Evaluation of Victorian low rank coal-based adsorbents for the removal of organic compounds from aqueous systems

Three activated carbons and two chars made from low rank coal were evaluated in terms of their ability to remove the organic compound 4-nitrophenol (4-NP) and natural organic matter (NOM) from aqueous systems. The adsorption equilibrium capacities of all adsorbents for 4-NP correlated with the micropore area of the adsorbents. Adsorption rates showed improved removal with decreasing particle size and higher carbon mass loadings. A pseudo first order model was used to fit the kinetic data, with a correlation coefficient of 0.995–0.999 for all systems.

The adsorption capacity for NOM, as measured by UV-absorbing DOC, correlated well with the pore volume and pore surface areas for pores with diameters in the range 2.7–21 nm. The trend in the adsorption capacities and removal rates of the adsorbents for NOM provided evidence that the pore size distribution is one of the most important physical characteristics of activated carbon for the adsorption of NOM.

The performance of activated low rank coal based materials was comparable to a high quality coconut-based commercial carbon in batch systems. Although the non-activated char adsorbents gave poor performance, they have potential for use in applications where poor performance can be outweighed by lower cost.     

Adsorption of mercury(II) by coal fly ash

Coal fly ash, an industrial solid waste, was found to have a good adsorption capacity for mercury(II). Adsorption of mercury(II) on coal fly ash conforms to Freundlich's adsorption model. Several parameters such as time of equilibration, effect of pH, effect of initial concentration of solute, effect of fly ash dose etc. were studied. The maximum adsorption was observed after shaking for 3 h. Solution pH was the most important parameter affecting the adsorption. The optimum pH range was 3.5–4.5. There was total adsorption of mercury below 10 mg l⁻¹. The performance of coal fly ash as an adsorbent was found to be significant when compared with activated powdered charcoal.     

Color and chlorinated organics removal from pulp mills wastewater using activated petroleum coke

Delayed petroleum coke, a waste by-product from the oil sand industry, was utilized in the production of activated carbon. The activated carbon was then evaluated for color and chlorinated organics reduction from pulp mill wastewater. The activation of the petroleum coke was evaluated using a fixed bed reactor involving carbonization and activation steps at temperature of 850 degrees C and using steam as the activation medium. The activation results showed that the maximum surface area of the activated coke was achieved at an activation period of 4 h. The maximum surface area occurred at burnoff and water efficiency of 48.5 and 54.3%, respectively. Increasing the activation period to 6 h resulted in a decrease in the surface area. Methylene blue adsorption results indicated that the activation process was successful. Methylene blue adsorbed per 100 g of applied activated coke was 10 times higher than that adsorbed by raw petroleum coke. Adsorption equilibrium results of the bleached wastewater and the activated coke showed that significant color, COD, DOC and AOX removal (> 90%) was achieved when the activated coke dose exceeded 15,000 mg/L. Adsorption isotherms, in terms of COD, DOC, UV and color were developed based on the batch equilibrium data. Based on these isotherms, the amount of activated coke required to achieve certain removal of color and AOX can be predicted. The utilization of the petroleum coke for the production of activated carbon can provide an excellent disposal option for the oil sand industry at the same time would provide a cheap and valuable activated carbon.     

两种碳基材料对二级出水中有机物的去除特性

针对活性炭与活性焦两种碳基吸附材料,分别开展静态吸附与动态过滤实验,考察了两者对城镇再生水厂二级出水中有机物的去除效果。结果表明:活性焦介孔及大孔丰富,对应孔体积为0.436 cm³/g,为活性炭的1.6倍;准二级动力学模型更适用于两种材料对COD的吸附动力学拟合,活性焦动力学吸附速率常数k₂为活性炭的2倍;水温为22℃时,活性焦与活性炭对COD的Langmuir饱和吸附量分别为230.38、94.14 mg/g。在近4个月的连续运行中,活性焦滤柱对有机物的去除效果全程优于活性炭滤柱,尽管两滤柱在由单纯吸附向生物吸附降解转化的过程中对有机物的去除率有所降低,但对COD的去除率仍可分别稳定在28.43%和22.26%。活性焦颗粒与活性炭颗粒表面ATP含量最高分别为7032.94、5753.52 ng/g。此外,活性焦滤柱对1~10 ku有机物组分,以及腐殖酸类物质、溶解性微生物代谢产物等不同荧光特性有机物均有较好的去除效果。与活性炭相比,活性焦对再生水厂二级出水中有机物的去除效果更优。     

