UV/TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜,研究了UV-Vis/TiO2以及UV/TiO2/H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况.研究结果表明,TiO2在暗处对酞酸酯没有降解作用;UV/TiO2体系能有效光降解DBP和DEHP,TiO2具有明显的光催化作用,增强因子分别为fDBP=2.06,fDEHP=1.53;在一定浓度范围内DBP在UV/TiO2体系中的降解速率与其初始浓度成负一级动力学关系;UV/TiO2/H2O2体系对DBP的光降解能力远大于UV/TiO2和UV/H2O2体系,H2O2能显著提高TiO2的光催化活性.     

UV／TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜，研究了UV-Vis／TiO2以及UV／TiO2／H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明，TiO2在暗处对酞酸酯没有降解作用；UV／TiO2体系能有效光降解DBP和DEHP，TiO2具有明显的光催化作用，增强因子分别为，fDBP=2．06，fDEHP=1．53；在一定浓度范围内DBP在UV／TiO2体系中的降解速率与其初始浓度成负一级动力学关系；UV／TiO2／H2O2体系对DBP的光降解能力远大于UV／TiO2和UV／H2O2体系，H2O2能显著提高TiO2的光催化活性。     

TiO2/H2O2/UV和TiO2/O3/UV降解对氯苯甲酸和喹啉的试验研究

主要叙述TiO2/H2O2/UV和TiO2/O3/UV体系降解对氯苯甲酸（4-CBA）和喹啉的试验研究.研究表明,（1）在TiO2/H2O2/UV体系里目标物降解速度先随过氧化氢投加量的增加而提高,但超过一定浓度之后便开始下降;（2）在TiO2/O3/UV体系中,目标降解物的反应速度都非常快,且臭氧浓度高的时候降解速度更快;（3）二氧化钛催化剂在TiO2/O3/UV体系中作为积极因素有助于提高反应速率,而在TiO2/H2O2/UV体系是消极因素,会降低反应速率.     

TiO2/H2O2/UV和TiO2/O3/UV降解对氯苯甲酸和喹啉的试验研究

主要叙述TiO2/H2O2/UV和TiO2/O3/UV体系降解对氯苯甲酸(4-CBA)和喹啉的试验研究.研究表明,(1)在TiO2/H2O2/UV体系里目标物降解速度先随过氧化氢投加量的增加而提高,但超过一定浓度之后便开始下降;(2)在TiO2/O3/UV体系中,目标降解物的反应速度都非常快,且臭氧浓度高的时候降解速度更快;(3)二氧化钛催化剂在TiO2/O3/UV体系中作为积极因素有助于提高反应速率,而在TiO2/H2O2/UV体系是消极因素,会降低反应速率.     

UV/H2O2/草酸铁络合物光降解邻苯二甲酸二丁酯研究

研究了邻苯二甲酸二丁酯(DBP)在UV/H2O2/草酸铁络合物体系中的光降解.结果表明,UV/H2O2/草酸铁络合物能有效地光解DBP;在pH值为4时,DBP光解速率最快,中性和碱性条件下光解效率降低;DBP的光解速率随H2O2浓度的升高而增大,但H2O2浓度较大时,其对·OH的清除作用使DBP的光解速率减慢;[Fe3 ]/[C2O42]＜1/10,DBP光解速率随Fe3 浓度增大明显提高,[Fe3 ]/[C2O42]＞1/10时,引起DBP光解速率的增加不明显.     

4种高级氧化法处理高浓度正丙醇废水的动力学比较

研究了1%和10%(V/V)模拟正丙醇废水在UV/TiO2体系、UV/H2O2体系、Fe2+/H2O2体系和UV/TiO2/Fe2+/H2O2体系等4种工艺条件下的降解动力学过程,对比了降解动力学特点及工艺参数对动力学常数的影响,优化工艺参数。结果表明,UV/TiO2体系和Fe2+/H2O2体系的降解过程可分为零级反应阶段和一级反应阶段,转折点分别在反应开始后2 h和氧化剂浓度为6.7 g/L,UV/H2O2体系和UV/TiO2/Fe2+/H2O2体系分别符合零级反应和一级反应规律;相同工艺参数条件下,6 h反应后,组合工艺UV/TiO2/Fe2+/H2O2体系在处理效率达85%,比前3个体系分别高52.0%、8.3%和32.0%,与UV/TiO2体系和Fe2+/H2O2体系的处理效率之和持平,其协同效应提高了速率常数,在目标物浓度降低时依然可维持较高降解速率。而目标物浓度提高10倍后,UV能量利用率提高35.5倍,氧化剂用量是Fe2+/H2O2体系的1/7.1。     

