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.     

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。     

新型水处理活性炭选型技术

活性炭依其原料不同、生产工艺不同,而有不同的吸附性能.使用简易的活性炭选型方法,可以减少应用测试时的备选炭型,从而大大降低活性炭水处理技术的运行成本.以碘值、甲基蓝值、苯酚值和丹宁酸值4种吸附容量性能指标为依据的活性炭选型技术,可以有效地预测活性炭对于水中各种大小不同污染物的去除能力.BET测试结果证明了这4项指标数据对于活性炭孔径分布预测的准确性.2,4-二氯苯酚和腐殖酸等目标化合物的吸附容量实验结果也都验证了这4项指标的预测功用,说明这种简便的活性炭选型技术有着广泛的应用价值.     

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.     

玉米芯掺杂对污泥基活性炭性能的影响

针对以城市污水厂剩余污泥为原料制备的污泥基活性炭微孔性差、比表面积低的缺陷,将一定比例玉米芯掺杂到污泥中以期改善活性炭性质。通过对活性炭的比表面积、孔结构、碘值、表面官能团测定以及表面电镜分析,探讨了不同比例玉米芯掺杂对活性炭物理化学性质的影响,并以苯酚和硝基苯为目标物,对比考察所制活性炭对有机物的吸附性能。实验结果表明,随着玉米芯掺杂比例的提高,活性炭微孔体积及比表面积明显增大,但活性炭表面官能团种类及数量变化不明显。所制活性炭表面都以酸性基团为主。结果显示苯酚和硝基苯吸附值与活性炭表面酸性基团含量关系密切,因此,玉米芯的掺杂对苯酚和硝基苯的吸附没有明显的促进作用。     

Application of High Gradient Magnetic Separation to Fine Particle Control

The char produced in the thermolysis of granulated scrap tyres has few market outlets, reducing the economic viability of the thermolytic process. This paper reports the potential of this char as a low-cost precursor of porous carbons. The tyre-derived char was demineralized in either alkaline or acidic media to reduce its ash, zinc, sulfur, and silica contents. The lowest impurity content was achieved with an HNO₃/H₂O treatment. The resulting demineralized char was then subjected to activation by KOH or CO₂. The Brunauer-Emmett-Teller (BET)-specific surface area of the activated carbon produced by the KOH treatment was 242 m²/g, whereas that of the CO₂-activated carbon was 720 m²/g. The textural properties of the latter product were similar to those of some commercial activated carbons. The use of tyre-derived char as a precursor of porous carbons could render the thermolytic treatment of scrap tyres more economically attractive.

Implications: Char produced in thermolysis of granulated scrap tyres has a few market outlets; in this paper an alternative for its use is presented. The char was converted into activated carbon with textural properties similar to those of some commercial activated carbons. This process could render the thermolytic treatment of scrap tyres more economically attractive.     

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.     

废活性炭微波再生新工艺的研究

提出用微波加热-二氧化碳活化法再生乙酸乙烯合成用触媒载体废活性炭工艺.采用条件实验法研究了活化时间、二氧化碳流量和微波功率对活性炭碘吸附值,亚甲基蓝吸附值和再生得率的影响,得到微波辐射加热二氧化碳活化再生乙酸乙烯用触媒载体废活性炭的最佳工艺条件为活化时间25 min,二氧化碳流量0.2 L/min,微波功率700 W.在此条件下制得的活性炭碘吸附值为1158.02 mg/g、亚甲基蓝吸附值为240 mg/g、得率为74.19%.并对活性炭进行了比表面积的测定和孔结构的分析,活性炭的比表面积为1308.13 m2/g,总孔容为0.76 mL/g.     

A comparative study of anaerobically digested and undigested sewage sludges in preparation of activated carbons.

Disposal of sewage sludge is an increasingly expensive and environmentally sensitive problem throughout the world. Preparation of activated carbon from sewage sludge offers an attractive re-use alternative to the traditional disposal routes. The objective of this research work was to compare anaerobically digested sewage sludge (DS) and undigested sewage sludge (US) as source materials in the preparation of activated carbons. Prior to the preparation the properties of the two types of sewage sludges were determined and compared. Subsequently the sludge samples were activated with 5 M ZnCl2 solution and thereafter pyrolysed at heating temperature of 650 degrees C for 2 h with the heating rate of 15 degrees C/min under a nitrogen atmosphere. The produced activated carbons were characterised by surface area and porosity analysis, CHN elemental composition and ash contents determination, and aqueous phase phenol adsorption tests. The results indicate that in comparison with the DS, the US had a higher carbon content and lower ash content, and accordingly yielded a better activated carbon with a higher BET surface area, pore volume, carbon content and phenol adsorption capacity.     

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.     

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.     

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.     

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.     

