Deodorization of dimethyl sulfide using a discharge approach at room temperature

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

Adsorption Characteristics of Activated Carbon and XAD4 Resin for the Removal of Hazardous Organic Solvents

A comparative study has been conducted on adsorption/desorption of six hazardous organic vapors on synthetic resin (XAD4) and activated carbon, using a differential reactor involving the expansion of a quartz spring. While both sorbents can effectively remove the organic vapors, it was observed that at low concentrations activated carbon adsorbed more organic vapor than synthetic resin. At higher, industrial concentrations, the resins adsorbed more vapor as demonstrated by the slopes of the equilibrium isotherms. The resin also showed much higher desorptlon.

The effective Intraparticle diffusion coefficients (D_e) were observed to be strongly dependent on solute concentration. Pore diffusion dominated the adsorption/desorption of the six organic vapors on XAD4 resin. For the carbon system, pore diffusion dominated the adsorption but surface diffusion contributed to the desorptlon process. This is believed to be due to higher Interaction of the adsorbates with activated carbon.     

Combined effect of adsorption and biodegradation of biological activated carbon on H2S biotrickling filtration

In order to evaluate the combined effect of adsorption and biodegradation of H(2)S on activated carbon surface in biotrickling filtration, four laboratory-scale biofiltration columns were operated simultaneously for 120h to investigate the mechanisms involved in treating synthetic H(2)S streams using biological activated carbon (BAC). The first three columns (A, B, C) contained a mixture of activated carbon and glass beads, with the carbons (BAC or virgin activated carbon (VAC)) and conditions (with or without liquid medium recirculation) differentiated. The last column (D) used 100% glass beads with liquid medium recirculation. Air streams containing 45ppmv H(2)S were passed through the columns at 4s of gas retention time (GRT) and liquid flow rate was set at 0.71mlmin(-1). Column D got its breakthrough in 3min of operation, indicating a negligible contribution of glass beads to the adsorption of H(2)S. The removal efficiency (RE) of Columns B and C using VAC dropped quickly to 30% within the first 8h, and afterwards continued to drop further but slowly. Column A using BAC stayed at 25% of RE throughout the operation time. A thorough investigation of the H(2)S oxidation products, i.e., various S species in both aqueous (recirculation media) and solid phases (BAC and VAC), was conducted using ICP-OES, IC, XRF, and CHNS elemental analyzer. BAC demonstrated a better performance than columns with adsorption only. Water film was found to enhance H(2)S removal. The percentage of sulphate in the total sulphur of the BAC system improved to twice of that of VAC system, indicating sulphate is the main product of H(2)S biofiltration. The observed pH drop in BAC system double confirmed that the presence of biodegradation in the biofilm over carbon surface did profound effect on the oxidation of H(2)S, compare to the systems with adsorption only.     

浸渍-碱性微波法载磁活性炭粉对壬基酚的吸附

利用浸渍-碱性微波法制备载磁粉末活性炭,通过等温吸附实验和动力学吸附实验,研究对比了其与原料活性炭、浸渍载铁活性炭对壬基酚的吸附性能。采用氮气吸附仪、FTIR、XRD、国标(GB/T12496.19-1999)邻菲啰啉分光度法及VSM,分别对3种样品进行了物相结构、表面官能团、铁含量及磁性能的分析,并探讨了吸附机理。结果表明,浸渍-碱性微波法载磁活性炭的总孔容及孔隙率均有较大提高;其吸附等温线符合Freundich方程,吸附动力学过程符合准二级动力学方程与孔道内扩散模型,相关系数R2均大于0.900。原活性炭经一定浓度的铁盐溶液浸渍后,铁含量由2%提高到8%。在碱性、N2气氛条件下微波后,铁系物主要存在形式为零价铁和Fe3O4,制得的载磁活性炭饱和磁化强度为1.12 emu/g。     

微波法污水厂污泥制备活性炭的研究

研究了以污水厂污泥为原料、微波辐照下磷酸活化法制备污泥活性炭的工艺条件,探讨了微波功率、辐照时间以及磷酸浓度对活性炭碘值的影响.结果表明,微波功率480 W、辐照时间315 s、磷酸浓度40%～45%的条件下,制备的污泥活性炭碘值为301 mg/g,总孔孔容是0.37 mL/g,平均孔径8.8 nm,比表面积168 m2/g.将该污泥活性炭用于处理TNT红水,吸附效果良好.     

