光催化功能材料及其提升湖库水环境质量的验证研究

仇健; 朱浩; 李广鹏; 庞治; 耿波; 陈斌; 袁宇栋; 刘向辉; 许亮; 张磊; 杨海超

doi:10.12153/j.issn.1674-991X.20210204

光催化功能材料及其提升湖库水环境质量的验证研究

doi: 10.12153/j.issn.1674-991X.20210204

仇健^{1, 3,},
朱浩¹,
李广鹏¹,
庞治¹,
耿波¹,
陈斌¹,
袁宇栋¹,
刘向辉¹,
许亮¹,
张磊^2, ,,
杨海超²

1.
江苏双良环境科技有限公司
2.
中国环境科学研究院环境技术工程有限公司
3.
中国科技开发院江苏分院

基金项目: 国家水体污染控制与治理科技重大专项（2017ZX07204-002）

详细信息

作者简介:
仇健(1983—)，男，工程师，硕士，主要从事环境催化材料开发与应用研究，njqiujian@163.com

通讯作者:
张磊(1964—)，男，副研究员，硕士，主要从事环境工程研究， wwkk12345@sina.com

中图分类号: X524
计量
- 文章访问数: 283
- HTML全文浏览量: 163
- PDF下载量: 39
- 被引次数: 0
出版历程
- 收稿日期: 2021-05-26

Study on photocatalytic functional material and verification of its application for improving water environment quality of lake and reservoir

1.
Jiangsu Shuangliang Environmental Technology Co., Ltd.
2.
Environmental Technology & Engineering Co., Ltd., Chinese Research Academy of Environmental Sciences
3.
Jiangsu Branch of China Academy of Science Technology Development

摘要

摘要: 为验证石墨烯基氧化钛光催化功能材料在实际工况条件下的适用性及其对污染水体的净化效果，分别选择云南省大理州西湖（ST-1）及浙江省舟山市嵊泗县的长弄塘水库（ST-2）进行为期105~107 d的野外原位围隔试验验证研究。结果表明：光催化功能材料与土著生物耦合（光催化耦合生态净化技术）对2种类型水体中污染物降解具有较好的效果，试验期间ST-1和ST-2水体中的氨氮、总磷浓度和COD分别下降71.8%、45.5%和27.3%以及3.8%、62.1%和33.3%；该技术实施后水体溶解氧浓度较稳定，分别为6.05~9.50和6.60~10.60 mg/L，水体透明度分别提升109.0%和185.7%；另外，该技术对藻类具有抑制作用，ST-1、ST-2试验组与对照组相比，藻类总生物量分别下降了30.3%和64.6%。
- 光催化耦合生态净化 /
- 湖库 /
- 治理 /
- 水质 /
- 抑藻
Abstract: In order to verify the applicability of the photocatalytic functional materials, graphene based titanium oxides, under actual working conditions and their purification effect on polluted water, two sites were selected respectively in Xihu Reservoir of Dali Bai Autonomous Prefecture, Yunnan Province (ST-1) and Changnongtang Reservoir of Shengsi County, Zhoushan City, Zhejiang Province (ST-2), to carry out field in situ enclosure tests for 105-107 days. The results showed that the use of photocatalytic functional materials coupled with indigenous organisms (or photocatalysis coupling ecological purification technology) had a good effect on reducing pollutants in two different types of water. During the experiment, the concentrations of NH₃, TP and COD decreased by 71.8%, 45.5% and 27.3% together with 3.8%, 62.1% and 33.3%, at ST-1 and ST-2 respectively. After the implementation of the technology, the concentration of dissolved oxygen in the water was relatively stable, which were 6.05-9.50 and 6.60-10.60, respectively. The transparency of water body was improved by 109.0% and 185.7%, respectively. In addition, the technology had inhibitory effect on algae. Compared with the control group, the total biomass of algae in ST-1 and ST-2 decreased by 30.3% and 64.6%, respectively.
- photocatalytic coupled with ecological purification /
- lake and reservoir /
- restoration /
- water quality /
- algae inhibition

