Preparation of activated carbons from raw and biotreated agricultural residues for removal of volatile organic compounds

Activated carbons with diverse physical and chemical properties were produced from four agriculture residues, including raw barley husk, biotreated barley husk, rice husk, and pistachio shell. Results showed that with adequate steam activation (30-90 min, 50% H2O(g),/50% N2), activated carbons with surface areas between 360 and 950 m2 g(-1) were developed. Further increases in the activation time destroyed the pore structure of activated carbons, which resulted in a decrease in the surface area and pore volume. Biotreated agricultural residues were found to be suitable precursors for producing mesoporous activated carbons. The oxygen content of activated carbons increased with increasing activation time. Results from X-ray photoelectron spectroscopy examination further suggested that H2O molecules react with the carbon surface, enhancing the deconvoluted peak area of carbonyl and carboxyl groups. Equilibrium adsorption of toluene indicated that the adsorption capacities increased with an increase in the inlet toluene concentration and a decrease in temperature. The adsorption isotherms were successfully fitted with Freundlich, Langmuir, and Dubinin-Radushkevich equations. Activated carbons derived from agricultural residues appear to be more applicable to adsorb volatile organic compounds at a low concentration and high-temperature environment.     

Low-cost adsorbents from bio-waste for the removal of dyes from aqueous solution

Activated carbons (ACs) were developed from bio-waste materials like rice husk and peanut shell (PS) by various physicochemical activation methods. PS char digested in nitric acid followed by treatment at 673 K resulted in high surface area up to ～585 m²/g. The novelty of the present study is the identification of oxygen functional groups formed on the surface of activated carbons by infrared and X-ray photoelectron spectroscopy and quantification by using temperature programmed decomposition (TPD). Typical TPD data indicated that each activation method may lead to varying amounts of acidic and basic functional groups on the surface of the adsorbent, which may be a crucial factor in determining the adsorption capacity. It was shown that ACs developed during the present study are good adsorbents, especially for the removal of a model textile dye methylene blue (MB) from aqueous solution. As MB is a basic dye, H₂O₂-treated rice husk showed the best adsorption capacity, which is in agreement with the acidic groups present on the surface. Removal of the dye followed Langmuir isotherm model, whereas MB adsorption on ACs followed pseudo-second-order kinetics.     

UTILIZATION OF AGRICULTURAL WASTE CORN COB FOR THE PREPARATION OF CARBON ADSORBENT

In the present study, a series of activated carbons were prepared from agricultural waste corn cob by chemical and physical activations with potassium hydroxide (KOH)/potassium carbonate (K₂CO₃) and carbon dioxide (CO₂). The effect of process variables such as impregnation ratio, impregnation time, activation temperature and soaking time of CO₂ was studied in order to relate these preparation parameters with the physical properties of final carbon products. The resulting activated carbons were characterized by nitrogen adsorption[ch-[chdesorption isotherms at 77 K. The surface areas and pore volumes of carbons were estimated by the BET equation, the Langmuir equation and the t-plot method. Under the experimental conditions investigated, the main parameters in the activation of corn cob were found to be the impregnation ratio and activation temperature. The soaking time of CO₂ is another important variable, which had a strong effect on the pore volume development. The BET surface area and total pore volume were as large as about 2000 m²/g and about 1.0 cm³/g, respectively. This study showed that the activation of agricultural waste corn cob with KOH/K₂CO₃ and CO₂ was suitable for the preparation of large-surface-area activated carbons.     

Production of Activated Carbons from Pyrolysis of Waste Tires Impregnated with Potassium Hydroxide

ABSTRACT

Activated carbons were produced from waste tires using a chemical activation method. The carbon production process consisted of potassium hydroxide (KOH) impregnation followed by pyrolysis in N₂ at 600-900 °C for 0-2 hr. The activation method can produce carbons with a surface area (SA) and total pore volume as high as 470 m²/g and 0.57 cm³/g, respectively. The influence of different parameters during chemical activation, such as pyrolysis temperature, holding time, and KOH/tire ratio, on the carbon yield and the surface characteristics was explored, and the optimum preparation conditions were recommended. The pore volume of the resulting carbons generally increases with the extent of carbon gasified by KOH and its derivatives, whereas the SA increases with degree of gasification to reach a maximum value, and then decreases upon further gasification.     

