Pore structure and adsorption properties of carbonized material prepared from waste paper

We have already reported the adsorptivity and pore structure of activated carbon made from waste newspaper in order to use the waste paper for purposes other than paper-making stock. However, manufacturing the activated carbon may not necessarily be an advantageous method based on environmental concerns and the effective use of the resource because the reaction during the activating process is endothermic and the amount of carbon consumed is significant. Here, we examine the pore structure and adsorption properties of waste newspaper used as an adsorbent in the form of a carbonized material. Waste newspaper was carbonized for 2 h in the temperature range 400°–1000°C. The specific surface area of the carbonized material obtained, 418 m²/g, was highest for the sample carbonized at 800°C, which was equal to or greater than that of commercially available charcoal. Moreover, the iodine adsorption number of 581 mg/g was the highest and the rate of adsorption was the fastest for the sample carbonized at 800°C. However, the humidity control capability was highest for the material carbonized at 600°–700°C. It has been determined that it is advantageous to carbonize waste paper at 800°C in order to use the carbonized material as an adsorbent, while carbonization at 600°–700°C is more advantageous for use as a humidity control material. Received: June 23, 2000 / Accepted: January 17, 2001     

Porous structure of activated carbon prepared from waste newspaper

In an earlier report, we presented a method for preparing activated carbon from waste newspaper as a way to recycle used paper for a purpose other than producing raw material for paper-making. In this article, we consider the porous structure of the activated carbon that affects its adsorption properties for various substances. The specific surface area of activated carbon prepared from waste newspaper was 838 m²/g, the micropore volume was 0.368 ml/g, and the mesopore volume was 0.138 ml/g, which is about the same as commercially available activated carbon. The activated carbon prepared from waste newspaper usually has a high content of ash, which makes little contribution to the adsorption properties. In particular, as compared with reagent-activated carbon, the quantities of mesopores with a pore radius of 3–25 nm and macropores with a pore radius of 25–250 nm were 8 and 14 times larger, respectively. Activated carbon prepared from waste newspaper has a well-developed porous structure, particularly in the mesopore and macropore ranges. Received: July 12, 1999 / Accepted: March 8, 2000     

Improved enzymatic hydrolysis of waste paper by ozone pretreatment

Waste paper samples made from newsprint, copier paper, and magazine paper, as well as samples of kraft pulp and thermomechanical pulp, were pretreated with ozone to improve enzymatic hydrolysis. The ozone treatment of pulps of newsprint and of magazine paper increased the specific surface areas and total pore volumes while decreasing the lignin content so that these values became similar to those of thermomechanical pulps. These morphological and chemical changes in the pulps resulted in the increased access of cellulase to the pulp fiber surface and increased enzymatic hydrolysis. For copier paper, in which the lignin content was very low, additives on the pulp fiber surface were oxidized and removed by ozone treatment and extraction, and this allowed improved enzymatic hydrolysis. In contrast, surface areas and total pore volumes of kraft pulp and bleached kraft pulp were decreased by the ozone treatment, resulting in morphological changes in the pulps that decreased enzymatic hydrolysis.     

Catalytic degradation of PP with an Fe/activated carbon catalyst

We investigated the function of Fe and activated carbon (AC) as a catalyst by comparing Fe/AC with Fe/SiO₂ or AC, and also the effect of H₂ as a reaction gas on the product distribution in the catalytic degradation of polypropylene. Supported Fe promotes H₂ consumption to decompose solid residues, and AC support degrades heavy oil to produce light oil. As a result, using Fe/AC as a catalyst gives the maximum yield of the liquid product. For the reaction conditions, with a high reaction temperature or a long reaction time, the product distribution is more influenced by the thermal degradation than by the catalytic degradation. For the amount of Fe to load, 5wt% is the optimum condition in our reaction system. We demonstrated the mechanism of the degradation of polyolefins with hydrogen-capping catalysts.     

