Comparing pyrolysis characteristics of Daqing multi-source oil sludge

doi:10.16085/j.issn.1000-6613.2021-0900

Abstract

Abstract:

Daqing Oilfield is the largest oilfield in China. It has a history of more than 50 years since it was exploited in 1959. By 2020, the annual output of crude oil has stabilized to about 30 million tons. A large amount of oily sludge is produced during oil exploitation. Oily sludge is a kind of hazardous waste the needs to be treated with safe and clean disposal approaches. Pyrolysis technology can realize harmless reduction and efficient recovery of oil resources. In this study, the pyrolysis characteristics of oil sludge from different sources in Daqing Oilfield are analyzed to provide theoretical basis for the selection of treatment techniques. Firstly, the pyrolysis characteristics and gas products releasing of oily sludge are evaluated by TG-FTIR-MS. Subsequently, the three-phase products distribution obtained from pyrolysis is conducted with a fixed bed pyrolysis furnace at the final temperature of 600℃. The oil and solid products are analyzed in detail by GCMS, XRD, and FTIR. Results demonstrate that the pyrolysis oil is mainly composed of medium and low chain alkanes, while olefins and alcohols are little. SiO₂ and CaCO₃ are the main components in the pyrolysis residue.

Key words: Daqing oilfield, waste disposal, pyrolysis, thermodynamics, pollutant release, petroleum

摘要：

大庆油田是我国第一大油田，自1959年开采后已有50多年的发展历史，到2020年原油年产量已稳定到3000万吨左右。石油开采过程伴随大量含油污泥的产生，含油污泥属于危险废物，需要寻求安全清洁的处置方式。热解技术在实现无害减量的同时可实现油品资源的高效回收。本文对大庆油田不同来源含油污泥热解特性进行分析，为含油污泥处理方案选择提供理论依据。首先通过热重-红外-质谱（TG-FTIR-MS）联用测试了多源油泥样品的热解特性以及气体产物释放规律；然后采用固定床热解炉在600℃的终温下对多源含油污泥样品进行热解试验，得到三相产率；借助色谱-质谱联用（GCMS）、X射线衍射（XRD）和红外光谱（FTIR）测试对油相产物和固相产物进行详细分析。结果表明热解油以中低链烷烃为主，烯烃和醇含量相对较低，热解渣中主要以SiO₂和CaCO₃为主。

关键词: 大庆油田, 废物处理, 热解, 热力学, 污染物释放, 石油

CLC Number:

TE992.3

LIN Fawei, ZHENG Fa, LI Jiantao, LYU Yahui, SONG Xuefeng, XU Chengjun, MA Wenchen, CHEN Guanyi. Comparing pyrolysis characteristics of Daqing multi-source oil sludge[J]. Chemical Industry and Engineering Progress, 2021, 40(S2): 421-433.

林法伟, 郑发, 李建陶, 吕雅慧, 宋学峰, 许成君, 马文臣, 陈冠益. 大庆多源含油污泥热解特性的对比[J]. 化工进展, 2021, 40(S2): 421-433.

