Activated carbon supported TiO2-photocatalysis doped with Fe ions for continuous treatment of dye wastewater in a dynamic reactor

Fe-doped TiO2 coated on activated carbon (Fe-TiO2/AC, FTA) composites were prepared by an improved sol-gel method and characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray di ractometry, inductively coupled plasma mass spectrometry and BET surface area analysis. Obtained FTA composites were applied to the continuous treatment of dye wastewater in a dynamic reactor. The e ects of Fe ion content, catalyst content, UV-lamp power and flowrate of the continuous treatment of dye wastewater on degradation e ciency were analyzed to determine the optimum operating conditions of dye wastewater degradation. Continuous photocatalytic experiments provided interesting results that FTA had a high chemical oxygen demand (COD) removal rate compared with TiO2, Fe doped TiO2 (FT) and TiO2 coated on activated carbon (TA). In particular, when using the FTA catalyst with a Fe ion content of 0.33%, the kinetic content (k = 0.0376) of COD removal was more than the sum of both TA (0.0205) and 0.33% FT (0.0166). FTA showed a high photoactivity because of a synergistic e ect between Fe ions and AC on TiO2, which is higher than the individual e ects of AC or Fe ions on TiO2. Additionally, for the photocatalytic degradation of dye wastewater, the optimum Fe ion content, catalyst content, UV-lamp power and flowrate were 0.33%, 6 g/L, 60 W (two lamps) and 300 mL/hr, respectively. An investigation of catalyst reuse revealed that the 0.33% FTA showed almost no deactivation in photocatalytic degradation of naturally treated wastewater.     

ZVI/EDDS/Air体系降解水中2,4-二氯酚的研究

建立零价铁(ZVI)、乙二胺二琥珀酸(EDDS)和曝气三者组成的类Fenton(ZVI/EDDS/Air)处理体系,考察了初始EDDS浓度、铁粉投加量、曝气速率、2,4-二氯酚(2,4-DCP)浓度、初始pH以及反应温度等对水溶液中2,4-DCP降解的影响.结果表明,该体系能有效降解2,4-DCP,并且其降解规律符合准一级动力学方程.在2,4-DCP质量浓度100 mg·L-1、EDDS浓度0.80 mmol.L-1、铁粉投加量20 g·L-1、曝气速率为2 L.(min.L)-1的最佳实验条件下室温反应1 h,2,4-DCP的降解率达到99%.ZVI/EDDS/Air体系对氯酚的降解较ZVI/EDTA/Air体系具有环境友好、反应条件温和,而且对2,4-DCP的降解效果好等优点.     

零价铁与过硫酸盐异相芬顿降解活性艳橙X-GN

采用零价铁(Fe~0)与过硫酸盐构建异相类芬顿体系,由Fe0腐蚀释放Fe~(2+)催化S_2 O_8~(2-)产生硫酸根自由基快速降解偶氮染料活性艳橙,考察了初始p H值、Fe~0投加量、过硫酸盐投加量和温度对降解过程的影响。结果表明,当活性艳橙初始浓度为100 mg/L、pH值为7、Fe~0投加量为0.5 g/L、过硫酸盐投加量为1 mmol/L和反应温度为30℃时,反应60 min后活性艳橙降解率达到92.6%。酸性条件和提高反应温度均有利反应的进行,而且活性艳橙的降解率在初始pH值为9时也高于90%。反应过程符合准一级动力学,表观反应速率常数k为0.0513 min~(-1)(30℃)。UV-Vis扫描显示,活性艳橙的发色基团在反应过程中被破坏。由Fe~0与S_2O_8~(2-)构成的异相Fenton体系可作为一种高效手段用于染料废水的处理。     

负载型纳米TiO2/AC对偶氮染料的光催化降解研究

以钛酸四丁酯和粒状活性炭(AC)为主要原料,采用溶胶-凝胶-浸渍法制备出负载型纳米TiO2/AC催化剂.在流化床反应器中分别对2种典型的偶氮类染料橙黄G、活性艳红X-3B模拟废水进行了光催化降解研究,探讨了pH值、外加氧化剂对光催化降解率的影响,并对催化剂进行了回收再生利用试验.结果表明,TiO2/AC催化剂具有良好的光催化活性、吸附特性及可再生性,60 min后对2种染料反应的光催化降解率分别可达到99.71%和97 12%,反应180 min后的TOC去除率分别达到81.54%和81.99%;反应后TiO2/AC催化剂回收率大于95%,经焙烧再生后对橙黄G反应60 min的光催化降解率仍高达95.93%.     

