牡蛎壳改性及联合释氧复合材料修复地下水氨氮污染实验研究

doi:10.19657/j.geoscience.1000-8527.2021.073

现代地质 ›› 2022, Vol. 36 ›› Issue (02): 583-590.DOI: 10.19657/j.geoscience.1000-8527.2021.073

牡蛎壳改性及联合释氧复合材料修复地下水氨氮污染实验研究

吴福贤¹(), 李玮¹^,²^,³(), 李水云⁴, 陈晓丹¹, 谢林伸¹, 成功¹, 常旭¹, 陈纯兴¹, 韩龙¹

1. 国家环境保护饮用水水源地管理技术重点实验室,深圳市环境科学研究院,广东深圳 518001
2. 中山大学土木工程学院,广东珠海 519028
3. 中国地质大学(北京) 地下水循环与环境演化教育部重点实验室,北京 100083
4. 南方科技大学,广东深圳 518000

收稿日期:2020-04-04 修回日期:2022-02-20 出版日期:2022-04-10 发布日期:2022-06-01
通讯作者: 李玮
作者简介:李玮,男,高级工程师,1986年出生,环境工程专业,从事城市水环境管理和污染防治研究。Email: liwei@meeb.sz.gov.cn。
吴福贤,男,硕士,1993年出生,水文地质学专业,主要从事水污染治理。Email: 48649816@qq.com。
基金资助:
国家自然科学基金项目(41702276);科技部“水体污染控制与治理”科技重大专项(2015ZX07206-006)

Experimental Study on Oyster Shell Modification and Combined Oxygen Release Composite Materials for Remediation of Ammonia Nitrogen Pollution in Groundwater

WU Fuxian¹(), LI Wei¹^,²^,³(), LI Shuiyun⁴, CHEN Xiaodan¹, XIE Linshen¹, CHENG Gong¹, CHANG Xu¹, CHEN Chunxing¹, HAN Long¹

1. State Environmental Protection Key Laboratory of Drinking Water Source Management and Technology, Shenzhen Academy of Environmental Sciences, Shenzhen, Guangdong 518001, China
2. School of Civil Engineering, Sun Yat-Sen University, Zhuhai, Guangdong 519028, China
3. MOE Key Laboratory of Groundwater Circulation and Environmental Evolution, China University of Geosciences (Beijing), Beijing 100083, China
4. Southern University of Science and Technology, Shenzhen, Guangdong 518000, China

Received:2020-04-04 Revised:2022-02-20 Online:2022-04-10 Published:2022-06-01
Contact: LI Wei

摘要/Abstract

摘要：

为研究以牡蛎壳-释氧复合材料为填料的渗透反应格栅去除地下水氨氮污染的效果及其经济实用性,开展了相关室内实验:采用高温加热方式对牡蛎壳进行改性,通过测定牡蛎壳改性后的比表面积判定其吸附效果;以过氧化钙为释氧化合物,将其与水泥、石英砂/牡蛎壳粒、钙基膨润土以一定比例混合制成粒径约1.8 cm球型释氧材料,采用静态实验研究不同原料配比的释氧材料的释氧性能;最后研究了两种不同粒径牡蛎壳粒-释氧复合材料修复地下水氨氮的效果及不同供氧方式下不同吸附材料修复地下水氨氮的效果及其经济实用性。结果表明:对牡蛎壳粒进行高温改性,牡蛎壳粒高温条件下会产生团聚现象,比表面积随煅烧温度升高呈下降趋势,高温改性方式并不能有效改善牡蛎壳粒吸附性能;实验中制作的释氧材料在95天的实验期间,各实验柱的溶解氧量可以保持在18 mg/L左右,且在嗜碱菌作用下pH值得以有效降低,所制作的释氧材料可为硝化细菌长期在溶解氧低的地下水环境中生长提供氧气;以牡蛎壳-释氧复合材料为填料的渗透反应格栅通过耐碱硝化细菌的硝化作用可以将氨氮浓度从50 mg/L降至约35 mg/L,不同粒径牡蛎壳粒修复效果差异不明显。使用牡蛎壳-释氧复合材料渗透反应格栅长期修复地下水氨氮,不仅可以达到活性炭及沸石作为骨架的修复效果,而且更加具有经济实用性。

