活性炭协同Fe2+催化H2O2氧化处理染料废水及其表面附着污染物对催化活性的影响

采用动态连续处理装置研究颗粒活性炭（GAC）催化H2O2氧化活性红X-3B染料（RRX-3B）的效能以及GAC表面吸附污染物对催化性能的影响,考察GAC与Fe2+协同催化作用。研究结果表明：RRX-3B的处理效果随着流速的增加而逐渐降低;新GAC/H2O2体系降解效果优于单独GAC吸附与单独H2O2氧化,GAC重复使用存在部分失活现象使其脱色率和COD去除率下降,且表面预先吸附污染物的GAC在重复使用过程中下降更为明显;固定H2O2投加量为5 mmol·L-1,按n（Fe2+）：n（H2O2）为1:20投加Fe2+,GAC与Fe2+联合体系能持续有效使RRX-3B氧化脱色,重复使用4次后脱色率仍可达99.65%,GAC和Fe2+之间存在协同催化H2O2降解RRX-3B的作用。GAC表面附着的Fe2+能够加强催化作用,且有效延长其使用寿命。     

微波诱导改性活性炭催化降解邻苯二甲酸二甲酯

通过HNO3、H2O2、NaOH对活性炭进行浸渍改性,采用BET、SEM、Boehm、FT-IR对改性前后的活性炭进行表征,研究了改性前后的活性炭在不同反应体系对DMP的降解效果和动力学,探讨了微波诱导改性前后的活性炭催化降解DMP的机理。结果表明,3种改性活性炭的BET比表面积、总孔容、微孔孔容和平均孔径均有所增加。HNO3、H2O2改性后表面酸性基团增加、碱性基团减少,而NaOH改性呈现相反的理化特征变化。活性炭理化特征的变化可能与化学改性剂溶液的酸碱性、氧化还原性有关。微波诱导改性前后的活性炭催化体系对DMP的降解率大于单独吸附或单纯微波辐射体系,且均符合一级反应动力学。在微波诱导改性前后的活性炭催化体系中,改性前后的活性炭通过表面吸附-微波诱导氧化协同作用极大地提高了对DMP的降解率。     

Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase

Di-(2-ethyl hexyl) phthalate (DEHP), a recalcitrant and an endocrine disrupting chemical, was studied for its removal from wastewater by advanced oxidation process. The effects of pH, transition metal ions, and granular activated carbon (GAC) were investigated. Removal of DEHP increased with increase in pH and among metal ions Cr(III) was found to be the most active catalyst to remove DEHP. In the case of GAC, original carbon (G0) and GAC pre-ozonated in gas phase for 10 min (G10) were tested as catalysts in catalytic ozonation and found G0 to be more active than G10. This is because, during pre-ozonation, basic groups like chromene, pyrones and also graphene layers were oxidized to acidic surface oxygen groups. These basic surface groups are reported to be active catalytic centres for ozone decomposition into .OH which is a strong oxidant. According to kinetic manipulations, DEHP degradation rate constant due to .OH was affected by the catalyst while that due to direct ozonation is same in all cases with or without catalyst. G0 was doped with chromia gels (G0/CrA) to combine the benefits of homogeneous and heterogeneous catalysis. G0/CrA showed lower catalytic efficiency than that of only G0. This might be because of changes in surface structure of GAC caused by doping of chromia gel and changes in chemical nature of Cr(III) during formation of gel. A good correlation was found between the rate constants of ozone decay and DEHP degradation (R2=0.96). This correlation confirms that ozone decomposition into .OH is a critical factor for the activity of a catalyst during ozonation.     

CuFe2O4/activated carbon composite: a novel magnetic adsorbent for the removal of acid orange II and catalytic regeneration

CuFe2O4/activated carbon magnetic adsorbents, which combined the adsorption features of activated carbon with the magnetic and the excellent catalytic properties of powdered CuFe2O4, were developed using a simple chemical coprecipitation procedure. The prepared magnetic composites can be used to adsorb acid orange II (AO7) in water and subsequently, easily be separated from the medium by a magnetic technique. CuFe2O4/activated carbon magnetic adsorbents with mass ratio of 1:1, 1:1.5 and 1:2 were prepared. Magnetization measurements, BET surface area measurements, powder XRD and SEM were used to characterize the prepared adsorbents. The results indicate that the magnetic phase present is spinel copper ferrite and the presence of CuFe2O4 did not significantly affect the surface area and pore structure of the activated carbon. The adsorption kinetics and adsorption isotherm of acid orange II (AO7) onto the composites at pH 5.2 also showed that the presence of CuFe2O4 did not affect the adsorption capacity of the activated carbon. The thermal decomposition of AO7 adsorbed on the activated carbon and the composite was investigated by in situ FTIR, respectively. The results suggest that the composite has much higher catalytic activity than that of activated carbon, attributed to the presence of CuFe2O4. The variation of the adsorption capacity of the composites after several adsorption-regeneration cycles has also been studied.     

