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.     

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.     

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.     

京津冀及周边地区低碳经济发展水平评价

随着应对全球气候变化进程的不断推进,“低碳经济”已逐渐成为世界各国实现经济社会可持续发展的必由之路.京津冀及周边地区社会经济发展较不平衡,整体推进低碳经济发展存在较大的困难,为有效促进低碳经济发展的策略选择,本文通过构建低碳经济发展水平评价指标体系,对京津冀及周边地区的低碳经济发展状况进行评价.结果显示,京津冀及周边地区低碳经济发展水平差异较大：北京低碳经济水平相对较高,其他地区距离低碳经济发展水平尚有较大差距.由此,京津冀及周边地区应根据地区经济发展特点及其低碳经济发展状况,采取不同的低碳发展策略选择,以有效推进低碳经济发展模式的顺利转型.     

CALPUFF模型在某露天煤矿煤尘模拟中的应用

煤炭露天开采是我国煤炭生产的主要方法,为了验证CALPUFF模型在露天开采中,对煤尘浓度的模拟情况,本文耦合使用MM5/CALMET及CALPUFF软件,对某露天煤矿煤尘浓度进行模拟,并与监测值进行对比分析,发现监测值和模拟值的相关系数最高可达0.88,说明模拟值具有较高可信度.     

HRT对厌氧氨氧化反应器脱氮效能的影响

利用UAFB反应器富集培养了厌氧氨氧化细菌,并在此基础上考察水力停留时间(HRT)对厌氧氨氧化系统处理效果的影响。结果表明:HRT对厌氧氨氧化系统影响较大,当HRT为4 h时,系统出水NH4+-N、NO2--N去除率降至65%~60%,出水浓度则分别为15 mg/L、20 mg/L,表明过短HRT会导致含氮污染物去除不完全;HRT为6 h时,系统中NH4+-N去除率均在95%以上,出水NH4+-N≈1 mg/L。系统中NO2--N去除率均在92%以上,出水NO2--N≤5 mg/L;当HRT继续延长至10 h,去除效果无明显变化,出水NH4+-N≈1 mg/L,NO2--N≤5 mg/L,NO3--N平均5.6 mg/L。因此,在该研究中HRT为6 h效果最佳,总氮容积去除负荷为0.57 kg/(m3·d),厌氧氨氧化(ANAMMOX)反应器氨氮去除量、亚硝态氮去除量和硝态氮生成量之比为1∶1.19∶0.39。     

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。     

AMF对宿根高粱抗氧化特性及铯富集能力的影响

通过盆栽试验研究了Glomus geosporum,Glomus mosseae,Glomus versiforme以及Glomus etunicatum等4种丛枝菌根真菌(AMF)对土壤低放核素铯污染胁迫下宿根高粱抗氧化特性和铯富集能力的影响。结果表明,AMF处理均不同程度的增加了宿根高粱地上部和地下部CAT、SOD活性以及根系活力,显著降低了H2O2含量和·O2-产生速率(P<0.05),以G.mosseae和G.etunicatum处理效果较好;同时,外源AMF处理显著增加了宿根高粱地上部和地下部Cs含量、富集系数和转运系数(P<0.05),降低了Cs在土壤中的残留量,均以G.mosseae和G.etunicatum处理效果较好。     

三氯生对土壤酶活性的影响

为了明确三氯生对土壤生态环境的安全性,以3种土壤酶为指标,采用室内培养试验,研究了不同浓度的三氯生对土壤脲酶、酸性磷酸酶和过氧化氢酶活性的影响。研究结果表明,不同浓度水平的三氯生对3种土壤酶活性的影响效果不同。低浓度(≤50 mg/kg)三氯生作用下,脲酶活性先降低后增加,最后恢复到对照水平,高浓度(100 mg/kg)三氯生胁迫下脲酶活性先降低后恢复最后又被抑制。而对酸性磷酸酶活性来说,三氯生在低浓度时(≤50 mg/kg)先刺激后抑制酶活性,最后磷酸酶活性恢复到对照水平,高浓度下(100 mg/kg)三氯生先抑制后刺激再抑制磷酸酶活性,最后磷酸酶活性恢复到对照水平。各浓度水平的三氯生在培养的初期(21 d)对土壤过氧化氢酶活性没有影响,随着培养时间延长(≥28 d),低浓度(≤50 mg/kg)三氯生刺激了酶活性,高浓度(100 mg/kg)的三氯生抑制了过氧化氢酶活性。总体来说,高浓度的三氯生对土壤环境存在不利影响。     

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。