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.     

Removal of cyanotoxins from surface water resources using reusable molecularly imprinted polymer adsorbents

Introduction

Microcystins (MCs; cyclic heptapeptides) are produced by freshwater cyanobacteria and cause public health concern in potable water supplies. There are more than 60 types of MCs identified to date, of which MC-LR is the most common found worldwide. For MC-LR, the WHO has established a threshold value of 1???g?L^?1 for drinking water. The present MCs removal methods such as coagulation, flocculation, adsorption, and filtration showed low efficiency for removing dissolved MC fraction from surface waters to the stipulated limit prescribed by WHO based on MC health impacts. The search for cost-effective and efficient removal method is still warranted for remediation of dissolved MC-LR-contaminated water resources.

Materials and methods

Molecularly imprinted polymer (MIP) adsorbent has been prepared using non-covalent imprinting approach. Using MC-LR as a template, itaconic acid as a functional monomer, and ethylene glycol dimethacrylate as a cross-linking monomer, a MIP has been synthesized. Computer simulations were used to design effective binding sites for MC-LR binding in aqueous solutions. Batch binding adsorption assay was followed to determine binding capacity of MIP under the influence of environmental parameters such as total dissolved solids and pH.

Results and discussion

The adsorptive removal of MC-LR from lake water has been investigated using MIPs. The MIP showed excellent adsorption potential toward MC-LR in aqueous solutions with a binding capacity of 3.64???g?mg^?1 which is about 60% and 70% more than the commercially used powdered activated carbon (PAC) and resin XAD, respectively. Environmental parameters such as total organic carbon (represented as chemical oxygen demand (COD)) and total dissolved solids (TDS) showed no significant interference up to 300?mg?L^?1 for MC-LR removal from lake water samples. It was found that the binding sites on PAC and XAD have more affinity toward COD and TDS than the MC-LR. Further, the adsorption capacity of the MIP was evaluated rigorously by its repeated contact with fresh lake water, and it was found that the adsorption capacity of the MIP did not change even after seven adsorption/desorption cycles. The contaminated water of MC-LR (1.0???g?L^?1) of 3,640?L could be treated by 1?g of MIP with an estimated cost of US $1.5.

Conclusions

The adsorption capacity of the MIP is 40% more than commercially used PAC and resins and also the polymer showed reusable potential which is one of the important criteria in selection of cyanotoxins remediation methods.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Ultra-high adsorption of Hg0 using impregnated activated carbon by selenium

Activated carbon was one of the main adsorptions utilized in elemental mercury (Hg⁰) removal from coal combustion flue gas. However, the high cost and low physical adsorption efficiency of activated carbon injection (ACI) limited its application. In this study, an ultra-high efficiency (nearly 100%) catalyst sorbent-Se_x/Activated carbon (Se_x/AC) was synthesized and applied to remove Hg⁰ in the simulated flue gas, which exhibited 120 times outstanding adsorption performance versus the conventional activated carbon. The Se_x/AC reached 17.98 mg/g Hg⁰ adsorption capacity at 160 °C under the pure nitrogen atmosphere. Moreover, it maintained an excellent mercury adsorption tolerance, reaching the efficiency of Hg⁰ removal above 85% at the NO and SO₂ conditions in a bench-scale fixed-bed reactor. Characterized by the multiple methods, including BET, XRD, XPS, kinetic and thermodynamic analysis, and the DFT calculation, we demonstrated that the ultrahigh mercury removal performance originated from the activated Se species in Se_x/AC. Chemical adsorption plays a dominant role in Hg⁰ removal: Selenium anchored on the surface of AC would capture Hg⁰ in the flue gas to form an extremely stable substance-HgSe, avoiding subsequent Hg⁰ released. Additionally, the oxygen-containing functional groups in AC and the higher BET areas promote the conversion of Hg⁰ to HgO. This work provided a novel and highly efficient carbon-based sorbent -Se_x/AC to capture the mercury in coal combustion flue gas.

Selenium-modified porous activated carbon and the interface functional group promotes the synergistic effect of physical adsorption and chemical adsorption to promote the adsorption capacity of Hg⁰.

