Production of granular activated carbons from select agricultural by-products and evaluation of their physical,chemical and adsorption properties

Representative samples of soft, low density, group 1 (rice straw, rice hulls, sugarcane bagasse) and hard, high density, group 2 agricultural by-products (pecan shells) were converted into granular activated carbons (GACs). GACs were produced from group 1 and 2 materials by physical activation or from group 2 materials by chemical activation. Carbons were evaluated for their physical (hardness, bulk density), chemical (ash, conductivity, pH), surface (total surface area), and adsorption properties (molasses color removal, sugar decolorization) and compared with two commercial reference carbons. The results show that the type of by-product, binder, and activation method determine the properties of GACs. Regardless of the binder, sugarcane bagasse showed a better potential than rice straw or rice hulls as precursor of GACs with the desirable properties of a sugar decolorizing carbon. Pecan shells produced GACs that were closest to the reference carbons in terms of all the properties investigated.     

Adsorption of volatile organic compounds by pecan shell- and almond shell-based granular activated carbons

The objective of this research was to determine the effectiveness of using pecan and almond shell-based granular activated carbons (GACs) in the adsorption of volatile organic compounds (VOCs) of health concern and known toxic compounds (such as bromo-dichloromethane, benzene, carbon tetrachloride, 1,1,1-trichloromethane, chloroform, and 1,1-dichloromethane) compared to the adsorption efficiency of commercially used carbons (such as Filtrasorb 200, Calgon GRC-20, and Waterlinks 206C AW) in simulated test medium. The pecan shell-based GACs were activated using steam, carbon dioxide or phosphoric acid. An almond shell-based GAC was activated with phosphoric acid. Our results indicated that steam- or carbon dioxide-activated pecan shell carbons were superior in total VOC adsorption to phosphoric acid-activated pecan shell or almond shell carbons, inferring that the method of activation selected for the preparation of activated carbons affected the adsorption of VOCs and hence are factors to be considered in any adsorption process. The steam-activated, pecan shell carbon adsorbed more total VOCs than the other experimental carbons and had an adsorption profile similar to the two coconut shell-based commercial carbons, but had greater adsorption than the coal-based commercial carbon. All the carbons studied adsorbed benzene more effectively than the other organics. Pecan shell, steam-activated and acid-activated GACs showed higher adsorption of 1,1,1-trichloroethane than the other carbons studied. Multivariate analysis was conducted to group experimental carbons and commercial carbons based on their physical, chemical, and adsorptive properties. The results of the analysis conclude that steam-activated and acid-activated pecan shell carbons clustered together with coal-based and coconut shell-based commercial carbons, thus inferring that these experimental carbons could potentially be used as alternative sources for VOC adsorption in an aqueous environment.     

Activated carbons from flax shive and cotton gin waste as environmental adsorbents for the chlorinated hydrocarbon trichloroethylene

Agricultural by-products represent a considerable quantity of harvested commodity crops. The use of by-products as precursors for the production of widely used adsorbents, such as activated carbons, may impart a value-added component of the overall biomass harvested. Our objective in this paper is to show that flax shive and cotton gin waste can serve as a precursor for activated carbon that can be used for adsorption of trichloroethylene (TCE) from both the liquid and gas phases. Testing was conducted on carbon activated with phosphoric acid or steam. The results show that activated carbon made from flax shive performed better than select commercial activated carbons, especially at higher TCE concentrations. The activation method employed had little effect on TCE adsorption in gas or vapor phase studies but liquid phase studies suggested that steam activation is slightly better than phosphoric acid activation. As expected, the capacity for the activated carbons depended on the fluid phase equilibrium concentration. At a fluid concentration of 2 mg of TCE/L of fluid, the capacity of the steam activated carbon made from flax shive was similar at 64 and 80 mg TCE/g of carbon for the vapor and liquid phases, respectively. Preliminary cost estimates suggest that the production costs of such carbons are $1.50 to $8.90 per kg, depending on activation method and precursor material; steam activation was significantly less expensive than phosphoric acid activation.     

Activated carbon from char obtained from vacuum pyrolysis of teak sawdust: pore structure development and characterization

The preparation of activated carbon from vacuum pyrolysis char of teak sawdust was studied and the results are presented in this paper. The effects of process variables such as temperature and activation time on the pore structure of activated carbons were studied. The activated carbon prepared from char obtained by vacuum pyrolysis has higher surface area and pore volume than that from atmospheric pyrolysis char. The BET surface area and pore volume of activated carbon prepared from vacuum pyrolysis char were 1150 m2/g and 0.43 cm3/g, respectively.     