Effect of ZnCl<Subscript>2</Subscript> impregnation ratio on pore structure of activated carbons prepared from cattle manure compost: application of N<Subscript>2</Subscript> adsorption-desorption isotherms

Activated carbons were prepared from cattle manure compost (CMC) by ZnCl₂ activation with various ZnCl₂/CMC mass ratios. Based on the N₂ adsorption-desorption isotherms, mathematical models including the Dubinin-Radushkevich (DR) equation, the α_s plot, and the Horvath-Kawazoe method were used to analyze the pore structural characteristics of the prepared activated carbons. It was found that for carbons possessing both micro-and mesopores, the DR method provided a more accurate estimation than the α_s method for the extent of microporosity. The effect of the ZnCl₂ impregnation ratio on the pore structure was discussed using the DR method. The results revealed that pore evolution involved three distinct regions with increases in the amount of impregnated ZnCl₂: raising the ZnCl₂/CMC mass ratio from 0.00 to 0.50 resulted in a 19-fold increase in micropore volume (V_me ^D) but caused no change in the mesopore volume (V_me ^D); increasing the ZnCl₂/CMC mass ratio from 0.50 to 1.00 led to an increment in V_mi ^D of about 50% and in V_me ^D of 170%; while raising the ratio from 1.50 to 2.50 caused a slight decrease in V_mi ^D but a 200% increment in the value of V_me ^D.     

ACF床动态吸附及脱附性能试验研究

利用活性炭纤维(ACF)床在热态下进行动态吸附及脱附性能试验,研究了W/Q、水蒸汽含量对ACF吸附性能的影响,并利用ACF的选择性吸附性能,采用分段吸附,以达到同时高效吸附SO2和NOx.对ACF床进行了水洗脱附与负吸热空气法脱附试验.     

Utilization of turkey manure as granular activated carbon: physical, chemical and adsorptive properties

The high availability of large quantities of turkey manure generated from turkey production makes it an attractive feedstock for carbon production. Pelletized samples of turkey litter and cake were converted to granular activated carbons (GACs) by steam activation. Water flow rate and activation time were changed to produce a range of activation conditions. The GACs were characterized for select physical (yield, surface area, bulk density, attrition), chemical (pH, surface charge) and adsorptive properties (copper ion uptake). Carbon physical and adsorptive properties were dependent on activation time and quantity of steam used as activant. Yields varied from 23% to 37%, surface area varied from 248 to 472 m(2)/g and copper ion adsorption varied from 0.72 to 1.86 mmol Cu(2+)/g carbon. Copper ion adsorption greatly exceeded the values for two commercial GACs. GACs from turkey litter and cake show considerable potential to remove metal ions from water.     

城市污泥制备水中重金属吸附剂及其吸附特性研究

本实验利用城市污水厂的脱水污泥,通过化学活化法制备活性炭.研究活化温度、活化时间、固液比和活化剂浓度等因素对制备污泥活性炭的影响,确定氯化锌法制备污泥活性炭的最佳工艺为活化温度550 ℃、活化时间30 min、固液比1∶2、氯化剂浓度45％.将制备的污泥活性炭吸附Cu2＋,Cr6＋,Cd2＋3种重金属离子模拟废水,研究pH值、吸附时间、污泥投加量、温度等因素对吸附过程的影响.实验结果表明,剩余污泥对Cu2＋,Cr6＋,Cd2＋3种重金属离子都具有良好的吸附效果,在优化条件下,3种重金属离子去除率分别达到94％,76％,81％,吸附能力大小顺序为Cu2＋＞Cd2＋＞＋Cr6＋.     

Production and characterization of KOH-activated carbon derived from polychlorinated biphenyl residue generated by the sodium dispersion process

Polychlorinated biphenyl (PCB) residues from the sodium dispersion (SD) process were employed as the raw materials for the production of activated carbon using KOH activation. The pore properties, such as the specific surface area and pore size distribution, were characterized using the Barrett–Joyner–Halenda method and the Horvath–Kawazoe method based on the N₂ adsorption isotherm at 77 K. The activated carbon produced showed similar adsorption capacities and specific surface areas to the commercially available product. The effects of the activation conditions on the porosity of the activated carbon produced were studied. The most significant factor affecting the specific surface proved to be the activation temperature. The activated carbon produced from PCB residues from the high-temperature (423–443 K) SD process had a binary pore size distribution well developed in the 4 nm region and in the micropore region. The pore structure of the carbon produced from PCB residues from the low-temperature (333–393 K) SD process had a wide range of micropores and mesopores.     