HTML全文

图 1 试验水体照片

Figure 1. Photos of two test water bodies

下载: 全尺寸图片幻灯片

图 2 催化功能纤维表面的催化材料与功能纤维扫描电镜图

注：(a)、（b）图中比例尺分别为100 nm与100 μm。

Figure 2. SEM images for catalytic material on catalytic functional fiber surface and fibers themselves

下载: 全尺寸图片幻灯片

图 3 催化材料的X射线衍射图

Figure 3. X-ray diffraction image of catalytic material

下载: 全尺寸图片幻灯片

图 4 催化材料的漫反射光谱图

Figure 4. DRS spectra of catalytic material

下载: 全尺寸图片幻灯片

图 5 催化材料的电子顺磁共振图

Figure 5. EPR image of catalytic material

下载: 全尺寸图片幻灯片

图 6 催化功能纤维网膜与对照品P25网膜对罗丹明B的降解

Figure 6. Degradation of Rhodamine B by catalytic functional fiber omentum and reference P25 omentum

下载: 全尺寸图片幻灯片

图 7 试验期间水体DO浓度变化

Figure 7. Variations of DO concentration in two watersduring the test

下载: 全尺寸图片幻灯片

图 8 试验期间水体COD变化

Figure 8. Variations of COD in two waters during the test

下载: 全尺寸图片幻灯片

图 9 试验期间水体氨氮浓度变化

Figure 9. Variations of NH₃-N concentration in twowaters during the test

下载: 全尺寸图片幻灯片

图 10 试验期间水体TP浓度变化

Figure 10. Variations of TP concentration in twowaters during the test

下载: 全尺寸图片幻灯片

图 11 试验前后水体透明度变化

Figure 11. Water transparency changes before and after the test

下载: 全尺寸图片幻灯片

表 1 光催化功能材料纤维网膜技术参数

Table 1. Technical parameters of photocatalytic functional fiber membrane

项目	参数	项目	参数
基材材质	聚丙烯纤维	适用光照强度/lx	≥5 000
基材类型	1400D160F	适用流速/（cm/s）	≤0.5
RhB降解速率¹⁾/〔mg/(h·m²)〕	≥120	适用温度/℃	5~40
TP处理量¹⁾/（mg/m²）	≥10	适用水深/m	≥0.1
ORP提升率¹⁾/%	≥60	适用pH	6~9
网孔密度/（个/cm²）	9	网膜厚度/cm	0.2~0.3
1)为实验室数据。

下载: 导出CSV

表 2 试验水体概况

Table 2. Basic situation of two test water bodies

项目	ST-1	ST-2
所属地区	云南省大理州	浙江省舟山市
平均海拔/m	1 970	45
类型	高原湖泊	岛屿水库
气候类型	亚热带季风气候	亚热带海洋性季风气候
历年平均气温¹⁾/℃	−0.4（不结冰）~25.3	3.7~29.9
历年平均降水量¹⁾/mm	714.2	1 105.9
历年平均日照时长¹⁾/h	2 250.2	2 012.3
历年主导风向¹⁾	微风、西南风	东南风
水体面积/m²	11 500	15 000
水体最大水深/m	6	20
治理前水体水质²⁾	劣Ⅴ类	Ⅳ类
1)1981—2010年；2）GB 3838—2002《地表水环境质量标准》。

下载: 导出CSV

表 3 试验前水体水质指标数据及分类

Table 3. Water quality index data and classification before test

水体	DO浓度/(mg/L)	COD/(mg/L)	氨氮浓度/(mg/L)	TP浓度/(mg/L)	水体透明度/cm	综合水质类别
ST-1	6.20 (Ⅱ)	22.0 (Ⅳ)	0.390 (Ⅱ)	0.110 (Ⅴ)	66	Ⅴ
ST-2	10.60 (Ⅰ)	21.9 (Ⅳ)	0.158 (Ⅱ)	0.029 (Ⅲ)	70	Ⅳ

