颗粒活性炭吸附去除水中三氯乙烯的研究

通过吸附容量实验及微型快速穿透(MCRB)实验,考察了7种活性炭对水样中三氯乙烯(TCE)的去除效果.结果表明,表征活性炭对小分子化合物吸附容量的苯酚值可以预测各种活性炭对TCE的吸附容量;国内常用炭型对TCE的吸附性能与国际常用炭型相当.性价比更高;不同TCE初始浓度及低浓度甲醇对TCE吸附容量没有明显的影响,而自来水中天然有机物(NOM)的竞争吸附作用会降低活性炭对TCE的吸附容量;MCRB实验数据提供了较为准确的TCE平衡吸附容量.验证了各种活性炭对TCE的相对吸附容量,并显示使用2个串联活性炭炭床可以提高吸附容量利用率,节省处理费用,确保出水达标.     

简易水处理活性炭的选择和应用方法

首先介绍活性炭性能测试与水处理活性炭选炭、吸附技术选择、工艺应用的关系,其次报导两个活性炭选用方面的改进方法。通过重新定义、整合、完善现有活性炭性能指标,建立了以酚值、碘值、亚甲基蓝、丹宁酸值为吸附性能指标的选炭方法。这四种指标化合物的分子量与直径覆盖了大多数有机污染物的范围,用此法可减少活性炭应用测试的炭型。在活性炭精选和吸附工艺应用研究中,用微型炭柱进行穿透实验可弥补缩小式传统型、小型炭柱的不足。相对于国外现用微型柱的实验方法,文中介绍的微型柱快速穿透（MCRB）方法的设备要求较低,操作简单,可以在国内大多数实验室中进行;遇过对多种污染物质的实验结果,建立了MCRB方法的可信性和适用性。这两种新方法完善了活性炭水处理研究的实验体系,可降低其应用于水与污水处理的成本,有利于中国的环境保护。     

生物活性炭吸附工艺去除地下水中甲基叔丁基醚的可行性研究

甲基叔丁基醚(MTBE)是一种常见的汽油添加剂,但汽油油箱和地下储油罐的泄漏.造成了汽油及添加剂对地下水的污染.实验分析了生物活性炭吸附工艺去除地下水中MTBE的可行性,结果表明:(1)处理高MTBE进水(模拟新污染的地下水)实验时,对椰壳活性炭(简称椰壳炭)柱,煤质活性炭(简称煤质炭)柱采用菌液循环接种法接种来自美国...     

活性炭纤维吸附含溴甲烷气体的性能

采用动态吸附法在25℃下,测定了3种活性炭纤维(ACF-1、ACF-2和ACF-3)对含溴甲烷气体的吸附性能和回收效果,并对活性炭纤维的孔结构进行表征.探讨了孔结构、溴甲烷浓度、气体流量、循环使用次数等因素对活性炭纤维吸附溴甲烷性能的影响.结果表明,活性炭纤维比表面积大小及0.4～0.8 nm左右的微孔数量决定了其对溴甲烷吸附性能的优劣;气体中溴甲烷的浓度的提高使活性炭纤维对溴甲烷的穿透和饱和吸附量增加,而气体流量的增加则使活性炭纤维对溴甲烷的穿透和饱和吸附量降低,但两者均使穿透和饱和吸附时间缩短;活性炭纤维多次循环使用后,对溴甲烷的吸附容量明显地降低,循环12次后达到稳定吸附,其稳定吸附值为133.5 mg/g.     

新型水处理活性炭选型技术

活性炭依其原料不同、生产工艺不同,而有不同的吸附性能.使用简易的活性炭选型方法,可以减少应用测试时的备选炭型,从而大大降低活性炭水处理技术的运行成本.以碘值、甲基蓝值、苯酚值和丹宁酸值4种吸附容量性能指标为依据的活性炭选型技术,可以有效地预测活性炭对于水中各种大小不同污染物的去除能力.BET测试结果证明了这4项指标数据对于活性炭孔径分布预测的准确性.2,4-二氯苯酚和腐殖酸等目标化合物的吸附容量实验结果也都验证了这4项指标的预测功用,说明这种简便的活性炭选型技术有着广泛的应用价值.     