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。     

Photooxidation of naphthalenesulfonic acids: comparison between processes based on O(3), O(3)/activated carbon and UV/H(2)O(2)

The aim of the present study was to analyze and compare the efficacy of UV photodegradation with that of different advanced oxidation processes (O(3), UV/H(2)O(2), O(3)/activated carbon) in the degradation of naphthalenesulfonic acids from aqueous solution and to investigate the kinetics and the mechanism involved in these processes. Results obtained showed that photodegradation with UV radiation (254 nm) of 1-naphthalenesulfonic, 1,5-naphthalendisulfonic and 1,3,6-naphthalentrisulfonic acids is not effective. Presence of duroquinone and 4-carboxybenzophenone during UV irradiation (308-410 nm) of the naphthalenesulfonic acids increased the photodegradation rate. Addition of H(2)O(2) during irradiation of naphthalenesulfonic acids accelerated their elimination, due to the generation of ()OH radicals in the medium. Comparison between UV photodegradation 254 m and the advanced oxidation processes (O(3), O(3)/activated carbon and UV/H(2)O(2)) showed the low-efficacy of the former in the degradation of these compounds from aqueous medium. Thus, among the systems studied, those based on the use of UV/H(2)O(2) and O(3)/activated carbon were the most effective in the oxidation of these contaminants from the medium. This is because of the high-reactivity of naphthalenesulfonic acids with the *OH radicals generated by these two systems. This was confirmed by the values of the reaction rate constant of *OH radicals with these compounds k(OH), obtained by competitive kinetics (5.7 x 10(9) M(-1) s(-1), 5.2 x 10(9) M(-1) s(-1) and 3.7 x 10(9) M(-1) s(-1) for NS, NDS and NTS, respectively).     

Scrubbing intensification for sulphur and ammonia compounds removal

Operating conditions were optimised in a new compact scrubber in order to remove odorous sulphur (H(2)S and CH(3)SH) and ammonia compounds. The influence of the superficial gas and liquid velocities, pH, contactor length, inlet concentrations (sulphur compounds, ammonia, chlorine), and the mixing effects was characterised. Whereas abatement increased with velocities, pH and the chlorine concentration, an increase of inlet CH(3)SH concentration drove to a worse efficiency of process. Moreover, the contactor length and the presence of another pollutant in the gas phase only played a role on the methylmercaptan removal. Finally, the reactive consumptions were estimated at the outlet of the reactor. The chlorination by-product quantification permitted to understand the under-stoichiometry.     

Investigating the capacity of an activated sludge process to reduce volatile organic compounds and odor emissions.

The effects of hydrogen sulfide (H2S) diffusion into activated sludge (AS) on odor and volatile organic compound (VOC) concentrations in offgas were studied over an 8-week period. Most VOCs detected in the offgas of both aeration tanks were aromatic hydrocarbons. The VOC concentrations generally decreased when H2S was introduced to the AS compared with the control, indicating a negative effect of H2S on VOC removal. Two volatile organic sulfur compounds present in the test AS offgas showed an increase followed by a decrease during H2S peak loads. Six VOCs and odor concentration increased during the introduction of an H2S peak; however no correlation was observed between H2S and odor concentration. The increase in odor concentration resulted from the increase in the concentration of six aromatic VOCs, which had their removal slowed down during a 100-ppmv H2S peak. Activated sludge diffusion provides effective H2S removal with minimal affect on odor emissions.     

稻壳基活性炭的制备及其对亚甲基蓝吸附的研究

以稻壳为原料,采用K2CO3活化法和H3P04活化法制备了比表面积为1312m^2／g和682m^2／g的活性炭,通过扫描电子显微镜（SEM）、X-射线衍射仪（XRD）对样品进行了表征,并将孔隙发达的活性炭样品用于对亚甲基蓝的吸附,结果表明,K2CO3活化法制备的活性炭样品具有更多的微孔结构;随着亚甲基蓝溶液初始浓度的增加、活性炭吸附时间的延长,亚甲基蓝的去除率呈现逐渐降低和逐渐增大的变化规律,当pH值为6时,活性炭对亚甲基蓝的吸附效果最佳;稻壳基活性炭对亚甲基蓝的吸附等温线符合Langmuir模型,Qm最高可达476．2mg／g;热力学参数△G^0△H^0和△S^0均为负值,表明稻壳基活性炭对亚甲基蓝的吸附是一个自发的放热反应。     

