Influence of Ozonation of Humic and Fulvic Acids on Diuron Adsorption on Activated Carbon

The effect of ozonation on the competitor effect of humic and fulvic acids against diuron in adsorption on activated carbon in drinking water process has been studied. Ozonation treatment allows the removal of herbicides from drinking waters by modification of humic and fulvic acids structures. These latest are responsible for their adsorption variation on activated carbon. An ozone dose similar to that used in industrial pre-ozonation (1.3?mg ozone/l) does not cause significant transformations of humic and fulvic acids which could decrease their competitor effect and increase significantly the adsorption capacity of the activated carbon for a well-adsorbed pesticide like diuron.     

Removal of organic matter by coagulation enhanced with adsorption on PAC

The removal of humic acids and phenol from model solution by coagulation and adsorption on powdered activated carbon (PAC) was investigated. A PAX XL-69 polyaluminum chloride was applied as a coagulant. The adsorption of humic acids and phenol on activated carbon for single- and bi- component solutions was studied. It was found that coagulation without PAC addition was less effective than the adsorption-coagulation integrated system. Coagulation enhanced with adsorption on activated carbon was more effective when coagulation was preceded by adsorption than when the two processes were carried out simultaneously. The best results were obtained at pH 7. Phenol and color were removed pletely, UV₂₅₄ absorbance was reduced by about 99% and COD-Mn was reduced by 81-89%.     

MIEX和PAC对微污染水源水的水质净化效果比较

研究了MIEX和PAC两种水处理吸附剂对微污染水源水的水质净化性能。实验分别考察了MIEX和PAC对DOC和UV₂₅₄的去除效率,并通过凝胶渗透色谱和三维荧光光谱分析,研究了MIEX和PAC对不同相对分子质量区间以及不同种类有机物的去除规律。在正常的吸附剂投加量下(MIEX 5~8 ml·L^-1,PAC 30~50 mg·L^-1),MIEX对DOC和UV₂₅₄的平均去除率比PAC高23%和20%。但随着吸附剂投加量的增加,两者去除效率差别逐渐减小,MIEX对DOC和UV₂₅₄的最大去除率仅比PAC高6%~8%。与PAC相比,MIEX去除的有机物相对分子质量分布范围更广,特别是对中等分子量(5000~50000)有机物,其去效率明显高于PAC。MIEX对腐殖酸和富里酸类有机物的去除率略高于PAC,而对蛋白质类有机物的去除率则远高于PAC。动力学分析表明,MIEX和PAC对DOC的吸附去除过程符合准二级动力学,MIEX对有机物的吸附速率是PAC的40倍左右。     

Modifications to the surface chemistry of low-rank coal-based carbon catalysts to improve flue gas nitric oxide removal

The effectiveness of carbons as low-temperature selective catalytic reduction (SCR) catalysts will depend upon their physical and chemical properties. Surface functional groups containing oxygen are closely related to the catalytic activity of carbons. These groups are expected to change the interaction between the carbon surface and the reactants through a variation in adsorption and reaction characteristics. This paper presents a more detailed study of the effects of either gas-phase sulfuric acid or oxygen oxidation treatments on the catalytic NO reduction by low-rank coal-based carbon catalysts. Raw and treated carbons were characterized by N₂ and CO₂ surface areas, TPD and ash content. NO removal capacity of carbons was determined by passing a flow containing NO, H₂O, O₂, NH₃ and N₂ through a fixed bed of carbon at 150°C and 4 s of residence time, the effluent concentration being monitored continuously during the reaction. The effects of varying the type and conditions of the treatment on the physicochemical features of carbons were studied. The gas-phase sulfuric acid treatment (corresponding to a first step SO₂ removal) markedly enhanced carbon activities for NO removal. On the contrary, oxygen oxidation enhanced NO removal capacity of chars to a lower extent. Therefore, the carbons studied could be used in a combined SO₂/NO removal process, because the use and regeneration of the carbon in the first step is beneficial for the performance in the second one.     

