CN101157494A - 半烧水镁石在臭氧化净水中的应用及其方法 - Google Patents
半烧水镁石在臭氧化净水中的应用及其方法 Download PDFInfo
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Abstract
本发明提供了半烧水镁石在臭氧化净水中的应用及其方法，目的在于提高臭氧化降解水中有机物的效率。其特征是，将天然碱性矿物水镁石煅烧得到产物半烧水镁石，然后用其作为催化剂加入臭氧化降解有机污染物(比如苯酚，硝基苯以及苯胺)的体系中，达到促进污染物降解的效果。本发明充分利用天然矿物资源，对臭氧化降解硝基苯等难降解有机物有明显的促进效果，简单实用，成本低廉，不会产生二次污染，具有广阔的应用前景。
Description
技术领域
本发明属于环境水处理方法与技术领域，涉及一种矿物半烧水镁石在臭氧化净水中技术中的应用及其方法，通过在臭氧化曝气装置中加入天然水镁石矿的煅烧产物半烧水镁石，提高臭氧化降解有机污染物效率。
背景技术
臭氧的氧化性极强，其氧化还原电位为2.07。正是由于它的强氧化性，人们提出了臭氧化降解有机污染物的概念。但是臭氧在降解苯酚等芳香类有机物时，产生的小分子酸等副产物会抑制臭氧分子在水体中的分解，从而导致水体的COD值仍旧维持在一个较高的的范围；同时某些难降解的苯环类有机物(比如硝基苯、苯胺等)通过臭氧直接氧化难以达到较好的降解效果。为了进一步提高臭氧化的效率和进一步降低水体的COD值，人们提出了催化臭氧化进程，即是在臭氧化过程中在水体中加入催化剂，以达到促进有机物降解的目的[(1)B.Kasprzyk-Hordern，M.Ziólek and J.Nawrocki，Appl.Catal.B：Environ.46(2003)639.(2)B.Legube，N.Karpel Vel Leitner，Catal.Today 53(1999)61]。常用的催化剂主要有金属离子、金属氧化物和活性炭多孔材料等。然而，从实际应用的角度出发，目前使用的催化剂仍然存在许多不尽人意的地方。比如金属离子容易带来二次污染的问题，氧化物催化剂又需要分离且成本较高，活性炭吸附太严重需要分离重新处理。天然碱性矿物以其资源丰富、成本低而受到关注。目前，天然碱性矿物在水处理中的应用仍不多见。本发明正是为了使臭氧化净水技术能真正得到应用，将廉价的半烧水镁石应用到臭氧化净水技术中，获得了一种实用性强的去除水中有机污染物的技术。
发明内容
本发明的目的就是针对废水中难降解的有机污染物物(比如硝基苯、苯胺、苯酚等)以及降解过程中产生的小分子有机酸等会抑制臭氧化效率的现象，提出通过添加天然的碱性矿物水镁石在一定温度下的煅烧产物——半烧水镁石，使水体的pH值调至10-11之间，从而促进水中臭氧分解产生更多自由基，同时也消除了有机物降解过程中产生的小分子酸对水体的酸化产生的抑制作用，最终达到提高臭氧化降解有机物的效率的目的。
本发明的技术方案为：
半烧水镁石在臭氧化处理有机废水中的应用方法，其特征是：
将天然水镁石置于一定温度下煅烧一定时间后，得到产物半烧水镁石；将得到的半烧水镁石加入臭氧化装置(比如瓶、池、塔、罐等)中，搅拌使分散均匀，然后通臭氧。上述方法中，用来制备半烧水镁石的水镁石为天然矿物，其粒径为小于等于100目。
上述方法中，制备半烧水镁石时的煅烧温度为400-700℃。
上述方法中，制备半烧水镁石的煅烧时间为2-6小时。
上述方法中，在臭氧化降解有机废水的装置中加入的半烧水镁石的质量为装置中有机废水质量的0.1％-5％。
上述方法中，用来进行臭氧化处理的有机废水中有机物污染物的含量为1mg/L-1000mg/L。
本发明的优点：1.充分利用天然矿物资源。2.半烧水镁石的加入对臭氧化降解硝基苯等难降解有机物有明显的促进效果，当用于降解苯酚时，通臭氧60min时体系中苯酚和COD的去除率分别可达到100％和90％；当用于降解硝基苯和苯胺时，通臭氧120min时水体中两种有机污染物几乎完全去除。3.该方法简单实用，成本低廉，而且镁离子在水中不会产生二次污染。
附图说明
图1为实施例1所得半烧水镁石的XRD图。
图2为实施例2中苯酚浓度在单独臭氧化(a)和半烧水镁石催化臭氧化(b)下的降解曲线图。
图3为实施例2中水体COD值在单独臭氧化(a)和半烧水镁石催化臭氧化(b)下的去除曲线图。
图4为实施例3中硝基苯浓度在单独臭氧化(a)和半烧水镁石催化臭氧化(b)下的降解曲线图。
图5为实施例4中苯胺浓度在单独臭氧化(a)和半烧水镁石催化臭氧化(b)下的降解曲线图。
具体实施方式
下面通过具体实例进一步说明本发明半烧水镁石的制备及作为催化剂在臭氧化降解水体中难降解有机污染物中的应用。
实施例1.半烧水镁石的制备方法
先将天然水镁石样品粉碎研磨至100目，然后将得到的粉末样品至于马弗炉中，在500℃下煅烧6小时，就得到本发明中所用的催化剂半烧水镁石。
实施例2.半烧水镁石催化臭氧化降解水体中苯酚
