PD-DPR系统处理城市污水与高硝酸盐废水实现稳定亚硝酸盐积累和磷去除的特性

本研究以模拟城市污水和高硝酸盐废水为处理对象,在一个厌氧-缺氧-微曝气运行的SBR反应器内,将短程反硝化工艺(PD,NO_3~-→NO_2~--N)与反硝化除磷工艺(DPR)耦合,并通过联合调控进水C/N比、厌氧排水率和缺氧时间,考察了PD-DPR系统的亚硝酸盐积累特性和除磷性能.结果表明,经过140d,NO_3~-→NO_2~--N转化率(NTR)为80.1%,PO~(3-)_4-P去除率高达97.64%.在厌氧段(180 min),聚糖菌(GAOs)和聚磷菌(PAOs)对污水有机碳源进行充分利用,将其转化为内碳源;缺氧段(150 min),反硝化聚糖菌(DGAOs)和异养反硝化菌(DOHOs)分别进行内源和外源短程反硝化实现NO~-_2-N稳定积累,同时反硝化聚磷菌(DPAOs)进行高效反硝化吸磷;微曝气段(10 min),在不发生硝化反应的前提下,PAOs超量吸磷,提高了系统的除磷性能.系统出水NO~-_2-N/NH~+_4-N为1.31∶1(接近厌氧氨氧化工艺理论值1.32∶1),PO~(3-)_4-P浓度为0.30 mg·L~(-1),COD浓度为12.94 mg·L~(-1).其出水水质可满足与厌氧氨氧化(ANAMMOX)工艺耦合进行深度脱氮的需求.     

投加颗粒活性炭和二氧化锰对剩余污泥厌氧消化的影响

厌氧系统添加碳和金属纳米材料是强化厌氧消化的有效策略.为考察投加GAC和MnO₂对剩余污泥厌氧消化过程的影响,设置了空白组（R0）、GAC组（R1）、MnO₂组（R2）以及GAC/MnO₂组（R3）4组间歇实验,研究GAC和MnO₂的投加对剩余污泥厌氧消化效率、微生物活性和微生物群落结构的影响.结果表明,反应器运行28 d后,与R0相比,R1和R3的产CH₄速率分别提高了68.18%和51.35%,R2的产CH₄量降低了21.25%.GAC和MnO₂的单独或者混合投加,对厌氧发酵过程均有促进作用.Mn²⁺与剩余污泥释放的磷酸盐生成磷酸盐沉淀对厌氧代谢通道的阻塞作用,造成R2产CH₄效率变低.GAC优良导电性、吸附能力和MnO₂/Mn²⁺的催化作用是R3产CH₄效率增强的主要原因.正常代谢条件下,投加GAC、MnO₂和GAC/MnO₂均可以提高污泥厌氧消化系统微生物活性.微生物群落分析表明,GAC和MnO₂促进了产甲烷菌Methanobacterium和Methanosaeta的富集,强化了发酵细菌和产甲烷菌的种间电子传递,促进了剩余污泥厌氧发酵过程和CH₄的产生.     

连续流SNAD工艺处理猪场沼液启动过程中微生物种群演变及脱氮性能

为了实现合建式连续流同步部分亚硝化、厌氧氨氧化和反硝化SNAD(simultaneous partial nitrification,ANAMMOX,and denitrification)工艺处理实际猪场沼液,保持温度为(30±1)℃,控制溶解氧(DO)为(0.4±0.1)mg·L~(-1),首先通过逐步提高模拟进水氨氮浓度来实现SNAD工艺的启动,然后实现SNAD工艺处理实际猪场沼液的稳定运行.同时,采用高通量测序和实时定量PCR(qPCR)技术对反应器启动前后及沼液替换成功时关键生物种群进行分析.结果表明,150 d左右可实现SNAD工艺的启动, 298 d完成实际沼液的替换,其出水(NO~-_3-N+NO~-_2-N)/ΔNH~+_4-N小于0.11,对NH~+_4-N和TN的平均去除率为63.26%和55.71%.高通量测序结果表明,绿弯菌门(Chloroflexi,相对丰度50.78%)、变形菌门(Proteobacteria, 13.34%)、浮霉菌门(Planctomycetes, 9.26%)是沼液替换成功时污泥中的优势菌门;主要优势脱氮菌属Nitrosomonas的相对丰度由启动前1.55%增加到1.98%;两类具有厌氧氨氧化(ANAMMOX)功能菌Candidatus_Brocadia和Candidatus_Kuenenia的相对丰度分别从启动前0.01%和未检出(0.01%)增加到4.66%和4.18%;Denitratisoma作为主要的反硝化菌,丰度由启动前未检出(0.01%)增加到2.06%.qPCR结果表明,与接种污泥相比,沼液替换成功后AOB、ANAMMOX菌和反硝化菌的含量均有明显增加.将SNAD工艺用于实际猪场沼液处理,可实现高效稳定脱氮,节约后续处理成本.     