磷酸低温活化蔗渣基中孔生物炭及其影响因素

以甘蔗渣为原料,磷酸为活化剂,采用低温活化法制备蔗渣基中孔生物质炭.采用L9(34)4因素3水平正交实验,探讨制备蔗渣基中孔生物质炭的实验方案与工艺条件;分析了浸渍比、烘干时间、活化温度、活化时间在3个不同水平下,对蔗渣基生物质炭碘吸附值、亚甲基蓝吸附值的影响.结果表明,对蔗渣基生物质炭孔结构和得率影响最大的因素是活化温度,影响最小的因素是烘干时间;实验范围内,提高活化温度有利于材料中孔结构的形成;最佳条件下制备的蔗渣基生物质炭其低温氮气等温吸附线有明显的回滞环, BET比表面积和总孔容分别为939 m2/g和1.35 mL/g,中孔占总孔容比例为89%,亚甲基蓝吸附值高达240 mg/g,远高于木质净水用活性炭国家一级标准(135 mg/g),属于典型的中孔炭.     

高温载硫活性炭的制备及脱汞能力研究

研究了载硫温度、硫炭比(简称S/C),吸附温度等因素对载硫活性炭的硫含量、脱汞能力以及硫损失的影响,探讨载硫活性炭制备的工艺条件优化。结果表明,不同载硫温度下制备的载硫活性炭的气态Hg0吸附能力远强于原料活性炭;载硫温度不同时,负载到活性炭孔隙或表面上的硫的形态不同,导致了脱汞能力的差异,较合适的载硫温度为350℃;S/C为5%(质量分数,下同)时,随着吸附温度的升高,载硫活性炭的气态Hg0吸附量降低;在一定的载硫温度下,原料中S/C越高时,制备的载硫活性炭的硫含量越高、气态Hg0吸附能力越强,但其硫损失率也越高,从实际的使用效果来看,较合适的S/C为10%。     

Adsorption of phenolics on activated carbon--impact of pore size and molecular oxygen

The impact of pore size of activated carbon fibers (ACFs) on adsorption capacity and on the potential for oligomerization of phenolic compounds on the surface of ACFs in the presence of molecular oxygen has been investigated in this study. Compared with granular activated carbon (GAC), ACFs have unique pore size distributions, suitable to be used to elucidate the effect of pore structure on adsorption. Adsorption isotherm data were collected for o-cresol and 2-ethylphenol on four ACFs (ACC-10, ACC-15, ACC-20, and ACC-25) with different micropore volumes and BET surface area and on one type of GAC bituminous base. These isotherms were collected under anoxic (absence of molecular oxygen) and oxic (presence of molecular oxygen) conditions. No significant impact of the presence of molecular oxygen on adsorption capacity was noted for ACC-10. ACC-10 has an average pore width of 19.2 A and total pore volume of 0.43 cm3g(-1). On the other hand, for the remaining ACFs, which have larger average pore width and larger pore volume, significant increase in the adsorptive capacity had been observed when molecular oxygen was present. The GAC gave the greatest difference between anoxic and oxic conditions when compared to all the ACFs studied. Binary adsorption of o-cresol and 2-ethylphenol on ACFs with the least pore size (ACC-10) also showed no significant differences between oxic and anoxic environment. The binary system under both anoxic and oxic conditions was well predicted by the ideal adsorbed solution theory (IAST).     

Diffusive flux and pore anisotropy in sedimentary rocks

Diffusion of dissolved contaminants into or from bedrock matrices can have a substantial impact on both the extent and longevity of dissolved contaminant plumes. For layered rocks, bedding orientation can have a significant impact on diffusion. A series of laboratory experiments was performed on minimally disturbed bedrock cores to measure the diffusive flux both parallel and normal to mineral bedding of four different anisotropic sedimentary rocks. Measured effective diffusion coefficients ranged from 4.9×10(-8) to 6.5×10(-7)cm(2)/s. Effective diffusion coefficients differed by as great as 10-folds when comparing diffusion normal versus parallel to bedding. Differences in the effective diffusion coefficients corresponded to differences in the "apparent" porosity in the orientation of diffusion (determined by determining the fraction of pore cross-sectional area measured using scanning electron microscopy), with the difference in apparent porosity between normal and parallel bedding orientations differing by greater than 2-folds for two of the rocks studied. Existing empirical models failed to provide accurate predictions of the effective diffusion coefficient in either bedding orientation for all four rock types studied, indicating that substantial uncertainty exists when attempting to predict diffusive flux through sedimentary rocks containing mineral bedding. A modified model based on the apparent porosity of the rocks provided a reasonable prediction of the experimental diffusion data.     

