催化臭氧氧化处理DDNP废水的研究
摘要
二硝基重氮酚(DDNP)作为硝基重氮类起爆药的典型代表,因其具有爆炸性能优良、原料丰富、成本低廉及生产操作相对较为安全等优点而被广泛采用,特别被大量应用于制造工业爆破雷管。但是,DDNP生产废水中含有二硝基重氮酚、硝基化合物、硫化物、酚类等多种有害物质,属于噢毒性有机废水,如不妥善处理甚至不处理就直接排放,必然会污染环境,影响水体周围的生态环境及附近居民的身体健康。目前,已有多种针对此种废水的处理方案,但或因处理效果不理想,或因处理成本投入太大等缺点,均未得到广泛应用,更有部分DDNP生产企业因DDNP生产废水排放不达标而被迫停产。总之,DDNP废水给人们及社会带来了一系列问题。
本文采用催化臭氧氧化技术对DDNP废水进行处理,探讨了影响处理结果的各种因素并分析可能导致其产生的原因,获得了最佳工艺参数。试验结果表明,使用该工艺处理DDNP废水,处理水可以达到国家相应排放标准。因此,催化臭氧氧化技术在DDNP废水处理中的应用,有着实际的工程应用价值和广阔的发展前景,并对处理其它硝基酚类有机污染物废水有着重要的借鉴意义。
本文的主要内容包括以下4个方面:
首先,对经单纯臭氧处理预处理后的DDNP废水进行试验研究。考察了氧化时间、温度、pH值、臭氧浓度等主要工艺参数对处理效果的影响。结果表明:在氧化时间为40min、温度为20℃、pH值为9、臭氧浓度为1.32mg/L的条件下,CODcr可降低至140.04mg/L,色度为202倍,硝基酚含量为1.5mg/L。
其次,为增强处理效果,引入了催化剂强化氧化过程,在处理水中加入了具有催化作用的活性组分(铜、铁离子硝酸盐),筛选出了对废水处理效果最优的活性组分。
随后,将筛选出的催化剂活性组分浸渍于载体上,制备了非均相催化剂。研究了采用该催化剂催化氧化DDNP废水时pH值、温度、臭氧浓度、非均相催化剂吸附等因素对去除CODcr的影响。试验结果表明:当氧化时间为30min、温度20℃、pH值12、臭氧浓度1.32mg/L、流速为400ml/min时,CODcr可降低为73.15mg/L,色度为43倍,硝基酚含量为0.97mg/L,均达到工业排放标准。
最后,在试验数据基础上,初步计算臭氧利用率情况。单纯臭氧氧化DDNP废水时,臭氧利用率仅为41%左右;非均相催化臭氧氧化处理时,臭氧利用率有了大幅度的提高,可达到76%以上。
As a representative detonating explosives in the nitro-diazotized category, diazodinitrophenol(DDNP) has been widely used, because of its excellent performance, abundant raw materials, low cost and comparatively safe production, especially in manufacture of industrial blasting detonators. However, DDNP wastewater contain some hazardous substances, such as diazodinitrophenol, nitro-compound, sulfide and phenolic compound, all of which are toxic organic wastewater, exerting high pollution on the environment and impact on the healthy of nearby residents if proper handle is not given. Although there are some treatment programs, these programs fail to be widely used in the real operation because of their poor effect, or technical problems and the economic reasons. Some manufacturers forced to stop production because they can not reach the emission standards. Therefore, the DDNP wastewater brings about aseries of problems to people and the society.
The wastewater was treated by catalytic ozonation technology in this paper, effects of different factors on processing results were discussed and the reasons which may lead to its generating were analyzed, at last the optimum technological parameters were obtained. The result of the test shows that the treated water can reach the corresponding national wastewater discharge standards. All in all, this method which is used in the treatment of DDNP wastewater, has high potential value and broad application prospect. In the meantime, it can be also used for the reference in netrophenolic organic wastewater treatment.
The main contents of this article includes the following four aspects:
First of all, the paper examined the ozonization of DDNP wastewater. By employing the single-factor method, the study further investigated the effects of different technological parameters, including the processing time, temperature, pH value and the concentration of ozone. The result of the study showed that under such a condition of the processing time of 40 min, temperature of 20℃, pH value 9, the concentration of ozone of 1.32mg/L, the CODCr, nitrophenols, chroma could reach to 140.04mg/L, 1.5mg/L and 202.
Secondly, In order to enhance the effects of treatment, the strengthening oxidation process of catalysts was introduced, the catalysis of the active components(copper ion and iron ion nitrate salts) were added into treated water, the catalysis were screened out which had the best treatment effect towards the wastewater.
Thirdly, heterogeneous catalyst was prepared with the active ingredient of catalyst which soaks on the carrier. The pH value, reaction temperature, concentration of ozone, adsorption of heterogeneous catalysts in testing process, which influent the CODcr’s removal efficiency, are investigated. The results showed that under such a condition of the processing time of 30 min, temperature of 20℃, pH value 12, the concentration of ozone of 1.32mg / L, the velocity of flow of 400ml/min, the CODCr, chroma and nitrophenols could reach 73.15mg/L, 43 and 0.97mg/L, industrial emission standards can be reached.
Finally, based on the data of experiment, the utilization of ozone is preliminarily calculated. The utilization of ozone can be reached about 41percent when only use the ozone to dispose the DDNP wastewater. However, the utilization of ozone has great elevation, which can be reached above 76 percent when use heterogeneous catalytic ozonation to dispose DDNP wastewater.
