Contributions of hemicellulose, cellulose and lignin to the mass and the porous properties of chars and steam activated carbons from various lignocellulosic precursors

In this study, contributions of hemicellulose, cellulose and lignin to the mass and the porous properties of chars and activated carbons from various lignocellulosic materials were studied. A predictive calculation was established using the experimental results obtained for the three components separately to evaluate the carbonization and activation yields and their respective contributions to the chars and to the subsequent activated carbons of various precursors in term of weight fraction. These equations were validated. The results showed that lignin can be considering as being the major contributor of all chars and activated carbons. Besides, the evolution of the mean pore size versus the specific porous volume showed that each component contributes to the porosity of chars and activated carbons whatever is its weight contribution.     

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.     

Production and comparison of high surface area bamboo derived active carbons

High surface area activated carbons have been produced from the natural biomaterial bamboo, using phosphoric acid as the activating agent. The effects of phosphoric acid impregnation ratio, activation temperature, heating rate on the carbon surface area, porosity and mass yield are presented. Three of these bamboo derived active carbons, surface areas 1337, 1628 and 2123m(2)/g were assessed for their ability to adsorb Acid Red 18 dye from aqueous solution; these results were compared with three conventional adsorbents: activated carbon F400, bone char and peat. Isotherm data were analysed using Langmuir, Freundlich, Redlich-Peterson and Langmuir-Freundlich isotherms. Different isotherms provided the best fit correlations to the adsorption experimental data but the Langmuir-Freundlich equation provided the best overall correlation of data. The adsorption capacities of two of the selected bamboo derived carbons were much greater than the capacities of the other three adsorbents.     

Generalized Mechanochemical Synthesis of Biomass‐Derived Sustainable Carbons for High Performance CO2 Storage

Novel mechanochemical activation generates biomass‐derived carbons with unprecedented CO₂ storage capacity due to higher porosity than analogous conventionally activated carbons but similar pore size. The mechanochemical activation, or so‐called compactivation, process involves compression, at 740 MPa, of mixtures of activating agent (KOH) and biomass hydrochar into pellets/disks prior to thermal activation. Despite the increase in surface area and pore volume of between 25% and 75% compared to conventionally activated carbons, virtually all of the porosity of the biomass (sawdust and lignin) derived mechanochemically activated carbons is from small micropores (5.8–6.5 Å), which results in a dramatic increase in CO₂ storage capacity at 25 °C and low pressure (≤1 bar). The ambient temperature CO₂ uptake for a carbon derived from sawdust at 600 °C and a KOH/carbon ratio of 2, rises from 1.3 to 2.0 mmol g^?1 at 0.15 bar, and from 4.3 to 5.8 mmol g^?1 at 1 bar, which is the highest ever reported for carbonaceous materials. The mechanochemically activated carbons have a superior CO₂ working capacity for pressure swing adsorption and vacuum swing adsorption processes and, due to a high packing density, they exhibit excellent volumetric CO₂ uptake that is higher than for any material reported to date.     

Activated carbon from olive kernels in a two-stage process: industrial improvement

Activated carbons have been prepared from olive kernels and their adsorptive characteristics were investigated. A two stage process of pyrolysis-activation has been tested in two scales: (a) laboratory scale pyrolysis and chemical activation with KOH and (b) pilot/bench scale pyrolysis and physical activation with H(2)O-CO(2). In the second case, olive kernels were first pyrolysed at 800 degrees C, during 45 min under an inert atmosphere in an industrial pyrolyser with a throughput of 1t/h (Compact Power Ltd., Bristol, UK). The resulting chars were subsequently activated with steam and carbon dioxide mixtures at 970 degrees C in a batch pilot monohearth reactor at NESA facility (Louvain-la Neuve, Belgium). The active carbons obtained from both scales were characterized by N(2) adsorption at 77 K, methyl-blue adsorption (MB adsorption) at room temperature and SEM analysis. Surface area and MB adsorption were found to increase with the degree of burn-off. The maximum BET surface area was found to be around 1000-1200 m(2)/g for active carbons produced at industrial scale with physical activation, and 3049 m(2)/g for active carbons produced at laboratory with KOH activation. The pores of the produced carbons were composed of micropores at the early stages of activation and both micropores and mesopores at the late stages. Methylene blue removal capacity appeared to be comparable to that of commercial carbons and even higher at high degrees of activation.     