硝酸盐对土壤反硝化活性及蒽厌氧降解的影响

多环芳烃(polycyclic aromatic hydrocarbons,PAHs)在土壤中的反硝化降解是其厌氧去除的重要途径之一,但严格厌氧条件下反硝化电子受体(硝酸盐)对土壤反硝化活性及PAHs降解影响的报道还不多见.通过添加硝酸盐和蒽的厌氧微宇宙培养实验,探讨厌氧条件下硝酸盐对土壤蒽的厌氧降解及反硝化活性的影响.设置了不添加(N0)和添加硝酸盐(N30:30mg·kg~(-1))的两组处理,每组处理分别含3个蒽浓度(A0:0 mg·kg~(-1)、A15:15 mg·kg~(-1)、A30:30 mg·kg~(-1)),共6个处理(N_0A_0、N_0A_(15)、N_0A_(30)、N_(30)A_0、N_(30)A_(15)、N_(30)A_(30)).厌氧条件下25℃黑暗培养45 d,并于第3、7、15及45 d测定土壤N2O和CO2的产生速率、反硝化相关功能基因(nar G、nir K、nir S)丰度及蒽含量.结果表明,在培养第3 d检测到较强的反硝化活性,且硝酸盐及蒽均能显著促进土壤的反硝化酶活性.随着培养时间的延续,各处理中土壤反硝化活性急剧下降,蒽对土壤反硝化活性却表现出明显的抑制作用.方差分析的结果也表明,硝酸盐、蒽及其交互作用均能显著影响土壤的反硝化活性.3种反硝化功能基因中,只有narG和nirS基因的丰度在培养期间呈现逐渐升高的趋势,且它们能够受到硝酸盐、蒽及其交互作用的显著影响.厌氧条件下土壤蒽的最终去除率在33.83%~55.01%之间,添加硝酸盐对土壤蒽的去除率和降解速率均无显著影响,但高蒽含量(N_0A_(30)、N_(30)A_(30))处理的降解速率显著高于低蒽含量(N_0A_(15)、N_(30)A_(15))处理(P0.05).综上,硝酸盐的添加能显著影响土壤的反硝化活性及与反硝化相关的narG和nirS基因的丰度,但对土壤蒽的厌氧降解无显著影响.     

海洋厌氧氨氧化菌处理含海水污水的基质抑制及其动力学特性

采用ASBR反应器通过改变单一基质浓度分别研究了NH_4~+-N和NO_2~--N对海洋厌氧氨氧化菌脱氮效能的影响及其动力学特性.结果表明,保持进水NO_2~--N为105.6 mg·L~(-1),当进水NH_4~+-N浓度提高至1 200 mg·L~(-1)时,海洋厌氧氨氧化反应器仍保持较好的脱氮能力,未受到明显的抑制作用,NO_2~--N的去除率稳定在80.70%左右;当进水NO_2~--N浓度提高至265.6mg·L~(-1)时,反应器开始受到明显的抑制作用,NH_4~+-N的去除率下降至63.01%左右,随着进水NO_2~--N浓度继续提高至305.6mg·L~(-1)时,NH_4~+-N的去除率进一步下降至43.93%左右.利用Haldane模型和Aiba模型拟合NH_4~+-N和NO_2~--N抑制作用的动力学特性,得到了NRRmax、KS、Ki这3个动力学参数及出水基质浓度与总氮容积负荷(TNRR)之间的关系,根据进一步分析可知,Haldane模型更适合描述NH_4~+-N抑制作用下的动力学特性,Aiba模型更适合描述NO_2~--N抑制作用下的动力学特性,并得到NH_4~+-N和NO_2~--N的出水抑制浓度分别为3 893.625 mg·L~(-1)和287.208 mg·L~(-1),为海洋厌氧氨氧化菌处理含海水污水提供了理论依据.     