Removal of mercury(II) from aqueous solutions and chlor-alkali industry wastewater using 2-mercaptobenzimidazole-clay

The 2-mercaptobenzimidazole loaded natural clay was prepared for the removal of Hg(II) from aqueous media. Adsorption of the metal ions from aqueous solution as a function of solution concentration, agitation time, pH, temperature, ionic strength, particle size of the adsorbent and adsorbent dose was studied. The adsorption process follows a pseudo-second-order kinetics. The rate constants as a function of initial concentration and temperature were given. The adsorption of Hg(II) increased with increasing pH and reached a plateau value in the pH range 4.0-8.0. The removal of Hg(II) was found to be >99% at an initial concentration of 50 mg/l. Mercury(II) uptake was found to increase with ionic strength and temperature. Further, the adsorption of Hg(II) increased with increasing adsorbent dose and decrease with adsorbent particle size. Sorption data analysis was carried out using Langmuir and modified Langmuir isotherms for the uptake of metal ion in an initial concentration range of 50-1,000 mg/l. The significance of the two linear relationships obtained by plotting the data according to the conventional Langmuir equation is discussed in terms of the binding energies of the two population sites involved which have a widely differing affinity for Hg(II) ions. Thermodynamic parameters such as changes of free energy, enthalpy, and entropy were calculated to predict the nature of adsorption. It was found that the values of isosteric heat of adsorption were varied with surface loading. The chlor-alkali industry wastewater samples were treated by MBI-clay to demonstrate its efficiency in removing Hg(II) from wastewater.     

Adsorption and desorption characteristics of mercury(II) ions using aminated chitosan bead

Adsorption and desorption characteristics for mercury ions using aminated chitosan bead which showed very high affinity to mercury ions were studied. The adsorption of mercury ions using aminated chitosan bead was an exothermic process since binding strength each other increased as the temperature decreased. And the adsorption of mercury ions was almost completed in 100 min at 150 rpm. In case that adsorbent dose increased, mercury uptake capacity decreased, while, removal efficiency increased. The beads were not greatly affected by the ionic strength, organic material and alkaline-earth metal ions. Mercury ions adsorbed on aminated chitosan bead were desorbed effectively about 95% by EDTA and the adsorption capacity of the recycled beads can still be maintained at 90% level at the 5th cycle.     

天然气液化厂站脱汞的探讨

分析了吸附脱汞和氧化型吸收剂的脱汞效果,吸附脱汞的吸附剂包括煤基活性炭、活性炭纤维、活性焦、钙基吸附剂、壳聚糖类吸附剂.介绍了天然气脱汞的国内外工程实例.     

Adsorption of copper, lead and cobalt by activated carbon

The phenomena of lead, copper and cobalt adsorption by activated carbon from aqueous solution was studied in detail. Laboratory studies were conducted to evaluate and optimize the various process variables (i.e. carbon type, solution pH, equilibrium time and carbon dose). A quantitative determination of the adsorptive capacity of activated carbon to remove these metals was also determined.Significant differences were found in the ability of different types of activated carbons to adsorb lead, copper and cobalt from aqueous solution. Solution pH was found to be the most important parameter affecting the adsorption. It was found that there was practically no adsorption of lead, copper and cobalt by activated carbon below a well defined solution pH value for each metal. This critical solution pH value was found to be lower than the pH value associated with the formation of hydrolysis products. Of the ten commercially available activated carbons evaluated in these experiments, Barney Cheney NL 1266 was found to adsorb the largest percentage of lead, copper and cobalt. The adsorption of any single metal (lead, copper and cobalt) was hindered by the presence of the other metals; the metals apparently competed for adsorption sites.     

