吸附法处理甲基叔丁基醚污染物的研究进展

MTBE对地表水和地下水的污染已日益引起国内外的高度重视。对MTBE的性质、污染现状、处理技术及近年来国内外应用吸附法处理MTBE的研究进展作了一般综述,对分子筛、活性炭及吸附树脂这三种吸附剂对MTBE的吸附效果作了评述,对影响MTBE吸附效果的主要因素进行了讨论,并对吸附法处理MTBE的应用前景作了展望。     

地下水循环井技术处理土壤和地下水中甲基叔丁基醚研究

研究了MTBE在砂土中的静态吸附以及采用地下水循环井技术(GCW)去除砂土和地下水中MTBE的衰减规律。结果表明:MTBE在砂土中的吸附动力学符合准二级动力学方程,相关系数R2为0.99618,在砂土中的吸附平衡时间为24 h;吸附热力学符合Linear平衡吸附,吸附系数为0.00306 m3/kg。GCW运行30 h后,地下水饱和含水层中MTBE浓度由500 mg/L降至72.5 mg/L,去除率为85.5%;砂土中MTBE的吸附量由0.93 mg/g降至0.03 mg/g,去除率达96.4%。水平方向距GCW越近,MTBE的去除效率越快,垂直方向位于GCW上部的MTBE优先会被去除,最佳修复时间为运行15 h。GCW对砂土和地下水中高浓度MTBE具有良好的修复效果。     

不同粒径粉末活性炭对水中天然有机物吸附性能的比较研究

以吸附去除微污染水中天然有机物(natural organic matter,NOM)为目标,考察了粉末活性炭(PAC)在10~100μm内的粒径变化对其吸附性能的影响,并探讨了PAC粒径变化对不同相对分子质量NOM组分的分级吸附特性.3种不同粒径的PAC由市售PAC经过研磨筛分获得,按照中值粒径(d50)从小到大依次为:PAC-1(19μm)、PAC-2(46μm)和PAC-3(76μm).吸附实验结果表明,无论对模拟水样还是实际微污染水体中的NOM,随着PAC粒径的减小,PAC对NOM的吸附容量和吸附速率都显著提高.小粒径PAC吸附速率的增加一方面是由于粒径减小导致的有效吸附位点的增加,另一方面粒径减小也使得吸附质分子到达活性炭表面吸附位点的距离减小;而吸附容量的增加主要是由于粒径较小的PAC具有更大的外层比表面积和中孔孔容,有效减弱了相对分子质量大的NOM对活性炭的孔阻塞效应.此外,PAC粒径减小能显著增强其对天然水体中相对分子质量大于2 000的有机物组分的吸附,而对相对分子质量小于800的有机物组分的吸附影响相对较小.     

超滤处理东江水不可逆膜污染物的识别和活性炭对其吸附去除

利用超滤实验以及6种粉末活性炭吸附东江水有机物的水质数据,通过三维荧光光谱-平行因子分析(EEMPARAFAC),考察东江水中造成不可逆膜污染的主要组分和活性炭吸附这些组分的效果;随后进行活性炭对不可逆膜污染组分吸附效果与对应活性炭孔结构参数的相关性分析,揭示活性炭的表面物理性质对不可逆膜污染物吸附的影响.EEMPARAFAC模型识别出东江水含有2个类腐殖质荧光组分C1和C3,以及1个类蛋白质(类色氨酸)荧光组分C2,其中C2为主要不可逆膜污染物.同时,所有活性炭对3种荧光组分均有较好的吸附效果,其中对主要膜污染物C2的去除率可达54.0%~74.6%.相关性分析发现,活性炭对主要膜污染荧光组分C2吸附效果受活性炭微孔表面积的影响,而活性炭对两种次要膜污染荧光组分C1和C3吸附效果受活性炭中大孔表面积和BET比表面积影响.实验结果可为活性炭-超滤工艺处理东江水的活性炭选型提供技术指导.     

