氧气促进纳米零价铁除砷效果及其作用机制

为了探究氧气对纳米零价铁(nZVI)除砷的影响,考察了不同的氧含量(厌氧、低氧、中氧和高氧)条件下nZVI对As(Ⅲ)/As(V)的去除效果,并结合表征结果分析了氧气对nZVI除砷的影响机制。结果表明：氧气存在会显著促进nZVI对As(Ⅲ)/As(Ⅴ)的去除,但不同氧含量对nZVI除砷的促进程度有所不同;随着氧含量的增加,As(Ⅲ)/As(Ⅴ)的去除率呈现先增大后减小然后再增大的趋势。在初始砷浓度为50 mg·L⁻¹、nZVI投加量为200 mg·L⁻¹、O₂/nZVI摩尔比等于0.5时,砷的去除率达到最大,As(Ⅲ)和As(Ⅴ)体系中砷的去除率分别为96.27%和51.75%。固相表征结果表明：氧气对nZVI的氧化程度及除砷效果具有较大的影响,在低氧条件下,nZVI被少量氧化为无定型铁矿物进而提高除砷效果;在中氧条件下,nZVI被氧化为大量的溶解态Fe(Ⅱ)/Fe(Ⅲ),溶解态铁对砷没有去除效果,从而导致砷的去除率降低;在高氧条件下,nZVI被大量氧化,溶解态Fe(Ⅱ)/Fe(Ⅲ)进一步被氧化形成新的无定型铁矿物,可增强除砷效果。以上结果可为评估不同氧含量条件下纳米零价铁除砷效果以及人为强化纳米零价铁除砷效果提供参考。     

复合铁添加物对混合有机固废厌氧产氢的影响

将城镇污水处理厂的城市污泥与餐厨垃圾混合后,经厌氧消化处理后可产生能源气体氢气,从而达到资源化利用的目的.废铁屑是机械加工厂的固体废弃物,将其处理后可得到一种新型复合铁材料(FE/FEO).将城市污泥和餐厨垃圾预处理后按体积比1:1比例混合,分别等分放入2个反应器中,一个投加FE/FEO粉末作为为FE/FEO组,另一个...     

In situ sequential treatment of a mixed contaminant plume

Groundwater plumes often contain a mixture of contaminants that cannot easily be remediated in situ using a single technology. The purpose of this research was to evaluate an in situ treatment sequence for the control of a mixed organic plume (chlorinated ethenes and petroleum hydrocarbons) within a Funnel-and-Gate. A shallow plume located in the unconfined aquifer at Alameda Point, CA, was found to contain up to 218,000 μg/l of cis-1,2 dichloroethene (cDCE), 16,000 μg/l of vinyl chloride (VC) and <1000 μg/l of 1,1 dichloroethene (1,1 DCE), trans-1,2 dichloroethene (trans-1,2 DCE) and trichloroethene (TCE). Total benzene, toluene, ethylbenzene and xylenes (BTEX) concentrations were <10,000 μg/l. Contaminated groundwater was funneled into a gate, 3.0 m wide, 4.5 m long and 6.0 m deep (keyed into the underlying aquitard) where treatment occurred. The initial gate segment consisted of granular iron, for the reductive dechlorination of the higher chlorinated ethenes. The second segment, the biosparge zone, promoted aerobic biodegradation of petroleum hydrocarbons and any remaining lesser-chlorinated compounds, stimulated by dissolved oxygen (DO) and carbon dioxide (CO₂) additions via an in situ sparge system (CO₂ was used to neutralize the high pH produced from reactions in the iron wall). Groundwater was drawn through the gate by pumping two wells located at the sealed, downgradient, end. Over a 4-month period an estimated 1350 g of cDCE flowed into the treatment gate and the iron wall removed 1230 g, or 91% of the mass. The influent mass of VC was 572 g and the iron wall removed 535 g, corresponding to 94% mass removal. The other chlorinated ethenes had significantly lower influent masses (3 to 108 g) and the iron wall removed the majority of the mass resulting in >96% mass removal for any of the compounds. In spite of these high removal percentages, laboratory column tests indicated that at these levels of chlorinated contaminants, surface saturation of the iron grains likely contributed to lower than expected reaction rates. In the biosparge zone, mass removal of cDCE appeared to occur predominantly by biodegradation (65%) with volatilization (35%) being an important secondary process. The dominant removal process for VC was volatilization (70%) although significant biodegradation was also indicated (30%). Laboratory microcosm results confirmed the potential for aerobic biodegradation of cDCE and VC. When average influent field concentrations for cDCE and VC were 220,000 and 46,000 μg/l, respectively, the sequential treatment unit removed 99.6% of the total mass and when the influent concentrations decreased to 26,000 and 19,000 μg/l for cDCE and VC, respectively, >99.9% removal within the treatment gate was attained. BTEX compounds were found to be significantly retarded in the iron treatment zone. Although they did eventually break through the granular iron, and into the gravel transition zone, none of these compounds was detected in the biosparge zone. No noticeable interferences between the anaerobic (reductive) and aerobic parts of the system occurred during testing. The results of this experiment show that in situ treatment sequences are viable, although further work is needed to optimize performance.     

