电催化氧化脱除气田采出水中硫化物

张舸; 金艳; 李丽; 韩昫身; 高荔; 于建国

doi:10.14135/j.cnki.1006-3080.20210609003

电催化氧化脱除气田采出水中硫化物

doi: 10.14135/j.cnki.1006-3080.20210609003

张舸^1,,
金艳²,
李丽¹,
韩昫身¹,
高荔³,
于建国^1, ,

1.
华东理工大学资源过程工程教育部工程研究中心, 上海 200237
2.
苏州聚智同创环保科技有限公司, 江苏常熟 215513
3.
青岛职业技术学院, 山东青岛 266071

基金项目: 中国石油科技创新基金（2020D-5007-0502）；上海市青年科技英才扬帆计划（20YF1409500）；中央高校基本科研业务费专项基金（50321022017008）

详细信息

作者简介:
张舸：张　舸（1996—），女，河北唐山人，硕士生，主要研究方向：水污染控制。E-mail：gzhang@mail.ecust.edu.cn

通讯作者:
于建国， E-mail：jgyu@ecust.edu.cn

中图分类号: X741
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- 被引次数: 0
出版历程
- 收稿日期: 2021-06-09
- 网络出版日期: 2021-09-29

Removing Sulfide in Gas Field Produced Water by Electrooxidation

ZHANG Ge^1
,,
JIN Yan²,
LI Li¹,
HAN Xushen¹,
GAO Li³,
YU Jianguo^{1
, ,}

1.
Engineering Research Center of Resource Process Engineering, Ministry of Education, East China University of Science and Technology, Shanghai 200237, China
2.
Suzhou Juzhi Tongchuang Environmental Technology Co. Ltd., Changshu, Jiangsu 215513, China
3.
Qindao Technical College, Shandong, Qindao 266071, China

摘要

摘要: 为了防止含硫气田采出水中硫化物危害环境和人类健康，必须对其进行处理。采用污染小、效率高的电化学氧化法对高盐、高硬气田采出水的脱硫过程进行研究。选用Ti/RuO₂-SnO₂-IrO₂阳极材料，在极板间距0.05 m，电流密度200 A/m²，曝气量1 L/min，初始pH 9-10的条件下，模拟采出水（300 mg/L初始硫化物，2.5% NaCl）处理35 min后，脱硫率高达99.2%以上，单位能耗为5.52 kWh/kgS^2-。此外，本研究发现，针对高硬体系下的阴极结垢问题，利用倒极方法可有效去除结垢物，保证装置稳定运行。
- 气田采出水 /
- 硫化物 /
- 电氧化 /
- 金属氧化物涂层钛电极 /
- 阴极结垢
Abstract: Certain amounts of sulfide are present in gas field produced water and it brings negative effects on environment and human health, therefore, it is essential to remove sulfide first. Since the electrochemical oxidation method has the advantages of high efficiency without secondary pollution, here we introduced it into the sulfide removal process under the conditions of high salinity and hardness. Based on the cyclic voltammetry characteristics, sulfide removal efficiency, and economic analysis, Ti/RuO₂-SnO₂-IrO₂ was selected as the anode. The removal of sulfide by two-dimensional electrochemical oxidation follows zero-order kinetics, that is, in all reaction stages, residual sulfide concentration in solution has a linear relationship with time. Sulfide exists in the form of HS⁻ in the solution. When HS⁻ is oxidized, H⁺ will be released. Therefore, it is necessary to select a suitable initial pH and control the reaction time. The sulfide removal ratio and corresponding energy consumption of simulated gas field produced water with 300 mg/L sulfide and 2.5% NaCl were >99.2% and 55.2 kWh/kg S²⁻, respectively, with the electrode distance of 5 cm, current density of 200 A/m², aeration rate of 1 L/min, the initial pH of 9-10, and running time of 35 min. Moreover, reversing cathode and anode was found to effectively solve the problem of scaling on cathode caused by high Ca²⁺ and Mg²⁺ concentration.
- gas field produced water /
- sulfide /
- electrooxidation /
- metal oxide coated titanium electrode /
- cathode scaling

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图 1 三电极系统

Figure 1. Three-electrode system

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图 2 电催化氧化反应装置示意图

Figure 2. Schematic diagram of the electrocatalytic oxidation reaction device

1-DC power; 2-Cathode; 3-Anode; 4-Simulated gas field produced water; 5-Electrolytic cell

