Influence of solute dissociation constants on the optimum adsorption of weak electrolytes on activated carbons

The pH of solutions has dramatic effects on the adsorption capacity of activated carbons from solutions, while the adsorption curves for weak electrolytes acquired as a function of pH show maxima at some intermediate pH. This intermediate pH is usually near the pKa of the electrolyte. Some apparent controversy inherent in these statements has, however, motivated experimental and analytical investigation of these systems. The present investigation therefore employed standard ASTM techniques in the study of adsorption systems, as well as non-linear least squares regression techniques to predict adsorption on activated carbon. It was observed that the adsorption isotherms do not indicate the existence of clear adsorption maxima for pKa values above 10. The existence of both a maximum as well as a minimum on the adsorption of a range of moderately weak electrolytes is indicated. Good agreement was observed between experimental and predicted adsorption isotherms.     

活性炭三维电极电促吸附去除水中氟离子的研究

主要研究颗粒活性炭作为第三维电极电促吸附水中氟离子。通过在颗粒活性炭上施加不同电压,测定吸附容量和考察吸附动力学过程,结果表明,将电压控制在3~5 V范围内可有效增强三维电极的吸附容量,5 V电压下的电促吸附容量比开路电位下提高30%,同时此电促吸附反应符合一级反应动力学。在动态开放式实验中,所施加电压、含氟水样pH、电解质浓度、初始氟离子浓度和进水流量均对电促吸附容量产生影响。采用电子扫描电镜和氮气吸附脱附的方法比较吸附前后活性炭颗粒表面性质的变化,发现其表面并未发生氧化反应,孔容孔径也未发生明显变化,且孔径大小与电促吸附有一定的关联。综合这些实验结果表明,三维电极电促吸附可有效提高颗粒活性炭的吸附效果,这是由于活性炭电极表面产生双电层作用的结果,并非活性炭表面或者水溶液中产生氧化反应所至。     

Preparation of activated carbon using low temperature carbonisation and physical activation of high ash raw bagasse for acid dye adsorption

Activated carbons were prepared from bagasse through a low temperature (160 degrees C) chemical carbonisation treatment and gasification with carbon dioxide at 900 degrees C. The merit of low temperature chemical carbonisation in preparing chars for activation was assessed by comparing the physical and chemical properties of activated carbons developed by this technique to conventional methods involving the use of thermal and vacuum pyrolysis of bagasse. In addition, the adsorption properties (acid blue dye) of these bagasse activated carbons were also compared with a commercial activated carbon. The results suggest that despite the high ash content of the precursor, high surface areas (614-1433 m2 g(-1)) and microporous (median pore size from 0.45 to 1.2 nm) activated carbons can be generated through chemical carbonisation and gasification. The micropore area of the activated carbon developed from chars prepared by the low temperature chemical carbonisation provides favourable adsorption sites to acid blue dye (391 mg g(-1) of carbon). The alkalinity of the carbon surface and total surface area were shown to have complementary effects in promoting the adsorption of acid blue dye. Adsorption of the anionic coloured component of the acid dye was shown to be promoted in carbon exhibiting alkaline or positively charged surfaces. This study demonstrates that activated carbons with high acid dye adsorption capacities can be prepared from high ash bagasse based on low temperature chemical carbonisation and gasification.     

Roles of physical and chemical properties of activated carbon in the adsorption of lead ions

Elucidation of the roles of chemical and physical properties of activated carbons is an important basis for the systematic development of adsorbents with optimal properties specific for certain applications. Such an understanding has challenged most researchers and this has been attributed with the difficulty in decoupling the effect of chemical and physical properties that characterize activated carbons. This study proposed empirical modeling in resolving the effects of individual carbon properties in lead adsorption. A model based on lead adsorption and carbon properties including total surface area, mean pore size and heteroatom concentrations has been shown to adequately describe the lead adsorption onto activated carbons prepared from bagasse. To support this investigation a series of activated carbons were prepared from bagasse by physical and by chemical activation techniques. The surface chemical properties of the carbons were inferred from carbon pH and heteroatom concentrations. The physical characterizations of the carbons included total surface area by the BET technique and mean pore size measured using the Horvath-Kawazoe equation. Adsorption tests were conducted using a low concentration of lead (5 ppm) and the solution pH was maintained at 1.0 to maintain lead speciation to the un-complexed Pb(2+) ion. The adequacy of the proposed empirical models was statistically assessed. This form of analysis was shown to provide valuable information in tailor making adsorbents and selecting appropriate adsorbents for lead adsorption.     