铁氧化物/活性炭对饮用水中Sb(V)的吸附性能及机理

采用液相沉积法制备了铁氧化物/活性炭复合材料(Fe₂O₃@AC),通过单因素实验和正交实验优化了材料的制备条件,使用SEM、FTIR、XRD、XPS等分析方法对材料的形貌和性质进行了表征分析,通过吸附实验探究了Fe₂O₃@AC吸附除锑的效果及影响因素,并进一步对吸附除锑的机理进行了深入探讨。结果表明：最佳制备条件为纯水:乙醇:=4:1,Fe²⁺:Fe³⁺=1:1,总铁浓度为0.594 mol·L⁻¹,制备液pH=1.88。Fe₂O₃@AC吸附除锑的能力较其他金属基材料和活性炭有明显提高,锑原水质量浓度为38 μg·L⁻¹,Fe₂O₃@AC投加量为0.08 g·L⁻¹,吸附平衡后水中锑的去除率达97%,剩余锑质量浓度为1.06 μg·L⁻¹,满足国家饮用水卫生标准要求。微观表征显示铁氧化物颗粒成功负载于活性炭上,且铁氧化物晶体的结构完好。吸附反应符合准二级动力学和Langmuir等温模型,吸附反应以单层化学吸附为主,吸附类型为液膜扩散,颗粒内扩散,质量扩散的叠加形式。吸附方式为共沉淀,及溶解态锑与固相铁氧化物形成络合物,参与反应的官能团为—OH、—COOH、—Fe—OH、—Fe—O—Fe。     

纳米零价铁与黑曲霉发酵液联用对砷锑污染土壤的淋洗修复

土壤砷 (As) 、锑 (Sb) 污染对生态环境和人体健康有着潜在的风险,采用黑曲霉发酵液 (FB) 与纳米零价铁 (nZVI) 联用淋洗修复As、Sb污染土壤。通过振荡淋洗实验,探究nZVI强化FB淋洗去除As、Sb的效果及不同条件下对As、Sb淋洗效率的影响。结果表明,制备的FB对污染土壤中As和Sb有着较好的去除效果,去除率可达84.1%和71.8%;nZVI对FB去除As、Sb有强化作用,在nZVI质量浓度为0.1 g·L⁻¹、pH为1和淋洗时间为60 min的条件下,其淋洗效果最佳,对As、Sb淋洗效率可达96.6%和95.6%,修复后的土壤达到《土壤环境质量 建设用地土壤污染风险管控标准 (试行) 》 (GB 36600-2018) 二类用地标准。nZVI-FB对土壤中As、Sb的解吸动力学符合拟二级动力学方程。nZVI-FB能够有效的提取土壤中As、Sb的铁铝氧化物结合态。本研究结果可为As、Sb复合污染土壤的淋洗修复提供参考。     

印染污泥与铁尾矿磁化焙烧回收铁资源

我国铁尾矿累计堆存量超1×10¹⁰ t,主要为难选的赤铁矿、褐铁矿、菱铁矿等,由于脉石矿物组成复杂,重金属等有害杂质含量高,难以直接资源化利用。利用铁尾矿与印染污泥共同磁化焙烧,回收铁尾矿和印染污泥中铁资源,研究了焙烧温度、焙烧时间和印染污泥掺烧量对铁品位和铁回收率的影响及作用机制。最佳焙烧条件为,800 °C、30 min、印染污泥掺烧量15%,对焙烧产物进行120 mT的湿法磁选,得到铁品位63.78%,回收率92.58%的铁精矿。铁尾矿中的针铁矿失水留下孔隙转化为赤铁矿,进而被还原为磁铁矿,其还原路径为FeO(OH)→Fe₂O₃→Fe₃O₄。SEM+MAPPING分析结果表明,磁化焙烧后赤铁矿和铝化合物的连生体被破坏,通过磁选可提升铁精矿品位及回收率。本研究可为印染污泥和铁尾矿的协同处理及资源化利用提供参考。     