先取苯酚(分析纯)溶解于蒸馏水中，配制而成的初始浓度为100mg·L-1，初始COD值为227.0mg·L-1的模拟废水；然后分别取两份120ml模拟溶液，一份单独通臭氧，一份加入0.5g半烧水镁石(实施例1中制备得到的)搅拌均匀后通臭氧，并隔一段时间取水样分析水体中苯酚含量和水体COD值。其中所通的臭氧流量为5ml/min，气流中臭氧浓度为18.4mg/L。水溶液中苯酚含量用高效液相色谱(HPLC，SHIMADZU)测定，色谱柱为C-18-AR-II waters(4.6×250mm，COSMOSIL)，流动相采用甲醇/水＝0.5/0.5，流速为1ml/min，检测器为紫外可见吸收检测器(SPD-10A UV-VisDetector，SHIMADZU)，检测波长为210nm。水溶液的COD值是用国家标准重铬酸钾法(GB11914-89)测定的。臭氧浓度通过碘量滴定法标定。
实施例3.半烧水镁石催化臭氧化降解水体中硝基苯
先取硝基苯(分析纯)溶解于蒸馏水中，配制而成的初始浓度为100mg·L-1的模拟废水。然后分别取两份120ml模拟溶液，一份单独通臭氧，一份加入0.5g半烧水镁石(实施例1中制备得到的)搅拌均匀后通臭氧，并定时隔一段时间取水样分析水体中硝基苯含量。其中所通的臭氧流量为5ml/min，气流中臭氧浓度为18.4mg/L。水溶液中硝基苯含量用高效液相色谱(HPLC，SHIMADZU)测定，色谱柱为C-18-AR-IIwaters(4.6×250mm，COSMOSIL)，流动相采用甲醇/水＝0.5/0.5，流速为1ml/min，检测器为紫外可见吸收检测器(SPD-10A UV-Vis Detector，SHIMADZU)，检测波长为266nm。臭氧浓度通过碘量滴定法标定。
实施例4.半烧水镁石催化臭氧化降解水体中苯胺
先取苯胺(分析纯)溶解于蒸馏水中，配制而成的初始浓度为100mg·L-1的模拟废水。然后分别取两份120ml模拟溶液，一份单独通臭氧，一份加入0.5g半烧水镁石(实施例1中制备得到的)搅拌均匀后通臭氧，并定时隔一段时间取水样分析水体中苯胺含量。其中所通的臭氧流量为5ml/min，气流中臭氧浓度为18.4mg/L。水溶液中苯胺含量用高效液相色谱(HPLC，SHIMADZU)测定，色谱柱为C-18-AR-II waters(4.6×250mm，COSMOSIL)，流动相采用甲醇/水＝0.5/0.5，流速为1ml/min，检测器为紫外可见吸收检测器(SPD-10A UV-Vis Detector，SHIMADZU)，检测波长为230nm。臭氧浓度通过碘量滴定法标定。
Claims (6)
1.半烧水镁石在臭氧化降解废水中有机污染物中的应用及其方法，其特征在于按照如下步骤进行：
(1)将天然水镁石置于一定温度下煅烧一定时间后，得到产物半烧水镁石；
(2)将得到的半烧水镁石加入臭氧化降解有机污染物的装置中，搅拌使分散均匀，然后通臭氧。
2.根据权利1所述的反应步骤，其特征是：用来制备半烧水镁石的水镁石为天然矿物，其粒径为小于等于100目。
3.根据权利1所述的反应步骤，其特征是：制备半烧水镁石时的煅烧温度为400-900℃。
4.根据权利1所述的反应步骤，其特征是：制备半烧水镁石的煅烧时间为2-6小时。
5.根据权利1所述的反应步骤，其特征是：在臭氧化降解有机废水的装置中加入的半烧水镁石的质量为装置中有机废水质量的0.1％-5％。
6.根据权利1所述的反应步骤，其特征是：用来进行臭氧化处理的有机废水中有机物污染物的含量为1mg/L-1000mg/L。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588328A (zh) * | 2013-11-26 | 2014-02-19 | 南京大学 | 一种处理含苯类污染物污水时回收草酸镁的方法 |
| CN105366785A (zh) * | 2015-12-18 | 2016-03-02 | 北京伟创力科技有限公司 | 一种提高臭氧利用效率降低废水cod的方法 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588328A (zh) * | 2013-11-26 | 2014-02-19 | 南京大学 | 一种处理含苯类污染物污水时回收草酸镁的方法 |
| CN103588328B (zh) * | 2013-11-26 | 2016-01-20 | 南京大学 | 一种处理含苯类污染物污水时回收草酸镁的方法 |
| CN105366785A (zh) * | 2015-12-18 | 2016-03-02 | 北京伟创力科技有限公司 | 一种提高臭氧利用效率降低废水cod的方法 |
| US10266438B2 (en) | 2015-12-18 | 2019-04-23 | Beijing Welltrailing Science and Technology Company | Method for reducing cod of wastewater with improved utilization efficiency of ozone |
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