Lignin--from natural adsorbent to activated carbon: a review

The present review compiles the work done over the last few decades on the use of lignin and lignin-based chars and activated carbons as adsorbents for the removal of substances from water and focuses on the utilisation of lignin as adsorbent, its conversion to chars and activated carbons and the use of these materials as adsorbents. Moreover, the review also examines the textural and surface chemical properties of lignin-based activated carbons. The work so far carried out indicates that lignin is relatively non-reactive and probably the component of lignocellulosic precursors primarily responsible for the microporosity of activated carbons. Under appropriate conditions of activation it is possible to obtain materials with surface areas and pore volumes approaching 2000 m(2)g(-1) and 1cm(3)g(-1), respectively, and these materials have capacities for the aqueous phase adsorption of metallic pollutants that are comparable to those of commercial activated carbons. Relatively little work has so far been published and there is considerable scope for more detailed studies on the preparation, characterisation and adsorption applications of lignin-based activated carbons.     

Influence of preparation conditions in the textural and chemical properties of activated carbons from a novel biomass precursor: the coffee endocarp

In this work a novel biomass precursor for the production of activated carbons (AC) was studied. The lignocellulosic material used as precursor is the coffee bean endocarp, which constitutes an industrial residue from the Portuguese coffee industry. Activation by carbon dioxide and potassium hydroxide produces activated carbons with small external areas and pore volumes up to 0.22 and 0.43cm3g(-1), respectively, for CO2 and KOH activation. All the AC's produced are very basic in nature with point of zero charge higher than 8. SEM/EDX studies indicate the presence of K, O, Ca and Si. By FTIR it was possible to identify the formation on the AC's surface of several functional groups, namely phenol, alcohol, quinone, lactone, pyrone and ether as well as SiH groups. The tailoring of the porous and chemical structure of the activated carbons produced is possible by selecting the appropriate production conditions.     

Preparation of activated carbons from cattle-manure compost by zinc chloride activation

Dried cattle-manure compost was pyrolyzed by a one-step process to obtain activated carbon using chemical activation by zinc chloride. The influence of activation parameters such as ZnCl(2) to cattle-manure compost (ZnCl(2)/CMC) ratio, activation temperature and retention time on the final products was investigated. The resultant activated carbons were characterized by nitrogen adsorption-desorption isotherms at 77 K. The results showed that the surface area and pore volume of activated carbons, which were estimated by BET and t-plot methods, were achieved as high as 2170 m(2)/g and 1.70 cm(3)/g in their highest value, respectively. Thermogravimetric analysis (TGA) was carried out to monitor the pyrolysis process of cattle-manure compost (CMC) and ZnCl(2) impregnated one (ZnCl(2)/CMC). The capabilities of phenol adsorption were also examined for the CMC carbons prepared with various treatments.     

Preparation of activated carbons from corn cob catalyzed by potassium salts and subsequent gasification with CO2

In the present study, granular activated carbons were prepared from agricultural waste corn cob by chemical activation with potassium salts and/or physical activation with CO2. Under the experimental conditions investigated, potassium hydroxide (KOH) and potassium carbonate (K2CO3) were effective activating agents for chemical activation during a ramping period of 10 degrees C/min and subsequent gasification (i.e., physical activation) at a soaking period of 800 degrees C. Large BET surface areas (>1,600 m2/g) of activated carbons were thus obtained by the combined activation. In addition, this study clearly showed that the porosity created in the acid-unwashed carbon products is substantially lower than that of acid-washed carbon products due to potassium salts left in the pore structure.     

Production of activated carbon from bagasse and rice husk by a single-stage chemical activation method at low retention times

The production of activated carbon from bagasse and rice husk by a single-stage chemical activation method in short retention times (30-60min) was examined in this study. The raw materials were subjected to a chemical pretreatment and were fed to the reactor in the form of a paste (75% moisture). Chemicals examined were ZnCl2, NaOH and H3PO4, for temperatures of 600, 700 and 800 degrees C. Of the three chemical reagents under evaluation only ZnCl2 produced activated carbons with high surface areas. BET surface areas for rice husk were up to 750m2/g for 1:1 ZnCl2:rice husk ratio. BET surface areas for bagasse were up to 674m2/g for 0.75:1 ZnCl2:bagasse ratio. Results were compared to regular two-stage physical activation methods.     

Granular activated carbons from broiler manure: physical, chemical and adsorptive properties

Broiler manure produced at large concentrated facilities poses risks to the quality of water and public health. This study utilizes broiler litter and cake as source materials for granular activated carbon production and optimizes conditions for their production. Pelletized manure samples were pyrolyzed at 700 degrees C for 1 h followed by activation in an inert atmosphere under steam at different water flow rates, for a period ranging from 15 to 75 min. Carbon physical and adsorptive properties were dependent on activation time and quantity of steam used as activant, yields varied from 18% to 28%, surface area varied from 253 to 548 m2/g and copper ion adsorption varied from 0.13 to 1.92 mmol Cu2+/g carbon. Best overall performing carbons were steam activated for 45 min at 3 ml/min. Comparative studies with commercial carbons revealed the broiler cake-based carbon as having the highest copper ion efficiency.     

