大庆多源含油污泥热解特性的对比

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

摘要/Abstract

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

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

中图分类号:

TE992.3

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.

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.

图/表 16

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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

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