改性活性炭除亚砷酸盐的性能研究

制备了2种负载铁锰氧化物的改性活性炭（FM-GAC-1、FM-GAC-2）并研究其对水中的亚砷酸盐的去除性能.考察了2种改性活性炭除三价砷的吸附等温线、反应动力学及pH、温度、水中共存离子对其去除三价砷的影响,发现FM-GAC-1和FM-GAC-2对三价砷均有较好的去除效果,吸附容量分别为32.37、 26.67 mg·g^-1.吸附速率符合拟二级反应动力学,化学反应控制过程是改性活性炭除砷的限速步骤.pH值偏酸性有利于吸附的进行,温度升高,吸附容量有所下降,该吸附过程是自发的放热过程.同时,水体中的共存阴离子在其浓度值为三价砷的200倍时,SiO^2-₃、 PO^2-₃、NO^-₃对FM-GAC-1吸附三价砷有明显影响; SiO^2-₃、CO^2-₃对FM-GAC-2吸附三价砷有显著影响.总体上讲,FM-GAC-1较FM-GAC-2有更为优异的去除三价砷性能.     

载溴活性炭去除烟气中的单质汞

为提高活性炭对烟气中单质汞的吸附作用,利用溴对活性炭进行处理.通过对吸附容量和吸附动力学的测试,研究了载溴活性炭对气体中的单质汞的去除行为.结果表明,载溴可使活性炭对单质汞的吸附量显著增加,并加快对单质汞的吸附速率.实验条件下,当载溴量为0.33%时,活性炭对汞的饱合吸附量可增加约80倍,吸附容量达0.2mg/g;相对吸附系数增加了约40倍.溴负载量越高,吸附强化作用越显著.温度升高,载溴活性炭的吸附能力略有下降,烟气中的二氧化硫对单质汞的吸附速率略有抑制作用.     

溴酸根在颗粒活性炭上的还原

小试研究了溶液中溴酸根在颗粒活性炭上还原与溴离子生成的过程,考察pH、离子强度、温度和初始浓度对该过程的影响.结果表明,活性炭对溴酸根的去除性能与表面碱性官能团有一定相关性.其它阴离子对吸附/还原过程有阻碍作用,实验中影响顺序为ＮＯ^-₃>SO^２－₄ > Cl^-.溴酸根的吸附与溴离子的生成可分别用拟二级速率方程和粒子内扩散模型进行模拟,绝大部分相关系数在0.97以上.低pH和低离子强度有利于溴酸根的吸附与还原.15～42℃范围内吸附与还原速率随温度提高先降低后升高.实验中活性炭对溴酸根的最大吸附容量可达到769.23 μmol/g（98.4 mg/g）,但反应较慢且易受干扰.推测活性炭表面微孔部分对溴酸根的吸附也受到溴离子释放的阻碍.     

中孔结构对活性炭吸附卷烟烟气中有机物的影响

卷烟烟气中复杂化合物对大气环境的污染已经引起了全世界的关注.因此,本文以颗粒活性炭为原料,通过硝酸钙、水蒸气调控得到比表面积、微孔容量丰富且含有较高中孔率的介孔活性炭,研究了孔结构对三醋酸甘油酯和挥发性有机物吸附的影响.结果表明:活性炭对三醋酸甘油酯的吸附主要受到比表面积和微孔的影响,中孔对其吸附性能没有太明显的作用;中孔结构对苯、甲苯、丙酮的吸附可以起到明显的通道效应,大大提高了活性炭对挥发性有机物的去除能力.     

大孔强碱阴树脂去除饮用水中微量有机物

比较了大孔强碱阴树脂和颗粒活性炭在饮用水的深度处理中对有机物的去除效果。结果表明：(1)大孔强碱阴树脂的吸附容量比颗粒活性炭的大。在pH为8时,大孔强碱阴树脂对TOC的去除率最高。pH6～8时,对TOC的去除率没有明显的区别,而颗粒活性炭在pH为2时。对TOC的去除率最高;水温低能提高2种吸附材料的吸附容量。(2)在动态实验条件下。当流速相同,大孔强碱阴树脂的穿透时间明显比颗粒活性炭的长,大孔强碱阴树脂的制水量约是吸附床的10000倍。而颗粒活性炭却只有吸附床的4000倍。在饮用水的深度处理中,大孔强碱阴树脂可作为活性炭的最佳替代品。     