电化学法合成金属有机骨架化合物对含氧挥发性有机物的吸附性能

使用电化学法合成了3种金属有机骨架化合物(MOFs)Cu-BTC、MIL-100(Al)、ZIF-8,测定了3种MOFs对代表性含氧挥发性有机物(VOCs)异丙醇与乙酸乙酯的平衡吸附容量,并结合不同湿度条件下的穿透实验,考察了MOFs对于含氧VOCs的吸附性能。结果表明,ZIF-8对异丙醇和乙酸乙酯的平衡吸附容量最大,通过Langmuir模型拟合所得的异丙醇和乙酸乙酯理论最大吸附容量分别达到了530、613mg/g。在穿透实验中,总体上看,ZIF-8对异丙醇、乙酸乙酯的吸附容量利用率也最大,达到90.9%和87.8%。而随着湿度增加,3种MOFs的吸附容量利用率均下降。相比Cu-BTC和MIL-100(Al),ZIF-8在高湿度条件下能保持最佳的吸附性能。当相对湿度从3%±2%增加到90%±2%后,其对异丙醇、乙酸乙酯的穿透吸附量仅下降10.9%和22.7%。3种MOFs重复使用4次后仍能保持较好的吸附性能。     

去除饮用水中三卤甲烷和腐殖酸的活性炭选型方法

三卤甲烷(THMs)是水中天然有机物在氯化消毒过程中产生的对人体有致癌作用的挥发性有机物,腐殖酸是生成消毒副产物的主要前驱物.活性炭吸附是去除THMs和腐殖酸最常用的方法.不同炭型的活性炭对THMs和腐殖酸的吸附容量并不相同.以饮用水中最常见的THMs(即三氯甲烷)和腐殖酸为吸附对象,进行煤、椰壳和果壳3种不同材质活性炭的吸附容量实验.实验结果验证了苯酚值预测各类活性炭对小分子THMs吸附性能以及丹宁酸值预测各类活性炭对大分子腐殖酸吸附性能的有效性.具有丰富微孔和表面氧化程度较低的上海椰壳炭YK-2和上海果壳专用炭对三氯甲烷的吸附容量比上海原煤破碎高,大孔丰富的上海果壳专用炭和上海原煤破碎对腐殖酸的吸附性能高.将实验结果与美国环保局RREL(Risk Reduction Engineering Laboratory)水污染物处理数据库中相关信息对比发现,相比国外常用活性炭,国产活性炭对三氯甲烷的吸附性能与之相当或略高,具有更好的性价比,应用前景广阔.     

活性炭吸附对印染废水深度处理的研究

活性炭吸附处理可使印染废水生化出水符合直接排放或回用的标准.对不同活性炭进行性能指标测试,据此筛选出对大分子有机物吸附性能较好的3种不同材质的括性炭(混合炭、原煤炭和果壳炭),并进行吸附容量实验.同时,考察不同空床接触时间(EBCT)下的微型快速穿透(MCRB)实验.结果表明,果壳炭在3种备选炭中COD去除率和活性炭吸附容量利用率最高;1个大中型炭柱中的EBCT为20 min的果壳炭床至少可以连续使用8 d才需更换新炭,而后置炭床的串联会保证出水在8 d后继续达到<纺织染整工业污染物排放标准>(GB 4287-1992)中一级排放标准(COD<50 mg/L).     

甲基叔丁基醚（MTBE）在不同粘性土壤中的吸附特性

土壤对有机物的吸附是污染土壤及地下水原位修复技术中的重要参数.通过静态间歇吸附实验研究了甲基叔丁基醚(MTBE)在不同粘性土壤中的吸附特性.结果表明,MTBE在粘性土壤中的吸附行为均可用线性方程很好描述,粘粒是土壤对MTBE吸附的主要影响因素,吸附常数与土壤粘粒含量呈y=4.382×10-3x-0.817 ×10-3直线关系.对不同温度下的吸附数据分析发现,粘性土壤对MTBE的平衡吸附量随温度的升高而降低,由吸附热力学推导可得等量吸附焓变△H与平衡吸附量无关,且△H＜0,表明该吸附为故热过程.     

废弃物基活性炭吸附挥发性有机污染物特性的研究

研究了废弃物基活性炭对挥发性有机污染物中的典型组分--甲苯的吸附特性.结果表明,废弃物基活性炭吸附甲苯等温线的类型系优惠型吸附等温线,表明具有良好的吸附能力;同时其吸附甲苯时穿透时间的对数与甲苯入口浓度的对数之间具有良好的线性相关性,即可由吸附高浓度甲苯时的穿透时间估算低浓度时的穿透时间;动态吸附时废弃物基活性炭的中孔对甲苯亦具有一定的吸附性能.     

