Enhancement of thermophilic anaerobic digestion of thickened waste activated sludge by combined microwave and alkaline pretreatment

Pretreatment of thickened waste activated sludge (TWAS) by combined microwave and alkaline pretreatment (MAP) was studied to improve thermophilic anaerobic digestion efficiency. Uniform design was applied to determine the combination of target temperature (110–210°C), microwave holding time (1–51 min), and NaOH dose (0–2.5 g NaOH/g suspended solids (SS)) in terms of their effect on volatile suspended solids (VSS) solubilization. Maximum solubilization ratio (85.1%) of VSS was observed at 210°C with 0.2 g-NaOH/g-SS and 35 min holding time. The effects of 12 different pretreatment methods were investigated in 28 thermophilic batch reactors by monitoring cumulative methane production (CMP). Improvements in methane production in the TWAS were directly related to the microwave and alkaline pretreatment of the sludge. The highest CMP was a 27% improvement over the control. In spite of the increase in soluble chemical oxygen demand concentration and the decrease in dewaterability of digested sludge, a semi-continuous thermophilic reactor fed with pretreated TWAS without neutralization (at 170°C with 1 min holding time and 0.05 g NaOH/g SS) was stable and functioned well, with volatile solid (VS) and total chemical oxygen demand (TCOD) reductions of 28% and 18%, respectively, which were higher than those of the control system. Additionally, methane yields (L@STP/g-CODadded, at standard temperature and pressure (STP) conditions of 0°C and 101.325 kPa) and (L@STP/g VSadded) increased by 17% and 13%, respectively, compared to the control reactor.     

Modification of Ce02-ZrO2 catalyst by potassium for NOx-assisted soot oxidation

Potassium-modified ceria-zirconia catalyst was synthesized by wetness impregnation method. The ageing treatment was performed in static air at 800℃ for 20 hr to evaluate the thermal stability of the catalyst. The catalysts were characterized by X-ray diffraction,BET surface area, oxygen storage capacity, NOx-temperature programmed desorption and soot-temperature programmed oxidation measurements. By introduction of potassium, the maximum soot oxidation rate temperature (Tm) of the ceria-zirconia based catalyst decreased from 525 to 428℃ in the presence of NO under a loose contact mode. The shift of Tm of the K-modified catalyst after ageing is only 15℃. The enhanced activity of the aged catalyst mainly lies in the promotional effect of potassium on the NOx/oxygen storage cacity as well as the soot-catalyst contact.     

火焰原子吸收法测定地表水中钾钠钙镁的方法改进

用空气—乙炔火焰原子吸收测定地表水中钾钠钙镁时,将测钾钠用的消电离剂和测钙镁用的释放剂配成混合溶液,加入待测试样中,便可连续测定其中的钾钠钙镁。与现在常用的火焰原子吸收方法测得的结果一致,精密度和准确度符合规范要求,且方法简单快速。     

Removal of phosphate from wastewater using alkaline residue

Alkaline residue(AR) was found to be an efficient adsorbent for phosphate removal from wastewater. The kinetic and equilibrium of phosphate removal were investigated to evaluate the performance of modified alkaline residue. After treatment by NaOH(AR-NaOH), removal performance was significantly improved, while removal performance was almost completely lost after treatment by HCl(AR-HCl). The kinetics of the removal process by all adsorbents was well characterized by the pseudo second-order model. The Langmuir model exhibited the best correlation for AR-HCl, while AR was effectively described by Freundlich model. Both models were well fitted to AR-NaOH. The maximum adsorption capacities calculated from Langmuir equation were in following manner: AR-NaOH AR AR-HCl. Phosphate removal by alkaline residue was pH dependent process. Mechanisms for phosphate removal mainly involved adsorption and precipitation, varied with equilibrium pH of solution. For AR-HCl, the acid equilibrium pH( 6.0) was unfavorable for the formation of Ca-P precipitate, with adsorption as the key mechanism for phosphate removal. In contrast, for AR and ARNaOH, precipitation was the dominant mechanism for phosphate removal, due to the incrase on pH( 8.0) after phosphate removal. The results of both XRD and SEM analysis confirmed CaHPO4·2H2O formation after phosphate removal by AR and AR-NaOH.     