光催化降解水体异味物质2-MIB的机理

以水体异味物质2-甲基异莰醇(2-methylisoborneol,2-MIB)为研究对象,在紫外光(λ<380 nm)照射下,探讨TiO2(P25)对2-MIB的光催化降解特性及光化学作用机理。结果表明,UV/TiO2光催化体系可以有效去除水体异味物质2-MIB,紫外光照射60 min,对2-MIB的降解率达95%。同时研究了光催化降解体系介质pH,共存腐殖酸(HA)和过硫酸钾(K2S2O8)对UV/TiO2光催化体系降解2-MIB的影响,发现低浓度HA([HA]≤0.5 mg/L)可以提高2-MIB降解速率,当HA浓度高于0.5 mg/L,2-MIB降解反应受到抑制;同时当加入电子受体K2S2O8后,降解体系中活性物种羟基自由基(.OH)明显增加,提高了TiO2对2-MIB的降解能力。利用苯甲酸荧光光度法和POD-DPD显色法跟踪测定降解过程中羟基自由基(·OH)和过氧化氢(H2O2)的变化,表明光催化反应涉及·OH机理。     

酸性红R在UV-蒙脱土KSF-H_2O_2体系中光降解行为研究

以紫外杀菌灯(波长为254nm)为光源,研究了酸性红R在由蒙脱土KSF和H2O2组成的类Fenton体系中的光降解行为,研究了反应体系pH、H2O2浓度对偶氮染料酸性红R光催化降解的影响,分析了酸性红R的光降解动力学规律。结果表明:对于100mg/L的酸性红R,在pH为3.0、66mg/L的H2O2和质量浓度为1g/L的蒙脱土条件下,在UV/类Fenton体系可以获得较高的反应速率,经50min的光照,酸性红R的光降解率为87.2%;而在类Fenton体系中的光降解率只有56%左右,可见UV对类Fenton体系有明显的协同作用;酸性红R的光降解动力学规律符合Langmuir-Hinshelwood方程,反应速率常数为1.82mg/(L·min)。     

UV/TiO2光催化降解水体中的邻苯二甲酸二甲酯

酞酸酯是环境中普遍存在的有机污染物(内分泌干扰物)之一。利用UV/TiO2光催化降解水体中的邻苯二甲酸二甲酯(DMP),讨论了溶液pH、TiO2投加量及DMP初始浓度等因素对DMP降解的影响。结果表明,DMP为10mg/L左右时,TiO2投加量为0.2～0.5g/L、pH=7是比较理想的降解条件;DMP初始浓度越高,其降解率则越低。研究了Langmuir-Hinshelwood模式下DMP在TiO2表面的吸附与催化活性的关系,发现DMP主要通过吸附在催化剂的表面而非在溶液本体中发生降解。线性回归计算所得光照条件下的吸附常数远大于无光照条件下的吸附常数,可能是由于UV和TiO2体系之间产生协同效应,提高了UV/TiO2体系对DMP的降解效果。另外,初步分析了可能的降解反应机制。     

Fenton试剂协同TiO_2光催化降解三氯乙酸及协同机理

为了研究Fenton试剂协同TiO2光催化降解三氯乙酸(TCAA)的反应及其协同机理,在自制的光催化反应装置中分别考察了Fenton、UV/TiO2及Fenton/UV/TiO23个反应对TCAA的降解情况。研究结果表明,在TCAA初始浓度为2.0 mg/L,TiO2用量为1.0 g/L,紫外辐射光源为15 W(λmain=254 nm)的实验条件下,Fenton试剂协同TiO2光催化降解TCAA反应在pH 3~7范围内均有较高的降解率;TCAA在Fenton、UV/TiO2及Fenton/UV/TiO23个反应中的一级反应速率常数分别为0.0009、0.0131和0.0456 min-1;Fenton试剂与TiO2光催化反应间存在较明显的协同效应,其协同机理主要体现在两个方面:一是紫外光激发Fe(OH)2+和H2O2分解产生更多的·OH,二是Fenton试剂中部分被氧化成的Fe3+可与TiO2表面的光生电子结合被还原为Fe2+,抑制了光生电子与空穴的复合,从而提高了TiO2光催化降解TCAA的效率。     

镍网负载纳米TiO_2光催化反应器对酸性品红脱色效果实验研究

采用负载纳米TiO2的三维镍网装配了光催化反应器,就其对酸性品红溶液进行脱色效果进行了实验研究。考察了反应器的3种装配条件、品红初始浓度、pH值、H2O2投加量、紫外光剂量等因素对酸性品红脱色效果的影响。结果表明:UV灯+镍网+TiO2模式组合的反应器脱色效果最好;在相同的处理时间内酸性品红溶液的脱色率随起始浓度的增大而减小;将酸性品红溶液pH值调至5时脱色效果最明显,70 min的脱色率可高达94.8%。脱色效果还可以通过溶液中添加H2O2和控制紫外线剂量来调节。当溶液中H2O2投加量为0.5 g/L时,处理70 min后的脱色率可高达98.3%;到达反应界面紫外光剂量越多则能够获得越高的酸性品红脱色率。     

