, LIU Dafang, et al. Pyrolysis characteristics and kinetics analysis of waste computer printed circuit board[J]. Nonferrous Metals Science and Engineering, 2022, 13(1): 38-43.
17	MIAN Inamullah, LI Xian, JIAN Yiming, et al. Kinetic study of biomass pellet pyrolysis by using distributed activation energy model and Coats Redfern methods and their comparison[J]. Bioresource Technology, 2019, 294: 122099.
18	QIN Linbo, HAN Jun, HE Xiang, et al. Recovery of energy and iron from oily sludge pyrolysis in a fluidized bed reactor[J]. Journal of Environmental Management, 2015, 154: 177-182.
19	XU Guiying, CAI Xinghui, WANG Shan, et al. Characteristics, kinetics, infrared analysis and process optimization of co-pyrolysis of waste tires and oily sludge[J]. Journal of Environmental Management, 2022, 316: 115278.
20	NAQVI Salman Raza, TARIQ Rumaisa, SHAHBAZ Muhammad, et al. Recent developments on sewage sludge pyrolysis and its kinetics: Resources recovery, thermogravimetric platforms, and innovative prospects[J]. Computers & Chemical Engineering, 2021, 150: 107325.
21	LEE Sangho, KIM Young Min, SIDDIQUI Muhammad Zain, et al. Different pyrolysis kinetics and product distribution of municipal and livestock manure sewage sludge[J]. Environmental Pollution, 2021, 285: 117197.
22	王君. 基于热处理的含油污泥资源化利用技术[D]. 杭州: 浙江大学, 2018.
	WANG Jun. Resource recovery from oily sludge through thermal treatment technology[D]. Hangzhou: Zhejiang University, 2018.
23	杨天华, 佟瑶, 李秉硕, 等. SDS联合亚临界水预处理对污泥水热液化制油的影响[J]. 太阳能学报, 2021, 42(5): 477-482.
	YANG Tianhua, TONG Yao, LI Bingshuo, et al. Combined(SDS+subcritical water) pretreatment effect on hydro-liquefaction of municipal sludge[J]. Acta Energiae Solaris Sinica, 2021, 42(5): 477-482.
24	Nebojša MANIĆ, Bojan JANKOVIĆ, DODEVSKI Vladimir. Model-free and model-based kinetic analysis of Poplar fluff (Populus alba) pyrolysis process under dynamic conditions[J]. Journal of Thermal Analysis and Calorimetry, 2021, 143(5): 3419-3438.
25	WANG Qiuju, ZHANG Zhao, XU Guoren, et al. Pyrolysis behaviors of antibiotic fermentation residue and wastewater sludge from penicillin production: Kinetics, gaseous products distribution, and nitrogen transformation[J]. Journal of Analytical and Applied Pyrolysis, 2021, 158: 105208.
26	MPHAHLELE Katlego, MATJIE Ratale Henry, OSIFO Peter Ogbemudia. Thermodynamics, kinetics and thermal decomposition characteristics of sewage sludge during slow pyrolysis[J]. Journal of Environmental Management, 2021, 284: 112006.
27	ZHAO Ming, RAHEEM Abdul, MEMON Zaki Mohammad, et al. Iso-conversional kinetics of low-lipid micro-algae gasification by air[J]. Journal of Cleaner Production, 2019, 207: 618-629.
28	XU G, GAI X, WANG S, et al. Characteristics, kinetics, infrared analysis and process optimization of co-pyrolysis of waste tires and oily sludge[J]. Journal of Environmental Management, 2022, 316: 115278.
29	WANG Fei, GUO Chennan, LIU Xiangyue, et al. Revealing carbon-iron interaction characteristics in sludge-derived hydrochars under different hydrothermal conditions[J]. Chemosphere, 2022, 300: 134572.
30	Gamzenur ÖZSIN, Esin APAYDıN-VAROL, Murat KıLıÇ, et al. Pyrolysis of petroleum sludge under non-isothermal conditions: Thermal decomposition behavior, kinetics, thermodynamics, and evolved gas analysis[J]. Fuel, 2021, 300: 120980.
31	Leena PAULINE A, JOSEPH Kurian. Hydrothermal carbonization of oily sludge for solid fuel recovery-investigation of chemical characteristics and combustion behaviour[J]. Journal of Analytical and Applied Pyrolysis, 2021, 157: 105235.

