臭氧微纳米气泡处理焦化废水零排放工艺中浓盐水的效能

沈俊伯; 缪蔚; 胡楠; 李恩超; 李攀

doi:10.12153/j.issn.1674-991X.20240070

臭氧微纳米气泡处理焦化废水零排放工艺中浓盐水的效能

doi: 10.12153/j.issn.1674-991X.20240070

沈俊伯^1,,
缪蔚²,
胡楠¹,
李恩超²,
李攀^{1, 3, ,}

1.
同济大学环境科学与工程学院
2.
宝武水务科技有限公司
3.
同济大学污染控制与资源化研究国家重点实验室

基金项目: 国家重点研发计划项目（2021YFC3200805）

详细信息

作者简介:
沈俊伯（2000—），男，硕士研究生，主要从事水体污染的研究，2230497@tongji.edu.cn

通讯作者:
李攀（1980—），女，副教授，主要从事微纳米气泡的研究，lipan@tongji.edu.cn

中图分类号: X703
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出版历程
- 收稿日期: 2024-01-29

Efficiency of ozone micro nano bubbles in treating concentrated brine in zero discharge process of coking wastewater

SHEN Junbo^1
,,
MIAO Wei²,
HU Nan¹,
LI Enchao²,
LI Pan^{1, 3
, ,}

1.
College of Environmental Science and Engineering, Tongji University
2.
Baowu Water Technology, Co., Ltd.
3.
State Key Laboratory of Pollution Control and Resource Reuse, Tongji University

摘要

摘要:
焦化废水的零排放工艺中使用蒸汽机械再压缩（MVR）蒸发结晶处理膜浓缩液，最终产生超高盐浓缩液废水，其难以通过传统氧化方法进行处理。臭氧微纳米气泡技术能够提高臭氧传质效率、增强臭氧氧化能力，可望用于处理MVR浓缩母液。为验证该技术的工程应用可行性，以MVR浓缩母液为研究对象，对比臭氧微纳米气泡和普通大气泡2种曝气方式下臭氧传质速率以及有机物的降解效能，从技术、经济角度分析盐浓度和有机物浓度对2种臭氧氧化工艺处理效果的影响，以界定臭氧微纳米气泡技术处理高盐废水的适用范围。结果表明：随着盐浓度从0.1 mol/L增加至1 mol/L，微纳米气泡和普通大气泡的臭氧传质系数分别提高0.13和0.09倍，臭氧自分解速率分别升高2.10和1.38倍。在处理高盐、高有机物废水（TOC浓度为57.2~587.6 mg/L，电导率为3.47~28.6 mS/cm）时，臭氧微纳米气泡较普通大气泡的TOC去除率提升0.50~3.76倍，吨水能耗最大可降低71%；处理超高盐、超高有机物废水（TOC浓度为5 626 mg/L，电导率为164.3 mS/cm）时，臭氧微纳米气泡去除效果与普通大气泡趋于一致且吨水能耗更高。高盐废水的盐浓度和有机物浓度对臭氧微纳米气泡处理效能影响显著，工程应用中应根据废水特性选择合适的臭氧曝气方式。
- 焦化废水 /
- 微纳米气泡 /
- 臭氧氧化 /
- 臭氧传质系数 /
- 降解 /
- MVR浓缩母液
Abstract:
In the Zero Liquid Discharge (ZLD) process of coking wastewater, mechanical vapor recompression (MVR) evaporation crystallization is employed to treat membrane-concentrated liquor, ultimately yielding highly saline concentrated wastewater, which is challenging to treat using conventional oxidation methods. Ozone micro nano bubble technology can enhance ozone mass transfer efficiency and augment its oxidation capability, making it a promising method for treating MVR-concentrated discharge. To verify the feasibility of engineering applications of this technology, this study focused on MVR-concentrated discharge and compared the ozone mass transfer rate and organic degradation efficiency between ozone micro nano bubbles and conventional macrobubbles. It analyzed the impact of salinity and organic concentration on the treatment efficiency of both ozone oxidation processes from technical and economic perspectives, thereby delineating the applicable scope of ozone micro nano bubble technology for high-salinity wastewater treatment. The results indicated that as the salinity increased from 0.1 mol/L to 1 mol/L, the ozone mass transfer coefficients for ozone micro nano bubbles and conventional macrobubbles increased by 0.13 and 0.09 times, respectively, with the ozone self-decomposition rate rising by 2.10 and 1.38 times, respectively. When treating high-salinity and high-organic wastewater (TOC 57.2-587.6 mg/L, conductivity 3.47-28.6 mS/cm), ozone micro nano bubble technology could enhance TOC removal rates by 0.50 to 3.76 times compared to conventional macrobubble technology, while reducing energy consumption per ton of water by up to 71%. When treating ultra-high salinity and ultra-high organic wastewater (TOC 5 626 mg/L, conductivity 164.3 mS/cm), the removal efficiency of micro nano bubbles tended to align with that of conventional macrobubbles, albeit with higher energy consumption per ton of water. The salinity and organic concentration of high-salinity wastewater significantly affect the treatment efficiency of ozone micro nano bubbles, and the appropriate ozone aeration method should be selected based on the wastewater characteristics in engineering applications
- coking wastewater /
- micro nano bubbles /
- ozone oxidation /
- ozone mass transfer coefficients /
- degration /
- mechanical vapor recompression (MVR) concentrated discharge