Single and competitive adsorption of Cd and Zn onto a granular activated carbon

Single and competitive adsorption of cadmium and zinc onto granular activated carbon DARCO 12–20 mesh has been investigated. This activated carbon has been shown as an effective adsorbent for both metals. Cadmium and zinc removals increased with pH and decreased with molar metal/carbon ratio. Surface precipitation phenomena have been detected for the higher pHs and molar ratios. The adsorption process has been modelled on the surface complexation Triple Layer Model (TLM). For this purpose, the amphoteric nature of the activated carbon has been studied. Single metal adsorption data have been used to calibrate TLM parameters. A dependence of the adsorption constants on pH and molar metal/carbon ratio has been observed, and a correlation for log K_ads has been determined. In the competitive system, the removal efficiency of the activated carbon decreased for both metals. The TLM model, using surface complexation constants determined from single adsorption experiments, successfully predicted cadmium and zinc removal from the two metal solutions.     

Equilibrium modelling of individual and simultaneous biosorption of chromium(VI) and nickel(II) onto dried activated sludge

The biosorption of chromium(VI) and nickel(II) ions, both singly and in combination, by dried activated sludge was investigated in a batch system as a function of initial pH and single- and dual-metal ion concentrations. The working initial pH values for single chromium(VI) and nickel(II) biosorptions were determined as 1.0 and 4.5, respectively. It was observed that the co-ion effect on the equilibrium uptake became more pronounced as the co-ion concentration in solution increased and pH level increased for chromium(VI) and decreased for nickel(II). Adsorption isotherms were developed for both the single- and dual-metal ion systems at these two pH values and expressed by the mono- and multi-component Langmuir and Freundlich adsorption models and model parameters were estimated by the non-linear regression. It was seen that the mono-component adsorption equilibrium data fitted very well to both the mono-component adsorption models for both the components and the pH values studied while the multi-component Freundlich adsorption model adequately predicted the multi-component adsorption equilibrium data at moderate ranges of initial mixture concentrations for both the studied pH values.     

Adsorption of Cu(II), Cd(II) and Pb(II) from aqueous single metal solutions by succinylated twice-mercerized sugarcane bagasse functionalized with triethylenetetramine

This study describes the preparation of two new chelating materials, MMSCB 3 and 5, derived from succinylated twice-mercerized sugarcane bagasse (MMSCB 1). MMSCB 3 and 5 were synthesized from MMSCB 1 using two different methods as described by Gurgel and Gil (2009). In the first method MMSCB 1 was activated with 1,3-diisopropylcarbodiimide and in the second with acetic anhydride (to form an internal anhydride) and later both were reacted with triethylenetetramine in order to obtain MMSCB 3 and 5. New obtained materials were characterized by mass percent gain, concentration of amine groups, FTIR, and elemental analysis. MMSCB 3 and 5 showed mass percent gain of 19.9 and 57.1%, concentration of amine groups of 2.0 and 2.1 mmol/g, and nitrogen content of 5.8 and 4.4%. The capacity of MMSCB 3 and 5 to adsorb Cu²⁺, Cd²⁺, and Pb²⁺ from aqueous single metal ion solutions was evaluated at different contact times, pHs, and initial metal ion concentrations. Adsorption isotherms were well fitted by Langmuir model. Maximum adsorption capacities of MMSCB 3 and 5 for Cu²⁺, Cd²⁺, and Pb²⁺ were found to be 59.5 and 69.4, 86.2 and 106.4, 158.7 and 222.2 mg/g, respectively.     