钢铁企业节水评价指标体系的构建

针对中国钢铁行业尚未建立节水评价指标体系的现状,在广泛查阅资料的基础上,遵循科学合理性、目标导向性、实用性和可比性的原则,构建了钢铁企业节水评价指标体系。指标体系的建立使钢铁企业的节水成效具有横向和纵向可比性,有利于调动企业的节水积极性,促进节水技术的发展和推广,为钢铁企业开展节水工作指明目标和方向。     

零价铁耦合芬顿氧化法处理TNT红水

采用零价铁耦合芬顿氧化法处理TNT红水,研究了初始pH、零价铁投加量、过氧化氢（H2O2）投加量及温度对红水中总有机碳（TOC）去除效果的影响,同时进行了TOC去除过程中反应动力学的探讨。结果表明,零价铁耦合芬顿氧化体系可有效降解TNT红水中的2,4-二硝基甲苯-3-磺酸钠和2,4-二硝基甲苯-5-磺酸钠。在初始pH为2,温度为20 ℃的条件下,加入1.5 g·L-1零价铁反应1 h后,再加入100 mL·L-1H2O2反应4 h,红水中二硝基甲苯磺酸盐浓度从500 mg·L-1降至0 mg·L-1,去除率为100%,TOC浓度从150 mg·L-1降至30 mg·L-1,去除率达到80%。反应中TOC的降解过程遵循拟二级反应动力学方程。零价铁耦合芬顿氧化法可以作为TNT红水的有效处理途径。     

纳米零价铁和零价铁对餐厨垃圾暗发酵制氢过程铁离子和酶活性的影响

通过投加不同浓度的纳米零价铁(NZVI)和零价铁(ZVI),考察了暗发酵制氢过程中铁离子组成和浓度变化、氢化酶和脱氢酶活性,研究了2种添加剂强化餐厨垃圾高温((55±1) ℃)暗发酵制氢的作用机制。结果表明：投加NZVI和ZVI均可提高餐厨垃圾暗发酵制氢性能;当投加100 mg·L⁻¹ ZVI时,产氢效果最佳,最大产氢潜力和最大产氢速率分别为425.72 mL和66.32 mL·h⁻¹,是投加NZVI实验组的1.64倍和1.34倍,代谢途径是以乙醇型发酵为主的混合型发酵;在投加NZVI和ZVI后,暗发酵制氢末端产物的Fe²⁺和Fe³⁺浓度升高,投加300 mg·L⁻¹ NZVI和100 mg·L⁻¹ ZVI实验组Fe²⁺浓度最大,是未投加实验组的2倍和1.87倍;与反应前相比,Fe²⁺显著升高,Fe³⁺由于微生物利用与转化浓度降低,同时可有效提高氢化酶活性。投加100 mg·L⁻¹ ZVI不仅可提高氢化酶活性,还可提高脱氢酶活性。以上结果可为提高餐厨垃圾等复杂有机废物的高效能源化提供参考。     

硫酸盐还原菌污泥固定化特性

采用玉米芯为碳源,聚乙烯醇(PVA)为包埋载体,饱和硼酸(H3BO3)为交联剂,研究了硫酸盐还原菌污泥(SRBS)、铁屑、麦饭石共固处理合成煤矿酸性废水的最优配比与机理,并分析了固定化过程中小球稳定性及活性的变化规律。实验结果表明,SRBS投加量是影响处理效果的最显著因子,当投加30%SRBS、2%铁屑、3%麦饭石时SO42-、Mn2+去除率分别为94.13%和84.39%,溶液pH为7.03,未检测出Fe2+;随着交联时间的延长,小球膨胀率及SO42-还原率分别呈线性与指数下降,从保持小球稳定性与活性角度考虑,可将交联时间设定为4~8 h;该法可为市政污泥的处置以及生物法处理煤矿酸性废水的工程应用提供技术参考。