Kinetic assessment of the potassium ferrate(VI) oxidation of antibacterial drug sulfamethoxazole

Sulfamethoxazole (SMX), a worldwide-applied antibacterial drug, was recently found in surface waters and in secondary wastewater effluents, which may result in ecotoxical effects in the environment. Herein, removal of SMX by environmentally-friendly oxidant, potassium ferrate(VI) (K(2)FeO(4)), is sought by studying the kinetics of the reaction between Fe(VI) and SMX as a function of pH (6.93-9.50) and temperature (15-45 degrees C). The rate law for the oxidation of SMX by Fe(VI) is first-order with respect to each reactant. The observed second-order rate constant decreased non-linearly from 1.33+/-0.08 x 10(3) M(-1)s(-1) to 1.33+/-0.10 x 10(0) M(-1)s(-1) with an increase of pH from 7.00 to 9.50. This is related to protonation of Fe(VI) (HFeO(4)(-) <==> H(+) + FeO(4)(2-); pK(a,HFeO(4)) = 7.23) and sulfamethoxazole (SH <==> H(+) + S(-); pK(a,SH)=5.7). The estimated rate constants were k(11)(HFeO(4)(-) + SH) = 3.0 x 10(4) M(-1)s(-1), k(12)(HFeO(4)(-) + S(-)) = 1.7 x 10(2) M(-1)s(-1), and k(13) (FeO(4)(2-) + SH) = 1.2 x 10(0) M(-1)s(-1). The energy of activation at pH 7.0 was found to be 1.86+/-0.04 kJ mol(-1). If excess potassium ferrate(VI) concentration (10 microM) is used than the SMX in water, the half-life of the reaction using a rate constant obtained in our study would be approximately 2 min at pH 7. The reaction rates are pH dependent; thus, so are the half-lives of the reactions. The results suggest that K(2)FeO(4) has the potential to serve as an oxidative treatment chemical for removing SMX in water.     

Removal of carbonyl sulfide using activated carbon adsorption

Wastewater treatment plant odors are caused by compounds such as hydrogen sulfide (H2S), methyl mercaptans, and carbonyl sulfide (COS). One of the most efficient odor control processes is activated carbon adsorption; however, very few studies have been conducted on COS adsorption. COS is not only an odor causing compound but is also listed in the Clean Air Act as a hazardous air pollutant. Objectives of this study were to determine the following: (1) the adsorption capacity of 3 different carbons for COS removal; (2) the impact of relative humidity (RH) on COS adsorption; (3) the extent of competitive adsorption of COS in the presence of H2S; and (4) whether ammonia injection would increase COS adsorption capacity. Vapor phase react (VPR; reactivated), BPL (bituminous coal-based), and Centaur (physically modified to enhance H2S adsorption) carbons manufactured by Calgon Carbon Corp. were tested in three laboratory-scale columns, 6 in. in depth and 1 in. in diameter. Inlet COS concentrations varied from 35 to 49 ppmv (86-120 mg/m3). RHs of 17%, 30%, 50%, and 90% were tested. For competitive adsorption studies, H2S was tested at 60 ppmv, with COS at 30 ppmv. COS, RH, H2S, and ammonia concentrations were measured using an International Sensor Technology Model IQ-350 solid state sensor, Cole-Parmer humidity stick, Interscan Corp. 1000 series portable analyzer, and Drager Accuro ammonia sensor, respectively. It was found that the adsorption capacity of Centaur carbon for COS was higher than the other two carbons, regardless of RH. As humidity increased, the percentage of decrease in adsorption capacity of Centaur carbon, however, was greater than the other two carbons. The carbon adsorption capacity for COS decreased in proportion to the percentage of H2S in the gas stream. More adsorption sites appear to be available to H2S, a smaller molecule. Ammonia, which has been found to increase H2S adsorption capacity, did not increase the capacity for COS.     

Reusing H2S-exhausted carbon as packing material for odor biofiltration

Exhausted carbon coming from the H2S adsorption process is a big environmental problem in Wastewater Treatment Plants. In this study, reusing exhausted carbon as a carrier of sulfide-oxidizing bacteria in lab-scale biofilters was evaluated. The exhausted carbons from different heights of the adsorption bed have different exhaustion extents, i.e. characteristics in terms of sulfur content, pH and porosity. Therefore, four biofilters were packed separately with exhausted carbon from top, middle, bottom of H2S adsorption bed, and a mixture of the three, to investigate the suitability for further H2S biofiltration. The results showed a quick startup in these biofilters (approximately 80 h). The numbers of sulfide-oxidizing bacteria immobilized on activated carbon were approximately 4.8, 9.2 and 14 x 108 CFU g-1 top, middle and bottom carbon after the 240-h operation, respectively. In addition, the biofilters demonstrated a rapid recovery to the original removal efficiency (RE) within 2 h after the H2S spike loadings. After a 110-h shutdown, the RE was rapidly recovered for all the biofilters within 5 h, with a shorter time (1 h) observed for the bottom carbon biofilter. The H2S removal mechanism of these biofilters was studied through a full analysis of sulfur products in both liquid (recycling medium) and activated carbon, and variable characterization of activated carbon before and after biofiltration. This study shows that the exhausted carbon-based biofilter is a feasible and economical alternative to conventional odor biofiltration.     