本文采用催化臭氧氧化技术对DDNP废水进行处理,探讨了影响处理结果的各种因素并分析可能导致其产生的原因,获得了最佳工艺参数。试验结果表明,使用该工艺处理DDNP废水,处理水可以达到国家相应排放标准。因此,催化臭氧氧化技术在DDNP废水处理中的应用,有着实际的工程应用价值和广阔的发展前景,并对处理其它硝基酚类有机污染物废水有着重要的借鉴意义。
本文的主要内容包括以下4个方面:
首先,对经单纯臭氧处理预处理后的DDNP废水进行试验研究。考察了氧化时间、温度、pH值、臭氧浓度等主要工艺参数对处理效果的影响。结果表明:在氧化时间为40min、温度为20℃、pH值为9、臭氧浓度为1.32mg/L的条件下,CODcr可降低至140.04mg/L,色度为202倍,硝基酚含量为1.5mg/L。
其次,为增强处理效果,引入了催化剂强化氧化过程,在处理水中加入了具有催化作用的活性组分(铜、铁离子硝酸盐),筛选出了对废水处理效果最优的活性组分。
随后,将筛选出的催化剂活性组分浸渍于载体上,制备了非均相催化剂。研究了采用该催化剂催化氧化DDNP废水时pH值、温度、臭氧浓度、非均相催化剂吸附等因素对去除CODcr的影响。试验结果表明:当氧化时间为30min、温度20℃、pH值12、臭氧浓度1.32mg/L、流速为400ml/min时,CODcr可降低为73.15mg/L,色度为43倍,硝基酚含量为0.97mg/L,均达到工业排放标准。
最后,在试验数据基础上,初步计算臭氧利用率情况。单纯臭氧氧化DDNP废水时,臭氧利用率仅为41%左右;非均相催化臭氧氧化处理时,臭氧利用率有了大幅度的提高,可达到76%以上。
As a representative detonating explosives in the nitro-diazotized category, diazodinitrophenol(DDNP) has been widely used, because of its excellent performance, abundant raw materials, low cost and comparatively safe production, especially in manufacture of industrial blasting detonators. However, DDNP wastewater contain some hazardous substances, such as diazodinitrophenol, nitro-compound, sulfide and phenolic compound, all of which are toxic organic wastewater, exerting high pollution on the environment and impact on the healthy of nearby residents if proper handle is not given. Although there are some treatment programs, these programs fail to be widely used in the real operation because of their poor effect, or technical problems and the economic reasons. Some manufacturers forced to stop production because they can not reach the emission standards. Therefore, the DDNP wastewater brings about aseries of problems to people and the society.
The wastewater was treated by catalytic ozonation technology in this paper, effects of different factors on processing results were discussed and the reasons which may lead to its generating were analyzed, at last the optimum technological parameters were obtained. The result of the test shows that the treated water can reach the corresponding national wastewater discharge standards. All in all, this method which is used in the treatment of DDNP wastewater, has high potential value and broad application prospect. In the meantime, it can be also used for the reference in netrophenolic organic wastewater treatment.
The main contents of this article includes the following four aspects:
First of all, the paper examined the ozonization of DDNP wastewater. By employing the single-factor method, the study further investigated the effects of different technological parameters, including the processing time, temperature, pH value and the concentration of ozone. The result of the study showed that under such a condition of the processing time of 40 min, temperature of 20℃, pH value 9, the concentration of ozone of 1.32mg/L, the CODCr, nitrophenols, chroma could reach to 140.04mg/L, 1.5mg/L and 202.
Secondly, In order to enhance the effects of treatment, the strengthening oxidation process of catalysts was introduced, the catalysis of the active components(copper ion and iron ion nitrate salts) were added into treated water, the catalysis were screened out which had the best treatment effect towards the wastewater.
Thirdly, heterogeneous catalyst was prepared with the active ingredient of catalyst which soaks on the carrier. The pH value, reaction temperature, concentration of ozone, adsorption of heterogeneous catalysts in testing process, which influent the CODcr’s removal efficiency, are investigated. The results showed that under such a condition of the processing time of 30 min, temperature of 20℃, pH value 12, the concentration of ozone of 1.32mg / L, the velocity of flow of 400ml/min, the CODCr, chroma and nitrophenols could reach 73.15mg/L, 43 and 0.97mg/L, industrial emission standards can be reached.
Finally, based on the data of experiment, the utilization of ozone is preliminarily calculated. The utilization of ozone can be reached about 41percent when only use the ozone to dispose the DDNP wastewater. However, the utilization of ozone has great elevation, which can be reached above 76 percent when use heterogeneous catalytic ozonation to dispose DDNP wastewater.
引文
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[2]郑必清.生态文明的时代性和水环境建设.消费经济. 2008, 24(1):16-19
[3]郑利平,郭雨蓉.我国城市生活污水排海构想及其研究.环境保护. 2000, 12:30-34
[4]张锐.水污染:沉重的中国环境报告.北方观察. 2007, 9:24-26
[5] D. Manojlovic,D.R. Ostojic.ect. Removal of phenol and chlorophenols from water by new ozone generator. ScienceDirect 2007(213):116-122
[6]阳立平臭氧法处理高浓度苯酚废水.资源开发与市场. 2005, 21(2):86-88
[7]陈小龙.用表面活性剂改性的沸石处理DDNP生产废水技术研究中北大学硕士学位论文,2006
[8] Zhang Xuecai, Chen Shoubing, Cao Huaixin. Micro Electrolytic Treatment of Wastewater from Diazodinitrophenol Production. Fine Chemicals. 2003, 20(3):94-97
[9]陈双. DDNP生产废水处理的研究.福建化工. 1999, 1:31-34
[10]王海云,赵仁兴. DDNP废水处理方法研究综述. 2002, 31(5):25-28
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