Effect of operational factors on bioregeneration of binary phenol and 4-chlorophenol-loaded granular activated carbon using PVA-immobilized biomass cryogels

The effects of dry biomass density in cryogel beads, shaking speed and initial concentration ratio of phenol to 4-chlorophenol (4-CP) on the bioregeneration efficiencies of binary phenol and 4-CP-loaded granular activated carbon (GAC) for phenol and 4-CP, respectively, were investigated under the simultaneous adsorption and biodegradation approach. The results revealed higher bioregeneration efficiencies of binary-loaded GAC for phenol and 4-CP at higher dry biomass density but moderate shaking speed. The optimum dry biomass density in cryogel beads and shaking speed for use in bioregeneration were found to be 0.01 g/mL and 250 rpm, respectively. With respect to the initial phenol to 4-CP concentration ratio, the bioregeneration efficiencies were lower under increasing phenol and 4-CP initial concentrations, respectively, with the effect being more conspicuous under increasing 4-CP concentration. Higher bioregeneration efficiencies were achieved with the use of immobilized rather than suspended biomasses.     

改性Pd/GAC粒子电极吸附-电催化去除2,4,6-三氯苯酚

以6 mol·L⁻¹硝酸和450 ℃高温共同改性后的颗粒活性炭(granular activated carbon,GAC)为载体,采用硼氢化钠还原法制备了改性Pd/GAC粒子电极,研究了电极对2,4,6-三氯苯酚(2,4,6-trichlorophenol,2,4,6-TCP)的去除能力、动力学特征及脱氯机理。结果表明,通过改性,GAC的比表面积(560.791 m²·g⁻¹)提高了1.5倍,孔容提高了36.02%,对2,4,6-TCP的最大吸附容量为199.2 mg·g⁻¹。在优化条件下,改性粒子电极4 h内对30 mg·L⁻¹的2,4,6-TCP去除率达到94.7%,反应速率常数为0.014 min⁻¹,钯的催化活性为0.3 (min·mmol)⁻¹。通过对反应过程中有机氯和无机氯变化的分析,阐明了改性Pd/GAC粒子电极强化去除2,4,6-TCP的过程。从还原途径、直接和间接还原贡献等方面探究了改性粒子电极电催化脱氯机理。     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

Degradation of 4-chlorophenol by microwave irradiation enhanced advanced oxidation processes

In this work the synergistic effects of several microwave assisted advanced oxidation processes (MW/AOPs) were studied for the degradation of 4-chlorophenol (4-CP). The efficiencies of the degradation of 4-CP in dilute aqueous solution for a variety of AOPs with or without MW irradiation were compared. The results showed that the synergistic effects between MW and H2O2, UV/H2O2, TiO2 photocatalytic oxidation (PCO) resulted in a high degradation efficiency for 4-CP. The potential of MW/AOPs for treatment of industrial wastewater is discussed.     

吸附-电化学氧化耦合处理对氯苯酚废水及动力学

以毡状活性炭纤维为阳极,不锈钢为阴极,吸附-电化学氧化耦合降解对氯苯酚废水进行了研究。考察了吸附或耦合电化学氧化过程、电流密度、支持电解质硫酸钠浓度和活性炭纤维重复使用对废水COD去除率的影响,结果表明,采用吸附-电化学氧化耦合方法,当电流密度7.6 mA/cm2支持电解质（硫酸钠）浓度为1 g/L,处理时间为180 min,4-CP废水COD去除率可达97.09%。毡状活性炭纤维对4-CP的静态吸附过程符合Langmiu吸附等温方程。建立了吸附-电化学氧化COD去除动力学模型,动力学模型参数表明,对于COD的去除,电化学氧化作用比吸附作用大。     

Effect of adsorbents coated with titanium dioxide on the photocatalytic degradation of propoxur