5种颗粒活性炭对水中卤乙酸的等温吸附试验

通过等温吸附实验,考察了5种不同类颗粒活性炭(GAC)对消毒副产物卤乙酸(HAAs)中致癌风险较高的二氯乙酸、三氯乙酸的吸附行为.结果表明:二氯乙酸、三氯乙酸的吸附行为符合Langmuir等温式;进口活性炭A对二氯乙酸饱和吸附量是3种国产活性炭的4.4～5.7倍,是另一种进口活性炭B的3.8倍;对三氯乙酸的饱和吸附量是3种国产活性炭的4.0～5.4倍,是另一种进口活性炭B的2.6倍.针对进口活性炭A开展的进一步研究结果表明,二氯乙酸、三氯乙酸2组分的相对吸附量与2组分的相对浓度成正比关系,二氯乙酸吸附容量变化对平衡浓度的敏感程度不如三氯乙酸.     

O3/H2O2法降解甲基叔丁基醚（MTBE）的试验研究

采用自制鼓泡反应器对臭氧/双氧水(O3/H2O2)降解水中甲基叔丁基醚(MTBE)进行了试验研究,考察了进气(含O3)流量、H2O2 投加量、MTBE初始浓度、pH、温度等因素对MTBE降解的影响.结果表明,在MTBE初始浓度为10 mg·L-1,气体流量为0.5 L·min-1,温度293K, pH=6.5, H2O2 添加量为2.4mg·L1 条件下,反应30 min后, MTBE去除率可达75.5%, COD去除率为68.0%.降解得到的中间产物主要有叔丁基甲酯(TBF)、叔丁醇(TBA)、乙酸甲酯(MA)和丙酮(AC)等,据此探讨了O3/H2O2氧化MTBE的可能反应机理和降解途径.     

Aerobic degradation of methyl tert-butyl ether by a Proteobacteria strain in a closed culture system

The contamination of methyl ten-butyl ether （MTBE） in underground waters has become a widely concerned problem all over the world. In this study, a novel dosed culture system with oxygen supplied by H2O2 was introduced for MTBE aerobic biodegradation. After 7 d, almost all MTBE was degraded by a pure culture, a member of β-Proteobacteria named as PMI, in a closed system with oxygen supply, while only 40% MTBE was degraded in one without oxygen supply. Dissolved oxygen （DO） levels of the broth in closed systems respectively with and without H2O2 were about 5-6 and 4 mg/L. Higher DO may improve the activity of monooxygemase, which is the key enzyme of metabolic pathway from MTBE to tert-butyl alcohol and finally to CO2, and may result in the increase of the degrading activity of PM1 cell. The purge and trap GC-MS result of the broth in closed systems showed that tea-butyl alcohol, isopronol and acetone were the main intermediate products.     

Sensitivity of green and blue-green algae to methyl tert-butyl ether (MTBE) during a fifteen-day test

The test was designed to assess the toxicity of methyl tert-butyl ether (MTBE) to Chlorella ellipsoidea and Aphanizomenon flos-aquae during 15 d with concentrations of MTBE from high (2.00×104 mg/L) to low (2 mg/L). The results showed that the toxicity was low when the concentration of MTBE was 1.00×104-2.00×104 mg/L (the greatest inhibition of growth-rate was 70%-71%, occurring on day 1-5). Low concentrations (2-500 mg/L) stimulated algal growth up to the greatest effect of 85%-200% when the concentration of MTBE was 50-100 mg/L on day 3-5. The low concentrations may lead to an algal bloom owing to overabundance, which represents an aquatic ecological risk. However, the stimulatory effect occurred only during the day 1-5 and disappeared gradually during the day 13-15. The toxicity of MTBE (72-120 h EC50) is 6.65×103-9.58×103 mg/L for C. ellipsoidea and that is 1.14×104-2.00×104 mg/L for A. spiroides. We found that the toxicity and ecological risk of MTBE for the algal community structure were low. The toxicity was influenced by the duration of the test. We suggest that the duration of the test should not be shorter than half a life-cycle.     