Figures/Tables 16

References 29

1	WANG J, YIN J, GE L, et al. Characterization of oil sludges from two oil fields in China[J]. Energy & Fuels, 2010, 24(2): 973-978.
2	MRAYYAN B, BATTIKHI M N. Biodegradation of total organic carbons (TOC) in Jordanian petroleum sludge[J]. Journal of Hazardous Materials, 2005, 120(1/2/3): 127-134.
3	LIU J G, JIANG X M, ZHOU L S, et al. Pyrolysis treatment of oil sludge and model-free kinetics analysis[J]. Journal of Hazardous Materials, 2009, 161(2/3): 1208-1215.
4	MATER L, SPERB R M, MADUREIRA L A S, et al. Proposal of a sequential treatment methodology for the safe reuse of oil sludge-contaminated soil[J]. Journal of Hazardous Materials, 2006, 136(3): 967-971.
5	ROCHA O R S DA, DANTAS R F, DUARTE M M M B, et al. Oil sludge treatment by photocatalysis applying black and white light[J]. Chemical Engineering Journal, 2010, 157(1): 80-85.
6	谢磊. 含油污泥大物料量热重热解动力学研究[D]. 大连: 大连理工大学, 2013.
	XIE Lei. Study on macro-thermogravimetry kinetics of pyrolysis of oil sludge[D]. Dalian: Dalian University of Technology, 2013.
7	XU N, WANG W X, HAN P F, et al. Effects of ultrasound on oily sludge deoiling[J]. Journal of Hazardous Materials, 2009, 171(1/2/3): 914-917.
8	HU G J, LI J B, ZENG G M. Recent development in the treatment of oily sludge from petroleum industry: a review[J]. Journal of Hazardous Materials, 2013, 261: 470-490.
9	FISHER J A, SCARLETT M J, STOTT A D. Accelerated solvent extraction: an evaluation for screening of soils for selected US EPA semivolatile organic priority pollutants[J]. Environmental Science & Technology, 1997, 31(4): 1120-1127.
10	KHAN F I, HUSAIN T, HEJAZI R. An overview and analysis of site remediation technologies[J]. Journal of Environmental Management, 2004, 71(2): 95-122.
11	FONTS I, GEA G, AZUARA M, et al. Sewage sludge pyrolysis for liquid production: a review[J]. Renewable and Sustainable Energy Reviews, 2012, 16(5): 2781-2805.
12	陈立业. 浅谈大庆油田经济现状及发展对策[J]. 当代经济, 2016(5): 28-29.
	CHEN Liye. On the economic status and development countermeasures of Daqing Oilfield [J]. Contemporary Economics, 2016(5): 28-29.
13	李益飞. 青霉素菌渣热解产物特性及生物油催化脱氮机制[D]. 北京: 北京科技大学, 2021.
	LI Yifei. Characteristics of pyrolysis products of penicillin fermentation residue and mechanism of bio-oil catalytic denitrification[D]. Beijing: University of Science and Technology Beijing, 2021.
14	曹莹菲. 腐解过程中还田秸秆和土壤有机酸、质能及结构变化特征[D]. 杨凌: 西北农林科技大学, 2016.
	CAO Yingfei. Decomposition, organic acids, thermal and structure characteristic in crop residues and soils among straw returning[D]. Yangling: Northwest A & F University, 2016.
15	宫会丽. 烟叶近红外光谱特征提取与相似性度量研究[D]. 青岛: 中国海洋大学, 2014.
	GONG Huili. Feature extraction and similarity measure on tobacco near infrared spectra[D]. Qingdao: Ocean University of China, 2014.
16	WU Z H, OHTSUKA Y. Nitrogen distribution in a fixed bed pyrolysis of coals with different ranks: formation and source of N₂[J]. Energy & Fuels, 1997, 11(2): 477-482.
17	陈爽, 刘会娥, 郭庆杰. 含油污泥热解特性和动力学研究[J]. 石油炼制与化工, 2007, 38(7): 50-53.
	CHEN Shuang, LIU Huie, GUO Qingjie. Study on the pyrolysis behavior and kinetics of oily sludge[J]. Petroleum Processing and Petrochemicals, 2007, 38(7): 50-53.
18	彭发修. 含油污泥热解动力学研究[D]. 上海: 华东理工大学, 2012.
	PENG Faxiu. Study on dynamics of the oil sludge pyrolysis[D]. Shanghai: East China University of Science and Technology, 2012.
19	陈爽, 郭庆杰, 王志奇, 等. 含油污泥热解动力学研究[J]. 中国石油大学学报(自然科学版), 2007, 31(4): 116-120.
	CHEN Shuang, GUO Qingjie, WANG Zhiqi, et al. Study on pyrolysis kinetics of refinery oil sludge[J]. Journal of China University of Petroleum (Edition of Natural Science), 2007, 31(4): 116-120.
20	WENG J J, LIU Y X, ZHU Y N, et al. Online study on the co-pyrolysis of coal and corn with vacuum ultraviolet photoionization mass spectrometry[J]. Bioresource Technology, 2017, 244: 125-131.
21	MACPHEE J A, CHARLAND J P, GIROUX L. Application of TG-FTIR to the determination of organic oxygen and its speciation in the Argonne premium coal samples[J]. Fuel Processing Technology, 2006, 87(4): 335-341.
22	NOWICKI L, LEDAKOWICZ S. Comprehensive characterization of thermal decomposition of sewage sludge by TG-MS[J]. Journal of Analytical and Applied Pyrolysis, 2014, 110: 220-228.
23	ZUO W, JIN B S, HUANG Y J, et al. Thermal decomposition of three kinds of sludge by TG-MS and PY-GC/MS[J]. Journal of Thermal Analysis and Calorimetry, 2015, 121(3): 1297-1307.
24	LIN B C, HUANG Q X, ALI M, et al. Continuous catalytic pyrolysis of oily sludge using U-shape reactor for producing saturates-enriched light oil[J]. Proceedings of the Combustion Institute, 2019, 37(3): 3101-3108.
25	HU H Y, FANG Y, LIU H, et al. The fate of sulfur during rapid pyrolysis of scrap tires[J]. Chemosphere, 2014, 97: 102-107.
26	CHEN G Y, LI J T, LI K, et al. Nitrogen, sulfur, chlorine containing pollutants releasing characteristics during pyrolysis and combustion of oily sludge[J]. Fuel, 2020, 273: 117772.
27	FRIEBEL J, KÖPSEL R F W. The fate of nitrogen during pyrolysis of German low rank coals—a parameter study[J]. Fuel, 1999, 78(8): 923-932.
28	BERDNIKOV V I, GUDIM Y A. Formation of dioxins in high-temperature combustion of chlorine-bearing material[J]. Steel in Translation, 2015, 45(2): 89-93.
29	GAO Y X, DING R, WU S, et al. Influence of ultrasonic waves on the removal of different oil components from oily sludge[J]. Environmental Technology, 2015, 36(14): 1771-1775.

