Adsorption of phenol and its derivatives from water using synthetic resins and low-cost natural adsorbents: a review

In this article, the technical feasibility of the use of activated carbon, synthetic resins, and various low-cost natural adsorbents for the removal of phenol and its derivatives from contaminated water has been reviewed. Instead of using commercial activated carbon and synthetic resins, researchers have worked on inexpensive materials such as coal fly ash, sludge, biomass, zeolites, and other adsorbents, which have high adsorption capacity and are locally available. The comparison of their removal performance with that of activated carbon and synthetic resins is presented in this study. From our survey of about 100 papers, low-cost adsorbents have demonstrated outstanding removal capabilities for phenol and its derivatives compared to activated carbons. Adsorbents that stand out for high adsorption capacities are coal-reject, residual coal treated with H3PO4, dried activated sludge, red mud, and cetyltrimethylammonium bromide-modified montmorillonite. Of these synthetic resins, HiSiv 1000 and IRA-420 display high adsorption capacity of phenol and XAD-4 has good adsorption capability for 2-nitrophenol. These polymeric adsorbents are suitable for industrial effluents containing phenol and its derivatives as mentioned previously. It should be noted that the adsorption capacities of the adsorbents presented here vary significantly depending on the characteristics of the individual adsorbent, the extent of chemical modifications, and the concentrations of solutes.     

臭氧-生物活性炭工艺在废水处理中的研究与应用＊

概述活性炭吸附工艺、臭氧氧化工艺以及臭氧-生物活性炭工艺的降解机理、发展及应用;分析臭氧-生物活性炭工艺在国内外应用的典型案例,以及介绍该工艺在污水处理、污水深度处理以及中水回用方面的研究进展。     

Removal of phenol from aqueous solutions by adsorption

Experiments have been conducted to examine the liquid-phase adsorption of phenol from water by silica gel, HiSiv 3000, activated alumina, activated carbon, Filtrasorb-400, and HiSiv 1000. Experiments were carried out for the analysis of adsorption equilibrium capacities and kinetics. The adsorption isotherm model of the Langmuir-Freundlich type was the best to describe adsorption equilibrium data for phenol for the adsorbents studied. Results of kinetic experiments indicated that HiSiv 1000 had the highest rate of adsorption among the adsorbents studied and therefore more detailed studies were carried out with this adsorbent. The influence of particle size, temperature, and thermal regeneration on adsorption of phenol by HiSiv 1000 was evaluated. From particle size experiments it appeared that adsorption capacity of HiSiv 1000 did not change by changing the particle size, but the rate of adsorption decreased considerably by increasing the particle size. The effect of temperature on adsorption was studied by determining equilibrium isotherms for HiSiv 1000 at 25, 40, and 55 degrees C. The results showed that adsorption capacity decreased with increasing temperature. Thermal regeneration of HiSiv 1000 was performed at 360 degrees C. It was observed that adsorption capacity of HiSiv 1000 did not change after 14 regeneration cycles. Equilibrium experiments showed that the adsorption capacities of activated carbon and Filtrasorb-400 were several times higher than that of HiSiv 1000.     

挥发性有机废气净化技术研究进展

本文对生物净化技术、等离子体净化技术、吸附和催化氧化技术在控制废气中挥发性有机物的研究进展及应用进行了综述。气体生物净化技术在VOCs混合物和改进设备工艺方面开展的研究工作较多,等离子体净化技术与催化技术的组合越来越受到关注。吸附和催化氧化方面则着重在吸附剂（活性炭和沸石）吸附性能的进一步研究和新型催化剂的研制。     

Use of an activated carbon from antibiotic waste for the removal of Hg(II) from aqueous solution

Porous carbon has been prepared from waste antibiotic material by a chemical activation method using K(2)CO(3) as an activating reagent. Carbon was studied systematically by the adsorption of nitrogen and iodine. It was found that the process parameters such as activation temperature and activation time are crucial for preparing high-quality activated carbon. The proper choice of the preparation conditions allows to produce microporous activated carbon with a micropore volume up to 0.492 cm(3)/g and a BET surface area of 1260 m(2)/g. Adsorption of mercury(II) from an aqueous solution on antibiotic carbon was investigated under the varying conditions of agitation time, metal ion concentration and pH. The adsorption capacity of the carbon is 129 mg/g.     