微型快速穿透实验技术在活性炭液相吸附中的应用

穿透实验为液相吸附应用中预测实际活性炭床运行的必要测试.微型快速穿透(MCRB)实验技术采用粉碎筛分后的微小颗粒活性炭和微型穿透柱,可以加快实验速度、节省时间和资源,同时避免传统穿透实验中常遇到的问题.该实验技术操作较简单、用途广泛和设备要求较低,适合在国内大多数实验室中进行.MCRB实验技术弥补中国微型穿透实验的空白,与中小型、小型穿透柱实验方法构成完整活性炭穿透实验方法体系.     

Remediation of MTBE from drinking water: air stripping followed by off-gas adsorption

The widespread use of methyl tertiary butyl ether (MTBE) as an oxygenate in gasoline has resulted in the contamination of a large number of ground and surface water sources. Even though air stripping has been proven to be an effective treatment technology for MTBE removal, off-gas treatment often is required in conjunction with it. This study evaluated the combined treatment technologies of air stripping followed by off-gas adsorption on a pilot scale for the treatment of MTBE-contaminated water. The effect of air/water ratios on the treatment efficiency was studied, and the mass transfer coefficient was determined. Air/water ratios of 105:1, 151:1, 177:1, 190:1, 202:1, and 206:1 were used, and a treatment efficiency of >99% was achieved for all the runs conducted. The depth of packing required to achieve maximum treatment efficiency decreased with increasing air/water ratio. Relative humidity (RH) impacts on the MTBE adsorption capacity of a granular activated carbon (GAC) and carbonaceous resin were determined from pilot plant studies. Breakthrough profiles obtained from the pilot plant studies conducted at 20, 30, and 50% RH indicated that GAC has a higher adsorptive capacity than resin. The adsorptive capacity of GAC decreased with increasing RH, whereas RH did not impact the resin adsorptive capacity.     

Oxyanion flux characterization using passive flux meters: development and field testing of surfactant-modified granular activated carbon

We report here on the extension of Passive Flux Meter (PFM) applications for measuring fluxes of oxyanions in groundwater, and present results for laboratory and field studies. Granular activated carbon, with and without impregnated silver (GAC and SI-GAC, respectively), was modified with a cationic surfactant, hexadecyltrimethylammonium (HDTMA), to enhance the anion exchange capacity (AEC). Langmuir isotherm sorption maxima for oxyanions measured in batch experiments were in the following order: perchlorate>chromate>selenate, consistent with their selectivity. Linear sorption isotherms for several alcohols suggest that surfactant modification of GAC and SI-GAC reduced (approximately 30-45%) sorption of alcohols by GAC. Water and oxyanion fluxes (perchlorate and chromate) measured by deploying PFMs packed with surfactant-modified GAC (SM-GAC) or surfactant-modified, silver-impregnated GAC (SM-SI-GAC) in laboratory flow chambers were in close agreement with the imposed fluxes. The use of SM-SI-GAC as a PFM sorbent was evaluated at a field site with perchlorate contamination of a shallow unconfined aquifer. PFMs packed with SM-SI-GAC were deployed in three existing monitoring wells with a perchlorate concentration range of approximately 2.5 to 190 mg/L. PFM-measured, depth-averaged, groundwater fluxes ranged from 1.8 to 7.6 cm/day, while depth-averaged perchlorate fluxes varied from 0.22 to 1.7 g/m2/day. Groundwater and perchlorate flux distributions measured in two PFM deployments closely matched each other. Depth-averaged Darcy fluxes measured with PFMs were in line with an estimate from a borehole dilution test, but much smaller than those based on hydraulic conductivity and head gradients; this is likely due to flow divergence caused by well-screen clogging. Flux-averaged perchlorate concentrations measured with PFM deployments matched concentrations in groundwater samples taken from one well, but not in two other wells, pointing to the need for additional field testing. Use of the surfactant-modified GACs for measuring fluxes of other anions of environmental interest is discussed.     