Surface characteristics of crop-residue-derived black carbon and lead(II) adsorption

Previous studies demonstrated that black carbon (BC) in soils arising from the burning of crop residues is a highly effective adsorbent for organic contaminants. This work evaluated the adsorptive ability of BC for heavy metals in relation to the BC surface characteristics. Two BC samples, rice carbon (RC) and wheat carbon (WC) isolated from the burning residues of rice straw and wheat straw, respectively, were characterized for their surface properties with reference to a commercial activated carbon (AC). While RC and WC had lower surface areas than AC, the two BC samples possessed higher surface acidities and thus lower pH of the isoelectric points (pH IEP) than AC as indicated by titration, FTIR, and zeta potential measurements. The Pb(II) adsorption by RC and WC was higher than that by AC and increased significantly with increasing pH, suggesting the electrostatic interactions between positive Pb(II) species and negatively charged functional groups on RC and WC as the primary adsorptive forces. A reduction in the total positive charge of Pb(II) species with increasing pH as computed by MINTEQA2 suggested that the deprotonation of surface functional groups of RC and WC was the controlling factor of the adsorption. The Pb(II) adsorption decreased with increasing ionic strength, due to the screening role of Na+ in neutralizing the negative charge of RC and WC. This study demonstrated that BC may be an important adsorbent of heavy metals in soil and that the adsorption may be significantly influenced by environmental conditions.     

Immobilization of Hg(II) in water with polysulfide-rubber (PSR) polymer-coated activated carbon

An effective mercury removal method using polymer-coated activated carbon was studied for possible use in water treatment. In order to increase the affinity of activated carbon for mercury, a sulfur-rich compound, polysulfide-rubber (PSR) polymer, was effectively coated onto the activated carbon. The polymer was synthesized by condensation polymerization between sodium tetrasulfide and 1,2-dichloroethane in water. PSR-mercury interactions and Hg-S bonding were elucidated from x-ray photoelectron spectroscopy, and Fourier transform infra-red spectroscopy analyses. The sulfur loading levels were controlled by the polymer dose during the coating process and the total surface area of the activated carbon was maintained for the sulfur loading less than 2 wt%. Sorption kinetic studies showed that PSR-coated activated carbon facilitates fast reaction by providing a greater reactive surface area than PSR alone. High sulfur loading on activated carbon enhanced mercury adsorption contributing to a three orders of magnitude reduction in mercury concentration. μ-X-ray absorption near edge spectroscopic analyses of the mercury bound to activated carbon and to PSR on activated carbon suggests the chemical bond with mercury on the surface is a combination of Hg-Cl and Hg-S interaction. The pH effect on mercury removal and adsorption isotherm results indicate competition between protons and mercury for binding to sulfur at low pH.     

Adsorption kinetics of fluoride on low cost materials

Adsorption is one important technique in fluoride removal from aqueous solutions. The viability of adsorption techniques is greatly dependent on the development of adsorptive materials. A large number of materials have been tested at a fluoride concentration greater than 2 mg/l, and the lowest limit for fluoride reduction by them is about 2 mg/l. Decreasing the fluoride concentration to less than 2 mg/l, most of the tested materials displayed a very low capacity of fluoride removal.

This paper has concentrated on investigating the adsorption kinetics and adsorption capacity of low cost materials at a low initial fluoride concentration. The experiments were carried out at a natural pH, and radioisotope ¹⁸F rather than ¹⁹F was used since ¹⁸F can be rapidly measured by measuring the radioactivity with a resolution of 1×10⁻¹³ mg or 0.01 μCi. The tested materials are hydroxyapatite, fluorspar, calcite, quartz and quartz activated by ferric ions. Their adsorption capacities follow the order:

Hydroxyapatite>Fluorspar>Quartz activated using ferric ions>Calcite>Quartz

The uptake of fluoride on hydroxyapatite is an ion-exchange procedure and follows the pseudo-first- and second-order equations, while the uptake of fluoride on the others is a surface adsorption and follows the pseudo-second-order equation. Calcite has been seen as a good adsorbent in fluoride removal and has been patented. However, our data suggested that its adsorption capacity is only better than quartz.