提高污泥碱性发酵挥发酸积累的新方法

为了加大剩余污泥在碱性条件下的水解酸化程度,本研究尝试了两种新的能促进污泥碱性发酵产酸的方式,分别是向批式的污泥碱性发酵系统中投加未灭菌发酵污泥和投加灭菌发酵污泥,结合温度的影响(10℃和35℃)分别考察了这两种方式对污泥水解酸化效果的影响.结果表明,中温有利于水解酶和产酸菌作用的发挥,增大了污泥的水解酸化程度,体系内有明显的挥发酸(VFAs)积累.35℃条件下,两种方式都在很大程度上促进了新鲜污泥的水解酸化程度,经灭菌后的发酵污泥的投加较等量的未灭菌的发酵污泥的投加效果更为显著.前者的水解速率是后者的2倍,发酵末期酸积累量为后者的1.5倍,且前者在较长的发酵时间内VFAs含量维持恒定.分析两种方式能促进污泥水解酸化的原因得到:未灭菌发酵污泥的投加是向系统中引入了一定量的产酸菌,灭菌发酵污泥的投加引入了大量的较易水解的有机底物.水解产物的增加能在更大程度上影响产酸的效果.因此,中温条件下向污泥碱性发酵系统中投加经灭菌处理后的发酵污泥是提高剩余污泥发酵产酸量更为有效的方式.     

天津市夏季蜂窝状溶蚀器涂层溶液浓度确定的实验研究

于2013年7月1日～8月31日,在天津市南开大学理化楼楼顶,采用蜂窝状溶蚀器进行了溶蚀器涂层溶液最适浓度的探究实验.结果表明,在天津夏季,蜂窝状溶蚀器的碳酸钠涂层溶液最适浓度为3%,柠檬酸涂层溶液最适浓度为6%.含有溶蚀器系统的颗粒物采样法与传统采样法对比发现,含蜂窝状溶蚀器的采样系统所得到的PM2.5样品浓度有86%低于传统方法所得到的PM2.5样品浓度,其原因主要为1酸/碱性气体被去除,使其无法与富集在采样膜上的颗粒物发生反应,也无法吸附到颗粒物上;2溶蚀器系统采样过程中,部分颗粒物被捕集到溶蚀器上;3酸/碱性气体被去除,导致气-粒平衡被打破,部分颗粒物组分向气态转化.     

利用热活化过硫酸盐技术去除阿特拉津

利用热活化过硫酸盐(S2O2-8)技术去除水中的阿特拉津(ATZ).结果表明,增加溶液中S2O2-8浓度或提高溶液反应温度,可加速ATZ的降解.ATZ的降解是一个二级反应,其速率和溶液中ATZ和S2O2-8的浓度都成正比.初始pH为3.0~10.0时,S2O2-8对ATZ都有很好的降解效果,在酸性和中性时,降解效率高于碱性条件.利用自由基探针发现,在酸性和中性条件下,起降解作用的主要是SO·-4,而碱性条件下OH·占主导.ATZ的降解受到Cl-、CO2-3和腐殖质(HA)的影响.其中,Cl-对反应的影响比较复杂,低浓度时Cl-会生成具有高氧化还原电位的Cl·促进ATZ的降解,而高浓度时Cl·会继续反应生成氧化能力相对较弱的Cl2·-,从而抑制反应的进行.HA和CO2-3都对反应有明显的抑制作用.     

有机无机缓释复合肥对不同土壤微生物群落结构的影响

缓控释肥料作为一类新型肥料已成为近年来的研究热点,但对土壤微生物群落多样性影响规律的研究甚少.研究采用磷脂脂肪酸法分析缓释复合肥(SRF)、化肥(CF)和普通复合肥(CCF)分别施入酸性土和微碱性土恒温培养10、30、60和90d后的微生物群落结构多样性.结果表明,缓释复合肥等肥料施入2种土壤恒温培养(10~90 d)后检测到多种细菌(13:0,i14:0,14:0,i15:0,a15:0,i16:0,16:12OH,16:1w5c,16:0,i17:0,a17:0,cy17:0,17:02OH,i18:0,18:0,cy19:0w8c),2种放线菌(10Me17:0和10Me18:0)和1种真菌(18:1w9c).SRF在酸性土壤培养前期(10 d和30 d)较CF显著增加真菌PLFA含量8.3%和6.8%,在培养后期(60 d和90 d)较CCF显著增加真菌PLFA含量22.7%和17.1%;SRF较CF和CCF显著增加微碱性土壤在整个恒温培养期(30 d除外)土壤细菌、真菌和革兰氏阳性菌PLFA含量.酸性土壤培养30 d和90 d时一般饱和脂肪酸/单烯不饱和脂肪酸PLFA值以SRF显著高于不施肥(CK)、CF和CCF,而在微碱性土壤上SRF仅在恒温培养60d时显著高于CK、CF和CCF;SRF较CCF显著降低酸性土壤(30~90 d)和微碱性土壤(10~60 d)异构PLFA/反异构PLFA值.从2种土壤PLFA种类、含量以及相对丰度等可知缓释复合肥较化肥和普通复合肥提高了土壤微生物PLFA种类和含量以及减弱对微生物生存环境的胁迫,缓释复合肥在2种土壤中尤其对酸性土的作用明显.通过研究缓释复合肥对土壤微生物群落结构多样性的影响,以期为农业生产上广泛施用缓释复合肥提供科学依据.     