关键词: 牡蛎壳改性, 释氧材料, 渗透反应格栅, 地下水, 氨氮污染修复

Abstract:

Laboratory experiments were carried out on the performance and economic applicability of permeable reactive barrier filled with modified oyster shell-oxygen releasing composite material, with the aim to mitigate groundwater ammonia nitrogen pollution. Calcium peroxide was used as the oxygen-releasing compound, and mixed with cement, quartz sand/oyster-shell grain and calcium bentonite in a certain proportion, in order to make a spherical oxygen-releasing material with about 1.8 cm particle size. Finally, we studied the groundwater ammonia nitrogen repairing effects and their economic feasibility of two different size oyster-shell oxygen-releasing composite materials, and those of different adsorbent materials under different oxygen supply modes. The results indicate that the high-temperature modification of oyster-shell particles could not improve the comparative area of oyster shell. The specific surface area of oyster shell decreases with increasing calcination temperature and aggregation occurred. During the 95-day experiment, the dissolved oxygen of each experimental column was maintained at about 18 mg/L, and the basophilic bacterial action reduced the pH effectively. The oxygen-releasing material produced could provide the oxygen for the nitrifying bacterial growth in groundwater with low dissolved-oxygen for a long period of time. By the nitrification of alkali-resistant nitrifying bacteria, the permeable reactive barrier filled with oyster shell oxygen-releasing composite material could reduce the ammonia nitrogen concentration from 50 to 35 mg/L, whilst the repairing effect by oyster shell particles of different sizes is unobvious. In the long term, it is more economical to use oyster shells as adsorbents, and to use oxygen-releasing materials as oxygen supply. The use of the permeable reactive barrier (filled with modified oyster shell-oxygen) releasing composite material for long-term groundwater ammonia nitrogen repair is both effective and economical with activated carbon and zeolite framework.

Key words: modification of oyster shell, oxygen-releasing material, permeable reactive barrier, groundwater, ammonia remediation

中图分类号:

P641.1
X52

吴福贤, 李玮, 李水云, 陈晓丹, 谢林伸, 成功, 常旭, 陈纯兴, 韩龙. 牡蛎壳改性及联合释氧复合材料修复地下水氨氮污染实验研究[J]. 现代地质, 2022, 36(02): 583-590.

WU Fuxian, LI Wei, LI Shuiyun, CHEN Xiaodan, XIE Linshen, CHENG Gong, CHANG Xu, CHEN Chunxing, HAN Long. Experimental Study on Oyster Shell Modification and Combined Oxygen Release Composite Materials for Remediation of Ammonia Nitrogen Pollution in Groundwater[J]. Geoscience, 2022, 36(02): 583-590.

图/表 14

表1 实验用不同粒径种类的牡蛎壳粒

Table 1 Oyster shells of different particle sizes in this experiment

名称	粒径/mm
牡蛎壳粒	<0.1	0.1~0.3	0.3~0.6	0.6~0.9

表2 不同粒径不同程度改性的牡蛎壳粒比表面积

Table 2 Specific surface area of oyster-shell particles modified with different particle sizes and degrees

序号	粒径/ mm	煅烧温度/℃	煅烧时间/min	比表面积/ (m²/g)
1	<0.1	0	0	3.86
3	0.1~0.3	0	0	2.18
4	0.1~0.3	100	60	2.17
5	0.1~0.3	150	60	2.22
6	0.1~0.3	200	60	1.88
7	0.1~0.3	400	60	1.07
9	0.1~0.3	700	60	0.34
11	0.1~0.3	800	60	0.75
12	0.1~0.3	900	60	0.74
13	0.1~0.3	1 000	60	0.72
15	0.1~0.3	1 100	60	0.65
16	0.1~0.3	1 150	60	0.56
17	0.1~0.3	1 200	60	0.50
18	0.3~0.6	0	0	1.34
19	0.6~0.9	0	0	0.83

