焙烧温度对CeO_2(ZrO_2)/TiO_2选择性催化脱硝性能的影响

采用溶胶-凝胶法并以不同温度焙烧制备一系列CeO_2(ZrO_2)/TiO_2(CZT)催化剂,考察了CZT催化剂固相结构、酸量、比表面积等性能与催化活性的关系。采用XRD、BET、NH3-TPD、H2-TPR以及XPS等表征技术对催化剂进行表征。结果表明:焙烧温度为450℃时CZT催化剂具有最高的催化活性,其在240~400℃的温度窗口内活性均高于90%,且具有较好的抗水和抗硫中毒能力。随着焙烧温度的提高,催化剂表面的Ce和Zr原子进入体相晶格且Ce0.5Zr0.5O2向Ce0.75Zr0.25O2转变,导致催化剂的储释氧能力和氧化还原性能降低。另外,锐钛矿和金红石型TiO_2晶粒尺寸的增加,催化剂的有效比表面积和总酸量降低,因此CZT催化活性随着焙烧温度的提高而有所降低。换言之,大的比表面积、良好的氧化还原性能、表面Ce4+的富集以及酸性位的增多均有利于NH3-SCR活性的提高。     

京津冀区域燃煤发电行业大气污染物排放时空变化特征研究

为了科学评估京津冀区域燃煤发电行业特别排放限值和超低排放相关要求实施后的大气污染物减排效果,以行业调查数据为基础,建立了2013年和2015年京津冀区域燃煤发电行业大气污染物排放清单,分析了装机容量与SO_2、NO_x和烟尘排放量的时空耦合关系,讨论了国家相关政策和标准的实施效果。结果显示:区域内2015年燃煤机组装机容量与2013年相比略有下降,SO_2、NO_x和烟尘排放量分别下降75.95%、83.09%和71.20%,减排效果明显。2015年100 MW以下等级机组3种污染物排放总量位居各机组首位,建议通过多种合理方式压减小型燃煤发电机组数量和排放浓度。     

氯代挥发性有机物CVOCs催化氧化的研究进展

氯代挥发性有机物(CVOCs)因其性质稳定、反应性差且毒性高,成为目前大气污染物净化技术中的难点。催化氧化法是去除CVOCs最有效的方法之一。对CVOCs催化氧化的研究进行综述,列举实例介绍了各类催化剂对常见CVOCs的催化研究现状,对催化性能、催化剂失活、反应机理等方面进行了详细分析,总结出积碳和氯中毒是催化剂失活的两大主要因素,而载体性质、活性组分分散度、水等对催化性能产生很大影响。最后,展望了未来催化剂的研究重点。     

复合生物阴极型微生物燃料电池处理废水及同步产电性能

为研究生物阴极在MFC（微生物燃料电池）中的应用,分别以粒径为2~4 mm的颗粒活性炭和粒径为2~4、4~8、8~12 mm的颗粒石墨为阴极基质材料,构建升流复合生物阴极型单室MFC,研究阴极基质材料的种类和粒径对MFC的产电性能和净水效能的影响.结果表明:当阳极基质材料为2~4 mm粒径的颗粒活性炭时,燃料电池中利用玻璃纤维取代离子交换膜,阴极基质材料为选用4~8 mm粒径颗粒石墨的反应柱产电量最大,为534 mV（外电阻为1 000 Ω）,最大功率密度达到631.6 mW/m3,库伦效率为3.82%;阴极的pH越低越有利于阴极的产电反应;不同阴极基质材料的MFC对COD_Cr去除率均在80%左右,TN、NH₄+-N及TP的去除率最高可分别达到79%、93%和34%.研究显示,阴极基质材料的种类和粒径对MFC的产电性影响较大,但对其净水效能的影响不大.      

Effect of MoO3 on vanadium based catalysts for the selective catalytic reduction of NOx with NH3 at low temperature

The selective catalytic reduction(SCR) activities of the MoO_3 doped V/WTi catalysts prepared by the incipient wetness impregnation method at low temperature were investigated.The results showed that the addition of MoO_3 could enhance the NO_ xconversion at low temperature and the best SCR activity was obtained when the dosage of MoO_3 reached5 wt.%. The NH3-TPD and DRIFTS experiments indicated that the addition of MoO_3 changed the type and number of acid sites on the surface of catalysts and reaction activities of acid sites were altered at the same time. The redox capacity and amount of active oxygen species got improved for V3Mo5/WTi catalyst, which could be confirmed by the H_2-TPR and transient response experiments. Water vapor inhibited the NO_xconversion at low temperature. Deposition of ammonium sulfate or bisulfate might be main reason for the loss of catalytic activity in the presence of SO_2 at low temperature. Choosing the suitable NH_3/NO ratio and elevation of reaction temperature both could weaken the influence of SO_2 on the SCR activity of the V3Mo5/WTi catalyst. Thermal treatment of the deactivated catalyst at350°C could get the low temperature activity recovered. The decrease of GHSV improved the de NO_x efficiency at low temperature and we speculated that the rational technological process and operation parameters could contribute to the application of this kind of catalysts in real industrial environment.     