生物滴滤塔净化甲基叔丁基醚废气的研究

应用生物滴滤塔处理甲基叔丁基醚废气,研究其挂膜启动及稳定运行阶段的降解性能,并考察了稳定期该系统的生物群落结构.结果表明,生物滴滤塔在停留时间为60 s,进气质量浓度为100 mg·m~(-3)的条件下,运行23 d后完成挂膜,填料上的生物量明显增加,去除率可维持在70%以上.反应器稳定运行时,去除负荷可达13.47 g·(m3·h)~(-1),矿化率可达68%;用Haldane模型拟合生物滴滤塔中去除负荷的变化趋势,获得理论ECmax为21.03 g·(m3·h)~(-1),KS为0.16 g·m~(-3),KI为0.99g·m~(-3).运用高通量测序技术分析生物膜中的微生物群落结构,发现其中优势菌属为Methylibium sp.和Blastocatella sp.,分别占11.33%和9.95%.     

Degradation of MTBE and TBA by a new isolate from MTBE-contaminated soil

Methyl ten-butyl ether （MTBE）, a gasoline additive, possesses serious problems to the environmental health. In the present study, a bacterial culture named A-3 which could effectively degrade MTBE was isolated from the MTBE contaminated soil. The isolate was identified as Chryseobacterium sp., a new species capable of degrading MTBE. In order to enhance its degradation ability, selected environment factors were investigated. The results showed that the optimal temperature was in the range of 25-30℃, the pH was 7.0, the inoculum size was 2 × 10^8 CFU/ml and the optimal concentration of MTBE was from 50 to 100 mg/L. The maximum MTBE utilization rate （Vmax） was 102 nmol MTBE/（mg cell protein.h）. Furthermore, it was found that the isolate could also degrade tert-butyl alcohol （TBA）. The degradation rates of TBA were much faster than those of MTBE. The additional TBA would lead to the decrease of the initial MTBE degradation rate and the inhibitory effect of TBA increased with the increase of TBA concentration. Similar protein profiles at least seven peptides were demonstrated after SDS-PAGE analysis of crude extracts obtained from the cells growing in MTBE and TBA culture.     

Sensitivity of green and blue-green algae to methyl tert-butyl ether

The toxicity of methyl tert-butyl ether (MTBE) to Chlorella ellipsoidea and Aphanizomenon flos-aquae was tested and assessed for a 15-d incubation with concentrations of MTBE from high (2.00×104 mg/L) to low (2 mg/L). The results showed that the toxicity was low when the concentration of MTBE was in the range 1.00×104-2.00×104 mg/L (the greatest inhibition of growth-rate was 70%-71%, occurred during the day 1-5). Low concentrations (2-500 mg/L) stimulated algal growth up to the greatest effect of 85%-200% w...     

车用汽油及含氧燃料的环境效应

基于7辆国6轻型车的WLTC循环测试,计算了汽油?E10和MTBE10(汽油中添加10％体积的甲基叔丁基醚)排放的温室气体的致暖效应(GWP)、臭氧生成潜势(OFP)和非甲烷有机气体(NMOG)排放.结果表明,车队平均N2O和CH4排放的GWP分别为0.6和0.07g CO2e/km.E10和MTBE10的非CO2温室...     

甲基叔丁基醚毒性研究综述

对国内外有关甲基叔丁基醚毒性的研究结果作了综述。目前的研究结果表明，不同的个体之间对ＭＴＢＥ及其代谢产物具有一定的遗传毒性和轻微的生殖毒性；可诱导肝细胞色素Ｐ－４５０活性的升高；多数试验显示，ＭＴＢＥ具有动物致癌效应；不同学者对于长期低浓度接触情况下，ＭＴＢＥ对人体健康可能会产生的影响存在争论。