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.     

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.     

Dye adsorption by sewage sludge-based activated carbons in batch and fixed-bed systems

The present research work deals with the production of activated carbons by chemical activation and pyrolysis of sewage sludges. The adsorbent properties of these sewage sludges based activated carbons were studied by liquid-phase adsorption tests. Dyes removal from colored wastewater being a possible application for sludge based adsorbents, methylene blue and saphranine removing from solution was studied. Pure and binary adsorption assays were performed in batch and fixed bed systems. In all cases studied, the adsorbents produced from sewage sludges were able to adsorb both the compounds considered here. Nevertheless, time required for reaching equilibrium, adsorptive capacity and fixed bed characteristic parameters were different for these two compounds. Methylene blue adsorption occurred faster than that of saphranine, and it was preferably adsorbed when treating binary solutions. It could be concluded that the sewage sludge-based activated carbons may be promising for dyes removal from aqueous streams.     

Activated carbons from waste biomass by sulfuric acid activation and their use on methylene blue adsorption

Preparation of the activated carbons from sunflower oil cake by sulphuric acid activation with different impregnation ratios was carried out. Laboratory prepared activated carbons were used as adsorbents for the removal of methylene blue (MB) from aqueous solutions. Liquid-phase adsorption experiments were conducted and the maximum adsorption capacity of each activated carbon was determined. The effects of various process parameters i.e., temperature, pH, initial methylene blue concentration, contact time on the adsorption capacity of each activated carbon were investigated. The kinetic models for MB adsorption onto the activated carbons were studied. Langmuir isotherm showed better fit than Freundlich isotherm for all activated carbon samples. The rates of adsorption were found to conform to the pseudo-second-order kinetics with good correlation. The separation factor (R(L)) revealed the favorable nature of the isotherm of the MB activated carbon system.     

Preparation of high adsorption capacity bio-chars from waste biomass

Bio-chars with high adsorption capacity derived from rice-husks and corncobs were prepared at different retention times (RTs) in a pyrolysis reactor. At a fixed pyrolysis temperature, the pyrolysis RT is a key factor influencing the surface areas and functional group contents of the bio-chars, and further influencing their adsorption capacities. The results indicate that the bio-char prepared at RT of 1.6 s exhibits a higher phenol adsorption capacity (589 mg g⁻¹) than other bio-chars and many activated carbons reported in the literature. An adsorption mechanism based on acid-base interaction and hydrogen binding between phenol and the functional groups was proposed to elucidate the adsorption process. An economic evaluation of the use of bio-chars as adsorbents was made.     

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.     

Upgrading sewage sludges for adsorbent preparation by different treatments

Addressing the adequate management of sludges produced at sewage plants is becoming a fundamental need as a consequence of the high production volumes, both current and forecasted, of this byproduct. European waste-treatment policies consider reuse of sludges as one of the preferred actions; along those lines this study proposes using sewage sludges as adsorbents for pollutants contained in wastewaters. As potential adsorbents, sludges dried at 105 degrees C, dried and pyrolyzed, or dried and chemically activated were tried. As adsorbate, methylene blue was used in order to characterize the adsorption capacity of the different materials. Although surface areas corresponding to pyrolyzed and chemically activated sludges were around 80 and 390 m2/g, respectively, both these materials exhibited poor levels of methylene blue adsorption which may have been due to their high proportions of micropores. Sludges only dried, on the contrary, showed significant methylene blue adsorption capacities.     

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.     

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.     