铜铁基改性活性炭对烟气中二价汞的吸附

随着工业的发展,环境问题日趋严重,而二价汞污染作为环境问题之一受到越来越多的关注。本文采用过体积浸渍法制备了铜基和铁基[CuCl₂,FeCl₃,Cu （NO₃）₂]改性的活性炭,考察了不同浓度以及煅烧温度制备的改性活性炭对模拟烟气中二价汞（HgCl₂）脱除性能的影响。通过吸附穿透实验的对比研究得出,无论是铜基或铁基改性的活性炭都对含氯化汞烟气有很好的吸附效果,并且300℃焙烧的0.01mol/L的氯化铜改性活性炭是深度脱除含氯化汞烟气效果最好的改性活性炭,其吸附量达到了4.55mg/g。在此基础上,进一步利用了XRD、BET、XPS常用表征手段研究了改性前后活性炭的物理化学特性,证明了铜基、铁基改性活性炭吸附氯化汞都是物理吸附与化学吸附共同作用的结果,并给出了相应的解释,以期为后续的科学研究提供一定的思路。     

NH4Cl改性活性炭脱除气态Hg0的特性分析

制备了原始活性炭与NH₄Cl改性活性炭,对其进行了物化特性表征,在固定床汞吸附实验台上考察了N₂气氛下颗粒粒径、NH₄Cl溶液浓度、SO₂、CO₂等因素对活性炭脱除Hg⁰性能的影响。研究结果表明：NH₄Cl浸渍改性没有造成活性炭孔隙结构的明显变化,但使得Cl元素成功担载到活性炭表面;随着颗粒粒径增大,活性炭吸附Hg⁰的外部传质速率、内部扩散速率均降低,较小的颗粒粒径有利于活性炭脱汞;由NH₄Cl改性在活性炭表面所产生的卤素官能团（AC-Cl）能够有效地氧化烟气中的Hg⁰,增强了活性炭对于Hg⁰的氧化吸附作用;SO₂能有限地促进原始活性炭的脱汞性能,对NH₄Cl改性活性炭脱汞性能则表现出先促进后抑制并主要体现抑制作用的现象,并且抑制作用随SO₂浓度的增大而增加;CO₂由于能在活性炭表面极化,且能与氨基官能团反应生成有利于吸附汞的羰基,促进了活性炭的脱汞性能。     

乙二酸和苯甲酸在活性炭上的脱附行为

低挥发性有机酸不仅自身污染环境而且显著促进颗粒污染物形成,对其吸脱附性能的研究有助于这类物质的控制。采用程序升温脱附(TPD)技术对乙二酸、苯甲酸在活性炭(AC)上的脱附行为进行了研究。结果表明,吸附主要发生在粗微孔(0.7~2 nm)、细微孔(<0.7 nm)中,对应TPD曲线中的吸附位Ⅰ、Ⅱ。粗微孔对乙二酸、苯甲酸的脱附活化能为101.63、112.43 kJ·mol^-1,吸附量均大于总吸附量的91%。细微孔对乙二酸、苯甲酸的脱附活化能为118.01、130.87 kJ·mol^-1,吸附量均小于总吸附量的9%。细微孔吸附强度高于粗微孔,但吸附量远低于粗微孔,因为细微孔对吸附质的迁移阻力较大,仅少量吸附质能进入细微孔中。苯甲酸在迁移中受到阻力较乙二酸大,在细微孔中吸附量更小,表现为分子筛分作用。     

Evaluation of humic acid photocatalytic degradation by UV–vis and fluorescence spectroscopy

Photodegradation of humic substances causes drastic changes in the UV–vis absorption and fluorescence properties of humic acids. In this study it is intended to fulfill the lack of knowledge about the spectral changes of humic acids during photocatalytic oxidation processes and elucidate the effects observed on the molecular size distribution of humic acid focusing on their analysis by UV–vis and fluorescence spectroscopy.

As confirmed by the spectroscopic evaluation of the molecular size distribution data, photocatalytic degradation of humic acid leads to the formation of lower molecular size (small fractions) and higher UV absorbing compounds. For fractions less than 10 kDa, UV₂₅₄ absorbing moieties in treated humic acid samples become higher than that of raw humic acid designating the generation of new species during photocatalysis. UV–vis spectroscopic changes were also evaluated by the parameters relating to the concomitant removal of the total organic carbon as well as by the ratios using absorption values at discrete wavelengths. Moreover, the fluorescence spectra of treated humic acid samples show decreasing intensity profiles with increasing photocatalytic irradiation time.     