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.     

活性炭吸附和脱附-等离子体氧化净化有机废气的研究

根据滑动弧放电等离子体适于降解高浓度有机物废气的特性,结合活性炭吸附法,提出了吸附器的吸附浓缩和热脱附-等离子体氧化净化有机废气的方法。在活性炭吸附过程中,最初2 h内甲苯净化率达到100%,随着时间的增加净化率下降;在热脱附滑动弧放电等离子体净化过程中,甲苯降解效率最高为97.3%。将滑动弧放电等离子体反应器出口气相产物收集进行FT-IR检测,发现放电后有CO2、CO、H2O和NO2产生,并分析了甲苯的降解机理。     

Preparation of carbonaceous adsorbent from straw and its adsorption performance for H2S removal

ABSTRACT

Activated carbonaceous were prepared from high-carbon, abandoned straw biomass. With hydrogen sulfide gas as the target pollutant, single factor experiments were employed to assess the effects of activator type, activation temperature, activation time, and liquid-material ratio on the adsorption performance of the prepared carbonaceous adsorbent. The materials were characterized using elemental analysis, SEM, FTIR, and BET. The results showed -OH, -CH-, and -C = O groups exist on the surface of the prepared adsorbent, specific surface area can reach 1104.84 m²?g^?1, total pore volume can reach 0.261 cm³?g^?1 and, where the pore volume is greater than 80%, well-developed pore structures were present that facilitated adsorption. The experimental results showed the adsorption time could reach 198 min with optimal ZnCl₂ activator concentration (30%), carbonization temperature (550°C), and liquid-to-material ratio (3:1). Compared with the existing activated carbon adsorbents, the adsorption effects and preparation cost of this absorbent are advantageous, and the absorbent has prospects for broad market application.     

稻壳基活性炭的制备及其对亚甲基蓝吸附的研究

以稻壳为原料，采用K2CO3活化法和H3P04活化法制备了比表面积为1312m^2／g和682m^2／g的活性炭，通过扫描电子显微镜（SEM）、X-射线衍射仪（XRD）对样品进行了表征，并将孔隙发达的活性炭样品用于对亚甲基蓝的吸附，结果表明，K2CO3活化法制备的活性炭样品具有更多的微孔结构；随着亚甲基蓝溶液初始浓度的增加、活性炭吸附时间的延长，亚甲基蓝的去除率呈现逐渐降低和逐渐增大的变化规律，当pH值为6时，活性炭对亚甲基蓝的吸附效果最佳；稻壳基活性炭对亚甲基蓝的吸附等温线符合Langmuir模型，Qm最高可达476．2mg／g；热力学参数△G^0△H^0和△S^0均为负值，表明稻壳基活性炭对亚甲基蓝的吸附是一个自发的放热反应。     

Preparation and characterization of activated carbons from tobacco stem by chemical activation

Activated carbons were prepared from tobacco stem by chemical activation using potassium hydroxide (KOH), potassium carbonate (K₂CO₃), and zinc chloride (ZnCl₂). The effects of the impregnation ratio (activating agent/precursor) and activating agents on the physical and chemical properties of activated carbons were investigated. The textual structure and surface properties of activated carbons were characterized by nitrogen (N₂) adsorption isotherm, scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), x-ray photoelectron spectroscopy (XPS), and thermogravimetry (TG). ZnCl₂, acting as a superior activating agent compared to the others, produced much more porosity. The maximum specific surface area reached 1347 m²/g, obtained by ZnCl₂ activation with an impregnation ratio of 4.0. Moreover, ZnCl₂ activation yielded products with an excellent thermostability, attributed to different activation mechanisms. Various oxygen functions were detected on the activated carbon surface, and hydroxyl and ester groups were found to be in the majority.

Implications: Tobacco stem, the residue from cigarette manufacturing, is usually discarded as waste, leading to serious resource waste and environmental problems. This study provides an effective utilization available for this solid residue by using it as the starting material in the preparation of activated carbon with chemical activation. Activated carbons with high specific area and various surface functions have been prepared, and the effects of the amount and type of activating agents on the physical and chemical properties of activated carbon were investigated as well.     