低含油污泥编号	C	H	N	S	含油率/%	高含油污泥编号	C	H	N	S	含油率/%
L-1#	14.88	2.62	0.09	0.82	13.9	H-1#	67.35	8.15	0.13	0.23	60.1
L-2#	22.85	3.78	0.24	0.91	29.6	H-2#	78.09	9.92	0.16	0.18	55.9
L-3#	23.66	3.80	0.17	2.38	18.2	H-3#	81.42	11.13	0.08	0.06	69.9
L-4#	18.82	3.26	0.18	1.04	16.4	H-4#	81.21	11.30	0.10	0.05	90.4
L-5#	17.63	2.87	0.16	1.00	16.1	H-5#	80.78	11.54	0.06	0.04	84.9

低含油污泥编号	C	H	N	S	含油率/%	高含油污泥编号	C	H	N	S	含油率/%
L-1#	14.88	2.62	0.09	0.82	13.9	H-1#	67.35	8.15	0.13	0.23	60.1
L-2#	22.85	3.78	0.24	0.91	29.6	H-2#	78.09	9.92	0.16	0.18	55.9
L-3#	23.66	3.80	0.17	2.38	18.2	H-3#	81.42	11.13	0.08	0.06	69.9
L-4#	18.82	3.26	0.18	1.04	16.4	H-4#	81.21	11.30	0.10	0.05	90.4
L-5#	17.63	2.87	0.16	1.00	16.1	H-5#	80.78	11.54	0.06	0.04	84.9

编号	阶段	拟合曲线	相关系数	E_a/kJ · mol^-1	A/K^-1	编号	阶段	拟合曲线	相关系数	E_a/kJ · mol^-1	A/K^-1
L-1#	2	y=-0.407-553.522x	0.995	4.506	2.483	H-1#	2	y=2.048-705.281x	0.986	5.741	22.677
L-1#	3	y=-1.142-135.647x	0.998	1.104	4.859	H-1#	3	y=1.208-105.638x	0.994	0.860	65.377
L-2#	2	y=-0.051-578.044x	0.996	4.705	3.393	H-2#	2	y=0.826-417.618x	0.960	3.399	11.296
L-2#	3	y=-0.780-114.792x	0.997	0.934	8.242	H-2#	3	y=0.579-55.166x	0.974	0.449	66.747
L-3#	2	y=-0.019-596.359x	0.993	4.854	3.395	H-3#	2	y=1.405-531.878x	0.972	4.329	15.826
L-3#	3	y=-0.826-107.739x	0.999	0.877	8.390	H-3#	3	y=0.976-68.509x	0.990	0.558	79.760
L-4#	2	y=0.002-664.065x	0.996	5.405	3.114	H-4#	2	y=1.972-686.868x	0.986	5.591	21.604
L-4#	3	y=-0.953-147.835x	0.999	1.203	5.384	H-4#	3	y=1.057-89.483x	0.999	0.728	66.373
L-5#	2	y=-0.201-603.061x	0.985	4.909	2.800	H-5#	2	y=2.400-808.187x	0.994	6.579	28.145
L-5#	3	y=-0.953-147.835x	0.999	1.203	5.384	H-5#	3	y=1.334-61.007x	0.988	0.497	128.495