UV-LED/NaClO工艺对水中对乙酰氨基酚的降解

采用NaClO、UV-LED和UV-LED/NaClO工艺去除水中的对乙酰氨基酚（AAP）,考察了NaClO投加量、pH值和腐殖酸（HA）等因素对UV-LED/NaClO工艺去除AAP的影响,研究了UV-LED/NaClO去除AAP过程中OH·、UV-LED、NaClO和氯自由基RCS（Cl·,Cl₂^·-,ClO·）的贡献值,评估了AAP降解过程中溶液急性毒性的变化.结果表明,UV-LED/NaClO可以有效降解.AAP.反应90min后,UV-LED、NaClO和UV-LED/NaClO工艺对AAP的去除率分别为4.42%、93.61%和100%.AAP的降解符合拟一级反应动力学模型（R²=0.9967）.AAP的去除随着NaClO投加量的增大而增加,中性条件有利于AAP的降解,HA对AAP去除具有抑制作用,HCO₃^-和NO₃^-可略微促进AAP的去除.当NaClO投加量为1mg/L,OH·、UV-LED、NaClO和RCS各组分对AAP去除的相对贡献率分别为0.82%、0.66%、33.78%和64.74%,UV-LED/NaClO工艺可以有效的降低溶液的急性毒性.     

臭氧-紫外光-活性炭联用氧化糠醛废水的研究

采用臭氧-紫外光-活性炭联用对糠醛废水进行了研究,实验考察了处理体系的pH值、糠醛废水的浓度、臭氧浓度、活性炭的使用次数以及臭氧-活性炭、臭氧-紫外光、臭氧-紫外光-活性炭联用几种不同工艺对糠醛去除效果的影响。结果表明,pH值为7.0、臭氧反应时间为160min、臭氧浓度为0.2mg/L,在此条件下进行处理,糠醛、废水的COD、BOD5的去除率可分别达到100%、54.3%、45.2%,废水的可生化性(BOD5/COD)由原来的0.37提高到0.61。活性炭可连续使用10次,对糠醛、废水COD的去除率没有太大影响。臭氧-紫外光-活性炭联用氧化糠醛废水的处理效果分别优于臭氧-活性炭、臭氧-紫外光联用。     

淀粉/ZVI-Ni-Cu三金属复合材料降解三氯乙烯和氯仿的效能

采用液相Na BH4还原法,制备出淀粉负载纳米铁镍双金属(淀粉/ZVI-Ni)和淀粉负载纳米铁镍铜三金属复合材料(淀粉/ZVI-Ni-Cu),并采用XRD、SEM、BET、XRF等仪器对其性能进行表征;进而对比其与纳米零价铁(ZVI)、淀粉负载零价铁(淀粉/ZVI)对三氯乙烯和氯仿的降解效果及影响淀粉/ZVI-Ni-Cu降解氯代烃的因素.结果表明:通过双金属和三金属的掺杂,可有效提高复合材料对氯代烃的降解,其降解效能关系为:淀粉/ZVI-Ni-Cu淀粉/ZVI-Ni/淀粉/ZVIZVI.其中淀粉/ZVI-Ni-Cu三金属复合材料在48 h内可实现氯代烃的完全降解.由于淀粉载体的加入,使得纳米金属材料成功地负载在淀粉上,复合材料的抗氧化性增强了,降解效果也更稳定可靠.     

Treatment and remediation of a wastewater lagoon using microelectrolysis and modified DAT/IAT methods

To examine treatment and remediation of a wastewater lagoon with poor biodegradability, a typical wastewater lagoon in Tianjin, China, was treated and remedied using microelectrolysis and modified demand aeration tank (DAT)/intermittent aeration tank (IAT) methods. After pretreatment by microelectrolysis, the removal e ciency of chemical oxygen demand (COD) was up to 64.6% and the ratio of BOC/COD in the e uent increased from 0.013 to 0.609. The removal rates of CODCr and NH+4 -N were a ected by sludge backflow rate, mixed liquor suspended solids (MLSS), and hydraulic retention time (HRT) in the modified DAT/IAT reactor. The highest removal rates of CODCr and NH+4 -N were up to 78.9% and 62.6%, respectively, when the sludge backflow rate was 38.0 mL/min, the total HRT was 8.0 hr and MLSS was 4088.0 mg/L. In this case, some protozoa and metazoa were observed in activated sludge and biofilm carriers. Most of chrominance was removed by microelectrolysis treatment, while the modified DAT/IAT methods were more e ective for CODCr and NH+4 -N removal.     