Photocatalytic oxidation of pesticides in aqueous media irradiated by UV light is a rapidly growing field of research. Therefore, the treatment technology for degradation of propoxur (an insecticide) using titanium dioxide coated on the supports such as activated carbon, zeolite, brick, quartz and glass beads, was performed in this research. Results show that GAC/TiO2 is the best complexing agent for oxidizing propoxur because of its adsorption properities. The others follow the sequence: plain TiO2 > glass beads > zeolite > brick > quartz. The degradation rate of propoxur with plain TiO2 is higher than that with TiO2/GAC complexing agent. But the mineralization rate of propoxur with plain TiO2 is lower than that with TiO2/GAC complexing agent. However, it can be concluded that using GAC as the support can improve the photocatalytic efficiency.     

改性核桃果皮基活性炭对Cu2+的吸附

以核桃外果皮制备活性炭及改性活性炭,对制得的活性炭进行表征,研究了5种活性炭对重金属Cu2+的吸附性能。研究表明,以氯化锌为活化剂制得的活性炭,其碘吸附值及表面酸性基团含量均高于磷酸活化制备的活性炭,改性后的活性炭吸附性能明显增强,碘吸附值最高达到678.53 mg·g-1,对Cu2+的最高去除率达到91.43%。吸附量和Cu2+去除率随时间、温度和pH的升高而增大,5种活性炭投加量增加,导致吸附量减小,但Cu2+去除率增大,吸附平衡时间为3 h。5种活性炭对Cu2+的吸附均符合准二级动力学模型。磷酸和氯化锌活化的活性炭吸附等温线符合Tempkin模型,而3种改性活性炭的吸附等温线则较好地符合Langmuir模型。     

Contribution of free radicals to chlorophenols decomposition by several advanced oxidation processes

The chemical decomposition of aqueous solutions of various chlorophenols (4-chlorophenol (4-CP), 2,4-dichlorophenol (2-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP)), which are environmental priority pollutants, is studied by means of single oxidants (hydrogen peroxide, UV radiation, Fenton's reagent and ozone at pH 2 and 9), and by the Advanced Oxidation Processes (AOPs) constituted by combinations of these oxidants (UV/H2O2 UV/Fenton's reagent and O3/UV). For all these reactions the degradation rates are evaluated by determining their first-order rate constants and the half-life times. Ozone is more reactive with higher substituted CPs while OH* radicals react faster with those chlorophenols having lower number of chlorine atoms. The improvement in the decomposition levels reached by the combined processes, due to the generation of the very reactive hydroxyl radicals. in relation to the single oxidants is clearly demonstrated and evaluated by kinetic modeling.     

微波活性炭法处理酸性红88废水及其机理

微波活性炭法（MW-GAC）处理模拟酸性红88（AR88）废水的实验结果显示,酸性红88的脱色率与固液比、微波辐照时间、微波功率正相关,而与其初始浓度（在10~100 mg·L-1范围内）负相关。溶液pH对脱色率的影响不大,pH为3时脱色率最高为99.7%。在MW-GAC处理过程中,微波和活性炭具有较强的协同作用,酸性红88经处理后,特征波长（UV506、UV310、UV254）吸收均锐减。活性炭表面检测到残留芳环、N-H和C-N,结合中间产物质谱检测结果,推断酸性红88在MW-GAC系统中的降解途径首先是偶氮键被破坏,然后形成芳庚和甲苯,随后开环并加成形成2,4-二甲基-1-庚烯,最后矿化形成CO2和H2O。     

Heterogeneous and homogeneous catalytic ozonation of benzothiazole promoted by activated carbon: kinetic approach

Ozone oxidation combined with activated carbon adsorption (O(3)/AC) has recently started to be developed as a single process for water and wastewater treatment. While a number of aspects of aqueous ozone decomposition are well understood, the importance and relationship between aqueous ozone decomposition and organic contaminant degradation in the presence of activated carbon is still not clear. This study focuses on determining the contribution of homogeneous and heterogeneous reactions to organic contaminants removal in O(3)/AC system. Benzothiazole (BT) was selected as a target organic pollutant due to its environmental concern. A reactor system based on a differential circular flow reactor composed by a 19 cm(3) activated carbon fixed bed column and 1 dm(3) storage tank was used. Ozone was produced from pure and dry oxygen using an Ozocav ozone generator rated at 5 g O(3)h(-1). Experimental results show that BT removal rate was proportional to activated carbon dosage. Activated carbon surface contribution to BT oxidation reactions with ozone, increased with pH in absence of radical scavengers. The radical reaction contribution within the pH range 2-11 accounted for 67-83% for BT removal in O(3)/AC simultaneous treatment. Results suggest that at pH higher than the pH of the point of zero charge of the activated carbon dissociated acid groups such as carboxylic acid anhydrides and carboxylic acids present on activated carbon surface could be responsible for the observed increase in the ozone decomposition reaction rate. A simplified mechanism and a kinetic scheme representing the contribution of homogeneous and heterogeneous reactions on BT ozonation in the presence of activated carbon is proposed.     