HTML全文

图 1 臭氧氧化装置示意

Figure 1. Schematic diagram of ozone oxidation device

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图 2 不同盐浓度下微米气泡和纳米气泡的粒径分布及图像

注：D₅₀（红色虚线）为微纳米气泡累积百分率为50%时所对应的粒径。

Figure 2. Particle size distribution diagrams and images of microbubbles and nanobubbles at different salt concentrations

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图 3 不同盐浓度下的液相臭氧浓度变化及臭氧传质系数

Figure 3. Changes in aqueous ozone concentration and ozone mass transfer coefficient at different salt concentrations

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图 4 臭氧微纳米气泡、普通大气泡处理不同浓度废水的TOC及UV₂₅₄去除率

Figure 4. Removal rate of TOC and UV₂₅₄ from wastewater with different concentrations by ozone micro nano bubble treatment and macrobubble treatment

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图 5 臭氧微纳米气泡、普通大气泡处理不同浓度废水的O/C和O/T变化

注：各个柱子代表每种废水不同时间的取样。

Figure 5. Changes in O/C and O/T ratios of wastewater samples with different concentrations during ozone micro nano bubble treatment and macrobubble treatment

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图 6 不同处理方式下2#废水反应前后三维荧光谱图及有机物变化

Figure 6. Three-dimensional fluorescence spectra of wastewater sample 2# before and after reaction and changes in organic matter under different treatment methods

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图 7 臭氧氧化处理MVR母液的吨水能耗与TOC去除率之间的关系

Figure 7. Relationship between energy consumption per ton of wastewater and TOC removal rate of MVR discharge treated by ozone oxidation

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表 1 待处理废水的主要成分和指标

Table 1. Main components and indexes of wastewater to be treated

废水	稀释倍数	电导率/（mS/cm）	pH	COD/（mg/L）	总有机碳（TOC）/（mg/L）	${\mathrm{SO}}_4^{2-} $/（mg/L）	Cl⁻/（mg/L）	UV₂₅₄
1#原废水	不稀释	164.30	9.34	11 100	5 626.0	149 220	74 310	0.870
2#废水	10倍	28.60	8.72	1 140	587.6	14 720	7 350	1.038
3#废水	50倍	6.44	7.45	253	117.7	2 941	1 437	1.030
4#废水	100倍	3.47	7.16	123	57.2	1 460	726	1.070
注：UV₂₅₄为稀释后的测定值，1#原废水稀释100倍，2#废水稀释10倍，3#废水稀释2倍，4#废水不稀释。

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表 2 盐浓度对不同臭氧曝气方式的气泡尺寸和传质参数的影响

Table 2. Impact of salt concentration on bubble size and mass transfer parameters by various ozone aeration methods

NaCl浓度/ （mol/L）	曝气方式	D₅₀		C_s/ （mg/L）	k_La/min⁻¹	k_d/min⁻¹
NaCl浓度/ （mol/L）	曝气方式	微米气泡/μm	纳米气泡/nm	C_s/ （mg/L）	k_La/min⁻¹	k_d/min⁻¹
0.1	大气泡			33.60	0.157	0.047
0.1	微纳米气泡	35.99	139.60	45.18	0.364	0.042
1	大气泡			23.46	0.171	0.112
1	微纳米气泡	102.11	197.50	29.20	0.413	0.130

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表 3 荧光积分区域划分范围

Table 3. Scope of fluorescence integral area

区域	有机物类型	激发波长（E_x）/nm	发射波长（E_m）/nm
Ⅰ	类酪氨酸	220~250	280~330
Ⅱ	类色氨酸	220~250	330~380
Ⅲ	类富里酸	220~250	380~550
Ⅳ	溶解性微生物产物	250~450	280~380
Ⅴ	类腐殖酸	250~450	380~550

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