Effects of free ammonia on volatile fatty acid accumulation and process performance in the anaerobic digestion of two typical bio-wastes

The effect of free ammonia on volatile fatty acid(VFA)accumulation and process instability was studied using a lab-scale anaerobic digester fed by two typical bio-wastes:fruit and vegetable waste(FVW)and food waste(FW)at 35°C with an organic loading rate(OLR)of 3.0 kg VS/(m~3·day). The inhibitory effects of free ammonia on methanogenesis were observed due to the low C/N ratio of each substrate(15.6 and 17.2,respectively). A high concentration of free ammonia inhibited methanogenesis resulting in the accumulation of VFAs and a low methane yield. In the inhibited state,acetate accumulated more quickly than propionate and was the main type of accumulated VFA. The co-accumulation of ammonia and VFAs led to an "inhibited steady state" and the ammonia was the main inhibitory substance that triggered the process perturbation. By statistical significance test and VFA fluctuation ratio analysis,the free ammonia inhibition threshold was identified as 45 mg/L. Moreover,propionate,iso-butyrate and valerate were determined to be the three most sensitive VFA parameters that were subject to ammonia inhibition.     

In-situ synthesis of TiO2 rutile/anatase heterostructure by DC magnetron sputtering at room temperature and thickness effect of outermost rutile layer on photocatalysis

TiO_2 rutile/anatase heterostructure thin films with varying rutile thickness have been in-situ synthesized via DC magnetron sputtering with Ar gas at room temperature. The crystal texture, surface morphology, energy gap and optical properties of the films have been investigated by X-ray diffraction meter, grazing incidence X-ray diffraction meter, Raman spectroscopy, scanning electron microscopy, and UV–visible spectrophotometer, which indicates that the rutile/anatase heterostructure films are successfully fabricated. The further degradation experiments display that the photocatalytic activity can be dramatically affected by the thickness of the outmost rutile layer and the 100 nm thickness exhibits the best performance in all of the TiO_2 thin films. With the increase of the outmost rutile layer, the optical band gap of TiO_2 film displays a systematic decrease slightly. However,the change in photocatalytic activity does not coincide with that in the band gap. The photoresponse and electrochemical properties of the thin films have been characterized to understand the mechanism of the varied photocatalytic activity.     

Effect of barium sulfate modification on the SO2 tolerance of V2O5 /TiO2 catalyst for NH3-SCR reaction

Sulfur poisoning of V_2O_5/BaSO_4–TiO_2(VBT),V_2O_5/WO_3–TiO_2(VWT) and V_2O_5/BaSO_4–WO_3–TiO_2(VBWT) catalysts was performed in wet air at 350℃ for 3 hr,and activities for the selective catalytic reduction of NO_x with NH_3 were evaluated for 200–500℃.The VBT catalyst showed higher NO_x conversions after sulfur poisoning than the other two catalysts.The introduction of barium sulfate contributed to strong acid sites for the as-received catalyst,and eliminated the redox cycle of active vanadium oxide to some extent,which resulted in a certain loss of activity.Readily decomposable sulfate species formed on VBT-S instead of inactive sulfates on VWT-S.These decomposable sulfates increased the number of strong acid sites significantly.Some sulfate species escaped during catalyst preparation and barium sulfate was reproduced during sulfur poisoning,which protects vanadia from sulfur oxide attachment to a great extent.Consequently,the VBT catalyst exhibited the best resistance to sulfur poisoning.     

流体剪切与超声空化破解剩余污泥的参数优化

为提高剩余污泥的破解效果并降低能耗,采用FS（fluid shear,流体剪切）、UC（ultrasonic cavitation,超声空化）、FS和UC联合工艺（FS-UC,UC-FS）破解剩余污泥,并应用单因素试验结合响应面法对联合工艺进行优化.结果表明:FS对剩余污泥破解效果一般,只在开始阶段具有较好效果,随作用时间延长,破解效果未有显著提高甚至下降.UC对剩余污泥破解效果明显,随作用时间延长,破解效果显著提升,但能耗也随之增大,EDR（energy disintegration ratio,效能比）明显下降.相同作用时间下,UC破解效果优于FS破解效果,UC破解剩余污泥的DD_COD（degree of disintegration,破解率）与EDR均明显高于FS方法.单因素试验得出的较优FS作用时间范围为2~8 min,较优UC作用时间范围为5~15 min.响应面法试验结果显示,联合工艺的剩余污泥破解效果和能量利用率均优于单一方法,联合工艺中FS-UC工艺的破解效果优于UC-FS工艺.FS-UC工艺的最佳参数:FS处理5.6 min再UC处理15.0 min,该条件下剩余污泥实际DD_COD为50.8%,EDR为26.8%.UC-FS工艺的最佳参数:先UC作用15.0 min再FS作用7.8 min,该条件下剩余污泥实际DD_COD为36.5%,EDR为17.1%.研究显示,以DD_COD和EDR为指标,4种工艺的高效性顺序为FS-UC > UC-FS > UC > FS,其中FS-UC工艺具有能耗低、破解效率高的特点,是4种工艺中剩余污泥破解效果最好的一种工艺.      

山林地表慢渗系统处理农村生活污水厂尾水研究

利用山区污水处理厂周边森林植被构建慢速渗滤污水处理系统,用来处理山区农村生活污水厂尾水。结果表明,慢渗系统能够深度净化污水尾水,对COD_(Cr)、NH_3-N、NO_3-N、TN、TP的平均去除率分别为23.8%、40.2%、14.3%、11.3%和23.6%。并且土层越深,COD_(Cr)、TN、TP浓度越低,相应的去除率越高,而NO_3-N、TN去除率则呈降低趋势;山体坡度越大,COD_(Cr)、氨氮浓度有升高趋势,硝态氮、TN、TP有降低趋势;而坡长越大,COD_(Cr)、NH_3-N、NO_3-N、TN浓度有降低趋势,TP有升高趋势。此外,植被类型对水样化学性质有一定影响,竹林更利于COD_(Cr)、NH_3-N、TP浓度的降低,针阔混交林更利于NO_3-N、TN浓度的降低。