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.     

基于树脂处理和电解联用的卤代消毒副产物控制

天然有机物(NOM)和溴离子是卤代消毒副产物的前体物,氯型阴离子交换树脂可以有效去除这2种前体物,同时交换出氯离子。交换出的氯离子与水源水中天然存在的氯离子通过电解可以产生自由氯用于消毒。将氯型阴离子 交换树脂处理与电解联用,通过建立和优化树脂处理与电解消毒方法,实现饮用水中卤代消毒副产物的控制。结果表明：树脂依次经过碱/酸洗、甲醇抽提和5次去离子水清洗后,可以有效减少树脂溶出,并降低氯离子和甲醇的影响;在2 L的模拟水源水样中加入20 mL树脂反应1 h后,可以去除93.7%的NOM和91.2%的溴离子;由树脂交换至水样中的氯离子通过电解氧化,可以在3 min内产生5 mg·L-1的氯。与单独的氯消毒相比,新方法可以削减86.4%的总有机卤 素(TOX)。     

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.     

以铁/活性炭为催化剂的非均相电-Fenton技术对水中苯酚的去除

以铁/活性炭(Fe/AC)作为催化剂,研究了非均相电-Fenton技术对水中苯酚的去除性能。采用等体积浸渍法制备了Fe/AC,利用BET、ICP-OES和XPS等分析方法对Fe/AC进行了表征。结果表明：3.94%的铁已成功负载在活性炭上;在催化剂用量为0.7 g·L⁻¹、电流密度为9 mA·cm⁻²和电解液初始pH为5的条件下,在反应90 min后,苯酚和总有机碳(TOC)的去除率分别达到了95.94%和64.51%。此外,经过8次连续运行实验后,Fe/AC仍表现出优异的催化性能和低铁渗出率,这说明其具有良好的稳定性和可重复使用性。对使用Fe/AC催化剂的非均相电-Fenton技术去除水中苯酚的过程机理进行了讨论,提出了阴极原位生成H₂O₂、Fe/AC吸附苯酚并催化H₂O₂分解为·OH进而氧化苯酚的机理。以上结果表明,使用Fe/AC作为催化剂的非均相电-Fenton技术在实际废水处理领域具有较好的应用前景。     

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。     

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.     

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.     

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.     

Ce-ZnO/AC在真空紫外下催化降解对二甲苯废气

将Ce掺杂ZnO光催化剂通过负载活性炭 (AC)的方式制备Ce-ZnO/AC吸附-催化复合材料,并以对二甲苯为典型挥发性有机污染物(VOC),研究其在真空紫外体系中光催化转化性能。结果表明：活性炭的负载能有效提高臭氧的利用效率,强化对二甲苯的去除率和矿化率;当Ce-ZnO与活性炭的负载比例为1∶2时,复合材料的光催化性能达到最优,此时对二甲苯的转化率达到95%以上;活性炭的负载不仅可使污染物与催化剂充分接触,还可有效利用臭氧从而产生·OH等自由基,协同促进对二甲苯的降解,同时更多的中间产物被降解。复合催化材料显示了良好的稳定性,在利用5次后,仍可再生恢复其光催化性能至初始状态。相对于单独的真空紫外光解,Ce-ZnO/AC吸附-催化复合材料与真空紫外体系耦合降解二甲苯的能量利用率提高了2倍,经济性好。     

3种表面修饰活性炭对水体中磷的吸附

为克服活性炭磷吸附能力有限的问题,使用ZnCl2、十六烷基三甲基氯化铵（CTAC）和Fe/Al（氢）氧化物纳米颗粒分别研究了物理结构法、表面活性剂法和载体法3 种表面修饰方法对活性炭磷吸附能力的影响。实验发现,载体法为3 种方法中最好的修饰方法。对载体法制备吸附剂的材料用量的比较发现,在Fe（III）和Al（III）摩尔比为9 ：1 的条件下,把1.5 g活性炭加入到总浓度为1 mol·L-1的200 mL Fe(III)和Al(III)混合溶液中,形成的纳米Fe/Al（氢）氧化物能够较好地利用活性炭表面,该复合材料1.5AC-Fe/Al在磷平衡浓度约为50 mg·L-1时吸附量达到29.3mg·g-1。该材料表征结果表明,纳米Fe/Al（氢）氧化物颗粒被成功负载在活性炭表面。在酸性条件下,复合材料表面的—H+和—OH2+所引起的静电吸附和配位交换是促进吸附带负电磷酸根离子的原因。     

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。     

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...     

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.     

UV/H2O2/Fe-FeOxH2x-3和UV/H2O2工艺降解水中富里酸的研究

采用硼氢化钠还原法制备核-壳结构的Fe-FeOxH2x-3复合材料,研究了富里酸在UV/H2O2和UV/H2O2/Fe-FeOxH2x-3两种不同反应体系下的降解情况。结果表明,核-壳结构Fe-FeOxH2x-3的存在,提高了UV/H2O2降解富里酸的反应速率,TOC去除达到84%。采用XAD树脂吸附法对反应前后的富里酸进行化学分级表征,结果表明,富里酸经反应后憎水酸（HoA）、弱憎水酸（WHoA）和憎水中性物质（HoN）都有所减少,进而转化为亲水性物质（HiM）;用超滤膜法对富里酸进行物理分级表征,考察了富里酸在反应前后分子量分布的变化情况。同时,富里酸经过反应后生成的中间产物降低了三氯甲烷生成趋势。     

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.