高效生物活性炭吸附工艺去除水体中甲基叔丁基醚的初步研究

通过对来自美国加州拉玛达(La Mirada)市污染点的原始菌源炭进行甲基叔丁基醚(MTBE)降解菌生物强化,试图建立具有更有效MTBE降解效果的生物活性炭(BAC)功能,尝试利用新形成的菌源炭覆盖新鲜椰壳活性炭(GAC)而达到新BAC功能的快速有效启动,并考察不同空床停留时间(EBCT)、GAC吸附饱和状态对BAC功能启动的影响。同时,对具有成熟BAC功能的炭柱中的混合菌落进行基于16SrDNA的聚合酶链反应(PCR)—变性梯度凝胶电泳(DGGE)分析,以确定混合菌落中的主要功能菌种属。结果表明,针对模拟的低MTBE浓度进水,新鲜GAC和菌源炭A添加体积分数分别为40%和60%的NAS柱出水MTBE质量浓度最终稳定低于0.005mg/L,平均去除率接近99%,出水MTBE完全达到美国环境保护署(EPA)的饮用水建议阈值(<20μg/L),建立了成熟的BAC功能;成熟的菌源炭可在30d左右通过覆盖法迅速实现新BAC功能的启动;EBCT的延长有利于新BAC功能的启动和维持,接种初期应尽量采用较长EBCT以保证取得足够和稳定的生物量;MTBE吸附饱和前后的GAC在启动新BAC功能时存在差异,鉴于吸附饱和GAC在接种初期会因MTBE解吸而造成出水MTBE浓度较高,建议采用新鲜活性炭覆盖需接种炭柱;BAC功能成熟炭柱中包括的5种主要菌种里有4种为未培养微生物,1种为未分类菌种,其理化性质和具体属性尚不明确。     

Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE)

Background Methyl tertiary butyl ether (MTBE) is a fuel additive which is used all over the world. In recent years it has often been found in groundwater, mainly in the USA, but also in Europe. Although MTBE seems to be a minor toxic, it affects the taste and odour of water at concentrations of < 30 μg/L. Although MTBE is often a recalcitrant compound, it is known that many ethers can be degraded by abiotic means. The aim of this study was to examine biotic and abiotic transformations of MTBE with respect to the particular conditions of a contaminated site (former refinery) in Leuna, Germany. Methods Groundwater samples from wells of a contaminated site were used for aerobic and anaerobic degradation experiments. The abiotic degradation experiment (hydrolysis) was conducted employing an ion-exchange resin and MTBE solutions in distilled water. MTBE, tertiary butyl formate (TBF) and tertiary butyl alcohol (TBA) were measured by a gas chromatograph with flame ionisation detector (FID). Aldehydes and organic acids were respectively analysed by a gas chromatograph with electron capture detector (ECD) and high-performance ion chromatography (HPIC). Results and Discussion Under aerobic conditions, MTBE was degraded in laboratory experiments. Only 4 of a total of 30 anaerobic experiments exhibited degradation, and the process was very slow. In no cases were metabolites detected, but a few degradation products (TBF, TBA and formic acid) were found on the site, possibly due to the lower temperatures in groundwater. The abiotic degradation of MTBE with an ion-exchange resin as a catalyst at pH 3.5 was much faster than hydrolysis in diluted hydrochloric acid (pH 1.0). Conclusion Although the aerobic degradation of MTBE in the environment seems to be possible, the specific conditions responsible are widely unknown. Successful aerobic degradation only seems to take place if there is a lack of other utilisable compounds. However, MTBE is often accompanied by other fuel compounds on contaminated sites and anaerobic conditions prevail. MTBE is often recalcitrant under anaerobic conditions, at least in the presence of other carbon sources. The abiotic hydrolysis of MTBE seems to be of secondary importance (on site), but it might be possible to enhance it with catalysts. Recommendation and Outlook MTBE only seems to be recalcitrant under particular conditions. In some cases, the degradation of MTBE on contaminated sites could be supported by oxygen. Enhanced hydrolysis could also be an alternative. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

土壤及其主要化学组分对五氯酚吸附特征研究

研究了土壤原样及其去锰氧化物、去铁氧化物、去有机质和去水溶性有机质(DOM)土壤样品对五氯酚(PCP)的吸附规律,分析了土壤及其主要化学组分对PCP的吸附机制.实验结果表明,Langmuir方程可较好地描述PCP在各土壤样品上的热力学吸附过程.PCP在土壤上的吸附行为与自身性质和土壤理化性质密切相关,有机质和铁氧化物对PCP的吸附起到促进作用,而锰氧化物和DOM则能在一定程度上抑制PCP的吸附.通过Langmuir方程得到的拟合结果,可判断PCP在各土壤样品上的最大吸附量为去锰氧化物土壤样品＞去铁氧化物土壤样品＞去DOM土壤样品＞土壤原样＞去有机质土壤样品.     