Physical and chemical properties of selected agricultural byproduct-based activated carbons and their ability to adsorb geosmin

The objectives of this study were to evaluate selected physical and chemical properties of agricultural byproduct-based activated carbons made from pecan shells and sugarcane bagasse, and compare those properties to a commercial coal-based activated carbon as well as to compare the adsorption efficiency of these carbons for geosmin. Comparison of the physical and chemical properties of pecan shell- and bagasse-based carbons to the commercial carbon, Calgon Filtrasorb 400, showed that pecan shell carbon, but not the bagasse carbon, compared favorably to Filtrasorb 400, especially in terms of surface area, bulk density, ash and attrition. A carbon dosage study done in a model system showed the amount of geosmin adsorbed to be greater for Filtrasorb 400 and the bagasse-based carbon at low carbon concentrations than for the pecan shell carbons, but geosmin adsorption was similar in all carbons at higher carbon dosages. Application of the Freundlich isotherm model to the adsorption data showed that carbons made by steam activation of pecan shells or sugarcane bagasse had geosmin adsorption characteristics most like those of the commercial carbon. In terms of physical, chemical and adsorptive properties, steam-activated pecan shell carbon most resembled the commercial carbon and has the potential to replace Filtrasorb 400 in applications involving removal of geosmin from aqueous environments.     

Steam activation of chars produced from oat hulls and corn stover

Oat hulls and corn stover were used to produce chars at approximately 500 degrees C. The carbon concentrations of oat hull char and corn stover chars produced were 72.3 and 68.0 wt.%, respectively. Both activation burn-off and Brunauer-Emmett-Teller (BET) surface area appear to exhibit a linear relationship with respect to activation time of oat hulls. As to corn stover activated carbons, there is no linear relationship between activation time and BET surface area. However, activation burn-off of and activation time appear to relate in a linear manner for the activated carbons produced from corn stover chars. Oat hull is better than corn stover as a raw material for the production of activated carbon.     

Enhanced adsorption of phenolic compounds, commonly encountered in olive mill wastewaters, on olive husk derived activated carbons

Olive husk was used for the preparation of activated carbon by chemical activation with KOH. The effects of carbonization and activation time on carbon properties were evaluated. The surface area of the produced carbons was measured by means of N(2) adsorption at 77K. The carbons with the highest surface area were further characterized by means of elemental analysis, particle size measurement, Boehm titration, zeta potential measurement, and temperature programmed desorption (TPD). Subsequently they were used for adsorption of a mixture of polyphenols consisting of caffeic acid, vanillin, vanillic acid, pi-hydroxybenzoic acid and gallic acid at two temperatures, and their adsorptive capacity was compared to a commercial carbon Acticarbon CX and found to be higher enough. The role of the porosity and surface groups are discussed in relation to the adsorption forces and the properties of the adsorbed substances. A thermodynamic interpretation of the results is also attempted.     

Acid-activated carbons from almond shells: physical,chemical and adsorptive properties and estimated cost of production

A series of phosphoric-acid activated carbons were made from almond shells using six different activation or activation/oxidation methods. The carbons were compared to each other and to two commercial carbons in an effort to ascertain the relative value of the carbons in terms of yield, surface area, attrition, surface functional groups, organic uptake, metal uptake, as well as estimated cost of production. Of the six methods investigated, the method that produced the best overall performing almond shell carbon and least expensive carbon in terms of production cost was the “Air-Activation” method. This method involved the simultaneous activation and oxidation of almond shells under an air atmosphere.     

Preparation and characterization of activated carbon produced from rice straw by (NH4)2HPO4 activation

Effects of different pretreatment protocols in (NH(4))(2)HPO(4) activation of rice straw on porous activated carbon evolution were evaluated. The pore structure, morphology and surface chemistry of obtained activated carbons were investigated by nitrogen adsorption, scanning electron microscopy and Fourier transform infrared spectroscopy. It was found that pretreatment combining impregnation with (NH(4))(2)HPO(4) and preoxidation could significantly affect the physicochemical properties of prepared activated carbons. The apparent surface area and total pore volume as high as 1154 m(2)/g and 0.670 cm(3)/g were obtained respectively, when combined process of impregnation followed by preoxidation at 200°C and activation at 700°C was carried out. Meanwhile, the activated carbon yield and maximum methylene blue adsorption capacity up to 41.14% and 129.5 mg/g were achieved, respectively. The results exhibited that (NH(4))(2)HPO(4) could be an effective activating agent for producing activated carbons from rice straw.     