MOx颗粒活性炭镀层粒子电极对苯酚的电催化降解特性

为研究半导体金属氧化物颗粒活性炭镀层粒子电极苯酚电催化性能,采用溶胶-凝胶、氧化还原与热分解方法,将TiO₂、MnO₂与SnO₂-Sb和SnO₂-Sb-Mn纳米金属氧化物镀层于AC(颗粒活性炭)表面,制备了催化型粒子电极,使用X-射线衍射(XRD)、扫描电镜(SEM)及循环伏安曲线(CV)对其物相组成、微观形貌及电催化活性进行表征与分析. 结果表明,这4类金属氧化物可以不同赋存状态存在于AC表面,粒子电极表面活性组分晶格尺寸分别为10.64、11.34、14.68及13.50 nm;催化型粒子电极电催化活性明显高于未负载AC,各粒子电极电催化活性顺序为SnO₂-Sb-Mn/AC>TiO₂/AC>SnO₂-Sb/AC>MnO₂/AC. 半导体金属氧化物镀层可提高填充床电极反应器苯酚废水的催化降解性能,废水苯酚及COD_Cr去除率显著提升,TiO₂/AC、MnO₂/AC、SnO₂-Sb/AC及SnO₂-Sb-Mn/AC粒子电极在电流密度为8.0 mA/cm2的条件下连续电解2.72 h,出水苯酚及COD_Cr去除率分别为87.1%、92.8%、90.4%、100.0%和92.5%、89.3%、88.7%、97.2%,高于AC粒子电极的84.2%和79.1%,并且可消除苯酚电催化反应中醌类物质积累.      

4-CP在零价铁/H_2O_2体系中的降解研究

文章对4-氯酚在非均相零价铁/H2O2体系中的降解进行了实验研究。结果表明,4-氯酚能在低pH零价铁/H2O2体系中迅速降解。pH对降解具有重要影响,当pH大于5,4-CP降解效果<10%。同时在低pH(pH3)环境下考察了铁粉和H2O2投加量的影响,在最佳条件下对溶液中亚铁离子的形成和过氧化氢的分解进行了进一步的实验研究。最后在对中间产物分析的基础上提出了4-CP降解路径假设。     

NaClO、UV及UV/NaClO消毒过程中TCC的去除特性及遗传毒性

采用NaClO、UV和UV/NaClO复合消毒等方式研究了三氯卡班（TCC）在消毒过程中的去除特性,考察了3种消毒方式中TCC溶液的遗传毒性变化,鉴定了TCC的降解产物并探讨了其降解机制,以UV/NaClO复合消毒为研究对象,考察了NaClO投加量、TCC初始浓度、溶液pH值和腐殖酸（HA）等因素对TCC去除的影响.结果表明,3种消毒技术对TCC的去除效果依次为UV/NaClO、UV、NaClO.消毒处理不同程度增加了TCC溶液的遗传毒性.LC-MS鉴定出了8种TCC的降解产物,降解途径主要为脱氯、加氯以及·OH/O^·氧化.UV/NaClO复合消毒对TCC的去除率在97%以上;TCC的去除与其初始浓度呈负相关;TCC的去除率随pH值的增大先升高后降低;低浓度的腐殖酸（HA）对TCC的去除有促进作用,高浓度则相反.     

UV/NaClO和UV/过碳酸钠工艺降解水杨酸的对比

采用UV/NaClO和UV/过碳酸钠(SPC)工艺降解水中水杨酸(SA),对比考察了氧化剂种类和投加量对SA去除的影响,采用淬灭法和电子顺磁共振波谱仪(EPR)鉴定识别了 2种工艺中的自由基,通过竞争动力学的方法计算了 SA与·OH、CO3·-的二级反应速率常数及反应体系中不同组分的贡献,从环境水样模拟、急性毒性和经济...     

