过氧化钙缓释技术在地下水污染修复中的应用研究

doi:10.11894/iwt.2019-0135

摘要/Abstract

摘要：

过氧化钙因具有可控的O₂和H₂O₂释放能力、热稳定性、反应产物无污染而逐渐应用于环境污染修复中，在多环芳烃、石油烃、农药、重金属等污染的工业场地修复方面展现出良好的发展前景。通过大量文献调研，较系统地总结和概括了过氧化钙释放氧气和自由基的机制、影响因素，在地下水污染修复中其他材料包封过氧化钙的控制释放技术，以及合成过氧化钙纳米粒子的研究进展，最后对过氧化钙缓释技术在工业污染场地地下水污染修复中的应用研究提出建议和展望。

关键词: 过氧化钙, 地下水污染, 缓释技术, 原位修复

Abstract:

Calcium peroxide has been gradually applied to the remediation of environmental pollution due to its controllable ability to release O₂ and H₂O₂, thermal stability and no pollution of reaction products. It shows good prospect in the removal of polycyclic aromatic hydrocarbons, petroleum hydrocarbons, pesticides, heavy metals and various other pollutants. The release mechanism of oxygen and free radicals of calcium peroxide, factors affecting the release of oxygen from calcium peroxide, the controlled release technology of using other materials to encapsulate calcium peroxide in groundwater pollution remediation and the research progress in the synthesis of calcium peroxide nanoparticles were systematically summarized and concluded. Finally, suggestions for future research directions of calcium peroxide were put forward.

Key words: calcium peroxide, groundwater pollution, controlled release technology, in-situ remediation

中图分类号:

蒲生彦,侯国庆,吕雪,李博文. 过氧化钙缓释技术在地下水污染修复中的应用研究[J]. 工业水处理, 2020, 40(8): 1-6, 22.

Shengyan Pu,Guoqing Hou,Xue Lü,Bowen Li. Review on application of calcium peroxide controlled-release technology in groundwater pollution remediation[J]. Industrial Water Treatment, 2020, 40(8): 1-6, 22.

https://www.iwt.cn/CN/Y2020/V40/I8/1

图/表 5

参考文献 38

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名称	主要组分	目标污染物	效果	参考文献
生物渗透屏障	过氧化钙、KH₂PO₄、（NH₄）₂SO₄和膨胀珍珠岩颗粒包裹的微生物	地下水中的甲基叔丁基醚（MTBE）	800 h内约50%的MTBE被有效去除	〔7〕
透水反应屏障	椰子壳生物炭、硅藻土、过氧化钙	地下水中多环芳烃	多环芳烃基本被去除	〔8〕
透水反应屏障	叠氮化钠、过氧化钙、沙子、浮石	地下水中萘	50 d内基本除去萘 100 d持续释放氧气	〔9〕
被动渗透反应性屏障	过氧化钙、柠檬酸盐、聚乙烯醇和竹子生物炭的质量比为20:2.2:9.2:31.5	地下水中的苯系物（BETX）	104 d内持续释放氧气	〔10〕
透水反应屏障	释氧化合物（ORC）微球、斜沸石、河砂	地下水中的铵态氮	氨氮几乎完全耗尽，转化为NO₃^--N、NO₂^--N	〔11〕
混凝土立方块	过氧化钙、水泥、砂、粉煤灰、氯化铵、磷酸钾和水质量比为1.5:1.4:0.7:1.3:0.7:0.8:2	地下水中的四氯乙烯（PCE）	100 d内持续释放氧气，50 d内去除大多数的PCE	〔12〕
生物炭球	过氧化钙、柠檬酸盐、聚乙烯醇和竹子生物炭的质量比为20:2.2:9.2:31.5	地下水中的BETX	104 d内持续释放氧气，可快速去除99%甲苯	〔10〕
新型释氧藻酸盐珠	过氧化钙、海藻酸钠、三氯化铝	地下水中的1，4-二氧环己烷	10 d内去除99%的1，4-二氧环己烷	〔13〕
释氧剂球	海藻酸钠包裹过氧化钙和硫酸亚铁	地下水中的苯	60 d完全去除地下水中的苯，70 d内持续释放氧气	〔14〕
过氧化钙/石蜡释氧剂	过氧化钙:石蜡:高岭土:河砂质量比为1.67:50:2:30	地下水中的锰	7 d内持续释放氧气，能有效去除地下水中锰	〔15〕