TEPA负载复合氧化活性炭吸附烟气中的CO2性能

以商业煤基活性炭为原料,经低浓度氧气焙烧、H₂O₂氧化改性,并以四乙烯五胺（TEPA）浸渍,得到胺负载复合氧化活性炭,用于模拟烟道气[(15%(体积)CO₂+85%(体积)N₂）+10%(体积)H₂O]中CO₂吸附。低浓度氧气焙烧后,活性炭的最大比表面积和孔体积分别为1421.82 m²/g、0.83 cm³/g。经复合氧化改性后,活性炭的介孔体积增大,表面含氧官能团增加,使得TEPA负载复合氧化活性炭的CO₂吸附性能提高。焙烧时间为4 h,H₂O₂氧化、负载40%TEPA的样品COAC-4-40TEPA,在60℃时CO₂饱和吸附量最高为2.45 mmol/g,是TEPA负载未改性活性炭AC-40TEPA的2.02倍。经过十次吸附循环后,COAC-4-40TEPA的 CO₂饱和吸附量可维持在92.24%,而TEPA的浸出量仅有0.67%。失活模型研究表明,COAC-4-40TEPA的初始吸附速率常数是AC-40TEPA的1.64倍,且失活速率常数低于AC-40TEPA。     

Adsorption of humic acid by powdered activated carbon in saline water conditions

The adsorption of humic acid (HA) by powdered activated carbon (PAC) in saline waters has been examined in the absence and presence of metal salt coagulants. The study showed that adsorption of HA by PAC can be significantly greater in saline water compared to freshwater and low conductivity water. An optimal adsorption was attained at saline concentrations corresponding to synthetic seawater diluted to 12.5-25% of its original concentration. In undiluted synthetic seawater the adsorption of HA from solution by PAC was comparable with that of local tap water in terms of initial adsorption rate and total removal. The enhanced adsorption is believed to be a combination of reduced electrostatic repulsion between the HA and PAC at high salt concentrations, and chemisorption due to chemical bonding between the functional groups. The effects of adding a metal salt coagulant, either aluminium sulphate or ferric chloride, on overall HA removal were found to depend strongly on the coagulant dose, solution pH and the sequence of addition of the PAC and metal salt coagulant. Addition of the PAC shortly before the coagulant was found to give the greatest removal of HA.     

Co改性活性炭吸附NO的实验研究

采用Co(NO_3)_2对活性炭进行改性,考察浸渍浓度和吸附温度等条件对活性炭吸附NO性能的影响,并对已吸附NO的0.3 mol·L~(-1)的Co(NO_3)_2改性活性炭进行再生。通过BET、SEM、吸附等温线和FT-IR表征样品的比表面积、颗粒形貌和表面官能团。结果表明,当浸渍溶液浓度为0.3 mol·L~(-1)时,吸附效果最佳,80 min时吸附效率达88.90%。活性炭的吸附效率随着温度升高而降低,用0.3 mol·L~(-1)Co(NO_3)_2改性的活性炭在200℃时的吸附效率大于90%,并可持续50 min。SEM和FT-IR表征结果表明,在Co(NO_3)_2改性的活性炭表面和孔隙生成了Co_3O_4,促进NO催化氧化为NO_2并进行吸附。加热再生后的0.3 mol·L~(-1)Co(NO_3)_2改性活性炭对NO的吸附效率在60 min内仍高于88.90%,再生效果较好,可持续再生利用。     

活性炭对单宁酸的吸附去除性能

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物质,腐殖酸是生成消毒副产物的主要前驱物。活性炭能够去除水中的多种有机污染物,其中对腐殖酸的去除性能可以通过单宁酸值来表征。通过间歇试验,研究了两种活性炭对单宁酸的吸附行为,探索其对单宁酸的吸附规律。结果表明308 K时,1#炭对单宁酸的饱和吸附量较大,为616.0 mg/g。升高温度有利于两种活性炭对单宁酸的吸附,表明吸附过程为吸热过程。此外,两种活性炭对单宁酸的吸附动力学可以用Largergren伪二级速率方程很好地拟合,吸附过程是双速过程。1#炭对单宁酸的吸附速率更快,比3#炭具有更高的单宁酸吸附性能。1#和3#炭对单宁酸的吸附活化能依次分别为17.5和3.9 kJ/mol,说明1#炭的反应速率随温度的升高增加得较快,符合Arrhenius的经验方程,吸附反应速率随温度升高而加快的规律,活性炭对单宁酸的吸附可认为是化学吸附。     

Application of an ozonation–adsorption–ultrafiltration system for surface water treatment

Investigations are presented on the effect of the preliminary ozonation on ultrafiltration (UF) and powdered activated carbon (PAC) /UF process performance, especially on permeate flux decline and the effectiveness of model organics removal. Flat membranes from regenerated cellulose were used. A model solution was prepared as a mixture of humic acids and phenol. PAC dosage was equal to 100 mg/l⁻¹. The ozone dosages were in the range of 1–3 mg O₃ l⁻¹ (0.2–0.6 mg O₃/mg TOC). It was found that the most advantageous configuration was preliminary ozonation with an ozone dosage of 0.4 mgO₃/mg TOC–UF. The permeate flux reached a value equal to the pure water flux value. Moreover, a very high effectiveness of model organics removal was obtained: TOC was reduced by about 96% and UV₂₅₄ absorbance was removed completely. When PAC was added to the feed containing humic acids without ozonation, a drop in a permeate flux was observed compared to UF. Similarly, the addition of PAC to feed treated with ozone resulted in a significant drop in the permeate flux in comparison with pure water flux, regardless of ozone dosage applied.     