Occurrence and microbial degradation of phthalate esters in Taiwan river sediments

Concentrations and microbial degradation rates were measured for eight phthalate esters (PAEs) found in 14 surface water and six sediment samples taken from rivers in Taiwan. The tested PAEs were diethyl phthalate (DEP), dipropyl phthalate (DPP), di-n-butyl phthalate (DBP), diphenyl phthalate (DPhP), benzylbutyl phthalate (BBP), dihexyl phthalate (DHP), dicyclohexyl phthalate (DCP), and di-(2-ethylhexyl) phthalate (DEHP). In all samples, concentrations of DEHP and DBP were found to be higher than the other six PAEs. DEHP concentrations in the water and sediment samples ranged from ND to 18.5 μg/l and 0.5 to 23.9 μg/g, respectively; for DBP the concentration ranges were 1.0–13.5 μg/l and 0.3–30.3 μg/g, respectively. Concentrations of DHP, BBP, DCP and DPhP were below detection limits. Under aerobic conditions, average degradation half-lives for DEP, DPP, DBP, DPhP, BBP, DHP, DCP and DEHP were measured as 2.5, 2.8, 2.9, 2.6, 3.1, 9.7, 11.1 and 14.8 days, respectively; under anaerobic conditions, respective average half-lives were measured as 33.6, 25.7, 14.4, 14.6, 19.3, 24.1, 26.4 and 34.7 days. In other words, under aerobic conditions we found that DEP, DPP, DBP, DPhP and BBP were easily degraded, but DEHP was difficult to degrade; under anaerobic conditions, DBP, DPhP and BBP were easily degraded, but DEP and DEHP were difficult to degrade. Aerobic degradation rates were up to 10 times faster than anaerobic degradation rates.     

Biodegradation of phthalate esters during the mesophilic anaerobic digestion of sludge

Phthalic acid esters (PAE) are commonly found in the sludge generated in the wastewater treatment plants. Anaerobic digestion followed by land application is a common treatment and disposal practice of sludge. To date, many studies exist on the anaerobic biodegradation rates of PAE, especially of the easily biodegradable ones, whereas the higher molecular weight PAE have reported to be non-biodegradable under methanogenic conditions. Furthermore, there is no information on the effect of the PAE on the performance of the anaerobic digesters treating sludge. In this study, the anaerobic biodegradation of di-n-butyl phthalate (DBP), di-ethyl phthalate (DEP) and di-ethylhexyl phthalate (DEHP) was investigated and their relative rates of anaerobic degradation were calculated. Also, the biological removal of PAE during the anaerobic digestion of sludge in bench-scale digesters was investigated using DBP and DEHP as model compounds of one biodegradable and one recalcitrant PAE respectively. The degradation of all the PAE tested in this study (DEP, DBP and DEHP) is adequately described by first-order kinetics. Batch and continuous experiments showed that DEP and DBP present in sludge are rapidly degraded under mesophilic anaerobic conditions (a first-order kinetic constant of 8.04 x 10(-2) and 13.69 x 10(-2)-4.35 day(-1) respectively) while DEHP is degraded at a rate between one to two orders of magnitude lower (0.35 x 10(-2)-3.59 x 10(-2) day(-1)). It is of high significance that experiments with anaerobic sludge of different origin (US and Europe) showed that degradation of DEHP occurs under methanogenic conditions. Accumulation of high levels of DEHP (more than 60 mg/l) in the anaerobic digester has a negative effect on DBP and DEHP removal rates as well as on the biogas production.     

组合工艺去除垃圾渗滤液中的DBP和DEHP

探讨了采用实验室规模的生物处理组合工艺(上流式厌氧污泥床+曝气生物滤池+缺氧反应器+膜生物反应器,UASB+BAF+ANO+MBR)处理垃圾渗滤液过程中,邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DE-HP)两种内分泌干扰物在各工艺段的去除效率和机理。测定结果表明,对于DBP和DEHP浓度分别为164.4μg/L和215.0μg/L的原水,总出水浓度分别降至11.8μg/L和10.4μg/L,去除率分别达到92.9%和95.2%,处理效果良好。其中DBP在处理工艺中逐级降解,主要是微生物的降解作用。MBR是DEHP的主要去除工艺段,去除比例达到56.6%,膜截留效果明显。采用生物处理组合工艺可实现对垃圾渗滤液中DBP和DEHP的同时高效去除。     