Surface chemistry of activated carbons and its relevance for effects of relative humidity on adsorption of chlorinated organic vapors

The effects of relative humidity (RH) on the adsorption of methylene chloride (METH) and 1,1,1-trichloroethane (TCEA) on two commercial activated carbons, made from bituminous coal (carbon BPL) and coconut shell (carbon PCB), were studied. Three levels of RH were tested by tracking the breakthrough curves of each adsorbate eluted from a fixed-bed adsorption column. Adsorption capacities for these adsorbates were decreased with increase of RH. The magnitude of the effect of water vapor on adsorption is greater for carbon BPL and METH than for carbon PCB and TCEA. The results of the effect of water vapor on the adsorption capacity observed in this study were further examined based on the chemical characterization of activated carbons and the fundamental physical differences between the adsorbates.     

Properties of pyrolytic chars and activated carbons derived from pilot-scale pyrolysis of used tires

Used tires were pyrolyzed in a pilot-scale quasi-inert rotary kiln. Influences of variables, such as time, temperature, and agent flow, on the activation of obtained char were subsequently investigated in a laboratory-scale fixed bed. Mesoporous pores are found to be dominant in the pore structures of raw char. Brunauer-Emmett-Teller (BET) surfaces of activated chars increased linearly with carbon burnoff. The carbon burnoff of tire char achieved by carbon dioxide (CO2) under otherwise identical conditions was on average 75% of that achieved by steam, but their BET surfaces are almost the same. The proper activation greatly improved the aqueous adsorption of raw char, especially for small molecular adsorbates, for example, phenol from 6 to 51 mg/g. With increasing burnoff, phenol adsorption exhibited a first-stage linear increase followed by a rapid drop after 30% burnoff. Similarly, iodine adsorption first increased linearly, but it held as the burnoff exceeded 40%, which implied that the reduction of iodine adsorption due to decreasing micropores was partially made up by increasing mesopores. Both raw chars and activated chars showed appreciable adsorption capacity of methylene-blue comparable with that of commercial carbons. Thus, tire-derived activated carbons can be used as an excellent mesoporous adsorbent for larger molecular species.     

Adsorption of mercury by activated carbon prepared from dried sewage sludge in simulated flue gas

Conversion of sewage sludge to activated carbon is attractive as an alternative method to ocean dumping for the disposal of sewage sludge. Injection of activated carbon upstream of particulate matter control devices has been suggested as a method to remove elemental mercury from flue gas. Activated carbon was prepared using various activation temperatures and times and was tested for their mercury adsorption efficiency using lab-scale systems. To understand the effect of the physical property of the activated carbon, its mercury adsorption efficiency was investigated as a function of its Brunauer–Emmett–Teller (BET) surface area. Two simulated flue gas conditions, (1) without hydrogen chloride (HCl) and (2) with 20 ppm HCl, were used to investigate the effect of flue gas composition on the mercury adsorption capacity of activated carbon. Despite very low BET surface area of the prepared sewage sludge activated carbons, their mercury adsorption efficiencies were comparable under both simulated flue gas conditions to those of pinewood and coal activated carbons. After injecting HCl into the simulated flue gas, all sewage sludge activated carbons demonstrated high adsorption efficiencies, that is, more than 87%, regardless of their BET surface area.

