Preparation of Activated Carbons from Raw and Biotreated Agricultural Residues for Removal of Volatile Organic Compounds

ABSTRACT

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.

IMPLICATIONS This paper presents data on the preparation of activated carbons from agricultural residues, especially the waste from biohydrogen generation. Experimental results indicated that with proper carbonization and steam activation, activated carbons with diverse characteristics can be produced from various agricultural residues. The resulting activated carbons effectively adsorb toluene. This work provides useful information for reutilization of these agricultural residues, helping in decreasing the cost of biological waste treatment and providing a cost-effective alternative to conventional adsorbent production and application.     

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.     

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。     

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.     

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

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

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.     

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-desorption 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.     

活性炭孔隙结构在其甲苯吸附中的作用

选用4种商用活性炭(AC),利用氮气绝热吸附、扫描电子显微镜(SEM)和傅立叶变换红外光谱(FTIR)测试了活性炭的物化性质。以甲苯为吸附质,在温度为298.15 K下进行了静态和动态吸附实验,研究了活性炭孔结构对其吸附性能、吸附行为、表面覆盖率和吸附能的影响。结果表明:活性炭的比表面积和孔容是其吸附性能主要影响因素,孔径在0.8～2.4 nm之间的孔容和甲苯吸附量之间存在较好的线性关系,且线性斜率随甲苯浓度增加而变大。甲苯吸附行为符合Langmuir吸附等温模型和准一阶动力学方程式。活性炭孔结构是甲苯吸附速率的主要制约因素。在甲苯快速吸附阶段,微孔为吸附速率主要制约因素,在甲苯颗粒内扩散阶段,微孔和表面孔为吸附速率的主要制约因素,在吸附末尾阶段,中孔和大孔为吸附速率的主要制约因素。4种活性积炭对甲苯的吸附能随其比表面变大而变大。     

Production of activated carbons from pyrolysis of waste tires impregnated with potassium hydroxide

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 degrees 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.     

微波法污水厂污泥制备活性炭的研究

研究了以污水厂污泥为原料、微波辐照下磷酸活化法制备污泥活性炭的工艺条件,探讨了微波功率、辐照时间以及磷酸浓度对活性炭碘值的影响.结果表明,微波功率480 W、辐照时间315 s、磷酸浓度40%～45%的条件下,制备的污泥活性炭碘值为301 mg/g,总孔孔容是0.37 mL/g,平均孔径8.8 nm,比表面积168 m2/g.将该污泥活性炭用于处理TNT红水,吸附效果良好.     

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

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

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.     

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.     

Optimising the preparation of activated carbon from digested sewage sludge and coconut husk.

Preparation of activated carbon from sewage sludge is a promising way to dispose of sewage sludge as well as to produce a low-cost adsorbent for pollutant removal. This research work aimed to optimise the condition for activated carbon preparation from anaerobically digested sewage sludge with the additive coconut husk. The sewage sludge sample was mixed with the additive coconut husk. The preparation condition variables investigated involved the concentration of the ZnCl2 solutions, heating temperature, dwell time and heating rate in pyrolysis and the mixing ratio of coconut husk to sewage sludge. Surface area, pore size distribution, aqueous phenol adsorption capacity and the production yield of the final products were determined and compared. Experimental results revealed that low concentrations of ZnCl2 solution tended to improve the microporosity of the final product. Heating temperature had a considerable impact on the surface area, pore size distribution and phenol adsorption capacity of the final products, whereas dwell time and heating rate performed comparatively insignificantly. The effect of increasing the mixing ratio of coconut husk to sewage sludge was principally to increase the microporosity of the final products. The activated carbon with the highest BET surface area was produced with the activation of 5 M ZnCl2 solution and, thereafter, pyrolysis at a heating temperature of 500 degrees C for 2 h with a heating rate of 10 degrees C/min. The mixing ratio of 1:4 in terms of coconut husk to sewage sludge based on their dried weights was found to be most cost effective.     

磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性

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

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

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

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

Catalytic decomposition of hydrogen peroxide and 4-chlorophenol in the presence of modified activated carbons

The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.     

Adsorption of acid dye onto activated carbons prepared from agricultural waste bagasse by ZnCl2 activation

A series of activated carbons were prepared from agricultural waste sugarcane bagasse by chemical activation with zinc chloride (ZnCl2) as an activating agent at 500 degrees C and 0.5 h soaking time. The Langmuir surface area and total pore volume were used to estimate the average pore diameter of the carbon products. The values of the surface area and pore volume increased linearly with increase in the impregnation ratio (IR) up to 100 wt%. The adsorption capacities of the derived adsorbents for Acid Orange 10 were measured at 20 degrees C and 40 degrees C to gain further insights into the acidic surface oxides of the adsorbent from the results of Fourier transform infrared (FTIR) spectroscopy analysis and pH measurement. Adsorption isotherms of the acid dye on adsorbents prepared were determined and correlated with common isotherm equations. It was found that the Langmuir model appears to fit the isotherm data better than the Freundlich model. The physical properties of these adsorbents were consistent with the parameters obtained from the isotherm equations.     

活性炭材料的活化与改性

活性炭是一种应用广泛的吸附催化剂 ,其性能取决于它的孔隙结构和表面化学性质。根据活性炭的表面特性对不同物质的吸附性能 ,对活性炭进行活化和改性处理 ,能进一步满足各种特殊用途的要求。本文概述了活性炭的各种活化和改性处理技术