炼油废水回用于循环冷却水系统深度处理技术

为解决水资源紧缺问题,提高工业水资源的利用率,减少污水排放,采用臭氧催化氧化—活性炭吸附—石灰软化的工艺组合,深度处理炼油厂中二级处理达标排放的污水,探讨最佳工艺参数的选择,进行二级出水回用于循环冷却水的试验研究。试验表明:在臭氧氧化接触时间为40min,活性炭柱吸附通水流量为2L/h,石灰乳投加量0.32g/L、碳酸钠溶液0.06～0.10g/L、石灰软化搅拌15～20min,能使整套工艺达到最佳处理效果。小试阶段COD、氨氮、总硬度及总碱度的去除率分别达到96.00%、44.49%、64.61%、67.85%,硫酸根和氯离子均有所下降,通过整套工艺深度处理后,所得中水可作为循环冷却系统补充水。     

活性炭的吸附机理及其在水处理方面的应用

本文从活性炭表面的物理性质和化学性质,介绍了活性炭吸附的一般机理。综述了活性炭在城市给水、工业废水及城市污水深度处理中的研究进展;混凝—活性炭吸附工艺在净水工程中的应用;臭氧—生物活性炭技术去除水中有机污染物的工艺;MBR/PAC组合工艺及工业上使用石灰石与活性炭联合去除污染物的技术;从活性炭吸附性能指标的选择、有机物分子量的分布、活性炭的改性等方面,提出了活性炭在水处理应用上的问题和展望。     

Changes in the nature of sewage sludge organic matter during a twenty-one-month incubation

Six sewage sludges from five sewage treatment plants in Australia were incubated for up to 21 months. Carbon losses at the end of the 21-mo incubation varied substantially. The remaining organic matter was isolated by treatment with hydrofluoric acid (HF) and characterized using a range of solid-state (13)C nuclear magnetic resonance (NMR) spectroscopic techniques. By every measure (signal distribution in cross polarization [CP] and Bloch decay [BD] spectra, carbon NMR observability determined by spin counting, and the appearance of proton spin relaxation editing subspectra), the chemical composition of the residual organic matter appeared to be little different from that of the original sludges, even for those sludges that experienced the greatest carbon losses. Importantly, these NMR properties distinguish sewage sludge organic matter from soil organic matter. Thus, it should be possible to follow the decomposition of sewage sludge organic matter applied to soils in the field using solid-state (13)C NMR spectroscopy.     

Preparation and characterization of activated carbon from a new raw lignocellulosic material: Flamboyant (Delonix regia) pods

Activated carbons were prepared from flamboyant pods by NaOH activation at three different NaOH:char ratios: 1:1 (AC-1), 2:1 (AC-2), and 3:1 (AC-3). The properties of these carbons, including BET surface area, pore volume, pore size distribution, and pore diameter, were characterized from N₂ adsorption isotherms. The activated carbons obtained were essentially microporous and had BET surface area ranging from 303 to 2463 m² g⁻¹.¹³C (CP/MAS and MAS) solid-state NMR shows that the lignocellulosic structures were completely transformed into a polycyclic material after activation process, thermogravimetry shows a high thermal resistance, Boehm titration and Fourier-transform infrared spectroscopy allowed characterizing the presence of functional groups on the surface of activated carbons. Scanning electron microscopy images showed a high pore development. The experimental results indicated the potential use of flamboyant pods as a precursor material in the preparation of activated carbon.     

利用粉煤灰处理采油废水的研究

利用电厂粉煤灰及灰场氧化塘对现河首站采油废水中的污染物进行吸附和生化处理试验。试验结果表明:粉煤灰具有类似活性炭的结构和比表面积,对废水中的石油类、COD、氨氮、挥发酚等污染物具有较强的吸附、沉降和过滤作用。     

Optimization of activated carbon production from empty fruit bunch fibers in one-step steam pyrolysis for cadmium removal from aqueous solution

The fast growth of the palm oil industry in Malaysia is associated with various waste products, namely the empty fruit bunches (EFB), which have a negative impact on the environment. Therefore, these wastes were utilized as a cheap raw material for the production of activated carbon (AC) with less energy consumption. One-step steam pyrolysis was used to produce AC from oil palm empty fruit bunch fibers (EFBF) by varying the operating parameters of temperature, steam flow rate, and activation time using two-level full factorial experimental design (FFD). Ten samples of AC were prepared and the optimized production conditions were chosen based on the ability to adsorb and remove cadmium. Physical activation comprised of carbonization for 30 min using nitrogen gas (N₂), followed by activation with steam at different flow rates (2.0, 3.0, and 4.0 ml/min), temperatures (600, 750, and 900°C) and times (15, 30, and 45 min). The AC sample produced at an activation temperature of 900°C with a steam flow rate of 2.0 ml/min and activation time of 15 min was selected as the best adsorbent with a total yield of 21.7%. It had adsorbed more than 97% of total cadmium from aqueous solution within 2 min of the contact time. Characterization of EFBF-based AC by SEM and BET surface area analysis had shown a good-quality adsorbent with highly active sites and well-developed pores with BET surface area of 635.16 m²/g. Experimental results indicated that the prepared AC from EFBF provide a promising solution in water and wastewater treatment.     