2,4-dichlorophenoxyacetic acid (2,4-D) micropollutant herbicide removing from water using granular and powdered activated carbons: a comparison applied for water treatment and health safety

Abstract

Activated carbons are well-known porous materials as an effective adsorbent used for the removal of emerging contaminants, such as herbicides, which are increasingly present in water bodies. Most water treatment plants, specially in Brazil, are unable to completely remove such contaminants by the conventional process and advanced treatment using activated carbons is required. The aim of this paper was to verify the influence of the activated carbons granulometry and specific surface area on the 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide removal efficiency using distilled-deionized water and filtered water collected from a conventional Water Treatment Plant. Commercial activated carbons samples used in this work were obtained from two different manufacturers. Activated carbons were analyzed by the specific surface area, pore size and volume distribution, nuclear magnetic resonance, infrared and x-ray spectroscopy, moisture, volatile matter and ash contents. Batch adsorption isotherms experiments were used and performed by Langmuir and Freundlich models. Granular and powdered activated carbons removed over 99% of 2,4-D in distilled water and near to 99% using filtered water. The activated carbons evaluated in this work presented high performance and played a key role in water treatment by removing 2,4-D herbicide, ensuring the protection of human health and the ecosystem.     

Adsorption of Cu2+ and methyl orange from aqueous solutions by activated carbons of corncob-derived char wastes

Corncob-derived char wastes (CCW) obtained from biomass conversion to syngas production through corncob steam gasification, which were often discarded, were utilized for preparation of activated carbon by calcination, and KOH and HNO₃ activation treatments, on the view of environment protection and waste recycling. Their adsorption performance in the removal of heavy metal ions and dye molecules from wastewater was evaluated by using Cu²⁺ and methyl orange (MO) as the model pollutant. The surface and structure characteristics of the CCW-based activated carbons (CACs) were investigated by N₂ adsorption, CO₂ adsorption, FT-IR, and He-TPD. The adsorption capacity varied with the activation methods of CACs and different initial solution concentrations, indicating that the adsorption behavior was influenced by not only the surface area and porosity but also the oxygen functional groups on the surface of the CACs. The equilibrium adsorption data were analyzed with the Langmuir, Freundlich, and Temkin isotherm models, and the adsorption kinetics was evaluated by the pseudo-first-order and pseudo-second-order models.     

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。     

Production of granular activated carbon from food-processing wastes (walnut shells and jujube seeds) and its adsorptive properties

Commercial activated carbon is a highly effective absorbent that can be used to remove micropollutants from water. As a result, the demand for activated carbon is increasing. In this study, we investigated the optimum manufacturing conditions for producing activated carbon from ligneous wastes generated from food processing. Jujube seeds and walnut shells were selected as raw materials. Carbonization and steam activation were performed in a fixed-bed laboratory electric furnace. To obtain the highest iodine number, the optimum conditions for producing activated carbon from jujube seeds and walnut shells were 2 hr and 1.5 hr (carbonization at 700°C) followed by 1 hr and 0.5 hr (activation at 1000°C), respectively. The surface area and iodine number of activated carbon made from jujube seeds and walnut shells were 1,477 and 1,184 m²/g and 1,450 and 1,200 mg/g, respectively. A pore-distribution analysis revealed that most pores had a pore diameter within or around 30–40 Å, and adsorption capacity for surfactants was about 2 times larger than the commercial activated carbon, indicating that waste-based activated carbon can be used as alternative.

Implications:Wastes discharged from agricultural and food industries results in a serious environmental problem. A method is proposed to convert food-processing wastes such as jujube seeds and walnut shells into high-grade granular activated carbon. Especially, the performance of jujube seeds as activated carbon is worthy of close attention. There is little research about the application of jujube seeds. Also, when compared to two commercial carbons (Samchully and Calgon samples), the results show that it is possible to produce high-quality carbon, particularly from jujube seed, using a one-stage, 1,000°C, steam pyrolysis. The preparation of activated carbon from food-processing wastes could increase economic return and reduce pollution.     

Characterization of activated carbons prepared from sugarcane bagasse by ZnCl2 activation.