The external mass transfer is a very slow and rate-determining step during fluoride removal from the aqueous solution. Under static conditions, there was no relative movement between adsorbents and solutions, the fluoride uptake was at a very slow rate and the adsorbent properties did not significantly affect the fluoride uptake. Under shaken conditions, the adsorption of fluoride was controlled by the adsorbent structure and chemical properties.     

Sorption kinetics of Fe(II), Zn(II), Co(II), Ni(II), Cd(II), and Fe(II)/Me(II) onto hematite

The reactions of Fe(II) and other divalent metal ions including Zn, Co, Ni, and Cd on hematite were studied in single and competitive binary systems with high sorbate/sorbent ratios in 10 mM PIPES (pH 6.8) solution under strict anoxic conditions. Adsorbed Me(II) was defined as extractable by 0.5 N HCl within 20 h, and fixed Me(II) was defined as the additional amount that was extracted by 3.0 N HCl within 7 days. Binary systems contained Fe(II) plus a second metal ion. The extent of uptake of divalent metal ions by hematite was in order of Fe> or =Zn>Co> or =Ni>Cd. For all metals tested, there was an instantaneous adsorption followed by a relatively slow stage that continued for the next 1-5 days. This sequence occurred in both single and binary systems, and could have been due to a variety of sorption site types or due to slow conversion from outer- to inner-sphere surface complexes due to increasing surface charge. Sorption competition was observed between Fe(II) and the other metal ions. The displacement of Fe(II) by Me(II) was in order of Ni approximately Zn>Cd, and the displacement of Me(II) by Fe(II) was in order of Cd>Zn approximately Ni>Co. Fixed Fe(II) was in order of Fe+Co (20%)>Fe+Cd (6%)>Fe approximately Zn (4%)>Fe approximately Ni (4%) after 30 days. There was no fixation for the other metals in single or binary systems.     

Enhancement of mercury(II) sorption from water by coal through chemical pretreatment

Enhancement of mercury(II) sorption from water by bituminous coal through chemical pretreatment was explored in the laboratory using batch sorption tests and downflow column studies. Both intensity of sorption and equilibrium sorptive capacity were enhanced significantly following nitric acid and hydrogen peroxide oxidation. Sulfurization and manganese oxide impregnation also showed promise. The chemically pretreated coal sorbents exhibited mercury sorption to a level higher than that accomplished using active carbon. Nitric acid or hydrogen peroxide oxidized or sulfurized coal may well replace active carbon in polishing mercury-laden waste following sulfide precipitation or removing mercury during municipal water treatment.     

Adsorption from Brazilian soils of Cu(II) and Cd(II) using cattle manure vermicompost

The potential of cattle manure vermicompost and Brazilian soils (whole soils and soils incubated with vermicompost) was assessed for adsorption of heavy metals such as Cu(II) and Cd(II) from aqueous solutions. Experimental data have been fitted to Langmuir and Freundlich isotherms to obtain the characteristic parameters of each model, with R ² values from 0.89 to 0.99. Based on the maximum adsorption capacity obtained from the Langmuir isotherm the affinity of the studied metals for the vermicompost and soils have been established as Cu(II) > Cd(II). The values of the separation factor, R _L, which has been used to predict affinity between adsorbate and adsorbent were between zero and 1, indicating that sorption was very favourable for Cu(II) and Cd(II) in synthetic solution. Addition of vermicompost to soils resulted in higher distribution coefficient, K _d, as compared with whole soils. The thermodynamic parameter, the Gibbs energy changes, was calculated for each system and the negative values obtained confirm that the adsorption processes are spontaneous. The ΔG° values for the substrates were between ?2.630±1.41 kJ mol^?1 and ?13.700±1.250 kJ mol^?1. Adsorption tests from multimetal systems confirm the affinity order obtained in the individual metal tests. The adsorption capacity for Cu(II) measured in individual tests is not reduced by the presence of Cd(II). There is also desorption of Cu(II) and Cd(II) previously bound to vermicompost, whole soils and soils incubated with vermicompost by DTPA. The experiment indicates the importance of cattle manure vermicompost and oxisol amended with vermicompost in relation to Cu(II) and Cd(II) adsorption from aqueous solution.     