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图 3 不同阳极材料在0.1 M Na₂S+0.1 M NaCl中的循环伏安曲线

Figure 3. Cyclic voltammetry curves of different anodes in 0.1 M Na₂S+0.1 M NaCl

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图 4 不同阳极材料的硫化物脱除效果

Figure 4. Sulfide removal effect with different anodes

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图 5 极板间距对硫化物脱除的影响

Figure 5. Effect of electrode distance on sulfide removal

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图 6 电流密度对硫化物脱除的影响

Figure 6. Effect of current density on sulfide removal

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图 7 曝气量对硫化物脱除的影响

Figure 7. Effect of aeration rate on sulfide removal

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图 8 NaCl含量对硫化物脱除的影响

Figure 8. Effect of NaCl concentration on sulfide removal

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图 9 不同初始浓度硫化物的脱除效果

Figure 9. Effect of sulfide concentration on sulfide removal

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图 10 硫化物在不同pH下的存在形式

Figure 10. Existing forms of sulfide at different pH

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图 11 初始pH对硫化物脱除的影响

Figure 11. Effect of initial pH on sulfide removal

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图 12 不同初始pH下阳极板的硫单质沉积情况

Figure 12. Sulfur deposition on anode at different initial pH

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图 13 不同初始pH下反应过程中硫化物存在形式的变化

Figure 13. Changes of sulfide existing form during the reaction with different initial pH

The initial pH of (a), (b), (c), (d), (e), (f) are 7, 8, 9, 10, 11, 12, 13, respectively

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图 15 倒极前后阴极板上的结垢情况

Figure 15. Scaling on the cathode before and after reversing electrodes

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图 14 钙镁离子对硫化物脱除的影响

Figure 14. Effect of Ca²⁺ and Mg²⁺ on sulfide removal

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表 1 川渝地区典型气田含硫情况及气田水中硫化物浓度^[1]

Table 1. H₂S content of typical gas fields and sulfide concentration in gas field water in Sichuan and Chongqing

H₂S content of typical sour gas field/(10⁻³kg·m⁻³)	Sulfide mass concentration in gas field water/(mg·L⁻¹)	Classification of sulfide- containing gas field water	Sulfide mass concentration range/(mg·L⁻¹)
Shapingchang (0.1-0.4)	0.1-32.0	Low	< 20
Xihekou (1.0-4.0)	4.5-72.0	Medium	20-100
Longwangmiao (4.0-12.0)	100.0-150.0	High	100-200
Puguang (180.0-250.0)	600.0-800.0	Extra high	> 200
Yuanba (80.0-85.0)	800.0-2500.0
Longgang (20.0-80.0)	820.0-1600.0

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表 2 磨溪206#采出水水样水质

Table 2. Composition of gas field produced water from Moxi 206#

No.	pH	Conductivity/ (mS·cm⁻¹)	${\;\rho}_{ \rm{Sulfide}}$/ (mg·L⁻¹)	${\;\rho}_{ \rm{COD}} $/ (mg·L⁻¹)	${\;\rho}_{ \rm{NH_3-N}} $/ (mg·L⁻¹)	${\;\rho}_{ \rm{Cl^{-1}}} $/ (10⁴mg·L⁻¹)	${\;\rho}_{ \rm{Na^{+}}} $/ (10⁴mg·L⁻¹)	${\;\rho}_{ \rm{Ca^{2+}}} $/ (mg·L⁻¹)	${\;\rho}_{ \rm{Mg^{2+}}} $/ (mg·L⁻¹)
1	6.43	43.9	303	88.0	60.9	1.71	1.09	588	68.2
2	6.32	53.6	348	75.0	75.8	2.09	1.31	730	93.6
3	6.73	41.6	287	250	70.1	1.58	1.07	443	51.4
4	6.37	53.2	300	275	77.0	2.09	1.30	736	86.4
5	6.80	39.3	286	50.0	57.3	1.48	0.986	427	48.3
6	6.79	46.1	263	125	73.4	1.81	1.14	617	75.5

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表 3 不同阳极材料的价格

Table 3. Prices of different anodes

Anode type	Price/ (10³CNY·m⁻²)	Anode type	Price/ (10³CNY·m⁻²)
Ti/TiO₂-RuO₂-IrO₂	10.19	Ti/IrO₂-RuO₂	21.02
Ti/IrO₂-Ta₂O₅	25.48	Ti/RuO₂-SnO₂-IrO₂	11.47
Ti/IrO₂-Ta₂O₅-SnO₂	26.75	Ti/SnO₂-Sb₂O₃	7.643
Ti/RuO₂-SnO₂	9.554	Ti/SnO₂-Sb₂O₃-IrO₂	29.30