Direct and indirect generation of waste in the Spanish paper industry

The paper industry has a relatively high degree of reliance on suppliers when compared to other industries. Exploring the role of the paper industry in terms of consumption of intermediate inputs from other industries may help to understand how the production of paper does not only generate waste by itself but also affects the amount of waste generated by other industries. The product Life Cycle Assessment (LCA) is a useful analytical tool to examine and assess environmental impacts over the entire life cycle of a product “from cradle to grave” but it is costly and time intensive. In contrast, Economic Input Output Life Cycle Assessment Models (IO-LCA) that combine LCA with Input–Output analysis (IO) are more accurate and less expensive, as they employ publicly available data. This paper represents one of the first Spanish studies aimed at estimating the waste generated in the production of paper by applying IO-LCA. One of the major benefits is the derivation of the contribution of direct and indirect suppliers to the paper industry. The results obtained show that there was no direct relationship between the impact on output and the impact on waste generation exerted by the paper industry. The major contributors to waste generation were the mining industry and the forestry industry.     

Preparation and performance of arsenate (V) adsorbents derived from concrete wastes

Solid adsorbent materials, prepared from waste cement powder and concrete sludge were assessed for removal of arsenic in the form of arsenic (As(V)) from water. All the materials exhibited arsenic removal capacity when added to distilled water containing 10–700 mg/L arsenic. The arsenic removal isotherms were expressed by the Langmuir type equations, and the highest removal capacity was observed for the adsorbent prepared from concrete sludge with heat treatment at 105 °C, the maximum removal capacity being 175 mg-As(V)/g. Based on changes in arsenic and calcium ion concentrations, and solution pH, the removal mechanism for arsenic was considered to involve the precipitation of calcium arsenate, Ca₃(AsO₄)₂. The enhanced removal of arsenic for the adsorbent prepared from concrete sludge with heat treatment was thought to reflect ion exchange by ettringite. The prepared adsorbents, derived from waste cement and concrete using simple procedures, may offer a cost effective approach for arsenic removal and clean-up of contaminated waters, especially in developing countries.     

Techno-economic evaluation of ultrasound and thermal pretreatments for enhanced anaerobic digestion of municipal waste activated sludge

To enhance the anaerobic digestion of municipal waste-activated sludge (WAS), ultrasound, thermal, and ultrasound + thermal (combined) pretreatments were conducted using three ultrasound specific energy inputs (1000, 5000, and 10,000 kJ/kg TSS) and three thermal pretreatment temperatures (50, 70 and 90 °C). Prior to anaerobic digestion, combined pretreatments significantly improved volatile suspended solid (VSS) reduction by 29-38%. The largest increase in methane production (30%) was observed after 30 min of 90 °C pretreatment followed by 10,000 kJ/kg TSS ultrasound pretreatment. Combined pretreatments improved the dimethyl sulfide (DMS) removal efficiency by 42-72% but did not show any further improvement in hydrogen sulfide (H₂S) removal when compared with ultrasound and thermal pretreatments alone. Economic analysis showed that combined pretreatments with 1000 kJ/kg TSS specific energy and differing thermal pretreatments (50-90 °C) can reduce operating costs by $44-66/ton dry solid when compared to conventional anaerobic digestion without pretreatments.     