下载: 导出CSV

表 5 试验后水体水质指标均值及类别

Table 5. Mean value of water quality indexes and classification after test

水体	DO浓度/(mg/L)	COD/(mg/L)	氨氮浓度/(mg/L)	TP浓度/(mg/L)	水体透明度/cm	水质综合类别
ST-1	10.60 (Ⅰ)	21.9 (Ⅳ)	0.158 (Ⅱ)	0.029 (Ⅲ)	70	Ⅳ
ST-2	8.38 (Ⅰ)	14.6 (Ⅱ)	0.152 (Ⅱ)	0.011 (Ⅱ)	200	Ⅱ

下载: 导出CSV

参考文献(23)

[1]	黄文钰, 吴延根, 舒金华.中国主要湖泊水库的水环境问题与防治建议[J]. 湖泊科学,1998,10(3):83-90. doi: 10.18307/1998.0315 HUANG W Y, WU Y G, SHU J H. Hydrographical environmental problems and countermeasures of main lakes and reservoirs in China[J]. Journal of Lake Sciences,1998,10(3):83-90. doi: 10.18307/1998.0315
[2]	裘知, 王睿, 李思亮, 等. 中国湖泊污染现状与治理情况分析[C]//湖泊湿地与绿色发展. 第五届中国湖泊论坛论文集. 长春:吉林人民出版社, 2015: 215-219.
[3]	王海珍, 陈德辉, 王全喜, 等.水生植被对富营养化湖泊生态恢复的作用[J]. 自然杂志,2002,24(1):33-36. doi: 10.3969/j.issn.0253-9608.2002.01.006 WANG H Z, CHEN D H, WANG Q X, et al. The effect of aquatic vegetation on ecological restoration of eutrophication lake[J]. Nature Magazine,2002,24(1):33-36. doi: 10.3969/j.issn.0253-9608.2002.01.006
[4]	秦伯强.太湖生态与环境若干问题的研究进展及其展望[J]. 湖泊科学,2009,21(4):445-455. doi: 10.3321/j.issn:1003-5427.2009.04.001 QIN B Q. Progress and prospect on the eco-environmental research of Lake Taihu[J]. Journal of Lake Sciences,2009,21(4):445-455. doi: 10.3321/j.issn:1003-5427.2009.04.001
[5]	王民浩, 孔德安. 城市水环境综合治理理论与实践: 六大技术系统[M]. 北京: 中国环境出版集团, 2019: 414.
[6]	FUJISHIMA A, ZHANG X T, TRYK D A. TiO₂ photocatalysis and related surface phenomena[J]. Surface Science Reports,2008,63(12):515-582. doi: 10.1016/j.surfrep.2008.10.001
[7]	FUJISHIMA A, ZHANG X T, TRYK D A. Heterogeneous photocatalysis: from water photolysis to applications in environmental cleanup[J]. International Journal of Hydrogen Energy,2007,32(14):2664-2672. doi: 10.1016/j.ijhydene.2006.09.009
[8]	马荧. 石墨烯/二氧化钛基多元复合膜光催化降解酚类污染物性能与机理研究[D]. 长春: 东北师范大学, 2020.
[9]	ASILTÜRK M, SAYLLKAN F, ARPAÇ E. Effect of Fe³⁺ ion doping to TiO₂ on the photocatalytic degradation of Malachite Green dye under UV and vis-irradiation[J]. Journal of Photochemistry and Photobiology A:Chemistry,2009,203(1):64-71. doi: 10.1016/j.jphotochem.2008.12.021
[10]	张国庆. 二氧化钛半导体光催化剂的制备、改性及其光催化性能研究[D]. 长春: 吉林大学, 2020.
[11]	刘义. 氮掺杂TiO₂和TiO₂/SiO₂的制备及光催化性能的研究[D]. 广州: 华南理工大学, 2010.
[12]	展海银, 周启星.环境中四环素类抗生素污染处理技术研究进展[J]. 环境工程技术学报,2021,11(3):571-581. doi: 10.12153/j.issn.1674-991X.20200154 ZHAN H Y, ZHOU Q X. Research progress on treatment technology of tetracycline antibiotics pollution in the environment[J]. Journal of Environmental Engineering Technology,2021,11(3):571-581. doi: 10.12153/j.issn.1674-991X.20200154