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表 4 不同极板间距下平均槽电压和能耗对比

Table 4. Comparison of average cell voltages and energy consumption with different electrode distances

Electrode distance/m	Treated water volume/L	Average cell voltage/V	Time for complete removal of sulfide/10³s	Energy consumption /(kWh/kgS^2-)	Energy consumption per ton of water /(kWh·t⁻¹)
0.03	0.190	4.32	2.04	58.7	18.3
0.05	0.340	5.04	3.84	71.8	22.4
0.07	0.480	5.87	5.34	83.5	26.0
0.09	0.620	6.48	7.02	93.6	29.1
0.11	0.760	7.43	8.22	102	31.7
0.20	1.43	11.4	15.0	152	47.3
Note: Initial sulfide concentration is 311.3 mg/L. Current is 1.425 A, i.e. current density is 200 A/m².

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表 5 不同电流密度下达到相同脱硫率（70%）时的平均槽电压和能耗对比

Table 5. Average cell voltages and energy consumption at different current densities with the same sulfide removal ratio (70%)

Current density /(A·m⁻²)	Current/A	Average cell voltage/V	Time for the same sulfide removal ratio/10³s	Energy consumption per ton of water/(kWh·t⁻¹)
100	0.694	4.87	3.60	11.3
150	1.040	5.29	2.70	13.8
200	1.387	5.94	2.22	16.9
250	1.734	6.22	1.80	18.0
300	2.081	7.13	1.62	22.3

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表 6 不同NaCl含量下的单位能耗

Table 6. Energy consumption with different NaCl concentrations

NaCl concentration /%	Current /A	Average cell voltage/V	The amount of removed sulfide after 50 min/10⁻⁵kg	Energy consumption /(kWh/kgS²⁻)
0.25	1.387	12.5	7.01	206
0.50	1.387	10.8	7.11	176
1.0	1.387	8.01	7.48	124
2.0	1.387	6.36	8.43	87.2
2.5	1.387	5.99	8.44	82.1
5.0	1.387	5.24	9.29	65.2
7.5	1.387	4.56	8.81	59.8
10	1.387	4.32	8.93	55.9

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表 7 不同初始硫化物浓度的动力学方程拟合模型

Table 7. Fitting kinetic equations for different initial sulfide concentrations

Initial sulfide concentration/(mg·L⁻¹)	Fitting kinetic equation	Reaction rate constant ·(mg·(L·s⁻¹))	R²
174.0	c=174.0−0.1556t	0.1556	0.9994
326.9	c=326.9−0.1561t	0.1561	0.9996
398.9	c=398.9−0.1593t	0.1593	0.9995
511.2	c=511.2−0.1727t	0.1727	0.9993
565.5	c=565.5−0.1687t	0.1687	0.9978

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参考文献(31)

