页岩油采出水水质综合特性及不稳定成因研究

doi:10.19965/j.cnki.iwt.2025-0287

摘要/Abstract

摘要：

页岩油采出水的水质特性复杂，不稳定性强，为其处理、贮存和资源化利用带来难度。以长庆油田庆阳地区8个位点的页岩油采出水为对象，通过多重指标检测技术解析其水质特性及特征污染组成，结合沉淀物形貌及成分剖析水质不稳定的内在成因。结果表明，页岩油采出水具有高盐度（TDS>13 000 mg/L）、高化学需氧量（COD>645.4 mg/L）、低可生化性（B/C<0.1）和高不稳定性（Zeta电位趋于0、聚合物分散系数PDI趋于1）特征，主要存在灰白色钙类沉淀（CaCO₃、CaSO₄）、棕褐色铁氧化物类沉淀〔Fe（OH）₃、Fe₂O₃〕和黑色FeS₂、FeS沉淀，并裹挟大量NaCl导致沉淀量增加。采出水不稳定性受无机及有机组分共同影响，烷基苯磺酸类表面活性剂降低了采出水的表面张力，促进水中颗粒物与高浓度Ca²⁺、HCO₃ ^-、SO₄ ^2-等离子在中性条件下聚集沉淀，并使Fe²⁺发生氧化水解反应持续析出。相关性分析结果显示，Cl^-、Ca²⁺、Mg²⁺和Ba²⁺主要贡献采出水中电导率，高浓度SO₄ ^2-和HCO₃ ^-对表面张力降低作用显著，是导致页岩油采出水水质不稳定的主要因素。

关键词: 页岩油采出水, 水质特性, 沉淀物组成, 不稳定成因

Abstract:

The water quality characteristics of shale oil produced water are complex and highly unstable, which poses difficulties for its treatment, storage, and resource utilization. This study focused on shale oil produced water from 8 sites in Qingyang area of Changqing Oilfield. Through multiple indicator detection techniques, the water quality characteristics and characteristic pollution composition were analyzed. Combined with sediment morphology and composition, the internal causes of water quality instability were analyzed. The results showed that shale oil produced water had characteristics of high salinity(TDS>13 000 mg/L), high chemical oxygen demand(COD>645.4 mg/L), low biodegradability(B/C<0.1), and high instability(Zeta potential tends to 0, Polydispersity Index PDI tends to 1),mainly consisting of white calcium precipitates(CaCO₃, CaSO₄), brown iron oxide precipitates(Fe(OH)₃, Fe₂O₃), and black precipitates (FeS₂, FeS), which were accompanied by a large amount of NaCl leading to an increase in precipitation. The instability of produced water was affected by both inorganic and organic components. Alkylbenzene sulfonic acid surfactants reduced the surface tension of produced water, promoted the aggregation and precipitation of particulate matter and high concentrations of Ca²⁺, HCO₃ ^-, SO₄ ^2- ions under neutral conditions, and continuously precipitated Fe²⁺through oxidative hydrolysis reaction. The correlation analysis results showed that Cl^-, Ca²⁺, Mg²⁺, and Ba²⁺ mainly contributed to the conductivity of the produced water. High concentrations of SO₄ ^2- and HCO₃ ^- significantly reduced surface tension and were the main factors leading to unstable water quality in shale oil produced water.

Key words: shale oil produced water, water quality characteristics, composition of sediment, cause of instability

中图分类号:

X703.1

白兰, 王兴, 杨百玉, 商永滨, 苑旭阳, 刘素珍, 李琢宇, 王庆宏, 陈春茂. 页岩油采出水水质综合特性及不稳定成因研究[J]. 工业水处理, 2026, 46(4): 57-66.

Lan BAI, Xing WANG, Baiyu YANG, Yongbin SHANG, Xuyang YUAN, Suzhen LIU, Zhuoyu LI, Qinghong WANG, Chunmao CHEN. Research on the comprehensive characteristics and instability causes of shale oil produced water quality[J]. Industrial Water Treatment, 2026, 46(4): 57-66.

https://gyscl.magtechjournal.com/CN/Y2026/V46/I4/57

图/表 9

图1 页岩油采出水静置水样形貌

Fig.1 Morphology of static water sample of shale oil produced water

表1 页岩油采出水综合污染指标

Table1 Comprehensive pollution indexes of shale oil produced water

水样名称	pH	TDS/ （mg·L^-1）	电导率/ （μS·cm^-1）	SS/ （mg·L^-1）	浊度/NTU	COD/ （mg·L^-1）	BOD/ （mg·L^-1）	B/C	石油类/ （mg·L^-1）
城壕采出水	7.23	23 800	39 500	676	432.5	4 238.9	400	0.094	9.97
岭八转采出水	6.34	23 400	39 100	74	37.5	3 572.5	250	0.070	2.65
西259综采出水	7.34	39 800	66 400	464	80.7	645.4	80	0.124	3.59
镇六转采出水	7.22	20 900	35 000	600	286.5	860.4	40	0.046	4.42
庄四联采出水	7.96	13 110	21 800	136	77.9	681.3	70	0.103	3.15
庄六注长6采出水	7.20	18 340	30 500	864	571.5	1 930.2	120	0.062	3.53
庄六注长8采出水	6.98	14 180	23 600	1 580	869.5	6 920.7	200	0.029	3.12
庄六注侏罗采出水	7.68	511	852	60	25	230.7	70	0.303	4.30

表2 页岩油采出水Zeta电位、PDI指数、表面张力、粒径中值分布

Table 2 Distribution of Zeta potential，PDI index，surface tension，and median particle size in shale oil produced water

	Zeta电位/mV	PDI指数	表面张力/（mN·m^-1）	粒径中值/nm
城壕采出水	0.059	0.329	56.09	985
岭八转采出水	0.051	0.346	70.35	3 682
西259综采出水	-0.044	1.000	45.99	3 881
镇六转采出水	0.043	0.295	61.33	919
庄四联采出水	-0.006	0.307	71.49	1 055
庄六注长6采出水	-0.100	0.796	70.53	6 724
庄六注长8采出水	-0.025	0.725	71.76	14 804
庄六注侏罗采出水	-0.051	0.903	72.30	1 712

图2 页岩油采出水XRD和SEM结果

Fig.2 XRD and SEM results of shale oil produced water

图3 页岩油采出水的阴阳离子浓度分布

Fig.3 Distribution of cation and anion concentrations in shale oil produced water

图4 页岩油采出水水质指标相关性热图

Fig.4 Correlation heatmap of water quality indicators in shale oil produced water

图5 页岩油采出水3D-EEM谱图

Fig.5 3D-EEM spectra of shale oil produced water

图6 页岩油采出水GC-MS及Orbitrap MS有机化合物类型

Fig.6 Types of organic compounds in shale oil produced water by GC-MS and Orbitrap MS

图7 页岩油采出水中不同类型沉淀物形成机制

Fig.7 Formation mechanism of different types of sediment in shale oil produced water

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