常温下加装脱硫装置的MCAnMBR处理高硫酸盐有机废水试验

研究了加装脱硫装置的沼气循环厌氧膜生物反应器对含高硫酸盐有机废水的处理效能.在26~34℃的室温下,历时63d成功地启动了加装脱硫装置的MCAnMBR反应器.调试初期,通过调节气路平衡和采用甲醇驯化的方法有效解决了MCAnMBR反应器在处理高硫酸盐有机废水时存在的跑泥和pH上升问题.结果表明,当控制HRT为120 h,有机负荷(以COD计)为3.61~4.36 kg·(m~3·d)~(-1),pH为7.18~7.61时,在23.3~25.4℃的室温下,对含SO_4~(2-)浓度为650~5 800 mg·L~(-1)的有机废水处理效果极佳,出水COD浓度最低可至23 mg·L~(-1),COD总去除率稳定在96.23%~99.77%,SO_4~(2-)还原率可达83.83%~95.51%.说明加装脱硫装置可有效解决硫化物的次级抑制作用问题,且通过梯度试验发现本反应器处理高硫酸盐有机废水的上限为:COD浓度18 000~21 000mg·L~(-1)、SO_4~(2-)浓度9082~9600 mg·L~(-1),COD/SO_4~(2-)为2.     

黄骅港三期筒仓防煤体高温对策研究

黄骅港三期是单个容量3万吨共24座筒仓的超大型群仓储煤系统,储煤主要来自神华集团所属煤矿,少部分为外购协作煤,多属易自燃煤种。为更有效控制火灾隐患,通过工艺流程分析及危险因素提取,试运营期间数据分析等,研究了致使煤体高温的危险因素和对策。发现运输过程中出现因雨淋而产生润湿热,因粉尘积聚发热的危险;筒仓储煤曾出现数天内温度从10℃升高到45℃,筒仓内有毒有害气体可能超限的危险;输煤皮带可能跑偏引起摩擦生热的危险等。试运营期间针对性采取了喷洒抑尘剂,设置警报系统及检测装置,加强皮带机监控和管理等安全措施。     

Chemically modified silica gel with 1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone: Synthesis, characterization and application as an efficient and reusable solid phase extractant for selective removal of Zn(II) from mycorrhizal treated fly-ash samples

1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone functionalized silica gel was synthesized and used as a highly efficient, selective and reusable solid phase extractant for separation and preconcentration of trace amount of Zn(II) from environmental matrices. The adsorbent was characterized by fourier transform infrared spectroscopy (FT-IR), elemental analysis,¹³C CPMAS NMR spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and BET surface area analysis. The dependence of zinc extraction on various analytical parameters such as pH, type and amount of eluent, sample flow rate and interfering ions were investigated in detail. The material exhibited superior adsorption efficiency for Zn(II) with high metal loading capacity of 1.0 mmol/g under optimum conditions. After adsorption, the recovery (> 98%) of metal ions was accomplished using 1.0 mol/L HNO₃ as an eluent. The sorbent was also regenerated by microwave treatment in milder acidic environment (0.1 mol/L HNO₃). The lower detection limit and preconcentration factor of the present method were found out to be 0.04 μg/L and 312.5 respectively. The modified silica surface possessed excellent selectivity for the target analytes and the adsorption/desorption process remained effective for at least ten consecutive cycles. The optimized procedure was successfully implemented for the extraction of Zn(II) from mycorrhizal treated fly ash and pharmaceutical samples with reproducible results.     

接种比例对酒糟与餐厨垃圾混合厌氧发酵产沼气的影响

采用酒糟与餐厨垃圾作为混合发酵物料,并接种消化污泥进行厌氧干式发酵,比较接种比例(inoculum to substrate ratios,ISRs)(VS质量比)分别为0.5、0.8、1.0、2.0时的甲烷产率和产量、体系VFA、碱度、游离氨等指标。结果表明:接种比例的提高可有效提高甲烷产生速率,缩短发酵周期,减弱较高浓度VFA引起的抑制作用。当ISRs=1.0时产甲烷效果较好,累计产甲烷率为222.58mL/g,VS去除率达83.4%,继续增加接种比例对发酵效果影响不显著。此外,试验中适宜的VFA/碱度值为0.3～1.2,过大或过小都有可能抑制产甲烷过程。     

Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents

Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2, and other two kinds of Pd-catalysts Pd(PPh₃)₄ and Pd₂(dba)₃. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.