Activated carbons were prepared from the agricultural waste of sugarcane bagasse by the chemical activation with zinc chloride (ZnCl2) at the activation temperature of 500 degrees C with soaking time of 0.5 hour. The influence of activation parameters on the final carbon products was examined by varying the impregnation ratio (i.e., mass ratio of added ZnCl2 to bagasse) and bagasse size. The physical properties of carbon products were characterized by nitrogen adsorption/desorption isotherms (at 77 K) and helium displacement method. The surface area and pore volume of carbons were thus obtained by the BET equation and t-plot method. Also, the particle density and porosity of carbons were estimated by the total pore volume and true density. The increases of the values of surface area and pore volume are approximately proportional to the impregnation ratio. The microporous carbon product with the BET surface area of 905 m2/g and total pore volume of 0.44 cm3/g was obtained in the present study. Further, the adsorption isotherms of two acid dyes from aqueous solutions onto the carbon products were performed at 30 degrees C. The results show that the adsorption isotherms of acid dyes with high molecular weight or large molecular size on the microporous adsorbents of activated carbons are plateau forms, indicating multilayer adsorptions, which may be attributed to the steric hindrance of the adsorbate molecules.     

Utilization of Arachis hypogaea hull,an agricultural waste for the production of activated carbons to remove phenol from aqueous solutions

Arachis hypogaea hulls, an agricultural waste, were used to prepare activated carbon by chemical activation with zinc chloride under four different activation atmospheres. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. The maximum Brunquer-Emmett-Teller (BET) surface area and micropore volume of the activated carbon was found to be 418 m²/g and 0.28 cm³/g, respectively. The activated carbon developed shows substantial capability to adsorb phenol from aqueous solutions. The kinetic data were fitted to the models of intraparticle diffusion, pseudo-second-order, and Lagergren, and followed more closely the pseudo-second-order chemisorption model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. Solution pH has significant effect on adsorption and the maximum uptake of phenol was reported at pH 3.5.     

80TH APCA Annual Meeting & Exhibition June 21-26, 1987

To increase U.S. petroleum energy-independence, the University of Texas at Arlington (UT Arlington) has developed a coal liquefaction process that uses a hydrogenated solvent and a proprietary catalyst to convert lignite coal to crude oil. This paper reports on part of the environmental evaluation of the liquefaction process: the evaluation of the solid residual from liquefying the coal, called inertinite, as a potential adsorbent for air and water purification. Inertinite samples derived from Arkansas and Texas lignite coals were used as test samples.

In the activated carbon creation process, inertinite samples were heated in a tube furnace (Lindberg, Type 55035, Arlington, UT) at temperatures ranging between 300 and 850 °C for time spans of 60, 90, and 120 min, using steam and carbon dioxide as oxidizing gases. Activated inertinite samples were then characterized by ultra-high-purity nitrogen adsorption isotherms at 77 K using a high-speed surface area and pore size analyzer (Quantachrome, Nova 2200e, Kingsville, TX). Surface area and total pore volume were determined using the Brunauer, Emmet, and Teller method, for the inertinite samples, as well as for four commercially available activated carbons (gas-phase adsorbents Calgon Fluepac-B and BPL 4?×?6; liquid-phase adsorbents Filtrasorb 200 and Carbsorb 30). In addition, adsorption isotherms were developed for inertinite and the two commercially available gas-phase carbons, using methyl ethyl ketone (MEK) as an example compound. Adsorption capacity was measured gravimetrically with a symmetric vapor sorption analyzer (VTI, Inc., Model SGA-100, Kingsville, TX). Also, liquid-phase adsorption experiments were conducted using methyl orange as an example organic compound. The study showed that using inertinite from coal can be beneficially reused as an adsorbent for air or water pollution control, although its surface area and adsorption capacity are not as high as those for commercially available activated carbons.

Implications: The United States currently imports two-thirds of its crude oil, leaving its transportation system especially vulnerable to disruptions in international crude supplies. UT Arlington has developed a liquefaction process that converts coal, abundant in the United States, to crude oil. This work demonstrated that the undissolvable solid coal residual from the liquefaction process, called inertinite, can be converted to an activated carbon adsorbent. Although its surface area and adsorption capacity are not as high as those for commercially available carbons, the inertinite source material would be available at no cost, and its beneficial reuse would avoid the need for disposal.     