Dehydrochlorination behavior of polyvinyl chloride and utilization of carbon residue: effect of plasticizer and inorganic filler

The dehydrochlorination behavior of plasticizer (DOP) and inorganic filler (CaCO₃) contained in PVC samples and the properties of the activated carbons produced from those carbon residues have been investigated. In the dehydrochlorination process, both additives contributed not only to a decrease in HCl yield but also to the prolonged evolution of HCl. Part of the Cl species were observed to be stabilized as CaCl₂ by reaction with calcium ions when CaCO₃ was added. More than 80% of chlorine removal was achieved in all samples at 533 K. The use of potassium as an activation agent led to the production of activated carbon with a specific surface area greater than 1000 m²/g at the low temperature of 1023 K and assisted also in the elimination of residual Cl species by the formation of KCl during activation. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Characteristics of azaarenes and dioxins in gases emitted from waste incinerators

In this study, we propose an analytical method to determine the fourteen of azaarenes present in flue gas samples collected according to Japanese Industrial Standard K 0311, which designates the method for the determination of dioxins in flue gas. Azaarenes can be analyzed using the acidic water phase after shaking extraction with dichloromethane, which is unnecessary for dioxin analysis. Flue gas samples were obtained from 24 waste incinerators in Japan, and azaarenes were detected in all the flue gas samples (0.21–3800 μg/m³ _N). The most abundant of the detected compounds were quinoline and isoquinoline. The concentration of azaarenes had a tendency to increase with that of polychlorinated dibenzo-p-dioxins and dibenzofurans. The isomer distribution of heptachloro-dibenzofurans (HpCDFs) was calculated using the computed Gibbs energy of formation (ΔG _f ) obtained by the semiempirical molecular orbital method at various temperatures. The calculated isomer distribution was fitted to the measured value of HpCDFs. It seems that the temperature obtained from the fitting calculations is an indicator of the cooling capacity of the combustion gas in an incinerator. The computed ΔG _f also explained the measured isomer distributions of azaarenes. It is suggested that the isomer distribution of azaarenes in the combustion process is thermodynamically controlled. This work was presented in part at the International Conference on Combustion, Incineration/Pyrolysis, and Emission Control, 2006, Kyoto     

活性炭材料在火电厂烟气脱硫脱硝中的应用

概述了传统活性炭和活性炭纤维材料独特的吸附性,介绍了活性炭材料在烟气脱硫脱硝中的应用原理.同时建议今后应在表面改性、脱硫脱硝反应机理等方面进行深入研究.     

Residual organic fluorinated compounds from thermal treatment of PFOA,PFHxA and PFOS adsorbed onto granular activated carbon (GAC)

Perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonate (PFOS) adsorbed onto granular activated carbon (GAC) were thermally treated in N₂ gas stream. The purpose was to assess the fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) during thermal regeneration of GAC, which had been used for water treatment. Mineralized F, residual PFASs including short-chained species, and volatile organic fluorine (VOF) were determined. In a temperature condition of 700 °C, VOF were 13.2, 4.8, and 5.9 % as for PFOA, PFHxA, and PFOS. However, the VOF decreased to 0.1 %, if the GAC and off-gas were kept at 1000 °C. No PFASs remained in GAC at 700–1000 °C; at the same time, short-chained PFASs were slightly detected in the aqueous trapping of off-gas at 800 and 900 °C conditions. The destruction of PFASs on GAC could be perfect if the temperature is higher than 700 °C; however, the process is competitive against volatile escape from GAC. Destruction in gaseous phase needs a temperature as high as 1000 °C. Destruction of PFASs on the surface of GAC, volatile escape from the site, and thermolysis in gas phase should be considered, as to thermal regeneration of GAC.     

Removal of ammoniacal nitrogen (N-NH3) from municipal solid waste leachate by using activated carbon and limestone.

The presence of ammoniacal nitrogen (N-NH3) in leachate is one of the problems normally faced by landfill operators. Slow leaching of wastes producing nitrogen and no significant mechanism for transformation of N-NH3 in the landfills causes a high concentration of ammoniacal nitrogen in leachate over a long period of time. A literature review showed that the removal of ammoniacal nitrogen from leachate was not well documented and to date, there were limited studies in Malaysia on this aspect, especially in adsorption treatment. The main objective of the present study was to investigate the suitability of activated carbon, limestone and a mixture of both materials as a filtering medium, in combination with other treatments capable of attenuating ammoniacal nitrogen which is present in significant quantity (between 429 and 1909 mg L(-1)) in one of the landfill sites in Malaysia. The results of the study show that about 40% of ammoniacal nitrogen with concentration of more than 1000 mg L(-1) could be removed either by activated carbon or a mixture of carbon with limestone at mixture ratio of 5:35. This result shows that limestone is potentially useful as a cost-effective medium to replace activated carbon for ammoniacal nitrogen removal at a considerably lower cost.     

