超临界水氧化技术研究进展

超临界水氧化技术是一种新兴的、高效的高级氧化技术具有广阔的应用前景。该方法具有独特的技术性和经济性。主要介绍超临界氧化技术的研究现状、应用领域,同时指出存在的问题和对策及发展前景分析。     

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Experimental study on filtration and continuous regeneration of a particulate filter system for heavy-duty diesel engines

This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（CDPF）. Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number（SPN） was close to100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.     

Genotoxicity removal of reclaimed water during ozonation

Genotoxicity in wastewater and reclaimed water now is gaining increased attention because of genotoxins' potential damage to the ecosystem and human health. The effect of ozonation on genotoxicity in reclaimed water was investigated. It was found that ozonation decreased the genotoxicy dramatically in three tertiary treatment plants. In the further batch ozonation experiment in laboratory,secondary effluent sample used exhibited the genotoxicity of(41.1 ± 4.1) μg 4NQO/L. Ozonation with a dose of 10 mg O3/L completely removed the genotoxicity in secondary effluent. However,after ozonation, the dissolved organic carbonvalue of the sample didn't change much but the specific ultraviolet absorbance(SUVA) value dropped sharply. With the help of Fourier transform infrared spectroscopy, ozonation was found to change chemical aliphatic carbon and C–O of the dissolved arganic matter, which might be the reason of the significant decreases of SUVA and genotoxicity.     

氧化沟工艺提标过程中总磷的技改分析

昆明第一污水处理厂氧化沟工艺至今已运行25 a,随着滇池水环境的恶化,昆明市于2010年将污水处理厂排放标准由原来的一级B标提升至一级A标,总磷的提标是整个提标过程中的重中之重。作者通过对除磷工艺的摸索,研究了除磷加药工艺优化运行的方式,确定了加药量的计算公式,为国内外其他水厂的提标技改,提供技术参考。     

催化臭氧氧化降解水溶液中亚甲基蓝的动力学研究

以废啤酒酵母为原材料、采用吸附-活化法制备得到负载过渡金属铁的活性炭(Fe/AC),对Fe/AC吸附亚甲基蓝(MB)性能和催化臭氧氧化MB效果进行了评价。Fe/AC对MB的吸附符合Langmuir等温吸附模型;20℃,pH=7的条件下,Fe/AC对MB的最大吸附量达到107.43 mg/g。吸附MB达到平衡的Fe/AC催化臭氧氧化降解水中MB,30 min内MB的转化率达到99%以上,5 h后总有机碳(TOC)的降解率达到70%。结合Fe/AC吸附MB特性和催化臭氧氧化MB行为,将Langmuir等温吸附模型分别与近似一级和二级反应动力学模型进行耦合,构建了Langmuir-Kinetic近似一级和近似二级耦合模型,均能较好地拟合MB转化率的动力学数据,但对体系的TOC去除率动力学数据的拟合度较低。     

700 t/d浮法玻璃窑脱硝技术工艺比选

由于对浮法玻璃窑烟气排放标准的提高,玻璃窑烟气需要进行脱硝系统的增设。文章介绍了目前国内重油浮法玻璃窑的烟气状况及主要脱硝方式。针对某700 t/d重油浮法玻璃窑烟气脱硝项目,对比了几种SCR脱硝布置方式,并通过综合考虑对原有余热锅炉影响程度、施工难度及运行费用等条件后,最终选择了适应于该现场的合理方案。最终方案因对余热锅炉热效率影响小,同时作为相对独立工艺系统无需对余热锅炉进行过多改造而确定为在余热锅炉前增设中高温SCR。     

锌离子对厌氧氨氧化脱氮效能的影响

通过序批实验的方法,直接接种厌氧氨氧污泥,研究了Zn2＋对厌氧氨氧化（Anammox）脱氮效能的影响。研究结果表明,当进水Zn2＋质量浓度小于2 mg/L时,对厌氧氨氧化生物活性有促进作用,可增强微生物的脱氮效能;当进水Zn2＋质量浓度在2 mg/L和4 mg/L之间时,脱氮效能无明显变化,说明对厌氧氨氧化微生物活性无明显影响;当进水Zn2＋质量浓度大于4 mg/L,对厌氧氨氧化反应有抑制作用,Zn2＋浓度越高,抑制作用越明显。 Zn2＋对厌氧氨氧化的半抑制质量浓度（CI,50）为32.3 mg/L,NO2--N与NH4＋-N转化比的平均值为1.28。     

化工废水的超临界水氧化研究

在超临界条件下,管式反应器中超临界水的各种参数是很难获得的。本文在管式反应器中,以空气作为氧化剂,以实际化工废水作为研究对象,开发设计了一套大型中试超临界水氧化(SCWO)系统,并将所有的反应过程都控制在623.2~793.2K和24MPa的条件下,对此套连续化SCWO中试设备对实际化工废水的处理效果进行了试验研究。试验结果表明:随着反应温度和停留时间的增加,COD的去除率明显升高;通过比较进、出水组分的GC-MS图谱可以看出,原水中存在15种主要难降解有机污染物,包括杂环化合物和多环胺类等,但在出水中仅发现一种有机污染物存在,且其浓度也仅仅约为初始浓度的10%。此外,还对整个SCWO系统的能量衡算进行了分析并得到了能量自平衡的曲面图,结果显示当化工废水的COD浓度在183~437g/L且流速控制在20.83~104.17kg/h的条件下,整个系统即能达到自平衡状态。