Comprehending adsorption of methylethylketone and toluene and microwave regeneration effectiveness for beaded activated carbon derived from recycled waste bamboo tar

ABSTRACT

Beaded activated carbons (BACs) were derived from waste bamboo tar through carbonization (500°C for 2 hr) followed by physical activation using carbon dioxide (800–900°C for 2–4 hr). The adsorbent was examined for their physical and chemical properties, adsorption capacities toward methylethylketone (MEK) and toluene, and regenerabilities under microwave heating. It was found that the maximum total surface area reached for bamboo-tar-derived BAC after physical activation was 1364 m² g^?1, and more than 95% of the area was attributed to the microporous structures. Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models were applied to the adsorption isotherm fitting, and the minimum R² for each model was 0.986, 0.915, and 0.943, respectively. The isosteric heats of adsorption calculated based on D-R parameters for methylethylketone and toluene were 44.04 to 51.50 and 45.88 to 73.27 KJ mol^?1, respectively. They were slightly over the range of physisorption and increased with adsorbate loading, which might be related to the micropore filling mechanism. Microwave regeneration under 600 W of power output removed most of the adsorbate (>93.03%) within 8 min. The results of this study are intended to benefit future study on waste-derived adsorbent in environmental applications.     

Preparation and characterisation of activated carbon from waste tea by physical activation using steam

ABSTRACT

In this study, the feasibility of preparing activated carbon from waste tea by physical activation using steam was investigated. The effects of activation temperature on yield and pore properties of the prepared activated carbon were studied. The yield decreased with increased activation temperature owing to the decomposition of cellulose and hemicellulose. The specific surface area and pore volume of the activated carbon were estimated using the Brunauer–Emmett–Teller method, Langmuir equation, and t-plot method. The specific surface area and micropore volume increased with increases in activation temperature, as additional volatile materials were released. The specific surface area significantly decreased at first but slightly increased with increasing activation time. The maximum specific surface area reached 995 m²/g at an activation temperature of 800 °C with a water flow rate of 0.075 g/min and a constant hold time of 0.5 hr. According to the nitrogen adsorption isotherms, micropores mainly developed when the activation temperature was below 800 °C, and both micropores and mesopores developed when it was above 800 °C. The results showed that activation temperature significantly affected micropore and mesopore volumes, as well as the specific surface area of the activated carbon. Overall, waste tea was found to be an attractive raw material for producing low-cost activated carbon.

Implications: Every year, a large amount of waste tea is generated after extraction. The high carbon content of waste tea showed that it can be used as raw material to produce activated carbon. This study investigated the feasibility of preparing activated carbon from waste tea by physical activation using steam. Temperature and time were found to have clear effects on pore properties. Our proposed method and raw material are more environmentally friendly and involve low cost. Furthermore, this offers a potential solution to the problems of waste tea disposal and low-cost activated carbon production.     

Physicochemical characteristics of carbonaceous adsorbent for dioxin-like polychlorinated biphenyl adsorption

It has been known that dioxin-like polychlorinated biphenyls (DL-PCBs) are present in almost all types of environments worldwide. Activated carbon treatment has been expected for the removal of DL-PCBs because it is a simple and low-cost removal technology. In the present study, the physicochemical properties of activated carbon were investigated to identify the characteristics of 16 different types of activated carbon on adsorption properties for DL-PCBs. To accomplish this, micropore volume, and pore diameter were calculated by t-plot analysis and the mesopore volume was analyzed by the Barrett-Joyner-Halenda (BJH) method. In addition, the Brunauer-Emmett-Teller (BET) surface area, pH, metal elements, and surface acid functional groups were analyzed. Then, adsorption experiments using DL-PCB in hexane solution were conducted, and the relationship between adsorption and physicochemical properties of activated carbon was investigated. The results showed that activated carbons having a surface area of 700-1200 m² g⁻¹ and micropores with diameters of about 0.7-0.8 nm exhibited high activity for the adsorption of PCBs. The results also clearly showed that the mesopore volume of activated carbon influenced the adsorption rate and the equilibrium adsorption.     

Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid

A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb’s Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.