石化废水浓缩液深度处理工艺研究

doi:10.19965/j.cnki.iwt.2024-0669

摘要/Abstract

摘要：

石化废水浓缩液有机物浓度高、盐度高，且通常含有氰、胺、酚、醇、有机酸碱、有机氯等毒性物质，导致单独的生化工艺对其处理效果不佳。探讨了活性焦吸附、混凝、电子束辐照（EB）、Fe/C微电解、催化臭氧氧化、过硫酸氢钾氧化等单项技术及其部分组合工艺对石化废水浓缩液的处理效果，结果表明，单项技术中EB、Fe/C微电解对COD的去除效果好，且在经济性、可行性方面更具优势，各组合工艺对COD也具有明显的去除作用，Fe/C微电解+ EB工艺处理后出水COD最低。测定了各工艺出水B/C，结果表明废水可生化性显著提高。为了充分发挥各工艺在提高石化废水浓缩液可生化性方面的优势，采用Fe/C微电解-活性污泥-EB-活性污泥组合工艺处理低盐度（盐质量分数≤1.05%）的石化废水浓缩液，处理后出水COD可以达到60 mg/L左右，而当采用该组合工艺处理盐度为1.55%的浓缩液时，需在废水中加入0.5 g/L葡萄糖作为补充碳源以增强生化工艺对盐的抗性，最终使得出水COD稳定在60~70 mg/L。

关键词: 石化废水浓缩液, Fe/C微电解, 电子束辐照, 生化处理

Abstract:

The concentrated petrochemical wastewater contains high concentrations of organic compounds and salts, and usually also contains toxic substances such as cyanide, amine, phenol, alcohol, organic acid and alkali, organic chlorine, etc., resulting in poor treatment of it by individual biochemical processes. The treatment effect of singletechnology such as adsorption by activated coke, coagulation, electron beam irradiation (EB), Fe/C microelectrolysis, catalytic ozone oxidation, and potassium hydrogen persulfate oxidation, as well as some combination processes, on concentrated petrochemical wastewater was explored. The results showed that EB and Fe/C microelectrolysis had better COD removal effects among the technologies, and had more advantages in terms of economy and feasibility. Each combination process also had a significant COD removal effect, and the Fe/C microelectrolysis+EB process had the lowest effluent COD after treatment. The B/C of effluent from various processes was measured, and the results showed a significant improvement in the biodegradability of the wastewater. In order to fully utilize the advantages of various processes in improving the biodegradability of concentrated petrochemical wastewater, the Fe/C microelectrolysis-activated sludge-EB-activated sludge combination process was used to treat low salinity (salt mass fraction<1.05%) concentrated petrochemical wastewater. The effluent COD could reach about 60 mg/L. When using this combination process to treat concentrate with salt mass fraction of 1.55%, 0.5 g/L glucose needed to be added to the wastewater as supplementary carbon source to enhance the resistance of the biochemical process to salt, with ultimately the effluent COD of 60-70 mg/L.

Key words: concentrated petrochemical wastewater, Fe/C microelectrolysis, electron beam irradiation, biochemical treatment

中图分类号:

X703.1

周月东, 张忠磊, 陈海, 陈川红, 何仕均, 王诗宗, 王建龙. 石化废水浓缩液深度处理工艺研究[J]. 工业水处理, 2025, 45(8): 182-189.

Yuedong ZHOU, Zhonglei ZHANG, Hai CHEN, Chuanhong CHEN, Shijun HE, Shizong WANG, Jianlong WANG. Research on advanced treatment process of concentrated petrochemical wastewater[J]. Industrial Water Treatment, 2025, 45(8): 182-189.