编号	阶段	拟合曲线	相关系数	E_a/kJ · mol^-1	A/K^-1	编号	阶段	拟合曲线	相关系数	E_a/kJ · mol^-1	A/K^-1
L-1#	2	y=-0.407-553.522x	0.995	4.506	2.483	H-1#	2	y=2.048-705.281x	0.986	5.741	22.677
L-1#	3	y=-1.142-135.647x	0.998	1.104	4.859	H-1#	3	y=1.208-105.638x	0.994	0.860	65.377
L-2#	2	y=-0.051-578.044x	0.996	4.705	3.393	H-2#	2	y=0.826-417.618x	0.960	3.399	11.296
L-2#	3	y=-0.780-114.792x	0.997	0.934	8.242	H-2#	3	y=0.579-55.166x	0.974	0.449	66.747
L-3#	2	y=-0.019-596.359x	0.993	4.854	3.395	H-3#	2	y=1.405-531.878x	0.972	4.329	15.826
L-3#	3	y=-0.826-107.739x	0.999	0.877	8.390	H-3#	3	y=0.976-68.509x	0.990	0.558	79.760
L-4#	2	y=0.002-664.065x	0.996	5.405	3.114	H-4#	2	y=1.972-686.868x	0.986	5.591	21.604
L-4#	3	y=-0.953-147.835x	0.999	1.203	5.384	H-4#	3	y=1.057-89.483x	0.999	0.728	66.373
L-5#	2	y=-0.201-603.061x	0.985	4.909	2.800	H-5#	2	y=2.400-808.187x	0.994	6.579	28.145
L-5#	3	y=-0.953-147.835x	0.999	1.203	5.384	H-5#	3	y=1.334-61.007x	0.988	0.497	128.495

[1]	WANG Shengyan, DENG Shuai, ZHAO Ruikai. Research progress on carbon dioxide capture technology based on electric swing adsorption [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 233-245.
[2]	DONG Jiayu, WANG Simin. Experimental on ultrasound enhancement of para-xylene crystallization characteristics and regulation mechanism [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4504-4513.
[3]	LI Zhiyuan, HUANG Yaji, ZHAO Jiaqi, YU Mengzhu, ZHU Zhicheng, CHENG Haoqiang, SHI Hao, WANG Sheng. Characterization of heavy metals during co-pyrolysis of sludge with PVC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4947-4956.
[4]	LI Haidong, YANG Yuankun, GUO Shushu, WANG Benjin, YUE Tingting, FU Kaibin, WANG Zhe, HE Shouqin, YAO Jun, CHEN Shu. Effect of carbonization and calcination temperature on As(Ⅲ) removal performance of plant-based Fe-C microelectrolytic materials [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3652-3663.
[5]	TAN Lipeng, SHEN Jun, WANG Yugao, LIU Gang, XU Qingbai. Research progress on blending modification of coal tar pitch and petroleum asphalt [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3749-3759.
[6]	YAO Liming, WANG Yazhuo, FAN Honggang, GU Qing, YUAN Haoran, CHEN Yong. Treatment status of kitchen waste and its research progress of pyrolysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3791-3801.
[7]	ZHANG Shan, ZHONG Zhaoping, YANG Yuxuan, DU Haoran, LI Qian. Enrichment of heavy metals in pyrolysis of municipal solid waste by phosphate modified kaolin [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3893-3903.
[8]	SUO Hansheng, JIA Mengda, SONG Guang, LIU Dongqing. Digital twin-driving force for petrochemical smart factory [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3365-3373.
[9]	YANG Xuzhao, LI Qing, YUAN Kangkang, ZHANG Yingying, HAN Jingli, WU Shide. Thermodynamic properties of Gemini ionic liquid based deep eutectic solvents [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3123-3129.
[10]	LI Ruolin, HE Shaolin, YUAN Hongying, LIU Boyue, JI Dongli, SONG Yang, LIU Bo, YU Jiqing, XU Yingjun. Effect of in-situ pyrolysis on physical properties of oil shale and groundwater quality [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3309-3318.
[11]	LI Dongxian, WANG Jia, JIANG Jianchun. Producing biofuels from soapstock via pyrolysis and subsequent catalytic vapor-phase hydrotreating process [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2874-2883.
[12]	DAI Hang, GAO Ruixue, LI Yiguo, ZHU Jin, WANG Jinggang. Research progress on the synthesis of excellent impact and transparency polyesters with high glass transition temperature [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2555-2565.
[13]	WANG Zhiwei, GUO Shuaihua, WU Mengge, CHEN Yan, ZHAO Junting, LI Hui, LEI Tingzhou. Recent advances on catalytic co-pyrolysis of biomass and plastic [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2655-2665.
[14]	MA Runmei, YANG Haichao, LI Zhengda, LI Shuangxi, ZHAO Xiang, ZHANG Guoqing. Influence analysis of coating on deformation and frictional wear of mechanical seal end for high-speed bearing cavity [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1688-1697.
[15]	LIANG Yijing, MA Yan, LU Zhanfeng, QIN Fusheng, WAN Junjie, WANG Zhiyuan. Experimental investigation on the anti-coking performance of La_1-_x Sr _x MnO₃ perovskite coating [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1769-1778.