高温载硫活性炭的制备及脱汞能力研究

研究了载硫温度、硫炭比(简称S/C),吸附温度等因素对载硫活性炭的硫含量、脱汞能力以及硫损失的影响,探讨载硫活性炭制备的工艺条件优化。结果表明,不同载硫温度下制备的载硫活性炭的气态Hg0吸附能力远强于原料活性炭;载硫温度不同时,负载到活性炭孔隙或表面上的硫的形态不同,导致了脱汞能力的差异,较合适的载硫温度为350℃;S/C为5%(质量分数,下同)时,随着吸附温度的升高,载硫活性炭的气态Hg0吸附量降低;在一定的载硫温度下,原料中S/C越高时,制备的载硫活性炭的硫含量越高、气态Hg0吸附能力越强,但其硫损失率也越高,从实际的使用效果来看,较合适的S/C为10%。     

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.     

Experimental design methodology for the preparation of carbonaceous sorbents from sewage sludge by chemical activation--application to air and water treatments

The objective of this study is to optimize experimental conditions of sorbent preparation from sewage sludge using experimental design methodology. Series of carbonaceous sorbents have been prepared by chemical activation with sulfuric acid. The sorbents produced were characterized, and their properties (surface chemistry, porous and adsorptive properties) were analyzed as a function of the experimental conditions (impregnation ratio, activation temperature and time). Carbonaceous sorbents developed from sludge allow copper ion, phenol and dyes (Acid Red 18 and Basic Violet 4) to be removed from aqueous solution as well as VOC from gas phase. Indeed, according to experimental conditions, copper adsorption capacity varies from 77 to 83 mg g(-1), phenol adsorption capacity varies between 41 and 53 mg g(-1) and VOC adsorption capacities (acetone and toluene) range from 12 to 54 mg g(-1). Each response has been described by a second-order model that was found to be appropriate to predict most of the responses in every experimental region. The most influential factors on each experimental design response have been identified. Regions in which optimum values of each factor were achieved for preparation of activated carbons suitable for use in wastewater and gas treatments have been determined using response surfaces methodology. In order to have a high mass yield and to minimize the energetic cost of the process, the following optimal conditions, 1.5 g of H2SO4 g(-1) of sludge, 700 degrees C and 145 min are more appropriate for use of activated carbon from sludge in water and gas treatments.     

改性竹活性炭去除汞离子

采用溴化钾、碘化钾和硫磺对竹活性炭掺杂改性,利用电感耦合等离子体发射光谱仪测定滤液中汞离子浓度,用除汞效率和吸附容量评价活性炭对溶液中汞离子的吸附性能,探讨其吸附机理。结果表明,掺杂改性明显提高了竹活性炭的除汞性能。原竹活性炭的除汞效率为78.6%,吸附容量为2.210 mg/g;经碘化钾、溴化钾和硫磺掺杂改性后的竹活性炭除汞效率分别为94.3%、93.8%和88.8%,吸附容量分别为2.830、2.813和2.663 mg/g;经溴化钾(碘化钾)和硫磺联合改性的竹活性炭对水溶液中汞离子的吸附性能性能又有提高,其中以先载硫后载溴化钾的方法除汞效果最好,除汞效率达96.6%,吸附容量为2.898 mg/g。     

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.     

Electrochemical and FTIR studies of the mutual influence of lead(II) or iron(III) and phenol on their adsorption from aqueous acid solution by modified activated carbons

Cyclic voltammetry and spectral FTIR studies of the influence of activated carbon surface modification on the co-adsorption of metal cation (lead or iron) and phenol from aqueous acidic solution were carried out. The diversity in surface chemical structure was achieved by applying different procedures of inorganic matter removal and by modifying the carbon samples in various ways: heating under vacuum, aminoxidation in an ammonia-oxygen atmosphere, oxidation with concentrated nitric acid. The quantities of adsorbed metal ions (Pb(2+) or Fe(3+)) and phenol from solutions containing cation or phenol separately or in a mixture were determined. The adsorption capacity from acidic aqueous acidic solution depends on the chemical properties of the activated carbon surface (e.g., decrease in phenol adsorption with relative lower basicity of the adsorbent). The electrochemical parameters of electrodes made from the carbon samples were estimated, and some possible electrochemical reactions were determined from voltammograms recorded in acid electrolyte solution containing adsorbed species (separately or as a mixture). Relationships were found between metal ion adsorption and electrochemical behavior of Pb(2+)/Pb(4+) and Fe(3+)/Fe(2+) couples on the one hand, and the presence of phenol in the solutions tested and the influence of surface chemistry of the carbon electrodes on electrochemical processes on the other. The changes in adsorption capacity with respect to the adsorbates used and the changes in FTIR spectra of the carbons as a result of adsorption and/or coupling phenol molecules are discussed.     

Adsorption of phenolic compounds by activated carbon--a critical review

Adsorption of phenol and its derivatives on activated carbons is considered based on numerous papers related to this issue. Special attention is paid to the effects of carbon surface functionalities, pH of solution and heterogeneity effects that accompany adsorption of phenolic compounds. Moreover, in this paper the most important aspects are overviewed referring to irreversible adsorption of phenols and impact of different substituents of phenolic compounds on their uptake by activated carbons is considered. Finally, some remarks pertaining to applications of novel adsorbents for phenol adsorption are discussed and illustrated by means of a few examples.