     

Quantification of activated carbon contents in soils and sediments using chemothermal and wet oxidation methods

Activated carbon (AC) strongly sorbs organic pollutants and can be used for remediation of soils and sediments. A method for AC quantification is essential to monitor AC (re)distribution. Since AC is black carbon (BC), two methods for BC quantification were tested for AC mixed in different soils and sediments: i) chemothermal oxidation (CTO) at a range of temperatures and ii) wet-chemical oxidation with a potassium dichromate/sulfuric acid solution. For three soils, the amount of AC was accurately determined by CTO at 375 °C. For two sediments, however, much of the AC disappeared during combustion at 375 °C, which could probably be explained by catalytic effects by sediment constituents. CTO at lower temperatures (325-350 °C) was a feasible alternative for one of the sediments. Wet oxidation effectively functioned for AC quantification in sediments, with almost complete AC recovery (81-92%) and low remaining amounts of native organic carbon (5-16%).     

Mercury removal from incineration flue gas by organic and inorganic adsorbents

Experiments were performed to investigate various adsorbents for their mercury removal capabilities from incineration flue gases. Four different materials were tested; Zeolite, Bentonite, activated carbon (AC), and wood char. Real incineration off-gas and in-lab simulated combustion flue gases (N2 + Hg) were used. Three cylindrical-shaped sorbent columns with 5 cm in diameter and 20 cm in length were used. The gas flow rate was fixed at 660 l/h at all times. Concentrations of NO, CO, O2, CO2, SO2, H2O, HCl, and mercury were continuously monitored. Mercury removal efficiencies of natural Zeolite and Bentonite were found to be much lower than those of the referenced AC. Amount of Hg removed were 9.2 and 7.4 microg/g of Zeolite and Bentonite, respectively. Removal efficiencies of each layer consisted of inorganic adsorbents were no higher than 7%. No significant improvement was observed with sulfur impregnation onto the inorganic adsorbents. Organic adsorbents (wood char and AC) showed much higher mercury removal efficiencies than those of inorganic ones (Zeolite and Bentonite). Mercury removal efficiency of wood char reached over 95% in the first layer, showing almost same effectiveness as AC which currently may be the most effective adsorbents for mercury. Amount of mercury captured by wood char was approximately 0.6 mg/g of wood char, close to the amount captured by AC tested in this study. Hence, wood char, made from the waste woods through a gasification process, should be considered as a possible alternative to relatively expensive AC.     

Removal of acutely hazardous pharmaceuticals from water using multi-template imprinted polymer adsorbent

Molecularly imprinted polymer adsorbent has been prepared to remove a group of recalcitrant and acutely hazardous (p-type) chemicals from water and wastewaters. The polymer adsorbent exhibited twofold higher adsorption capacity than the commercially used polystyrene divinylbenzene resin (XAD) and powdered activated carbon adsorbents. Higher adsorption capacity of the polymer adsorbent was explained on the basis of high specific surface area formed during molecular imprinting process. Freundlich isotherms drawn showed that the adsorption of p-type chemicals onto polymer adsorbent was kinetically faster than the other reference adsorbents. Matrix effect on adsorption of p-type chemicals was minimal, and also polymer adsorbent was amenable to regeneration by washing with water/methanol (3:1, v/v) solution. The polymer adsorbent was unaltered in its adsorption capacity up to 10 cycles of adsorption and desorption, which will be more desirable in cost reduction of treatment compared with single-time-use activated carbon.     

NiO/AC催化臭氧氧化去除水中的苯酚

采用低温湿式浸渍法制备了负载氧化镍/活性炭(简称NiO/AC)催化剂。在不同pH、叔丁醇浓度等条件下,对NiO/AC与臭氧联合催化臭氧氧化苯酚的降解效果等进行了研究。用XRD、SEM及BET技术分析了活性炭与催化剂的组成、形貌及结构变化。结果表明,镍以棒状氧化镍的形式负载在活性炭表面,与AC相比,NiO/AC比表面积减少了47.9%。在O3/NiO/AC与苯酚的反应体系中,反应遵循羟基自由基(HO.)机理,苯酚的去除率比单独臭氧氧化提高了29%,且与溶液pH呈正相关。NiO/AC催化性能较稳定,镍离子最大析出浓度仅为7 mg/L,可重复使用。     