表3 不同编号释氧材料的原料配比方案

Table 3 Raw material proportion schemes for the different numbers of oxygen-releasing materials

原料编号	过氧化钙	水泥	石英砂/牡蛎壳粒	钙基膨润土
1号	1.4	1.4	1(石英砂)	1
2号	1.4	2.0	1(石英砂)	1
3号	1.4	2.8	1(石英砂)	1
4号	1.4	1.4	1(石英砂)	1.48
5号	1.4	1.4	1(牡蛎壳粒)	1

图1 释氧材料(a)及其释氧性能静态实验(b)示意图

Fig.1 Oxygen-release material (a) and its static experiment (b) of oxygen-release performance

表4 一维渗透反应格栅去除氨氮柱实验材料装填参数

Table 4 Loading parameters of one-dimensional PRB experimental material for ammonia nitrogen column removal

编号	第一层			第二层
编号	介质	厚度/cm	用量/g	介质	厚度/cm	用量/g
柱A	石英砂	2	301.8	牡蛎壳 (0.1~0.3 mm)	24	679.5
柱A	石英砂	2	301.8	释氧材料	24	1 493.6
柱B	石英砂	2	300.8	牡蛎壳粒 (0.6~0.9 mm)	24	811.9
柱B	石英砂	2	300.8	释氧材料	24	1 492.7

图2 一维柱实验示意图

Fig.2 Schematic diagram of one-dimensional experiment

图3 不同吸附材料及两种供氧方式修复氨氮的效果实验图表5 不同吸附材料修复氨氮的效果对比实验装填参数

Fig.3 Experimental setup on different adsorption materials and two oxygen-supply methods for ammonia nitrogenrestoration

Table 5 Comparison of the effects by different adsorption materials on the ammonia nitrogen restoration experiment filling parameters

编号	供氧方式	材料装填
编号	供氧方式	名称	粒径/mm	质量/g	高度/cm
柱a1	曝气 (功率6 W)	天然沸石	1~2	394.4	12
柱b1		牡蛎壳	1~2	368.7	12
柱c1		活性炭	1~2	225.3	12
柱a2	释氧材料 (使用量44 g)	天然沸石	1~2	394.4	12
柱b2		牡蛎壳粒	1~2	368.7	12
柱c2		活性炭	1~2	225.3	12

图4 牡蛎壳粒(未煅烧)比表面积随粒径变化 (a)及随煅烧温度(b)变化趋势

Fig.4 Variation of specific surface area of oyster shell particles (uncalcined) with particle size (a) and calcination temperature (b)

图5 各实验柱溶液的溶解氧量(a)及pH值(b)随时间变化趋势

Fig.5 Variation of dissolved oxygen(a)and pH(b)of each column with time

图6 柱A(a)及柱B(b)各取样点氨氮质量浓度趋势

Fig.6 Variation trends of ammonia nitrogen concentration at each sampling point of column A (a) and B (b)

图7 柱A(a)及柱B(b)各取样点亚硝酸盐氮质量浓度趋势

Fig.7 Variation trends of nitrite nitrogen concentration at each sampling point in column A (a) and B (b)

图8 两种供氧方式的柱实验氨氮净修复量随时间变化表6 不同吸附材料及供氧方式费用

Fig.8 Variation plot of the net ammonia nitrogen reduction in the column experiment with two oxygen supply modes

Table 6 Cost of different adsorption materials and oxygen supply methods

编号	供氧方式	材料装填	实验天数/d	经济性
编号	供氧方式	材料装填	实验天数/d	材料单价/ (元/kg)	吸附材料费用总计/元		供氧费用总计/元		合计 /元
柱a1	曝气装置(功率 6 W)	天然沸石	8	8.9	3.51	1.73		5.24
柱b1		牡蛎壳粒	8	2.0	0.74	1.73		2.47
柱c1		活性炭	8	16.0	3.60	1.73		5.33
柱a2	释氧材料	天然沸石/ 释氧材料	8	8.9/7.2	3.51	0.32		3.83
柱b2		牡蛎壳粒/ 释氧材料	8	2.0/7.2	0.74	0.32		1.05
柱c2		活性炭/ 释氧材料	8	16.0/7.2	3.60	0.32		3.92