https://www.iwt.cn/CN/Y2025/V45/I8/182

图/表 9

参考文献 16

[1]	TIAN Xiangmiao， SONG Yudong， SHEN Zhiqiang，et al. A comprehensive review on toxic petrochemical wastewater pretreatment and advanced treatment［J］. Journal of Cleaner Production，2020，245：118692. doi:10.1016/j.jclepro.2019.118692
[2]	陈健杰. 金属基核壳臭氧氧化催化剂的制备及其在高盐石化废水深度处理中的应用［D］. 北京：北京化工大学，2023.
	CHEN Jianjie. Preparation of metal-based core-shell ozone oxidation catalyst and its application in advanced treatment of high-salinity petrochemical wastewater［D］. Beijing：Beijing University of Chemical Technology，2023.
[3]	李海鹏，麻微微. 石化废水处理厂特征污染物变化及水质安全研究［J］. 工业水处理，2024，44（6）：88-93.
	LI Haipeng， MA Weiwei. Changes of typical pollutants and water quality safety in a petrochemical wastewater treatment plant［J］. Industrial Water Treatment，2024，44（6）：88-93.
[4]	DONG Pei， XU Zhenzhan， MA Xiaolin，et al. Simple preparation of monolithic N-doped electrode for efficient EF remediation of petrochemical wastewater：Performance，degradation pathways，and mechanism of different N-doped positions［J］. Chemical Engineering Journal，20，473：145237. doi:10.1016/j.cej.2023.145237
[5]	SHI Jingxin， HUANG Wenping， HAN Hongjun，et al. Review on treatment technology of salt wastewater in coal chemical industry of China［J］. Desalination，2020，493：114640. doi:10.1016/j.desal.2020.114640
[6]	KARGI F， DINÇER A R. Use of halophilic bacteria in biological treatment of saline wastewater by fed-batch operation［J］. Water Environment Research，2000，72（2）：170-174. doi:10.2175/106143000x137248
[7]	GUO Jingbo， MA Fang， CHANG C C，et al. Start-up of a two-stage bioaugmented anoxic-oxic（A/O） biofilm process treating petrochemical wastewater under different DO concentrations［J］. Bioresource Technology，2009，100（14）：3483-3488. doi:10.1016/j.biortech.2009.02.059
[8]	QIN Jianjun， OO M H， TAO Guihe，et al. Feasibility study on petrochemical wastewater treatment and reuse using submerged MBR［J］. Journal of Membrane Science，2007，293（1/2）：161-166. doi:10.1016/j.memsci.2007.02.012
[9]	CAMPO R， DI BELLA G. Petrochemical slop wastewater treatment by means of aerobic granular sludge：Effect of granulation process on bio-adsorption and hydrocarbons removal［J］. Chemical Engineering Journal，2019，378：122083. doi:10.1016/j.cej.2019.122083
[10]	王宇航. A/O-MBBR-臭氧催化氧化-一体化BAF处理石化污水的应用研究［D］. 南昌：华东交通大学，2017.
	WANG Yuhang. Application of A/O-MBBR-ozone catalytic oxidation-integrated BAF in petrochemical wastewater treatment［D］. Nanchang：East China Jiaotong University，2017.
[11]	郑贝贝，霍莹，付连超，等. 微波耦合铁碳微电解预处理石化废水的试验［J］. 净水技术，2020，39（2）：98-110.
	ZHENG Beibei， HUO Ying， FU Lianchao，et al. Experiment of microwave coupled ferrocarbon micro-electrolysis process for petrochemical wastewater pretreatment［J］. Water Purification Technology，2020，39（2）：98-110.
[12]	WANG Jianlong， XU Lejin. Advanced oxidation processes for wastewater treatment：Formation of hydroxyl radical and application［J］. Critical Reviews in Environmental Science and Technology，2012，42（3）：251-325. doi:10.1080/10643389.2010.507698
[13]	WANG Shizong， WANG Jianlong. Electron beam radiation coupled to flocculation for advanced treatment of coking and dyeing wastewater：Performance and synergistic effect［J］. Journal of Cleaner Production，2024，454：142344. doi:10.1016/j.jclepro.2024.142344
[14]	ZHANG Zhonglei， HU Dongming， CHEN Hai，et al. Enhanced degradation of triclosan by gamma radiation with addition of persulfate［J］. Radiation Physics and Chemistry，2021，180：109273. doi:10.1016/j.radphyschem.2020.109273
[15]	贺银莉. 好氧颗粒污泥结合共代谢处理石化废水的研究［D］. 大连：大连理工大学，2011.
	HE Yinli. Study on treatment of petrochemical wastewater by aerobic granular sludge combined with co-metabolism［D］. Dalian：Dalian University of Technology，2011.
[16]	ZHANG Zhonglei， YANG Qi， WANG Jianlong. Degradation of trimethoprim by gamma irradiation in the presence of persulfate［J］. Radiation Physics and Chemistry，2016，127：85-91. doi:10.1016/j.radphyschem.2016.06.019