Nanoscale zero-valent iron/AC as heterogeneous Fenton catalysts in three-dimensional electrode system

In the present work, nanoscale zero-valent iron/activated carbon (NZVI/AC) was investigated as heterogeneous Fenton catalyst in three-dimensional (3D) electrode system for methyl orange (MO) degradation. Some important operating parameters such as cathodic potential, pH, and O₂ flow rate were investigated, exhibiting good decolorization. The mineralization of MO was significantly improved by 20–35 % compared to two-dimensional (2D) AC system at the optimum conditions. Although the TOC removal of AC was higher than NZVI/AC due to its good adsorption capacity initially, heterogeneous Fenton catalysis played a more and more important roles in the following test. After eight runs, NZVI/AC still exhibited excellent catalytic properties with low iron leaching. Further, a relatively comprehensive mechanism of NZVI/AC as particle electrodes in 3D system was proposed.     

Pore structure effects on Ca-based sorbent sulfation capacity at medium temperatures: activated carbon as sorbent/catalyst support

The reaction between three different Ca-based sorbents and SO2 were studied in a medium temperature range (473-773 K). The largest SO2 capture was found with Ca(OH)2 at 773 K, 126.31 mg SO2 x g Ca(OH)2(-1), and the influence of SO2 concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sulfated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO2, one kind of CaO/ activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO2 than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO2 and Ca-based sorbents and the prepared CaO/AC sorbents/catalysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the desulfurization reaction. AC acting as the support can play a role to supply O2 to increase the affinity to SO2. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO2 adsorption.     

Assessment of emissions and removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) at start-up periods in a hazardous waste incinerator

A study was conducted to observe the changes in polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) levels and congener profiles in the flue gas of a hazardous waste incinerator during two start-up periods. Flue gas samplings were performed simultaneously through Air Pollution Control Devices (APCDs) (including boiler outlet, electrostatic precipitator (ESP) outlet, wet scrubbers (WS) outlet, and activated carbon (AC) filter outlet) in different combustion temperatures during a planned cold (long) start-up and an unplanned warm (short) start-up. The results showed that PCDD/F concentrations could be elevated during the start-up periods up to levels 3–4 times higher than those observed in the normal operation. Especially lower combustion temperatures in the short start-ups may cause high PCDD/F concentrations in the raw flue gas. Assessment of combustion temperatures and Furans/Dioxins values indicated that surface-catalyzed de novo synthesis was the dominant pathway in the formation of PCDD/Fs in the combustion units. PCDD/F removal efficiencies of Air Pollution Control Devices suggested that formation by de novo synthesis existed in ESP also when in operation, leading to increase of gaseous phase PCDD/Fs in ESP. Particle-bound PCDD/Fs were removed mainly by ESP and WS, while gaseous phase PCDD/Fs were removed by WS, and more efficiently by AC filter.

Implications: This paper evaluates PCDD/F emissions and removal performances of APCDs (ESP, wet scrubbers, and activated carbon) during two start-up periods in an incinerator. The main implications are the following: (1) start-up periods increase PCDD/F emissions up to 2–3 times in the incinerator; (2) low combustion temperatures in start-ups cause high PCDD/F emissions in raw gas; (3) formation of PCDD/Fs by de novo synthesis occurs in ESP; (4) AC is efficient in removing gaseous PCDD/Fs, but may increase particle-bound ones; and (5) scrubbers remove both gaseous and particle-bound PCDD/Fs efficiently.     

活性焦和活性炭负载纳米铁处理TNT红水中的二硝基甲苯磺酸钠

以活性焦和活性炭为载体,采用液相还原法制备了负载纳米铁,比较了两种负载纳米铁对TNT红水中难降解物质二硝基甲苯磺酸钠(包括2,4-DNT-3-SO3Na和2,4-DNT-5-SO3Na)的去除能力。实验结果表明,作为负载材料活性焦的相对有效比表面积与孔体积要优于活性炭,而且有利于更好地发挥出负载纳米铁的优势。单位面积活性焦负载纳米铁去除2,4-DNT-5-SO3Na的能力明显高于活性炭负载纳米铁,单位面积活性焦负载纳米铁去除2,4-DNT-3-SO3Na的能力在较小投加量条件下高于活性炭负载纳米铁,但均随投加量的增加而下降;而对于活性炭负载纳米铁,其单位面积去除能力基本不受投加量的影响,而且对二硝基甲苯磺酸钠的去除率高于活性焦负载纳米铁。耦合混凝沉淀的总去除效果表明,单位面活性焦负载纳米铁对2,4-DNT-5-SO3Na的去除能力高于活性炭负载纳米铁,而对2,4-DNT-3-SO3Na的去除能力则低于活性炭负载纳米铁。     