臭氧光催化降解水中甲醛的研究

研究比较了3种光化学方法对水中低浓度甲醛的降解效果,考察了初始pH值、甲醛浓度和臭氧投加速率等因素对臭氧光催化(TiO_2/UV/O_3)降解甲醛的影响。结果表明,紫外臭氧(UV/O_3)、光催化(TiO_2/UV)和TiO_2/UV/O_3对甲醛的降解均符合表观一级反应动力学,TiO_2/UV/O_3降解甲醛的一级表观速率常数大于TiO_2/UV与UV/O_3之和,说明臭氧、光催化有明显的协同作用。pH值对臭氧光催化降解甲醛的速率几乎没有影响;甲醛初始浓度增加,表观反应速率常数下降,但甲醛的绝对去除量仍随初始浓度的增加而显著增加;臭氧投加速率增加,降解速率增加。甲醛降解的主要中间产物为甲酸,但甲酸在臭氧光催化反应过程中也快速降解而被矿化,说明臭氧光催化是一种能安全有效去除甲醛的方法。     

TiO2薄膜光催化降解双酚A的研究

采用sol-gel法制备TiO2薄膜.以该薄膜为催化剂,研究了在H2O2存在的条件下,对内分泌干扰物质双酚A的光催化降解反应.分别讨论了pH值、H2O2的加入量、双酚A的初始浓度以及光照时间对降解反应的影响.结果表明,在pH=4,30 mg/L的H2O2中对初始浓度为50 mg/L的双酚A溶液光照180 min有较好的降解效果.     

Effect of DBP/DEHP in vegetable planted soil on the quality of capsicum fruit

Field experiment was conducted to investigate the di-n-butyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) contamination in Capsicum annum fruit grown in DBP and DEHP contaminated soil, and to evaluate the effect of DBP and DEHP on the quality of capsicum fruit. The top layer soil (0-10 cm) of plots was treated with a mixture of DBP and DEHP (1:1 w/w) and capsicum seedlings were transplanted. After 90 days, capsicum fruit, shoot and root samples were collected. DBP and DEHP concentration in various parts of the samples were determined by gas chromatography. Vitamin C and capsaicin contents in fruit were determined using 2,4-dinitrophenylhydrazine colorimetric analysis and sodium nitrite-sodium molybdate colorimetric analysis, respectively. The results showed that DBP concentration in fruit, shoot and root increased with the increase of soil-applied DBP/DEHP concentration, but DEHP was not detected in all samples. When the soil-applied DBP/DEHP concentration was 5, 10, 20, 40, 80 and 160 mg kg(-1) soil, compared with control, vitamin C and capsaicin content in capsicum fruit decreased by 1.6%, 5.9%, 10.6%/o, 18.2%, 19.2%, 22.6% and 1.6%, 2.5%, 12.9%, 20.1%, 22.2%, respectively. Pearson correlation analysis demonstrated that the decrease of vitamin C and capsaicin content was negatively correlated to the increase of DBP concentration in capsicum fruit, which suggested that DBP uptake by the plant might be mainly responsible for quality degradation of capsicum fruit.     

固相萃取—气相色谱—质谱测定再生水中邻苯二甲酸酯类物质

探讨了一种再生水中邻苯二甲酸酯类物质的测定方法——固相萃取—气相色谱—质谱,检测了相关再生水标准中涉及的邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)两类物质。在质量浓度为20～1 000μg/L时,两类物质的回归方程的相关系数均大于0.999,检出限分别是0.060、0.002μg/L,DBP、DEHP的相对标准偏差分别为4.1%～7.4%、5.1%～6.1%。利用固相萃取技术进行预处理,平均加标回收率为96.6%、89.6%。检测了北京市4座再生水厂出水中DBP和DEHP含量,其中,DBP在1.74～5.59μg/L,低于《城市污水再生利用景观环境用水水质》(GB/T 18921—2002)规定的限值(不超过0.1mg/L),但高于《城市污水再生利用地下水回灌水质》(GB/T 19772—2005)规定的限值(不超过3μg/L);DEHP在0.42～4.93μg/L,满足GB/T 19772—2005要求(不超过8μg/L)。     

混凝-催化氧化-水解酸化-生物接触氧化法处理染料废水的中试研究

采用混凝-催化氧化-水解酸化-生物接触氧化法处理高浓度难降解分散染料废水.比较分析了O_3、UV/TiO_2/O_3,UV/O_3/H_2O_23种高级氧化法的处理效果.结果表明,UV/TiO_2/O_3对废水COD和色度有较高的去除率.可明显改善废水的可生化性,废水的BOD_5/COD由0.05～0.07升高至0.42～0.46.在混凝沉淀单元HRT为1.5 h.催化氧化单元(UV/TiO_2/O_3)HRT为3.0 h,水解酸化HRT为10.0 h,生物接触氧化HRT为10.0 h的最佳条件下,该组合工艺对废水COD和色度总的去除率分别可达95.0%、99.5%.