工艺类别	工艺主要条件	浓缩液原水 COD/（mg·L^-1）	曝气脱碳酸后废水 COD/（mg·L^-1）	出水COD/ （mg·L^-1）
活性焦吸附	活性焦125 g/L，吸附1.5 h	162.4	137	90
混凝	PFS吸附质量分数0.2%	162.4	137	132.6
EB	电子束吸收剂量1 kGy	166.4	146.6	130.4
EB	电子束吸收剂量3 kGy	168	144	113.6
Fe/C微电解	铁碳石投加量2.8 kg/L	166.4	146.6	106
催化臭氧氧化	0.005 4% H₂O₂+5 mg/L O₃	166.4	146.6	163.2
PMS氧化	投加量0.2 g/L	168	136	124
	投加量0.4 g/L	168	136	112
	投加量0.5 g/L	138	116	89
	投加量0.6 g/L	168	136	100
	投加量0.8 g/L	168	136	96

工艺类别	工艺主要条件	浓缩液原水 COD/（mg·L^-1）	曝气脱碳酸后废水 COD/（mg·L^-1）	出水COD/ （mg·L^-1）
活性焦吸附	活性焦125 g/L，吸附1.5 h	162.4	137	90
混凝	PFS吸附质量分数0.2%	162.4	137	132.6
EB	电子束吸收剂量1 kGy	166.4	146.6	130.4
EB	电子束吸收剂量3 kGy	168	144	113.6
Fe/C微电解	铁碳石投加量2.8 kg/L	166.4	146.6	106
催化臭氧氧化	0.005 4% H₂O₂+5 mg/L O₃	166.4	146.6	163.2
PMS氧化	投加量0.2 g/L	168	136	124
	投加量0.4 g/L	168	136	112
	投加量0.5 g/L	138	116	89
	投加量0.6 g/L	168	136	100
	投加量0.8 g/L	168	136	96

组合工艺	浓缩液原水COD/（mg·L^-1）	曝气脱碳酸后废水COD/（mg·L^-1）	出水COD/（mg·L^-1）
混凝+EB（3 kGy）	166.4	146.6	127.8
Fe/C微电解+混凝	150	132	108
Fe/C微电解+PMS（0.2 g/L）氧化+混凝	150	132	100
Fe/C微电解+PMS（0.2 g/L）氧化+混凝+EB（1 kGy）	150	132	92
Fe/C微电解+PMS（0.2 g/L）氧化+EB（1 kGy）+混凝	150	132	104
Fe/C微电解+混凝+H₂O₂（0.002%）+EB（1 kGy）	150	132	112
Fe/C微电解+混凝+EB（1 kGy）	150	132	104
Fe/C微电解+混凝+EB（3 kGy）	168	142	105.6
PMS氧化（0.5 g/L）+EB（1 kGy）	138	116	89
PMS氧化（0.5 g/L）+EB（2 kGy）	138	116	90
PMS氧化（0.5 g/L）+EB（4 kGy）	138	116	97
PMS氧化（0.5 g/L）+EB（8 kGy）	138	116	91

组合工艺	浓缩液原水COD/（mg·L^-1）	曝气脱碳酸后废水COD/（mg·L^-1）	出水COD/（mg·L^-1）
混凝+EB（3 kGy）	166.4	146.6	127.8
Fe/C微电解+混凝	150	132	108
Fe/C微电解+PMS（0.2 g/L）氧化+混凝	150	132	100
Fe/C微电解+PMS（0.2 g/L）氧化+混凝+EB（1 kGy）	150	132	92
Fe/C微电解+PMS（0.2 g/L）氧化+EB（1 kGy）+混凝	150	132	104
Fe/C微电解+混凝+H₂O₂（0.002%）+EB（1 kGy）	150	132	112
Fe/C微电解+混凝+EB（1 kGy）	150	132	104
Fe/C微电解+混凝+EB（3 kGy）	168	142	105.6
PMS氧化（0.5 g/L）+EB（1 kGy）	138	116	89
PMS氧化（0.5 g/L）+EB（2 kGy）	138	116	90
PMS氧化（0.5 g/L）+EB（4 kGy）	138	116	97
PMS氧化（0.5 g/L）+EB（8 kGy）	138	116	91

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