Study on the treatment of petrochemical industrial wastewater by EGSB-SBR-ozone oxidation combined process

doi:10.19965/j.cnki.iwt.2024-0202

Abstract

Abstract:

Petrochemical industrial wastewater, due to its high COD concentration, toxic and difficult to degrade substances and complex composition, may cause serious harm to the ecological environment, water safety and human health, which requires effective treatment before discharge. A EGSB-SBR-ozone oxidation combined proceess was constructed to investigate its effect on the treatment of mixed water produced by a petrochemical enterprise with SAR concentration condensate, RO concentrate, maleic anhydride wastewater and PPG wastewater. The results showed that in anaerobic treatment, the EGSB process was more effective in treating this mixed water, and the volumetric loading (in terms of COD) could reach about 5 kg/(m³·d) when the influent COD was 4 000-9 000 mg/L. The COD removal rate could be stabilized at more than 80%, and the CH₄ production rate (in terms of the standard volume of CH₄ produced by consuming a unit of COD) could be up to 300 mL/g. The effluent from the anaerobic process was further treated by aerobic SBR process, which resulted in an average COD removal rate of more than 80%, with a maximum sludge load of 0.22 kg/(kg·d). The aerobic SBR effluent was treated in depth by ozone oxidation process with the ozone dosing ratio of 3.6 or less, and the average COD removal rate reached 60%. EGSB-SBR-ozone oxidation combined process had a better effect on the treatment of target mixed wastewater. In the actual project, the effluent could meet the secondary standard of Pollutant Emission Standards for Urban Wastewater Treatment Plants (GB 18918-2002) after further treatment by subsequent adsorption and high salt biofilter process.

Key words: anaerobic digestion, aerobic SBR process, ozone oxidation process, combined process, industrial wastewater

摘要：

石化工业废水因其COD高，含有毒及难降解物质且成分复杂，可能对生态环境、水体安全、人类健康造成严重危害，需要进行有效处理才能排放。构建了厌氧膨胀颗粒污泥床（EGSB）-SBR-臭氧氧化组合工艺，考察其对某石化企业产生的废酸再生（SAR）浓缩冷凝液、RO浓水、顺酐废水及聚丙二醇（PPG）废水等混合水的处理效果。结果表明，在厌氧处理中，EGSB工艺对该混合水的处理效果较好，当进水COD为4 000~9 000 mg/L时，容积负荷（以COD计）可达到5 kg/（m³·d）左右，COD去除率可稳定在80%以上，CH₄产率（以消耗单位质量COD产生的CH₄标准体积计）可达300 mL/g。厌氧工艺的出水经好氧SBR工艺进一步处理，COD平均去除率可达80%以上，最高污泥负荷（单位质量VSS处理COD的质量）达到0.22 kg/（kg·d）。好氧SBR出水经臭氧氧化工艺深度处理，臭氧投加比在3.6以下，COD平均去除率达60%。EGSB-SBR-臭氧氧化组合工艺对目标混合废水的处理效果较好，在实际工程项目中，经后续吸附、高盐生物滤池工艺进一步处理后能满足《城镇污水处理厂污染物排放标准》（GB 18918—2002）二级标准。

关键词: 厌氧消化, 好氧SBR工艺, 臭氧氧化, 组合工艺, 工业废水

CLC Number:

X703

Fan ZHAO, Qian GONG, Yanhe HAN, Zhi GUO, Hua JI, Xuejiao MA. Study on the treatment of petrochemical industrial wastewater by EGSB-SBR-ozone oxidation combined process[J]. Industrial Water Treatment, 2025, 45(3): 129-136.

赵帆, 龚茜, 韩严和, 郭智, 季华, 马雪姣. EGSB-SBR-臭氧氧化组合工艺处理石化工业废水的研究[J]. 工业水处理, 2025, 45(3): 129-136.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2024-0202