[1]	翁邦华, 杨杰, 陈昌介, 等. 气田水中硫化物控制指标及处理措施[J]. 天然气工业, 2019, 39(3): 109-115.
[2]	李彦俊, 魏宏斌. 废水处理中硫化物去除技术的研究与应用[J]. 净水技术, 2010, 29(6): 9-12,56.
[3]	闫玉乐, 王凤伟, 周博涵, 等. 油气田含硫污水处理技术[J]. 广东化工, 2017, 44(19): 108-109.
[4]	诸爱士, 兰益周, 唐晓璐. 活性二氧化氯处理含硫模拟废水[J]. 浙江科技学院学报, 2012, 24(4): 310-315.
[5]	陈国强, 曹建国, 汪卫东, 等. 冶炼废水中硫化物的处理实验研究[J]. 中国矿业, 2015, 24(S2): 109-111.
[6]	徐洪斌, 柳理芹, 杨苗青, 等. 臭氧氧化处理含硫皮革废水的实验研究[J]. 工业水处理, 2016, 36(1): 52-54.
[7]	宋玲, 程志强, 蓝艳, 等. 元坝气田采出水除硫工艺技术应用实践[J]. 工业用水与废水, 2018, 49(4): 43-46.
[8]	SHIVASANKARAN N, BALAN A V, SANKAR S P, et al. Removal of hydrogen sulphide and odour from tannery & textile effluents[J]. Materials Today:Proceedings, 2020, 21: 777-781.
[9]	ALTAŞ L, BÜYÜKGÜNGÖR H. Sulfide removal in petroleum refinery wastewater by chemical precipitation[J]. Journal of Hazardous Materials, 2008, 153(1/2): 462-469.
[10]	杨艺程, 刘仁军, 肖乐业, 等. 含硫废水的理论分析及脱硫试验研究[J]. 燃料与化工, 2012, 43(6): 41-43,46.
[11]	周永生, 陆惠刚, 黄燕华, 等. 沉淀法预处理硫辛酸厂高质量浓度含硫废水试验研究[J]. 常州大学学报(自然科学版), 2014, 26(4): 59-62.
[12]	陈一萍, 谢志洞. 碳纳米管对水中硫化物吸附性能的研究[J]. 皮革与化工, 2013, 30(6): 6-9.
[13]	戴一民, 黄壁成. 生物质基多孔吸附模拟含硫废水[J]. 明胶科学与技术, 2016, 36(2): 92-99.
[14]	BALASUBRAMANI U, VENKATESH R, SUBRAMANIAM S, et al. Alumina/activated carbon nano-composites: synthesis and application in sulphide ion removal from water[J]. Journal of Hazardous Materials, 2017, 340: 241-252.
[15]	周西臣, 曲虎, 刘静, 等. 气提法去除油田污水中H₂S的实验研究[J]. 工业水处理, 2012, 32(1): 66-69.
[16]	梁宏宝, 韩东, 陈洪涛, 等. 吹脱法处理油田集输系统污水中H₂S小型工艺试验[J]. 油气田地面工程, 2017, 36(9): 24-28.
[17]	韩金枝, 付腾飞, 王燕. 无色硫细菌处理含硫废水的试验研究[J]. 环境科技, 2010, 23(5): 4-7.
[18]	FENG S, LIN X, TONG Y, et al. Biodesulfurization of sulfide wastewater for elemental sulfur recovery by isolated Halothiobacillus neapolitanus in an internal airlift loop reactor[J]. Bioresource Technology, 2018, 264: 244-252.
[19]	SUN Z, PANG B, XI J, et al. Screening and characterization of mixotrophic sulfide oxidizing bacteria for odorous surface water bioremediation[J]. Bioresource Technology, 2019, 290: 1-9.
[20]	王琳, 金艳, 宋兴福, 等. 三维电催化氧化处理对硝基苯酚废水[J]. 华东理工大学学报(自然科学版), 2018, 44(3): 289-295,315.
[21]	常华, 周理, 苏伟. 硫化氢吸收液的电化学分解条件研究[J]. 天然气工业, 2006, 26(8): 138-140,176.
[22]	田建勋, 祁贵生, 刘有智, 等. 碳酸钠溶液吸收硫化氢富液的直接电解工艺[J]. 化工进展, 2015, 34(2): 325-329.
[23]	崔磊. 电化学法脱除溶液中硫离子的研究[D]. 成都: 西南石油大学, 2012.
[24]	VAIOPOULOU E, PROVIJN T, PRÉVOTEAU A, et al. Electrochemical sulfide removal and caustic recovery from spent caustic streams[J]. Water Research, 2016, 92: 38-43.
[25]	NTAGIA E, FISET E, HONG L T C, et al. Electrochemical treatment of industrial sulfidic spent caustic streams for sulfide removal and caustic recovery[J]. Journal of Hazardous Materials, 2020, 388: 1-9.
[26]	张宁. 电化学阳极氧化硫化物的研究[D]. 南京: 南京理工大学, 2012.
[27]	曹志斌. 三维电极反应器的设计及应用研究[D]. 南京: 南京航空航天大学, 2009.
[28]	李雪, 冯岩, 于衍真. 三维电极体系在废水处理中的应用[J]. 中国资源综合利用, 2016, 34(4): 29-33.
[29]	ZHANG C, JIANG Y, LI Y, et al. Three-dimensional electrochemical process for wastewaters treatment: A general review[J]. Chemical Engineering Journal, 2013, 228: 455-467.
[30]	王婷婷. 硫化钠废碱液的催化氧化研究[D]. 北京: 北京化工大学, 2011.
[31]	WATERSTON K, BEJAN D, BUNCE N J. Electrochemical oxidation of sulfide ion at a boron-doped diamond anode[J]. Journal of Applied Electrochemistry, 2007, 37: 367-373.