Pyrolysis and catalytic pyrolysis as a recycling method of waste CDs originating from polycarbonate and HIPS

Pyrolysis appears to be a promising recycling process since it could convert the disposed polymers to hydrocarbon based fuels or various useful chemicals. In the current study, two model polymers found in WEEEs, namely polycarbonate (PC) and high impact polystyrene (HIPS) and their counterparts found in waste commercial Compact Discs (CDs) were pyrolysed in a bench scale reactor. Both, thermal pyrolysis and pyrolysis in the presence of two catalytic materials (basic MgO and acidic ZSM-5 zeolite) was performed for all four types of polymers. Results have shown significant recovery of the monomers and valuable chemicals (phenols in the case of PC and aromatic hydrocarbons in the case of HIPS), while catalysts seem to decrease the selectivity towards the monomers and enhance the selectivity towards other desirable compounds.     

Estimation and field measurement of methane emission from waste landfills in Hanoi, Vietnam

A methodology for estimating the methane emissions from waste landfills in Hanoi, Vietnam, as part of a case study on Asian cities, was derived based on a survey of documents and statistics related to waste management, interviews with persons in charge, and field investigations at landfill sites. The waste management system in Hanoi was analyzed to evaluate the methane emissions from waste landfill sites. The quantity of waste deposited into the landfill was evaluated from an investigation of the waste stream. The composition of municipal waste was surveyed in several districts in the Hanoi city area, and the quantities of degradable organic waste that had been deposited into landfill for the past 15 years were estimated. Field surveys on methane emissions from landfills of different ages (0.5, 2, and 8 years) were conducted and their methane emissions were estimated to be 120, 22.5, and 4.38 ml/min/m², respectively. The first-order reaction rate of methane generation was obtained as 0.51/year. Methane emissions from waste landfills were calculated by a first-order decay model using this emission factor and the amount of landfilled degradable waste. The estimates of methane emissions using the model accorded well with the estimates of the field survey. These results revealed that methane emissions from waste landfills estimated by regional-specific and precise information on the waste stream are essential for accurately determining the behavior of methane emissions from waste landfills in the past, present, and future.     

Desulfurization of coke oven gas from the coking of coking coal blended with a sorbent and waste plastic

A new way to implement the simultaneous reutilization of solid waste, the desulfurization of coke oven gas (COG), and even the desulfurization of coke by the co-coking of coking coal (CC) and waste plastic (WP) blended with a sorbent is proposed; the evolution of H₂S and the removal efficiency of H₂S from COG during the co-coking process were investigated in a lab-scale cylindrical reactor. The experimental results indicated that for the coking of CC blended with ZnO, Fe₂O₃, or blast furnace dust (BFD) as a sorbent, the instantaneous concentration of H₂S in COG was lower than 500 mg/m³ (which meets the technical specification requirement of the Chinese Cleaner Production Standard–Coking Industry, HJ/T 126-2003) when the molar ratio between the key component of the sorbent and the volatile S in CC or the CC/WP blend, n _Zn+Fe/n _S, was about 1.2 for ZnO and Fe₂O₃, but not for BFD under the same conditions, suggesting that ZnO and Fe₂O₃ are promising sorbents, but that BFD must be treated chemical or thermally before being used as a sorbent because of the size and complicated nature of the influence of its phase/chemical composition on its desulfurization ability. However, for the co-coking of CC and WP blended with ZnO as a sorbent, n _Zn+Fe/n _S must increase to 1.4 and 1.7 for 100/2 and 100/5 blends of CC/WP, respectively, to ensure a satisfactory efficiency for H₂S removal from COG. Part of this paper was presented at the International Symposium on EcoTopia Science 2005 (ISET05), Aug 8–9, 2005, Chikusa-ku, Nagoya, Japan