参考文献 16

[1]	2018年《中国生态环境状况公报》(摘录二)[J]. 环境保护, 2019, 47(12): 50-55.
[2]	HUANG G X, LIU F, YANG Y Z, et al. Ammonium-nitrogen-contaminated groundwater remediation by a sequential three-zone permeable reactive barrier (multibarrier) with oxygen-releasing compound (ORC)/clinoptilolite/spongy iron: column studies[J]. Environmental Science and Pollution Research, 2015, 22(5):3705-3714.
[3]	KUMAR N, COUTURE R M, MILLOT R, et al. Microbial sulfate reduction enhances arsenic mobility downstream of zerovalent-Iron-based permeable reactive barrier[J]. Environmental Science & Technology, 2016, 50: 7610-7617.
[4]	LI S P, HUANG G X, KONG X K, et al, Ammonium removal from groundwater using a zeolite permeable reactive barrier: a pilot-scale demonstration[J]. Water Science & Technology, 2014, 70(9): 1540.
[5]	LI Z R, YUAN S H, WAN J Z, et al. A combination of electrokinetics and Pd/Fe PRB for the remediation of pentachlorophenol-contaminated soil[J]. Journal of Contaminant Hydrology, 2011, 124:99-107.
[6]	LI R, FENG C P, HU W W, et al. Woodchip-sulfur based heterotrophic and autotrophic denitrification (WSHAD) process for nitrate contaminated water remediation[J]. Water Research, 2016, 89:171-179.
[7]	杨应钊. 地下水氨氮渗透反应格栅去除技术的改进与优化[D]. 北京: 中国地质大学(北京), 2013.
[8]	WEN D H, HO Y S, TANG X Y. Comparative sorption kinetic studies of ammonium onto zeolite[J]. Journal of Hazardous Materials, 2006, 133:252-256.
[9]	VIGNOLA R, BAGATIN R, ADF D’A, et al. Zeolites in a permeable reactive barrier (PRB): One year of field experience in a refinery groundwater-Part 1: The performances[J]. Chemical Engineering Journal, 2011, 178:204-209.
[10]	KRISHNANI K K, ZHANG Y, XIONG L J, et al. Bactericidal and ammonia removal activity of silver ion-exchanged zeolite[J]. Bioresource Technology, 2012, 117: 86-91.
[11]	SHIH P K, CHANG W L. The effect of water purification by oyster shell contact bed[J]. Ecological Engineering, 2015, 77:382-390.
[12]	DONG Y B, LIN H. Ammonia nitrogen removal from aqueous solution using zeolite modified by microwave-sodium acetate[J]. Journal of Central South University, 2016, 23(6):1345-1352.
[13]	YEN H Y, LI J Y. Process optimization for Ni(II) removal from wastewater by calcined oyster shell powders using Taguchi method[J]. Journal of Environmental Management, 2015, 161:344-349.
[14]	李芙蓉, 缪礼鸿, 文金丽. 利用好氧性嗜碱菌处理棉浆黑液的实验研究[J]. 工业安全与环保, 2009, 35(8): 20-21.
[15]	段莎丽, 孙亚琴, 伍阳, 等. 两株耐碱性亚硝化细菌的初步鉴定和特性研究[J]. 农业环境科学学报, 2007, 26(增刊): 406-409.
[16]	于金莲, 阎宁. 畜禽养殖废水处理方法探讨[J]. 给水排水, 2000, 26(9):44-47.

牡蛎壳改性及联合释氧复合材料修复地下水氨氮污染实验研究

Experimental Study on Oyster Shell Modification and Combined Oxygen Release Composite Materials for Remediation of Ammonia Nitrogen Pollution in Groundwater

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