UV/SPS降解水中三氯生的效能及动力学

采用短波紫外光激活过硫酸钠(UV/SPS)对水中三氯生(TCS)的去除进行了研究,考察了紫外光波长、紫外光强、过硫酸钠(SPS)投加量、pH值和腐殖酸(HA)等因素对TCS去除的影响,计算了自由基(·OH、SO_4~(·-))与TCS的二级反应速率常数及其对TCS去除的贡献值,鉴定了反应中主导自由基,对比了UV254/SPS和UV254/H_2O_2对天然水体中TCS的去除效果,GC/MS分析了TCS降解的中间产物及可能的降解路径.结果表明UV/SPS能有效去除TCS,紫外光波长为254nm,光强为11.5μW·cm-2,SPS浓度为1 mmol·L~(-1)时,100s后初始浓度为275μg·L~(-1)的TCS去除率可达98.15%,TCS降解过程符合拟一级反应动力学方程,其动力学常数K=0.039 2 s~(-1).实验范围内TCS去除的速率常数随紫外光强(I)和SPS投加量的增加而增大,波长对TCS去除影响不显著,中性条件不利于TCS降解,HA对TCS去除具有抑制作用.·OH和SO_4~(·-)与TCS反应速率常数分别为7.62×109L·mol~(-1)·s~(-1)、9.86×109L·mol~(-1)·s~(-1),UV254/SPS中主导自由基为SO_4~(·-),其对TCS去除贡献率为97.63%.UV254/SPS工艺更能有效地去除TCS,其拟一级动力学常数K值是UV254/H_2O_2工艺的4.13倍.TCS降解过程中主要生成了2,4-二氯苯酚(2,4-DCP)、苯酚等中间产物.     

零价铁-氧化剂联合降解土壤中硝基氯苯及土壤性质变化

硝基氯苯是重要的化工原料和中间体,其在土壤中的不断积累对生态环境和人体健康构成了严重威胁.高级氧化修复技术可以将有机污染物直接或间接矿化为CO_2和H_2O,从而成为近年来研究的重点.本文针对南京某化工厂搬迁遗留的硝基氯苯污染的场地土壤,研究了零价铁还原与氧化剂氧化的联合体系对硝基氯苯的降解率,并对反应过程的中间产物和动力学进行了分析,研究了降解后土壤性质的变化.结果表明,当采用KMnO_4、Fenton试剂、30%H_2O_2和Na_2S_2O_44种氧化剂直接氧化时,土壤中硝基氯苯的降解率分别为75.0%、62.9%、58.1%和41.5%;经零价铁还原1 h后,再施加氧化剂氧化处理,硝基氯苯降解率大幅提高,分别达到91.5%、88.5%、87.4%和70.4%.零价铁还原体系中间产物氯代苯胺浓度4 h时达到最大,施加氧化剂后迅速下降,4 h后下降至最低并维持较稳定水平;硝基氯苯氧化反应在单一氧化剂反应体系符合一级动力学方程,但在零价铁与氧化剂联合反应体系符合二级动力学方程;降解后的土壤性质有较大变化,CEC、TOC和土壤养分显著下降,Eh和EC显著增加,土壤pH除施加Na2S2O4下降显著外,施加KMnO_4、Fenton试剂、30%H_2O_2时下降较小,但同时添加零价铁土壤pH下降显著;土壤全N、全P、全K变化不显著,这些可为修复后土壤的再利用提供数据参考.