Development of easy made low cost bindless monolithic electrodes from biomass with controlled properties to be used as electrochemical capacitors

The aim of the work now reported is the development of low cost electrodes in the monolithic shape without the need for a pos-production step with potential to be used in supercapacitors. The tested materials were activated carbon fibres prepared and activated carbons made from coffee endocarp. The main functional groups identified were quinone, lactone, Si-H, phenol, hydroxyl, carbonyl and ether for activated carbon samples and amine, amide, pyrone, lactone, carbonyl and hydroxyl for activated carbon fibres samples. The nanostructure of the materials is predominantly microporous but with a significant variety of porosity development with BET surface area and pore volume given by α(s) method range from 89 to 1050 m(2) g(-1) and 0.04 to 0.50 cm(3) g(-1), respectively. The electrochemical properties of the materials were investigated using classic cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy. The higher specific capacitance achieved was 176 F g(-1).     

Effectiveness and mechanisms of dye adsorption on a straw-based biochar

A biochar (BC) generated from straw as a cost-effective substitute for activated carbon (AC) was tested for its adsorptive ability toward reactive brilliant blue (KNR) and rhodamine B (RB). BC and AC had similar surface areas but differed in porosity, surface acidity and point of zero surface charge. The two carbons were highly effective adsorbents for both dyes at pH 3.0 and 6.5. BC was slightly more effective than AC to adsorb RB due to the RB–BC electrostatic interactions and RB protonation at low pH. The two carbons reversed in their effectiveness to adsorb KNR for similar reasons. The π–π interactions between dye molecules and graphene layers of BC, the direct dye-BC electrostatic attraction/repulsion and the intermolecular hydrogen bonding are proposed to be the combined mechanisms for dye adsorption. Rich phenolic hydroxyls on the surface of BC are expected to enhance the π–π interactions.     

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.     

Study on activated carbon derived from sewage sludge for adsorption of gaseous formaldehyde

The aim of this work is to evaluate the adsorption performances of activated carbon derived from sewage sludge (ACSS) for gaseous formaldehyde removal compared with three commercial activated carbons (CACs) using self-designing adsorption and distillation system. Formaldehyde desorption of the activated carbons for regeneration was also studied using thermogravimetric (TG) analysis. The porous structure and surface characteristics were studied using N₂ adsorption and desorption isotherms, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results show that ACSS has excellent adsorption performance, which is overall superior to the CACs. Adsorption theory indicates that the ACSS outperforms the CACs due to its appropriate porous structure and surface chemistry characteristics for formaldehyde adsorption. The TG analysis of desorption shows that the optimum temperature to regenerate ACSS is 75 °C, which is affordable and economical for recycling.     

Adsorption of Cd(II) ions from aqueous solutions using activated carbon prepared from olive stone by ZnCl2 activation

This study is aimed to remove Cd(II) ions from aqueous solutions by adsorption. As adsorbent, activated carbon prepared from olive stone, an agricultural solid by-product was used. Different activating agent (ZnCl(2)) amounts and adsorbent particle size were studied to optimize adsorbent surface area. The adsorption experiments were conducted at different parameters such as, adsorbent dose, temperature, equilibrium time and pH. According to the experiments results, the equilibrium time, optimum pH, adsorbent dosage were found 60 min, pH > 6 and 1.0 g/50 ml respectively. The kinetic data supports pseudo-second order model and intra-particle model but shows very poor fit for pseudo-first order model. Adsorption isotherms were obtained from three different temperatures. These adsorption data were fitted with the Langmuir and Freundlich isotherms. In addition, the thermodynamic parameters, standard free energy (DeltaG(0)), standard enthalpy (DeltaH(0)), standard entropy (DeltaS(0)) of the adsorption process were calculated. To reveal the adsorptive characteristics of the produced active carbon, BET surface area measurements were made. Structural analysis was performed using SEM-EDS. The resulting activated carbons with 20% ZnCl(2) solution was the best sample of the produced activated carbons from olive stone with the specific surface area of 790.25 m(2)g(-1). The results show that the produced activated carbon from olive stone is an alternative low-cost adsorbent for removing Cd(II).     

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.