Pecan shell-based granular activated carbon for treatment of chemical oxygen demand (COD) in municipal wastewater

The present investigation was undertaken to compare the adsorption efficiency of pecan shell-based granular activated carbon with the adsorption efficiency of the commercial carbon Filtrasorb 200 with respect to uptake of the organic components responsible for the chemical oxygen demand (COD) of municipal wastewater. Adsorption efficiencies for these two sets of carbons (experimental and commercial) were analyzed by the Freundlich adsorption model. The results indicate that steam-activated and acid-activated pecan shell-based carbons had higher adsorption for organic matter measured as COD, than carbon dioxide-activated pecan shell-based carbon or Filtrasorb 200 at all the carbon dosages used during the experiment. The higher adsorption may be related to surface area as the two carbons with the highest surface area also had the highest organic matter adsorption. These results show that granular activated carbons made from agricultural waste (pecan shells) can be used with greater effectiveness for organic matter removal from municipal wastewater than a coal-based commercial carbon.     

Characterization of mesoporous activated carbons prepared by pyrolysis of sewage sludge with pyrolusite

Activated carbons were prepared from sewage sludge by chemical activation. Pyrolusite was added as a catalyst during activation and carbonization. The influence of the mineral addition on the properties of the activated carbons produced was evaluated. The results show that activated carbons from pyrolusite-supplemented sewage sludge had up to a 75% higher BET surface area and up to a 66% increase in mesoporosity over ordinary sludge-based activated carbons. Batch adsorption experiments applying the prepared adsorbents to synthetic dye wastewater treatment yielded adsorption data well fitted to the Langmuir isotherm. The adsorbents from pyrolusite-supplemented sludges performed better in dye removal than those without mineral addition, with the carbon from pyrolusite-augmented sludge T2 presenting a significant increase in maximum adsorption capacity of 50 mg/g. The properties of the adsorbents were improved during pyrolusite-catalyzed pyrolysis via enhancement of mesopore production, thus the mesopore channels may provide fast mass transfer for large molecules like dyes.     

Adsorption of Neutral Red onto Mn-impregnated activated carbons prepared from Typha orientalis

Activated carbon was prepared from an inexpensive and renewable carbon source, Typha orientalis, by H(3)PO(4) activation and then impregnated with different Mn salts and tested for its Neutral Red (NR) adsorption capacities. The amount of Mn impregnated in the activated carbon was influenced by the anion species. Impregnation with Mn decreased the surface area, changed the pore size and crystal structure, and introduced more acidic functional groups such as carboxyl, lactone and phenol groups. The optimum adsorption performance for all the activated carbons was obtained at pH 3.7, Mn-Carbon dose of 0.100g/100ml solution and contact time 4.5h. The adsorption isotherms fit the Langmuir isotherm equation. The kinetic data followed the pseudo-second-order model. The thermodynamic parameters indicated that the processes were spontaneous and endothermic. According to these results, the prepared Mn modified activated carbons are promising adsorbents for the removal of Neutral Red from wastewater.     

Preparation and characterization of activated carbon from rice bran

A study on the preparation of rice bran-based activated carbon was conducted, with and without an acid treatment step prior the activation process. The influence of the activation time on the structure of the activated carbons was evaluated. The acid treatment had a significant positive influence on sorption properties. The rice bran-activated carbon presented a BET surface area of 652m(2)g(-1) and a pore volume of 0.137cm(3)g(-1), with mesopores predominance (ca. 55%). These experimental results indicated the potential use of rice bran as a precursor in the activated carbon preparation process, thus representing an economically promising material.     

Physicochemical properties of carbons prepared from pecan shell by phosphoric acid activation

Activated carbons were prepared from pecan shell by phosphoric acid activation. The pore structure and acidic surface groups of these carbons were characterized by nitrogen adsorption, Boehm titration and transmittance Fourier infrared spectroscopy (FTIR) techniques. The characterization results demonstrated that the development of pore structure was apparent at temperatures 250 degrees C, and reached 1130m(2)/g and 0.34cm(3)/g, respectively, at 500 degrees C. Impregnation ratio and soaking time at activation temperature also affected the pore development and pore size distribution of final carbon products. At an impregnation ratio of 1.5, activated carbon with BET surface area and micropore volume as high as 861m(2)/g and 0.289cm(3)/g was obtained at 400 degrees C. Microporous activated carbons were obtained in this study. Low impregnation ratio (less than 1.5) and activation temperature (less than 300 degrees C) are favorable to the formation of acidic surface functional groups, which consist of temperature-sensitive (unstable at high temperature) and temperature-insensitive (stable at high temperature) two parts. The disappearance of temperature-sensitive groups was significant at temperature 300 degrees C; while the temperature-insensitive groups are stable even at 500 degrees C. FTIR results showed that the temperature-insensitive part was mostly phosphorus-containing groups as well as some carbonyl-containing groups, while carbonyl-containing groups were the main contributor of temperature-sensitive part.