Reductive transformation and detoxification mechanism of 2,4-dinitrochlorobenzene in combined zero valent iron and anaerobic-aerobic process

A combined zero valent iron (ZVI) and anaerobic-aerobic process was adopted for the treatment of 2,4-dinitrochlorobenzene (DNCB)-containing wastewater. The transformation pathway, reduction of acute toxicity and enhancement of biodegradability were investigated. After pretreatment by ZVI, DNCB in wastewater could be completely converted into 2,4-diaminochlorobenzene (DACB). The ratio of BOD₅/COD increased from 0.005 ± 0.001 to 0.168 ± 0.007, while EC_{50, 48 hr} (V/V) increased from 0.65% to 5.20%, indicating the enhancement of biodegradability and reduction of acute toxicity with the pretreatment by ZVI. DACB was further dechlorinated to m-phenylenediamine during the anaerobic process using methanol as electron donor, with EC_{50, 48 hr} increasing from 5.20% to 48.2%. After the subsequent anaerobic-aerobic process, m-phenylenediamine was degraded completely, with effluent COD of 67.5 ± 10.8 mg/L. This effluent of the subsequent anaerobic-aerobic process was not toxic to zebrafish. The combined ZVI and anaerobic-aerobic process offers bright prospects for the treatment of chlorinated nitroaromatic compound-containing wastewater.     

Enhancing anoxic denitrification of low C/N ratio wastewater with novel ZVI composite carriers

External organic carbon sources are needed to provide electron donors for the denitrification of wastewater with a low COD/NO₃^--N（C/N） ratio, increasing the treatment cost. The economic strategy is to enhance the bioactivity and/or biodiversity of denitrifiers to efficiently utilize organic substances in wastewater. In this study, novel zero-valent iron（ZVI） composite carriers were prepared and implemented in a suspended carrier biofilm reactor to enhance the bioactivity an...     

Enhancement of formaldehyde degradation by amine functionalized silica/titania films

Doping amine functional groups into SiO2/TiO2 films for enhancing the decomposition of formaldehyde has been investigated using the modified sol-gel method to prepare organic-inorganic hybrid photocatalysts via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and amine functional groups. n-(2-Aminoethyl)-3-aminopropyl-trimethoxysilane (AEAPTMS) and 3-aminopropyl-trimethoxysilane (APTMS) were selected to study the e ect of amine functional groups on the enhancement of formaldehyde adsorption and degradation under a UV irradiation process. Physicochemical properties of prepared photocatalysts were characterized with nitrogen adsorption-desorption isotherms measurement, X-ray di raction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. The results indicated that the APTMS/SiO2/TiO2 film demonstrated a degradation e ciency of 79% superior to those of SiO2/TiO2 and AEAPTMS/SiO2/TiO2 films due to the synergetic e ect of adsorption and photocatalytic properties. The APTMS/SiO2/TiO2 film can be recycled with about 7% decreasing of degradation e ciency after seven cycles.     

Oxidation of gaseous elemental mercury in a high voltage discharge reactor

Effects of the voltage waveform, discharge tooth wheel number and CO2/NO/SO2 concentration in the simulated flue gas on Hg0 oxidation were investigated using a link tooth wheel-cylinder reactor energized by di erent high voltage power supplies. Negative DC discharge induced more ozone production and a higher Hg0 oxidation e ciency than positive DC discharge and 12 kHz AC discharge. The discharge tooth wheel number had almost no e ect on the maximum Hg0 oxidation e ciency. The allowable supplied voltage decreased with the increase of discharge tooth wheel number. CO2 could stabilize the discharge process and increase the maximum voltage for a stable discharge. It has also been found that NO consumed O3 induced by high voltage discharge, thereby decreased Hg0 oxidation e ciency; while SO2 had a slight promoting e ect on Hg0 oxidation.     

Biodegradation of 2-naphthol and its metabolites by coupling Aspergillus niger with Bacillus subtilis

To explore biodegradation of 2-naphthol and its metabolites accumulated in wastewater treatment, a series of bio-degradation experiments were conducted. Two main metabolites of 2-naphthol, 1,2-naphthalene-diol and 1,2-naphthoquinone, were identified by high-performance liquid chromatography with standards. Combining fungus Aspergillus niger with bacterium Bacillus subtilis in the treatment enhanced 2-naphthol degradation e ciency, lowered the accumulation of the two toxic metabolites. There were two main phases during the degradation process by the kinetic analysis: 2-naphthol was first partly degraded by the fungus, producing labile and easily accumulated metabolites, and then the metabolites were mainly degraded by the bacterium, attested by the degradation processes of 1,2-naphthalene-diol and 1,2-naphthoquinone as sole source of carbon and energy. Sodium succinate, as a co-metabolic substrate, was the most suitable compound for the continuous degradation. The optimum concentration of 2-naphthol was 50 mg/L. The overall 2-naphthol degradation rate was 92%, and the CODCr removal rate was 80% on day 10. These results indicated that high degradation rate of 2-naphthol should not be considered as the sole desirable criterion for the bioremediation of 2-naphtholcontaminated soils/wastewater.     