样品	工业分析/%				元素分析/%					热值/MJ·kg^-1	含油率/%
样品	水分	挥发分	灰分	固定碳	C	H	O	N	S	热值/MJ·kg^-1	含油率/%
OS	54.4	26.35	19.04	0.21	22.80	3.17	29.88	0.43	1.89	8.48	23.87

样品	工业分析/%				元素分析/%					热值/MJ·kg^-1	含油率/%
样品	水分	挥发分	灰分	固定碳	C	H	O	N	S	热值/MJ·kg^-1	含油率/%
OS	54.4	26.35	19.04	0.21	22.80	3.17	29.88	0.43	1.89	8.48	23.87

样品	β^①/K·min^-1	第一阶段			第二阶段			第三阶段
样品	β^①/K·min^-1	T_i1^②/K	T_p1^③/K	-R_p1^④/%·min^-1	T_i2/K	T_p2/K	-R_p2/%·min^-1	T_i3/K	T_p3/K	-R_p3/%·min^-1
原样	10	106.11	343.11	13.28	343.11	510.11	11.90	510.11	650.09	3.67
160-10	10	110.15	338.06	13.83	338.06	505.01	11.02	505.01	658.16	3.92
200-10	10	107.88	338.03	13.95	338.03	506.04	9.91	395.26	655.90	4.34
240-10	10	110.04	335.14	14.76	335.14	505.04	9.55	505.04	650.19	4.50

样品	β^①/K·min^-1	第一阶段			第二阶段			第三阶段
样品	β^①/K·min^-1	T_i1^②/K	T_p1^③/K	-R_p1^④/%·min^-1	T_i2/K	T_p2/K	-R_p2/%·min^-1	T_i3/K	T_p3/K	-R_p3/%·min^-1
原样	10	106.11	343.11	13.28	343.11	510.11	11.90	510.11	650.09	3.67
160-10	10	110.15	338.06	13.83	338.06	505.01	11.02	505.01	658.16	3.92
200-10	10	107.88	338.03	13.95	338.03	506.04	9.91	395.26	655.90	4.34
240-10	10	110.04	335.14	14.76	335.14	505.04	9.55	505.04	650.19	4.50

转化率（α）	第一阶段		第二阶段		第三阶段
转化率（α）	E（FWO）/kJ·mol^-1	E（KAS）/kJ·mol^-1	E（FWO）/kJ·mol^-1	E（KAS）/kJ·mol^-1	E（FWO）/kJ·mol^--1	E（KAS）/kJ·mol^-1
0.20	85.35	97.94	151.89	145.66	177.58	200.61
0.25	87.80	100.68	156.48	149.32	179.48	202.69
0.30	90.65	103.84	155.76	153.72	177.34	200.45
0.35	92.61	106.08	158.29	157.63	176.08	199.28
0.40	95.71	109.49	162.56	160.79	175.13	198.37
0.45	95.31	109.16	167.86	161.54	170.94	194.13
0.50	98.63	112.90	174.18	167.03	169.44	192.63
0.55	100.13	114.48	184.45	173.93	165.88	189.06
0.60	100.92	115.48	188.80	179.75	163.91	186.98
0.65	103.37	118.47	187.62	186.06	159.87	182.82
0.70	105.51	120.55	192.20	191.55	157.66	180.66
0.75	108.11	123.46	190.07	193.46	156.01	179.08
0.80	112.38	128.12	193.62	195.96	153.08	176.17
均值	98.19	112.36	174.14	170.49	167.88	190.99