Optimizing process parameters of palm oil bleaching on locally prepared animal bone–based activated carbon using response surface methodology

Adsorptive bleaching potentials of activated animal bone on palm oil was investigated. Palm oil was obtained locally from the mesocarp of oil palm fruits. The obtained palm oil was degummed, neutralized, and subjected to proximate analysis before bleaching. The animal bone–based activated carbon used as a bleaching material was locally prepared by cleaning, drying, carbonization, and chemical activation process. The prepared activated carbon (CBAC) was characterized using Fourier transform infrared, scanning electron microscopy, Braummer–Emmett–Teller, and x‐ray diffraction (XRD) methods. Bleaching of the prepared palm oil on CBAC was done at different process conditions. The characterization results of BET analysis show that CBAC has a surface area of 593.270 m²/g, micropore surface area 595.56 m²/g, micropore volume 0.212 cm³/g, Langmuir surface area 1.38e+04 m²/g, and adsorption energy 3.998 KJ/mol. XRD analysis indicates gypsum as the dominant mineral in the activated carbon sample. The CBAC efficiency of 75.14% was obtained for time/temperature interactions at 50 min/120°C while at 25 g/50 min dosage/time interactions an efficiency of 75.17% was obtained.     

Odorants and malodors associated with land application of biosolids stabilized with lime and coal fly ash

Malodor emissions limit public acceptance of using municipal biosolids as natural organic resources in agricultural production. We aimed to identify major odorants and to evaluate odor concentrations associated with land application of anaerobically digested sewage sludges (Class B) and their alkaline (lime and coal fly ash)-stabilized products (Class A). These two types of biosolids were applied at 12.6 tonnes ha(-1) (dry weight) to microplots of very fine clayey Vertisol in the Jezreel Valley, northern Israel. The volatile organic compounds (VOCs) emitted from the biosolids before and during alkaline stabilization and after incorporation into the soil were analyzed by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry. Odor concentrations at the plots were evaluated on site with a Nasal Ranger field olfactometer that sniffed over a defined land surface area through a static chamber. The odors emitted by anaerobically digested sewage sludges from three activated sludge water treatment plants had one characteristic chemical fingerprint. Alkaline stabilization emitted substantial odors associated with high concentrations of ammonia and release of nitrogen-containing VOCs and did not effectively reduce the potential odor annoyance. Odorous VOCs could be generated within the soil after biosolids incorporation, presumably because of anaerobic conditions within soil-biosolids aggregates. We propose that dimethyl disulfide and dimethyl trisulfide, which seem to be most related to the odor concentrations of biosolids-treated soil, be used as potential chemical markers for the odor annoyance associated with incorporation of anaerobically digested sewage sludges.     

Waste materials for activated carbon preparation and its use in aqueous-phase treatment: a review

Commercial activated carbon is a preferred adsorbent for the removal of micropollutants from the aqueous phase; however, its widespread use is restricted due to high associated costs. To decrease treatment costs, attempts have been made to find inexpensive alternative activated carbon (AC) precursors, such as waste materials. Some reviews report the use of waste materials for the preparation of AC; however, these studies are restricted to either type of wastes, preparation procedures, or specific aqueous-phase applications. The present work reviews and evaluates literature dedicated both to the preparation of AC by recycling different types of waste materials and also to its application in various aqueous-phase treatments. It is clear that conventional (from agriculture and wood industry) and non-conventional (from municipal and industrial activities) wastes can be used to prepare AC, that can be applied in various aqueous treatment processes, namely to remove organic pollutants, dyes, volatile organic compounds, and heavy metals. Moreover, high surface areas can be obtained using either physical or chemical activation; however, combined treatments might enhance the surface properties of the adsorbent, therefore increasing its adsorption capacity. It is evident from the revision made that AC prepared from both conventional and non-conventional wastes might effectively compete with the commercial ones. This happens mostly when the activation procedures are optimized considering both the raw material used to produce the carbons and the contaminants to be removed.     