Removal of Cu(II) and Cd(II) from aqueous solution by seafood processing waste sludge

Dried waste slurry generated in seafood processing factories has been shown to be an effective adsorbent for the removal of heavy metals from dilute solutions. Characterization of the sludge surface with scanning electron microscope and X-ray microanalyzer were carried out to evaluate the components on the sludge surface that are related to the adsorption of metal ions. Aluminum and calcium, as well as organic carbon are distributed on the surface of sludge. Alkalimetric titration was used to characterize the surface acidity of the sludge sample. The surface acidity constants, pKa1s and pKa2s, were 5.80 and 9.55, respectively. Batch as well as dynamic adsorption studies were conducted with 10(-5) to 5 x 10(-3) M Cu(II) and Cd(II). A surface complexation model with the diffuse layer model successfully predicted Cu(II) and Cd(II) removals in single metal solutions. Predictions of sorption in binary-adsorbate systems based on single-adsorbate data fits represented competitive sorption data reasonably well over a wide range of conditions. The breakthrough capacity found from column studies was different for each metal ion and the data reflect the order of metal affinity for the adsorbent material very well.     

Removal of lead from contaminated water bodies using sea nodule as an adsorbent

Adsorption of water soluble lead on polymetallic sea nodule has been studied in detail. Complete decontamination of lead is possible by appropriate sea nodule dosing. Adsorption is also dependent on pH and best adsorption is achieved at pH 6. Beyond pH 6, the desorption of lead from sea nodule surface is practically zero. Residual metal concentrations in the filtrate after adsorption is negligible. Both Freundlich and Langmuir isotherms may reasonably explain adsorption of lead on sea nodule. Chemically bound moisture plays a very crucial role in lead adsorption. Lead adsorptive capability of sea nodule is practically destroyed when calcined at a temperature of 900 degrees C. Lead loading capacity of sea nodule has been estimated at 440 mg of lead per gram of sea nodule. The performance of sea nodule as a lead adsorbent has been successfully tested over six simulated lead contaminated water systems. Lead loading capacity of sea nodule compares favorably with other adsorbents like activated carbon, ion exchange resin, anionic clay, granulated blast furnace slag and natural and treated zeolites.     

Single- and multi-component adsorption of cadmium and zinc using activated carbon derived from bagasse--an agricultural waste

The use of low-cost activated carbon derived from bagasse, an agricultural waste material, has been investigated as a replacement for the current expensive methods of removing heavy metals from wastewater. With a view to find a suitable application of the material, activated carbon has been derived, characterized and utilized for the removal of cadmium and zinc. The uptake of cadmium was found to be slightly greater than that of zinc and the sorption capacity increases with increase in temperature. The adsorption studies were carried out both in single- and multi-component systems. Adsorption data on derived carbon follows both the Freundlich and Langmuir models. The data are better fitted by the Freundlich isotherm as compared to Langmuir in both the single- and multi-component systems. Isotherms have been used to obtain the thermodynamic parameters. The kinetics of adsorption depends on the adsorbate concentration and the physical and chemical characteristics of the adsorbent. Studies were conducted to delineate the effect of temperature, initial adsorbate concentration, particle size of the adsorbent and solid-to-liquid ratio. On the basis of these studies, various parameters such as mass transfer coefficient, effective diffusion coefficient, activation energy and entropy of activation were evaluated to establish the mechanisms. It was concluded that the adsorption occurs through a film diffusion mechanism at low as well as at higher concentrations.