Implications: We tested activated carbons prepared from dried sewage sludge to investigate the effect of their physical properties on their mercury adsorption efficiency. Using two simulated flue gas conditions, we conducted mercury speciation for the outlet gas. We found that the sewage sludge activated carbon had mercury adsorption efficiency comparable to pinewood and coal activated carbons, and the presence of HCl minimized the effect of physical property of the activated carbon on its mercury adsorption efficiency.     

Adsorption of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-metylphenoxyacetic acid onto activated carbons derived from various lignocellulosic materials

Adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-metylphenoxyacetic acid (MCPA) from aqueous solution onto activated carbons derived from various lignocellulosic materials including willow, miscanthus, flax, and hemp shives was investigated. The adsorption kinetic data were analyzed using two kinetic models: the pseudo-first order and pseudo-second order equations. The adsorption kinetics of both herbicides was better represented by the pseudo-second order model. The adsorption isotherms of 2,4-D and MCPA on the activated carbons were analyzed using the Freundlich and Langmuir isotherm models. The equilibrium data followed the Langmuir isotherm. The effect of pH on the adsorption was also studied. The results showed that the activated carbons prepared from the lignocellulosic materials are efficient adsorbents for the removal of 2,4-D and MCPA from aqueous solutions.     

A comparative study of anaerobically digested and undigested sewage sludges in preparation of activated carbons.

Disposal of sewage sludge is an increasingly expensive and environmentally sensitive problem throughout the world. Preparation of activated carbon from sewage sludge offers an attractive re-use alternative to the traditional disposal routes. The objective of this research work was to compare anaerobically digested sewage sludge (DS) and undigested sewage sludge (US) as source materials in the preparation of activated carbons. Prior to the preparation the properties of the two types of sewage sludges were determined and compared. Subsequently the sludge samples were activated with 5 M ZnCl2 solution and thereafter pyrolysed at heating temperature of 650 degrees C for 2 h with the heating rate of 15 degrees C/min under a nitrogen atmosphere. The produced activated carbons were characterised by surface area and porosity analysis, CHN elemental composition and ash contents determination, and aqueous phase phenol adsorption tests. The results indicate that in comparison with the DS, the US had a higher carbon content and lower ash content, and accordingly yielded a better activated carbon with a higher BET surface area, pore volume, carbon content and phenol adsorption capacity.     

Electrochemical and FTIR studies of the mutual influence of lead(II) or iron(III) and phenol on their adsorption from aqueous acid solution by modified activated carbons

Cyclic voltammetry and spectral FTIR studies of the influence of activated carbon surface modification on the co-adsorption of metal cation (lead or iron) and phenol from aqueous acidic solution were carried out. The diversity in surface chemical structure was achieved by applying different procedures of inorganic matter removal and by modifying the carbon samples in various ways: heating under vacuum, aminoxidation in an ammonia-oxygen atmosphere, oxidation with concentrated nitric acid. The quantities of adsorbed metal ions (Pb(2+) or Fe(3+)) and phenol from solutions containing cation or phenol separately or in a mixture were determined. The adsorption capacity from acidic aqueous acidic solution depends on the chemical properties of the activated carbon surface (e.g., decrease in phenol adsorption with relative lower basicity of the adsorbent). The electrochemical parameters of electrodes made from the carbon samples were estimated, and some possible electrochemical reactions were determined from voltammograms recorded in acid electrolyte solution containing adsorbed species (separately or as a mixture). Relationships were found between metal ion adsorption and electrochemical behavior of Pb(2+)/Pb(4+) and Fe(3+)/Fe(2+) couples on the one hand, and the presence of phenol in the solutions tested and the influence of surface chemistry of the carbon electrodes on electrochemical processes on the other. The changes in adsorption capacity with respect to the adsorbates used and the changes in FTIR spectra of the carbons as a result of adsorption and/or coupling phenol molecules are discussed.     