多循环CCRs法在分离燃煤锅炉尾部烟气中CO2方面的应用

随着温室效应和全球变暖的加剧,煤燃烧所排出的CO2作为引起温室效应的主要气体而引起人们的密切关注.由于燃煤锅炉所排放的尾气中所含的CO2的体积份额低、排放量大,而且处于微负压状态,因此目前控制和分离吸收CO2的方法,包括各类吸收法、吸附法、膜分离法和O2/CO2燃烧技术等,能够经济可行地适用于电力工业燃煤锅炉尾部烟气中CO2分离的方法非常少.与上述各类方法相比,钙基吸收剂CCRs(calcination/carbonation reactions)法是一种新兴的经济可行的分离燃煤锅炉尾部烟气中CO2的方法.对采用该法时,吸收剂的选择、吸收剂在多次CCRs过程中结构特点的变化、提高吸收剂对CO2的吸收容量以及防止吸收剂反应性的衰减等方面进行了详细的阐述.     

A sulfur-resistant CuS-modified active coke for mercury removal from municipal solid waste incineration flue gas

Environmental Science and Pollution Research - Adsorption is a typical method for air pollutant removal from flue gas. A CuS-modified active coke (CuS/AC) sorbent was developed to improve the...     

Quantification of elemental and total carbon in combustion particulate matter using thermal-oxidative analysis

The use of a two-step thermal-oxidative analysis (TOA) technique for quantification of the mass of total carbon (TC) and elemental carbon (EC) of turbine engine-borne particulate matter (PM) has been evaluated. This approach could be used in lieu of analysis methods which were developed to characterize diluted PM. This effort is of particular interest as turbine engine PM emissions typically have a higher EC content than ambient aerosols, and filter sample mass loadings can be significantly greater than recommended for existing analysis techniques. Analyses were performed under a pure oxygen environment using a two-step temperature profile; reference carbon and actual PM samples were used to identify appropriate analysis conditions. Thermal gravimetric analysis (TGA) methods were used to provide guidance on the nature of the carbon in several of the materials. This was necessary as a standard reference material does not exist for determination of the EC fraction in PM. The TGA also assisted in identifying an appropriate temperature range for the first-stage of the TOA method. Quantification of TC and EC for turbine engine PM samples using TOA was compared to results obtained using the NIOSH 5040 thermal-optical method. For first-stage TOA temperatures of 350°C and 400°C, excellent agreement between the techniques was observed in both the quantified TC and EC, supporting the viability for using TOA for analysis of turbine engine PM samples. A primary benefit of using TOA for these types of PM samples is that filters with relatively high PM mass loadings (sampled at the emission source) can be readily analyzed. In addition, an entire filter sample can be evaluated, as compared to the use of a filter punch sample for the NIOSH technique. While the feasibility of using a TOA method for engine PM samples has been demonstrated, future studies to estimate potential OC charring and oxidation of EC-type material may provide additional data to assess its impact on the OC/EC fractions for other carbon-type measurements.

Implications: This work presents results and procedures of an analytical method for the determination of total and elemental carbon, i.e., TC and EC present in combustion source particulate matter samples. In general, it is shown that the LECO TOA methodology is as reliable and comprehensive as NIOSH 5040 for determining TC and EC carbon types in particulate matter present in turbine emission sources, and should be considered as an alternative. Principles of the methodology, differences, and corresponding agreement with the standard NIOSH 5040 method and TGA analysis are discussed.     