From pollutant to solution of wastewater pollution: Synthesis of activated carbon from textile sludge for dye adsorption

Adsorption is an important process in wastewater treatment,and conversion of waste materials to adsorbent offers a solution to high material cost related to the use of commercial activated carbon.This study investigated the adsorption behaviour of Reactive Black 5(RB5)and methylene blue(MB)onto activated carbon produced from textile sludge(TSAC).The activated carbon was synthesized through chemical activation of precursor followed with carbonization at 650°C under nitrogen flow.Effects of time(0–200 min),pH(2–10),temperature(25–60°C),initial dye concentration(0–200 mg·L~(-1)),and adsorbent dosage(0.01–0.15 g)on dye removal efficiency were investigated.Preliminary screening revealed that TSAC synthesized via H_2SO_4activation showed higher adsorption behaviour than TSAC activated by KCl and ZnCl_2.The adsorption capacity of TSAC was found to be 11.98 mg·g~(-1)(RB5)and 13.27 mg·g~(-1)(MB),and is dependent on adsorption time and initial dye concentration.The adsorption data for both dyes were well fitted to Freundlich isotherm model which explains the heterogeneous nature of TSAC surface.The dye adsorption obeyed pseudo-second order kinetic model,thus chemisorption was the controlling step.This study reveals potential of textile sludge in removal of dyes from aqueous solution,and further studies are required to establish the applicability of the synthesized adsorbent for the treatment of waste water containing toxic dyes from textile industry.     

Continuous flow removal of acid fuchsine by dielectric barrier discharge plasma water bed enhanced by activated carbon adsorption

Continuous processes which allow for large amount of wastewater to be treated to meet drainage standards while reducing treatment time and energy consumption are urgently needed. In this study, a dielectric barrier discharge plasma water bed system was designed and then coupled with granular activated carbon (GAC) adsorption to rapidly remove acid fuchsine (AF) with high efficiency. Effects of feeding gases, treatment time and initial concentration of AF on removal efficiency were investigated. Results showed that compared to the N2 and air plasmas treatments, O2 plasma processing was most effective for AF degradation due to the strong oxidation ability of generated activated species, especially the OH radicals. The addition of GAC significantly enhanced the removal efficiency of AF in aqueous solution and shorten the required time by 50%. The effect was attributed to the ability of porous carbon to trap and concentrate the dye, increasing the time dye molecules were exposed to the plasma discharge zone, and to enhance the production of OH radicals on/in GAC to boost the degradation of dyes by plasma as well as in situ regenerate the exhausted GAC. The study offers a new opportunity for continuous effective remediation of wastewater contaminated with organic dyes using plasma technologies.     

Evaluation of humic acid, chromium (VI) and TiO2 ternary system in relation to adsorptive interactions

Batch adsorption studies were carried out for the assessment of the adsorptive interactions of the system composed of humic acid, Cr(VI) and TiO₂. These were preceded by a thorough investigation of the effect of the chromium ion concentration on the adsorption of humic acid onto TiO₂. The adsorption equilibrium of total chromium, humic acid, and titanium dioxide in water were examined separately and in all combinations in order to distinguish the effects based on the interaction of the components. The adsorption data for the binary system as well as the ternary system were modeled with a simple Freundlich model and the model parameters were compared in terms of Cr(VI) and humic acid as expressed by Color₄₃₆ (color forming moieties) and UV₂₅₄ (UV absorbing centers) parameters.

In binary systems composed of Cr(VI) and TiO₂ no direct relationship could be assessed between adsorption capacity values (K_F) and changes in chromium ion concentration. Chromium ion and humic acid interactions were followed by UV-Vis spectra. A minor change irrespective of added chromium ion concentration was observed for Color₄₃₆ and UV₂₅₄ parameters of humic acid (<5%). However, a significant alteration was observed at 365 nm wavelength indicating the formation of chromate esters. In ternary systems comprising humic acid, Cr(VI) and TiO₂, increasing Cr(VI) concentration five-fold did not cause drastic changes in the adsorption capacity values in terms of Cr(VI) concentration. On the other hand, the adsorption capacity values for color forming moieties as well as for UV absorbing centers of humic acid exhibited a decreasing trend with respect to increasing chromium ion concentration.     