双功能吸附剂的制备及其对水中毒死蜱的降解特性

对具有催化功能的负载Fe（Ⅲ）的活性炭进行了表征,与母体活性炭相比,其比表面积以及微孔体积均有所下降,酸性官能团的量有所增加;考察了普通浸渍法和超声浸渍法制备的双功能活性炭对毒死蜱的吸附和降解性能,结果表明,双功能活性炭对毒死蜱的吸附量有所降低,但对毒死蜱的降解能力增强,超声浸渍法所制备的活性炭对毒死蜱的降解能力要优于普通浸渍法所制备的活性炭。     

Properties of Pyrolytic Chars and Activated Carbons Derived from Pilot-Scale Pyrolysis of Used Tires

Abstract

Used tires were pyrolyzed in a pilot-scale quasi-inert rotary kiln. Influences of variables, such as time, temperature, and agent flow, on the activation of obtained char were subsequently investigated in a laboratory-scale fixed bed. Meso-porous pores are found to be dominant in the pore structures of raw char. Brunauer-Emmett-Teller (BET) surfaces of activated chars increased linearly with carbon burnoff. The carbon burnoff of tire char achieved by carbon dioxide (CO₂) under otherwise identical conditions was on average 75% of that achieved by steam, but their BET surfaces are almost the same. The proper activation greatly improved the aqueous adsorption of raw char, especially for small molecular adsorbates, for example, phenol from 6 to 51 mg/g. With increasing burnoff, phenol adsorption exhibited a first-stage linear increase followed by a rapid drop after 30% burnoff. Similarly, iodine adsorption first increased linearly, but it held as the burnoff exceeded 40%, which implied that the reduction of iodine adsorption due to decreasing micro-pores was partially made up by increasing mesopores. Both raw chars and activated chars showed appreciable adsorption capacity of methylene-blue comparable with that of commercial carbons. Thus, tire-derived activated carbons can be used as an excellent mesoporous adsorbent for larger molecular species.     

Carbon dioxide capturing technologies: a review focusing on metal organic framework materials (MOFs)

In this study, a relevant literature has been reviewed focusing on the carbon dioxide capture technologies in general, such as amine-based absorption as conventional carbon dioxide capturing technology, aqueous ammonia-based absorption, membranes, and adsorption material (e.g., zeolites, and activated carbons). In more details, metal organic frameworks (MOFs) as new emerging technologies for carbon dioxide adsorption are discussed. The MOFs section is intended to provide a comprehensive overview of MOFs including material characteristics and synthesis, structural features, CO₂ adsorption capacity, heat of adsorption and selectivity of CO₂.     

磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性

以甘蔗渣为原料,采用微波辅助H3PO4活化法制备富含含氧酸官能团的中孔生物质炭。通过扫描电子显微镜SEM、傅立叶变换红外光谱FT-IR等技术对生物质炭物理化学性质进行表征,并通过静态实验法,探讨炭样对亚甲基蓝的吸附行为及热力学性质。结果表明,H3PO4活化制备蔗渣生物质炭的适宜条件为浸渍比1：1,烘干时间10h,活化功率900W,活化时间22min,在此条件下制得的生物质炭得率为39．2％,碘值为817mg／g,亚甲基蓝值为229mg／g,为国家一级品标准的1．7倍。红外光谱分析表明,炭样表面以羟基、羰基、羧基等酸性官能团为主。静态吸附实验表明,Freundlich方程与Redlich—Peterson方程能较好地描述等温吸附行为,表现为优惠吸附。热力学研究表明,吸附吉布斯自由能（△G0）〈0,说明吸附反应是自发过程,而吸附标准焓变（△H0）〉70KJ／mol,表明亚甲基蓝在制备炭样上的吸附是吸热反应,升温有利于吸附,且化学反应在吸附过程中发挥了重要作用。     

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%。     

Equilibrium and kinetics of adsorption of phosphate onto iron-doped activated carbon

Purpose

Two series of activated carbons modified by Fe (II) and Fe (III) (denoted as AC/N-Fe^II and AC/N-Fe^III), respectively, were used as adsorbents for the removal of phosphate in aqueous solutions.