湿法再生吸附剂制备及用于大气CO2的直接捕集

基于湿法再生吸附技术,利用强碱性季铵盐树脂材料制备了异相吸附剂薄膜,应用于大气中极低CO2的直接分离,以对抗全球变暖。通过滴定法分析吸附剂材料的电荷密度和吸附容量,利用SEM分析不同工况下制备出来的膜材料的表观结构,并对膜材料进行CO2吸附性能的测试。结果发现,热处理能够明显提高膜材料的吸附性能,还研究吸附剂制备对吸附速率,吸附量和机械强度等性能的影响,发现粒径小于43μm的树脂粉末,按60％质量分数制成的500μm厚膜材料具有较优的综合性能。     

Distribution of volatile organic compounds during the combustion process in coal-fired power stations

This study concerns the distribution of volatile organic compounds (VOC) emitted during combustion processes in coal-fired power stations. Thermal desorption technique was employed to analyse VOC concentrations in gaseous emissions (trapped onto Carbotrap B sorbent) and solid samples (coal, fly ash and slag). An empirical parameter (Y) was employed to evaluate the relationships between the compounds emitted during a real combustion process and those obtained in coal analysis by thermal desorption. The Y calculation does not provide any information about VOC emissions through solid effluents as fly ash or slag. A comparison method was created for this purpose. The results obtained using this method confirm that combustion is almost complete for aromatic and aliphatic hydrocarbons. Chlorinated compounds are mainly formed during the combustion.     

Pore Structure Effects on Ca-Based Sorbent Sulfation Capacity at Medium Temperatures: Activated Carbon as Sorbent/Catalyst Support

Abstract

The reaction between three different Ca-based sorbents and SO₂ were studied in a medium temperature range (473–773 K). The largest SO₂ capture was found with Ca(OH)₂ at 773 K, 126.31 mg SO₂?g Ca(OH)₂ ^?1, and the influence of SO₂ concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sul-fated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO₂, one kind of CaO/activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO₂ than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO₂ and Ca-based sorbents and the prepared CaO/AC sorbents/cata-lysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the des-ulfurization reaction. AC acting as the support can play a role to supply O₂ to increase the affinity to SO₂. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO₂ adsorption.     

微波辅助空气氧化水溶液中的PCP

采用活性炭为催化剂,对微波辅助空气氧化水溶液中的五氯酚进行了处理研究.考察了活性炭投加量、微波功率、辐射时间和通气量对溶液中五氯酚的去除率的影响.结果表明,在通气量为0.2 L/min,微波功率800 W和微波辐射60 min时,五氯酚的去除率可达到90%以上;对微波辐射前后的滤液进行紫外扫描和pH分析,可证实五氯酚被降解.     

Performance evaluation of an in situ nitrous acid measurement system and continuous measurement of nitrous acid in an indoor environment

Nitrous acid (HONO) may cause adverse effects to mucous membranes and lung function when people are exposed to higher HONO concentrations than those present in typical indoor residential environments. Therefore, determination of HONO concentration in indoor environments is required to investigate occurrences of high HONO levels. In this work, a high-time-resolution measurement system was utilized to better understand the levels and dynamic behavior of HONO in an indoor environment. The performance of the in situ HONO analyzer applied to this work was evaluated using a 12-hr integrated annular denuder technique under ambient conditions. Both methods for the measurements of HONO were in good agreement, with a regression slope of 0.84, an intercept of 0.09, and correlation coefficient (r2) of 0.67. Indoor HONO and nitrogen oxide concentrations were also observed for approximately 5 days in winter in the living room of an apartment that had a gas range for cooking in the kitchen. Investigation of the relationships among nitric oxide (NO), nitrite (NO2), and HONO concentrations suggests that HONO production during combustion could be the result of direct emission, whereas the heterogeneous NO2 chemistry during the background period and after combustion was the possible pathway of HONO production. Controlled combustion experiments, performed at a burning rate of 50% valve setting, show peak HONO concentrations during the unvented combustion to be approximately 8-10 times higher than background levels depending on the time of day. At a burning rate setting of 50%, the peak concentration of HONO during unvented combustion was found to be 33-37% higher than those from "weak" (airflow = 340 m3/hr) and "strong" (airflow = 540 m3/hr) vented combustions. The decay rate of the HONO concentrations for the unvented combustion conditions was approximately 2-fold higher in the daytime than in the nighttime and significantly less than those of NO and NO2.