https://www.iwt.cn/EN/Y2025/V45/I3/129

Figures/Tables 11

References 24

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项目	SAR浓缩冷凝液	RO浓水	顺酐废水	PPG废水
pH	6.40	8.28	1.38	7.91
电导率/（μS·cm^-1）	22 000	5 620	20 030	688
TCOD/（mg·L^-1）	86 700	44	39 800	18 900
SCOD/（mg·L^-1）	86 800	43	38 520	18 840
TOC/（mg·L^-1）	31 425	18	17 552	4 602
DOC/（mg·L^-1）	31 965	18	17 448	4 452
BOD₅/（mg·L^-1）	35 400	<0.50	22 450	2 750
Na⁺/（mg·L^-1）	10 795	1 200	7.6	82.1
SS/（mg·L^-1）	—	—	21	2
NH₄ ⁺-N/（mg·L^-1）	4	<0.025	1.8	2.10
TN/（mg·L^-1）	12	24	4.2	19
NO₃ ^--N/（mg·L^-1）	7	9	<0.016	6.4
NO₂ ^--N/（mg·L^-1）	<0.001	0.01	<0.001	<0.001
TP/（mg·L^-1）	—	0.07	8.57	0.97
PO₄ ^3--P/（mg·L^-1）	<0.051	<0.051	<0.051	<0.051
SO₄ ^2-/（mg·L^-1）	<0.018	1 190	<0.018	133
Cl^-/（mg·L^-1）	<0.007	714	123	56
OH^-/（mg·L^-1）	<0.50	<0.50	<0.50	<0.50
HCO₃ ^-/（mg·L^-1）	8 025	310	<0.50	24
CO₃ ^2-/（mg·L^-1）	<0.50	13	<0.50	4
碱度（以CaCO₃计）/（mg·L^-1）	6 600	376	<0.50	23
总硬度（以CaCO₃计）/（mg·L^-1）	<1.0	468	7.14	65
VFA/（mmol·L^-1）	118	0.34	5.06	0.43
TDS/（mg·L^-1）	14 821	3 546	144	284

项目	SAR浓缩冷凝液	RO浓水	顺酐废水	PPG废水
pH	6.40	8.28	1.38	7.91
电导率/（μS·cm^-1）	22 000	5 620	20 030	688
TCOD/（mg·L^-1）	86 700	44	39 800	18 900
SCOD/（mg·L^-1）	86 800	43	38 520	18 840
TOC/（mg·L^-1）	31 425	18	17 552	4 602
DOC/（mg·L^-1）	31 965	18	17 448	4 452
BOD₅/（mg·L^-1）	35 400	<0.50	22 450	2 750
Na⁺/（mg·L^-1）	10 795	1 200	7.6	82.1
SS/（mg·L^-1）	—	—	21	2
NH₄ ⁺-N/（mg·L^-1）	4	<0.025	1.8	2.10
TN/（mg·L^-1）	12	24	4.2	19
NO₃ ^--N/（mg·L^-1）	7	9	<0.016	6.4
NO₂ ^--N/（mg·L^-1）	<0.001	0.01	<0.001	<0.001
TP/（mg·L^-1）	—	0.07	8.57	0.97
PO₄ ^3--P/（mg·L^-1）	<0.051	<0.051	<0.051	<0.051
SO₄ ^2-/（mg·L^-1）	<0.018	1 190	<0.018	133
Cl^-/（mg·L^-1）	<0.007	714	123	56
OH^-/（mg·L^-1）	<0.50	<0.50	<0.50	<0.50
HCO₃ ^-/（mg·L^-1）	8 025	310	<0.50	24
CO₃ ^2-/（mg·L^-1）	<0.50	13	<0.50	4
碱度（以CaCO₃计）/（mg·L^-1）	6 600	376	<0.50	23
总硬度（以CaCO₃计）/（mg·L^-1）	<1.0	468	7.14	65
VFA/（mmol·L^-1）	118	0.34	5.06	0.43
TDS/（mg·L^-1）	14 821	3 546	144	284

污泥	MLSS/（g·L^-1）		MLVSS/（g·L^-1）	VSS/TSS	密度/（g·mL^-1）	粒径/mm	光泽度	弹性	是否空心
某污水厂颗粒污泥	111	86		77.5%	1.03	2~3	较好	较好	否
石化企业污水厂厌氧罐内颗粒污泥	161	133		82.2%	1.02	1~2	较好	较好	否

污泥	MLSS/（g·L^-1）		MLVSS/（g·L^-1）	VSS/TSS	密度/（g·mL^-1）	粒径/mm	光泽度	弹性	是否空心
某污水厂颗粒污泥	111	86		77.5%	1.03	2~3	较好	较好	否
石化企业污水厂厌氧罐内颗粒污泥	161	133		82.2%	1.02	1~2	较好	较好	否

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