[13]	ANDREOZZI R, CAPRIO V, INSOLA A, et al. Advanced oxidation processes (AOP) for water purification and recovery[J]. Catalysis Today,1999,53(1):51-59. doi: 10.1016/S0920-5861(99)00102-9
[14]	HOFFMANN M R, MARTIN S T, CHOI W, et al. Environmental applications of semiconductor photocatalysis[J]. Chemical Reviews,1995,95(1):69-96. doi: 10.1021/cr00033a004
[15]	NOSAKA Y, DAIMON T, NOSAKA A Y, et al. Singlet oxygen formation in photocatalytic TiO₂ aqueous suspension[J]. Physical Chemistry Chemical Physics,2004,6(11):2917-2918. doi: 10.1039/b405084c
[16]	DAIMON T, NOSAKA Y. Formation and behavior of singlet molecular oxygen in TiO₂ photocatalysis studied by detection of near-infrared phosphorescence[J]. Journal of Physical Chemistry C,2007,111(11):4420-4424. doi: 10.1021/jp070028y
[17]	孙凌凌, 胡心科, 孙雪, 等.负载纳米TiO₂的弥散光纤降解高浓盐水中COD的研究[J]. 应用化工,2020,49(8):1992-1994. doi: 10.3969/j.issn.1671-3206.2020.08.028 SUN L L, HU X K, SUN X, et al. Study on the degradation of COD in high concentration brine by diffuse optical fiber loaded with nanometer TiO₂[J]. Applied Chemical Industry,2020,49(8):1992-1994. doi: 10.3969/j.issn.1671-3206.2020.08.028
[18]	杨春宇, 汪统岳, 陈霆, 等.基于光气候区的日照时数特征及变化规律[J]. 同济大学学报(自然科学版),2017,45(8):1123-1130. doi: 10.11908/j.issn.0253-374x.2017.08.004 YANG C Y, WANG T Y, CHEN T, et al. Variation characteristics of the sunshine duration in all Chinese light climate zones[J]. Journal of Tongji University (Natural Science),2017,45(8):1123-1130. doi: 10.11908/j.issn.0253-374x.2017.08.004
[19]	YAMAZOE S, HITOMI Y, SHISHIDO T, et al. Kinetic study of photo-oxidation of NH₃ over TiO₂[J]. Applied Catalysis B:Environmental,2008,82(1/2):67-76.
[20]	白润英, 郝俊峰, 刘建明, 等.光催化转化并回收水中农药有机磷[J]. 中国环境科学,2020,40(3):1132-1138. doi: 10.3969/j.issn.1000-6923.2020.03.024 BAI R Y, HAO J F, LIU J M, et al. Photocatalytic conversion and recycle of organic phosphorus within pesticides form aqueous solution[J]. China Environmental Science,2020,40(3):1132-1138. doi: 10.3969/j.issn.1000-6923.2020.03.024
[21]	DELASA H, BENITO SERRANO ROSALES. 光催化技术[M]. 北京: 科学出版社, 2010.
[22]	OFIR E, OREN Y, ADIN A. Comparing pretreatment by iron of electro-flocculation and chemical flocculation[J]. Desalination,2007,204(1/2/3):87-93.
[23]	任久长, 周红, 孙亦彤.滇池光照强度的垂直分布与沉水植物的光补偿深度[J]. 北京大学学报(自然科学版),1997,33(2):76-79. REN J C, ZHOU H, SUN Y T. Vertical distribution of light intensity and light compensation depth of submerged macrophyte in Lake Dianchi[J]. Acta Scicentiarum Naturalum Universitis Pekinesis,1997,33(2):76-79. ⊗