负载型颗粒活性炭催化过硫酸钠氧化降解橙黄G

通过在颗粒活性炭(GAC)上负载氧化铁,并以此作为催化剂(Fe/GAC)在常温常压下催化过硫酸钠(PS)产生硫酸根自由基降解偶氮染料橙黄G。研究了体系pH、氧化剂浓度、催化剂浓度对橙黄G去除率的影响,并且对催化剂的重复使用性能进行了测试。结果表明,在Fe/GAC/PS体系中,[OG]0=0.2 mmol/L,[GAC]=1 g/L,[PS]0=2 mmol/L,降解2 h后OG去除率为99%,且有较高的矿化率;随着氧化剂浓度和催化剂浓度的增加,OG的去除效率提高;催化剂有较好的重复使用性。利用扫描电镜(SEM)对催化剂进行了表征,可以看出在活性炭上成功负载氧化铁。利用化学分子探针竞争实验鉴定催化反应中的活性物种SO4-·和OH·。     

高级氧化工艺处理煤化工浓盐水

浓盐水处理是一项世界性难题,采用高级氧化工艺能有效去除废水中难降解有机物,从而提高其可处理性。分别采用臭氧氧化、O3/H2O2、GAC/O3和GAC/O3/H2O2等工艺处理煤化工浓盐水,研究了工艺参数对COD去除的影响,探索了有机物去除机理。研究表明,煤化工浓盐水中易被臭氧氧化的有机物大约占55%。增加臭氧投加量和气体流速能提高有机物去除效率。酸性条件下的COD去除率要高于碱性条件下。臭氧氧化、O3/H2O2、GAC/O3和GAC/O3/H2O2工艺中·OH稳定浓度分为4.1、37.7、5.9和41.3×10-14 mol/L。O3与H2O2之间存在明显协同作用,GAC与O3协同产生·OH的作用不明显,但GAC对氧化过程中生成的生物抑制物具有较好的吸附去除作用。GAC、O3和H2O2三者之间的协同作用有助于去除煤化工浓盐水中难降解有机物、提高出水可生化性和降低出水水质毒性。     

Microwave Process for Volatile Organic Compound Abatement

ABSTRACT

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.     

Microwave process for volatile organic compound abatement

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.     

活性炭纤维对染料的吸附性能研究

研究了聚丙烯腈活性炭纤维（P－ACF）、粘胶活性炭纤维（R－ACF）和颗粒活性炭（GAC）对5种红色染料的吸附能力,通过简单的模型,算出5种染料在两种活性炭纤维上的吸附速率常数。结果表明,尽管吸附能力随染料种类不同而有一定的差别,但总体上,聚丙烯腈活性炭纤维的吸附能力略低于颗粒活性炭,而粘胶活性炭纤维的吸附能力则远远优于前两种,对染料有着较大的吸附容量和较快的吸附速率。     

Modification of carbon-coated TiO2 by iron to increase adsorptivity and photoactivity for phenol

Carbon-coated TiO(2) modified by iron, were prepared from TiO(2) of anatase structure and PET modified by FeC(2)O(4). Catalysts were prepared by mixing powders of TiO(2) and modified PET and heating at different temperatures, from 400 to 800 degrees C under flow of Ar gas. High adsorption of phenol was observed on the catalyst heated at 400 degrees C, confirmed by FT-IR analysis. On this catalyst, fast rate of phenol decomposition was achieved by addition of small amount of H(2)O(2) to the reaction mixture. Phenol decomposition proceeded mainly through the direct oxidation of phenol species adsorbed on the catalyst surface due to the photo-Fenton reaction. Iron-modified carbon-coated TiO(2) catalysts heated at 500-800 degrees C showed almost no phenol adsorption or oxidation.