Method

The synthesized adsorbent materials were investigated by different experimental analysis means. The adsorption of phosphate on activated carbons has been studied in kinetic and equilibrium conditions taking into account the adsorbate concentration, temperature, and solution pH as major influential factors.

Results

Maximum removals of phosphate are obtained in the pH range of 3.78?C6.84 for both adsorbents. Langmuir isotherm adsorption equation well describes the experimental adsorption isotherms. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Results suggest that the main phase formed in AC/N-Fe^II and AC/N-Fe^III is goethite and akaganeite, respectively; the presence of iron oxides significantly affected the surface area and the pore structure of the activated carbon.

Conclusions

Studies revealed that iron-doped activated carbons were effective in removing phosphate. AC/N-Fe^II has a higher phosphate removal capacity than AC/N-Fe^III, which could be attributed to its better intra-particle diffusion and higher binding energy. The activation energy for adsorption was calculated to be 22.23 and 10.89 kJ mol^?1 for AC/N-Fe^II and AC/N-Fe^III, respectively. The adsorption process was complex; both surface adsorption and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.     

Adsorption and catalytic decomposition of methyl bromide and methyl iodide on activated carbons

Methyl bromide (MeBr) is commonly used for fumigating structures and commodities. Emission of MeBr during such treatments is environmentally detrimental because of the reaction of MeBr with stratospheric ozone. In this study we evaluated adsorption of MeBr and methyl iodide (MeI) – a potential MeBr replacement, on five commercial activated carbons, and studied water-initiated catalytic decomposition of adsorbed fumigants. All carbon samples showed great adsorption affinity to MeBr and MeI, with the adsorption capacity for MeI several times greater than that for MeBr on the same carbon. For the same fumigant, adsorption was affected by the type of carbon and the concentration of fumigant. Water initiated decomposition of both fumigants, liberating Br⁻ or I⁻ as a transformation product. The rate of decomposition increased with increasing temperature, and was also influenced by the carbon type. The half-life of MeBr or MeI on Centaur, a catalytically modified carbon, was <2 h at 80°C. The rapid decomposition of MeBr and MeI on wet carbons at elevated temperatures may be used to detoxify these fumigants after adsorption on activated carbons.     

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.     

玉米芯掺杂对污泥基活性炭性能的影响

针对以城市污水厂剩余污泥为原料制备的污泥基活性炭微孔性差、比表面积低的缺陷,将一定比例玉米芯掺杂到污泥中以期改善活性炭性质。通过对活性炭的比表面积、孔结构、碘值、表面官能团测定以及表面电镜分析,探讨了不同比例玉米芯掺杂对活性炭物理化学性质的影响,并以苯酚和硝基苯为目标物,对比考察所制活性炭对有机物的吸附性能。实验结果表明,随着玉米芯掺杂比例的提高,活性炭微孔体积及比表面积明显增大,但活性炭表面官能团种类及数量变化不明显。所制活性炭表面都以酸性基团为主。结果显示苯酚和硝基苯吸附值与活性炭表面酸性基团含量关系密切,因此,玉米芯的掺杂对苯酚和硝基苯的吸附没有明显的促进作用。     

改性竹活性炭去除汞离子

采用溴化钾、碘化钾和硫磺对竹活性炭掺杂改性,利用电感耦合等离子体发射光谱仪测定滤液中汞离子浓度,用除汞效率和吸附容量评价活性炭对溶液中汞离子的吸附性能,探讨其吸附机理。结果表明,掺杂改性明显提高了竹活性炭的除汞性能。原竹活性炭的除汞效率为78.6%,吸附容量为2.210 mg/g;经碘化钾、溴化钾和硫磺掺杂改性后的竹活性炭除汞效率分别为94.3%、93.8%和88.8%,吸附容量分别为2.830、2.813和2.663 mg/g;经溴化钾(碘化钾)和硫磺联合改性的竹活性炭对水溶液中汞离子的吸附性能性能又有提高,其中以先载硫后载溴化钾的方法除汞效果最好,除汞效率达96.6%,吸附容量为2.898 mg/g。