亚铁活化次氯酸钠降解土壤中阿特拉津

通过考察NaClO添加量、n（Fe2+）:n（NaClO）、反应时间、土壤pH、腐植酸与无机阴离子对阿特拉津降解效率的影响,对比Fe2+/NaClO氧化处理后土壤微生物群落的变化情况,探究了FeSO₄活化NaClO对土壤中阿特拉津的降解性能。结果表明:当NaClO添加量为10 mmol,n（Fe2+）:n（NaClO）为1:1时,阿特拉津降解效率最佳,为82%;其降解符合一级反应动力学模型;Fe2+/NaClO体系比单独的NaClO可产生更多的·OH参与阿特拉津降解;降解过程受土壤pH（3~9）影响较小;腐植酸和无机阴离子（Cl-、HCO₃-）对阿特拉津降解有消极影响。经过Fe2+/NaClO处理后土壤微生物门类丰度发生明显变化,如Proteobacteria门丰度由25.46%变化为72.73%。     

工业铁屑(零价铁)还原硝基苯影响因素研究

通过静态试验,研究了初始硝基苯浓度、零价铁含量和pH值对零价铁还原硝基苯的影响.结果表明,在pH值为7,硝基苯初始浓度为311.25mg/L条件下,零价铁含量分别是100、50和25g/L时,硝基苯的降解速率常数分别是-0.02991、-0.0165和-0.00783min-1,零价铁含量越大硝基苯的降解速率越大;在pH值为7,零价铁含量为50g/L条件下,硝基苯的初始浓度分别是127.5,311.25,467.01mg/L时,硝基苯的降解速率常数分别是-0.01532、-0.01235和-0.00891min-1;在硝基苯初始浓度为311.5mg/L,零价铁含量为50g/L条件下,pH值为2.94时,硝基苯的降解速率最大,pH值为7其次,pH值为11.89时的降解速率最小,酸性环境利于零价铁还原硝基苯的进行.由此可见,硝基苯浓初始浓度、零价铁含量和pH值对硝基苯的还原具有重大影响.     

草酸改性零价铁活化过硫酸盐降解地下水中2,4-DNT的研究

2,4-二硝基甲苯(2,4-DNT)作为重要的化工原料,由于储存和生产过程中的“跑冒滴漏”,已然成为地下水中常见有毒有害污染物之一,对人体健康和生态环境安全造成极大威胁. 以草酸与商品零价铁为原料,通过球磨法制备草酸化零价铁(OA-ZVIbm),并研究其活化过硫酸盐(PS)降解2,4-DNT的性能. 采用扫描电子显微镜(SEM)、X射线衍射(XRD)和傅里叶变换红外光谱(FT-IR)对活化剂进行表征,并考察活化剂和PS投加量、溶液初始pH及无机阴离子对2,4-DNT降解效果的影响. 结果表明:①通过球磨改性,零价铁表面氧化层被草酸亚铁壳层代替,加速铁核腐蚀生成Fe2+催化PS. ②在pH=7、0.2 g/L OA-ZVIbm和5 mmol/L PS的条件下,4.0 h内对50 mg/L 2,4-DNT降解率达到87.6%,降解过程符合准一级动力学方程. ③2,4-DNT降解率随OA-ZVIbm和PS投加量增加以及溶液初始pH的降低增加,但高浓度PS会抑制2,4-DNT的降解;NO₃?、CO₃2?、Cl?和SO₄2?通过淬灭自由基或者与亚铁离子发生共沉淀,对降解产生不同程度的抑制效果. ④自由基淬灭试验表明,体系中同时产生SO₄? ?、·OH和1O₂,但SO₄? ?在降解过程中起主导作用. ⑤降解中间产物鉴定表明,通过脱硝和氧化反应,2,4-DNT被降解成包括间苯二酚、丙二酸在内的毒性较小分子,可生化性显著提高. 研究显示,OA-ZVIbm能够高效活化PS,实现对地下水2,4-DNT的显著降解,具有一定的应用前景.