孔结构和表面化学性质对活性炭吸附性能的影响

测定了室温下3种活性炭(GAC-C、GAC-P和GAC-T)对CO2、CH4和N2的吸附性能,并对颗粒活性炭孔结构和表面化学性质进行了表征,探讨了孔结构和表面化学性质对活性炭吸附性能的影响。结果表明:由于吸附机理、孔结构、表面含氧官能团和分子极性的差异,CO2、CH4和N2在活性炭上的饱和吸附量和吸附常数的关系为CO2>CH4>N2;CH4和N2的饱和吸附量主要受活性炭微孔孔容的影响,N2和CO2饱和吸附量的差异分别是由0.572～2.0 nm的微孔和0.4～6 nm的孔引起的;CH4吸附常数主要受较大中孔和大孔影响,N2吸附常数与微孔密切相关,大孔对CO2的吸附常数影响最大。     

Ozonation of activated carbon and its effects on the adsorption of VOCs exemplified by methylethylketone and benzene

Ozonation can modify the surface property of an activated carbon such as specific surface area, pore volume, and functional group. Results indicate that ozonation can increase the specific surface area of an activated carbon from 783+/-51 to 851+/-25 m2/g due in part to increasing micropores (those below 15 A). However, there is no change in macropore and mesopore upon ozonation. The amount of oxygen functional group (OFG) increases from 197+/-4 to 240+/-4 microeq/g, mostly in hydroxyl and carboxyl groups upon ozone treatment. These oxygen-containing functional groups are stable in the temperature range 30-250 degrees C, but begin to decompose when temperature increases beyond 300 and 350 degrees C. When the temperature reaches 1200 degrees C, all OFGs virtually disappear. The effect of ozone treatment on the adsorption of volatile organic carbon (VOC) was exemplified by methylethylketone (MEK) and benzene. The adsorption density of MEK and benzene by ozone treated activated carbon (AC(O3)) are greater than that by the untreated (AC), with MEK being more adsorbable than benzene. Results of factorial analysis indicate that physical characteristics, namely, micropore, BET surface area, pore diameter (PD), micropore volume (MV) play an important role on benzene and MEK adsorption.     

Determination of spatially-resolved porosity, tracer distributions and diffusion coefficients in porous media using MRI measurements and numerical simulations

This work is focused on measuring the concentration distribution of a conservative tracer in a homogeneous synthetic porous material and in heterogeneous natural sandstone using MRI techniques, and on the use of spatially resolved porosity data to define spatially variable diffusion coefficients in heterogeneous media. The measurements are made by employing SPRITE, a fast MRI method that yields quantitative, spatially-resolved tracer concentrations in porous media. Diffusion experiments involving the migration of H(2)O into D(2)O-saturated porous media are conducted. One-dimensional spatial distributions of H(2)O-tracer concentrations acquired from experiments with the homogeneous synthetic calcium silicate are fitted with the one-dimensional analytical solution of Fick's second law to confirm that the experimental method provides results that are consistent with expectations for Fickian diffusion in porous media. The MRI-measured concentration profiles match well with the solution for Fick's second law and provide a pore-water diffusion coefficient of 1.75×10(-9)m(2)s(-1). The experimental approach was then extended to evaluate diffusion in a heterogeneous natural sandstone in three dimensions. The relatively high hydraulic conductivity of the sandstone, and the contrast in fluid density between the H(2)O tracer and the D(2)O pore fluid, lead to solute transport by a combination of diffusion and density-driven advection. The MRI measurements of spatially distributed tracer concentration, combined with numerical simulations allow for the identification of the respective influences of advection and diffusion. The experimental data are interpreted with the aid of MIN3P-D - a multicomponent reactive transport code that includes the coupled processes of diffusion and density-driven advection. The model defines local diffusion coefficients as a function of spatially resolved porosity measurements. The D(e) values calculated for the heterogeneous sandstone and used to simulate diffusive and advective transport range from 5.4×10(-12) to 1.0×10(-10)m(2)s(-1). These methods have broad applicability to studies of contaminant migration in geological materials.