Surface chemistry of activated carbons and its relevance for effects of relative humidity on adsorption of chlorinated organic vapors

The effects of relative humidity (RH) on the adsorption of methylene chloride (METH) and 1,1,1-trichloroethane (TCEA) on two commercial activated carbons, made from bituminous coal (carbon BPL) and coconut shell (carbon PCB), were studied. Three levels of RH were tested by tracking the breakthrough curves of each adsorbate eluted from a fixed-bed adsorption column. Adsorption capacities for these adsorbates were decreased with increase of RH. The magnitude of the effect of water vapor on adsorption is greater for carbon BPL and METH than for carbon PCB and TCEA. The results of the effect of water vapor on the adsorption capacity observed in this study were further examined based on the chemical characterization of activated carbons and the fundamental physical differences between the adsorbates.     

Effects of activated carbon types and service life on removal of endocrine disrupting chemicals: amitrol, nonylphenol, and bisphenol-A

Removal performances of endocrine disrupting chemicals (EDC) such as amitrol, nonylphenol, and bisphenol-A were evaluated in this study using granular activated carbon (GAC) adsorption. This study found that GAC adsorption was effective in removal of EDCs with high K_ow value. Nonylphenol and bisphenol-A were effectively adsorbed onto all carbons (including the used carbons) tested in this study. As indicated by K_ow value, nonylphenol was more effectively adsorbed than bisphenol-A. The coal-based carbon was found more effective than other carbons in the adsorption of nonylphenol and bisphenol-A due to its larger pore volume. The adsorption capacity reduced with the operation year, and the extent of the reduction was different depending upon the carbon type and the operation year. Amitrol was effectively removed by biological degradation, but was poorly adsorbed. Since the microbes residing at the used carbons already accustomed to amitrol, the used carbons removed amitrol better than the virgin carbons. Although the coal-based carbon showed the best removal performance of amitrol, GAC adsorption could not be recommended for amitrol removal because considerable portion of incoming amitrol (9–87%) passed through GAC adsorption column. According to this study, pore volume mainly influenced the adsorption capacity, but the surface charge was also important due to electrical interaction. The adsorption parameters for nonylphenol and bisphenol-A provided by this study could be valuable when GAC adsorption was considered to handle an accidental spill of nonylphenol and bisphenol-A.     

Matrix-immobilized organoclay for the sorption of polycyclic aromatic hydrocarbons and pentachlorophenol from groundwater

Sorbent materials consisting of organoclay immobilized onto the surface of a solid support were evaluated for use in pentachlorophenol (PCP) and polycyclic aromatic hydrocarbon (PAH) remediation of groundwater at a creosote-contaminated Superfund site. Cetylpyridinium-exchanged low pH montmorillonite clay (CP-LPHM) was bonded to either sand (CP-LPHM/sand) or granular activated carbon (GAC) (CP-LPHM/GAC) using the free acid form of carboxymethylcellulose as an adhesive. Effluent from an oil-water separator was eluted through equal bed volumes of composite (4 g 3:2 CP-LPHM/GAC or 13 g CP-LPHM/sand), affinity-extracted, and quantitatively analyzed by GC/MS. PCP, naphthalene, fluorene, phenanthrene, pyrene, and total PAHs were initially reduced by both CP-LPHM/GAC (> or =99%, 61%, 99%, > or =99%, 97%, and 94%, respectively) and CP-LPHM/sand (90%, 70%, 94%, 95%, 93%, and 86%, respectively). Complete breakthrough of naphthalene occurred after approximately 15 h of elution through 3:2 CP-LPHM/GAC and 22 h through CP-LPHM/sand. PCP showed complete breakthrough following 18 h of elution through 3:2 CP-LPHM/GAC and 26 h through CP-LPHM/sand. However, 50% breakthrough was not attained for higher molecular weight PAHs, as fluoranthene, pyrene, benzo[a]anthracene, and chrysene continued to be greatly reduced with both 3:2 CP-LPHM/GAC (98%, 95%, 94%, and 95%, respectively) and CP-LPHM/sand (75%, 73%, 76%, and 78%, respectively) after 48 h of continuous elution. Results confirm prior studies, indicating that these organoclay-containing composites have a high capacity for contaminants found in wood preserving waste. Further, results suggest that the inclusion of CP-LPHM may be useful as part of an effective strategy for groundwater remediation of high concentrations of PCP and PAHs, in particular high molecular weight and carcinogenic PAHs.