Adsorption–desorption characteristics of VOCs over impregnated activated carbons

An activated carbon was modified by impregnating with various acids or bases. The effects of adsorption capacity and impregnated contents on the textural properties of the impregnated activated carbons (IACs) were investigated. Furthermore, VOC adsorption and desorption experiments were carried out to determine the relationship between the adsorption capacity and chemical properties of the adsorbents. The effects of various parameters such VOC concentration, aspect ratio, flow rate, and impregnated contents were investigated. High adsorption capacity for the selected VOCs was obtained over 1 wt.% H₃PO₄/AC (1 wt.% PA/AC). As a result, IAC was found to be effective for VOC removal by adsorption with the potential for repeated use through desorption by simple heat treatment.     

磷酸中添加剂对核桃壳活性炭性能的影响

采用磷酸活化法制备核桃壳颗粒活性炭,研究了在磷酸浸渍液中加入不同种类和含量添加剂对活性炭性能的影响。以亚甲基蓝和碘吸附值表征活性炭的吸附性能,并对活性炭的孔结构参数、机械强度和微晶结构进行了测试分析。结果表明：在磷酸中分别添加柠檬酸、柠檬酸钠、硼酸和糖精浸渍处理核桃壳原料,所得活性炭的亚甲基蓝吸附值都得到提高,而碘吸附值降低,说明添加剂促使活性炭中的微孔扩大为中孔。其中,添加0.5%的柠檬酸钠得到最佳的亚甲基蓝和碘吸附值,分别达到236.5和744.1 mg/g。此外,磷酸中添加1%硼酸后得到的活性炭结构中含坚固的炭微晶,起到了增强孔结构的作用,机械强度为85.8%;而添加1%糖精得到的活性炭中的炭微晶几乎全部发生了石墨化转变,生成质软的石墨,使强度下降,机械强度仅为80.1%;添加0.5%柠檬酸钠的活性炭由于发达的孔隙结构且没有炭微晶的加固而强度较低(82.5%)。     

Regeneration of a vanadium pentoxide supported activated coke catalyst-sorbent used in simultaneous sulfur dioxide and nitric oxide removal from flue gas: Effect of ammonia

A vanadium pentoxide supported activated coke (V₂O₅/AC) catalyst-sorbent has been reported to be very active for simultaneous removal of SO₂ and NO under dry conditions at temperatures of 200 °C and below. Regeneration of the SO₂-captured catalyst-sorbent is a key step in operation of such a process, which influences the catalyst-sorbent's SO₂ and NO removal activities, lifetime, as well as recovery of sulfur. Due to limited information in this regard, this paper studies thermal regeneration of a V₂O₅/AC catalyst-sorbent with emphases on the effect of atmosphere. The optimum regeneration temperature is found to be 380 °C in an Ar stream and 300 °C in a 5% NH₃/Ar stream. Compared to the fresh V₂O₅/AC, the V₂O₅/ACs regenerated in Ar show lower SO₂ adsorption capacities and higher NO removal activities, while the regenerated V₂O₅/ACs by 5% NH₃/Ar show higher and stable SO₂ adsorption capacities and higher NO removal activities. Two types of reactions occur during the regeneration: reduction of the adsorbed sulfur species by carbon to SO₂ and CO₂, and oxidation of carbon by oxygen in the V₂O₅/AC to CO₂. The carbon consumption of the latter is much more than that of the former in an Ar atmosphere, but fully suppressed by the presence of 5% NH₃. Detailed analysis and characterization of the V₂O₅/AC subjected to the regenerations are presented.     

Solubilized coal as a substrate for biodesulfurization

Problem areas in a multi-step coal desulfurization process were investigated. The process involves mild hot air oxidation, followed by alkaline extraction to separate the resultant humic acid molecules from the insoluble pyrite and ash, and microbial removal of organic sulfur from the solubilized coal molecules. A computer-controlled and -monitored solubilization reactor for humic acid production was constructed. Studies designed to evaluate the physical/chemical nature and solubility characteristics of the humic acids were undertaken, with the ultimate aim of ensuring accessibility of sulfur atoms buried in the interior of these large hydrocarbon macromolecules. One per cent Tween-80 enhanced the solubility of humic acids four-fold. Radiotracer labelled humic acids containing 10.8 × 10⁻¹¹ Bq mg⁻¹ of ¹²⁵I were produced. These labelled humic acids will be used to develop an accurate and dependable assay for microbial organic desulfurization.