名称	主要组分	目标污染物	效果	参考文献
生物渗透屏障	过氧化钙、KH₂PO₄、（NH₄）₂SO₄和膨胀珍珠岩颗粒包裹的微生物	地下水中的甲基叔丁基醚（MTBE）	800 h内约50%的MTBE被有效去除	〔7〕
透水反应屏障	椰子壳生物炭、硅藻土、过氧化钙	地下水中多环芳烃	多环芳烃基本被去除	〔8〕
透水反应屏障	叠氮化钠、过氧化钙、沙子、浮石	地下水中萘	50 d内基本除去萘 100 d持续释放氧气	〔9〕
被动渗透反应性屏障	过氧化钙、柠檬酸盐、聚乙烯醇和竹子生物炭的质量比为20:2.2:9.2:31.5	地下水中的苯系物（BETX）	104 d内持续释放氧气	〔10〕
透水反应屏障	释氧化合物（ORC）微球、斜沸石、河砂	地下水中的铵态氮	氨氮几乎完全耗尽，转化为NO₃^--N、NO₂^--N	〔11〕
混凝土立方块	过氧化钙、水泥、砂、粉煤灰、氯化铵、磷酸钾和水质量比为1.5:1.4:0.7:1.3:0.7:0.8:2	地下水中的四氯乙烯（PCE）	100 d内持续释放氧气，50 d内去除大多数的PCE	〔12〕
生物炭球	过氧化钙、柠檬酸盐、聚乙烯醇和竹子生物炭的质量比为20:2.2:9.2:31.5	地下水中的BETX	104 d内持续释放氧气，可快速去除99%甲苯	〔10〕
新型释氧藻酸盐珠	过氧化钙、海藻酸钠、三氯化铝	地下水中的1，4-二氧环己烷	10 d内去除99%的1，4-二氧环己烷	〔13〕
释氧剂球	海藻酸钠包裹过氧化钙和硫酸亚铁	地下水中的苯	60 d完全去除地下水中的苯，70 d内持续释放氧气	〔14〕
过氧化钙/石蜡释氧剂	过氧化钙:石蜡:高岭土:河砂质量比为1.67:50:2:30	地下水中的锰	7 d内持续释放氧气，能有效去除地下水中锰	〔15〕

污染物	纳米粒子大小	合成方法	去除性能	参考文献
As（Ⅲ）	25~50 nm	化学沉淀法	对水中的重要参数没有任何不良影响，能去除水中88%As（Ⅲ）	〔24〕
碳氢化合物	120 nm	机械法	高达800 mg/L的苯被完全氧化，溶液中的汽油污染物在24 h内显着减少	〔28〕
2，4-二氯苯酚、甲苯	＜150 nm	化学法	在5 d内基本降解2，4-二氯苯酚，3 d内完全降解甲苯	〔26〕~〔27〕
苯	50 nm	化学沉淀法	70 d内纳米颗粒能够连续向水中释放氧气，在生物条件下施用400 mg/L CaO2能够在60 d后从地下水中完全去除苯	〔25〕
苯、石油烃	50 nm	化学沉淀法	Fe²⁺存在情况下，CaO₂对污染物的去除能力更高，4 d后从地下水中完全去除苯	〔14〕
三氯乙烯	50~200 nm	化学法	180 min内可去除86.1%三氯乙烯	〔29〕
苯	50 nm	化学沉淀法	过氧化钙纳米粒子能大幅提高苯的去除效率和浮游细菌的数量，但会略微降低微生物种群的丰富度	〔30〕

污染物	纳米粒子大小	合成方法	去除性能	参考文献
As（Ⅲ）	25~50 nm	化学沉淀法	对水中的重要参数没有任何不良影响，能去除水中88%As（Ⅲ）	〔24〕
碳氢化合物	120 nm	机械法	高达800 mg/L的苯被完全氧化，溶液中的汽油污染物在24 h内显着减少	〔28〕
2，4-二氯苯酚、甲苯	＜150 nm	化学法	在5 d内基本降解2，4-二氯苯酚，3 d内完全降解甲苯	〔26〕~〔27〕
苯	50 nm	化学沉淀法	70 d内纳米颗粒能够连续向水中释放氧气，在生物条件下施用400 mg/L CaO2能够在60 d后从地下水中完全去除苯	〔25〕
苯、石油烃	50 nm	化学沉淀法	Fe²⁺存在情况下，CaO₂对污染物的去除能力更高，4 d后从地下水中完全去除苯	〔14〕
三氯乙烯	50~200 nm	化学法	180 min内可去除86.1%三氯乙烯	〔29〕
苯	50 nm	化学沉淀法	过氧化钙纳米粒子能大幅提高苯的去除效率和浮游细菌的数量，但会略微降低微生物种群的丰富度	〔30〕

pH	不同温度下的k（H₂O₂）/（10^-1 L·mmol^-1·min^-1）			k（H₂O₂）增加百分比^a/%	不同温度下k（O₂）/（10^-1 L·mmol^-1·min^-1）			k（O₂）增加百分比^b/%
pH	10 ℃	22 ℃	35 ℃	k（H₂O₂）增加百分比^a/%	10 ℃	22 ℃	35 ℃	k（O₂）增加百分比^b/%
6	2.57	2.86	3.04	18.29	0.56	0.58	0.61	8.93
6.5	1.07	1.38	1.51	41.12	0.26	0.29	0.36	38.46
7	0.67	0.71	0.94	40.30	0.11	0.16	0.27	145.45
8	0.17	0.20	0.25	47.06	0.034	0.071	0.090	166.67
k百分比下降^c	93.39	93.01	91.78	—	93.93	87.93	84.74	—

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