生物法处理含酚废水的研究

为了降低炼油厂污水处理场的酚负荷,对催化裂化汽提塔所排含酚废水的预处理进行了研究。进行了煤渣吸附实验,酚的生物降解动力学实验及酚在兼氧条件下的处理实验;采用４－氨基安替比林光度法测定酚浓度。实验结果表明采用煤渣填料－生物膜反应器,酚的去除率可达９０％,酚的生物降解符合一级反应动力学,酚类物质可在兼氧条件下降解     

Characterization of sewage sludge organic matter using solid-state carbon-13 nuclear magnetic resonance spectroscopy

Six sewage sludges from five sewage treatment plants in Australia were characterized using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Spectra were acquired both before and after removal of mineral components through treatment with hydrofluoric acid (HF). Carbon mass balance indicated that little organic matter was lost on HF treatment, which significantly improved NMR sensitivity and spectral resolution, and decreased acquisition time and hence cost of NMR analysis. Two NMR techniques were used, the standard cross polarization (CP) technique and Bloch decay (BD). The BD technique had not been applied previously to the analysis of sewage sludge. For each sludge sample, both before and after HF treatment, the BD spectrum contained significantly more alkyl carbon. Spin counting, another technique applied to sewage sludge here for the first time, showed that the BD spectra of the HF-treated sludges were quantitative, while approximately 30% of the CP NMR signal went undetected. The discrepancy between CP and BD spectra was attributed to the presence of alkyl carbon with such high molecular mobility that the efficiency of cross polarization is affected. This study shows that sewage sludge organic matter is significantly different in chemistry to soil organic matter and has implications for the application of sewage sludge to agricultural land.     

Application of 'waste' wood-shaving bottom ash for adsorption of azo reactive dye

The utilization of wood-shaving bottom ash (WBA) for the removal of Red Reactive 141 (RR141), an azo reactive dye, was investigated. WBA/H(2)O and WBA/H(2)SO(4) were made by treating WBA with water and 0.1M H(2)SO(4), respectively, to increase adsorption capacity. Adsorption of RR141 from reactive dye solution (RDS) and reactive dye wastewater (RDW) by WBA/H(2)O and WBA/H(2)SO(4) involved the BET surface area and pore size diameter. Properties of adsorbents, effect of contact time, initial pH of solution, dissolved metals and elution studies indicated that the decolorisation mechanism involved both chemical adsorption and precipitation with calcium ions. In addition, the WBA/H(2)SO(4) surface might contain sulphate-cation complexes that were specific to enhancing dye adsorption from RDW. The adsorption isotherm had a best fit by the Freundlich model. Freundlich parameters showed that WBA/H(2)O used more heterogeneous surface than WBA/H(2)SO(4) and activated carbon for RDW adsorption. A thermodynamic study indicated that RDW adsorption was an endothermic process. The maximum dye adsorption capacities of WBA/H(2)O, WBA/H(2)SO(4) and activated carbon obtained from a Langmuir model at 30 degrees C were 24.3, 29.9, and 41.5mgl(-1), respectively. In addition, WBA/H(2)O and WBA/H(2)SO(4) could reduce colour and high chemical oxygen demand (COD) of real textile wastewater. According to the difficulty in the elution study, it was an environmentally safe disposal of this waste. Therefore, WBA, a waste from combustion of wood shavings, was suitable to be used as an effective adsorbent for azo reactive dye removal.     

生物活性炭技术在水处理中的应用

生物活性炭技术是将吸附和生物分解结合起来的水处理新技术。本文简述了生物活性炭的净水原理和形成方式,以及生物活性炭在处理微污染水源水、生活污水和工业废水方面的研究进展,并对生物活性炭技术的发展进行了展望。     

Advanced solid-state carbon-13 nuclear magnetic resonance spectroscopic studies of sewage sludge organic matter: detection of organic "domains"

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.     

Adsorption of pharmaceuticals to microporous activated carbon treated with potassium hydroxide, carbon dioxide, and steam

Adsorption of sulfapyridine, tetracycline, and tylosin to a commercial microporous activated carbon (AC) and its potassium hydroxide (KOH)-, CO-, and steam-treated counterparts (prepared by heating at 850°C) was studied to explore efficient adsorbents for the removal of selected pharmaceuticals from water. Phenol and nitrobenzene were included as additional adsorbates, and nonporous graphite was included as a model adsorbent. The activation treatments markedly increased the specific surface area and enlarged the pore sizes of the mesopores of AC (with the strongest effects shown on the KOH-treated AC). Adsorption of large-size tetracycline and tylosin was greatly enhanced, especially for the KOH-treated AC (more than one order of magnitude), probably due to the alleviated size-exclusion effect. However, the treatments had little effect on adsorption of low-size phenol and nitrobenzene due to the predominance of micropore-filling effect in adsorption and the nearly unaffected content of small micropores causative to such effect. These hypothesized mechanisms on pore-size dependent adsorption were further tested by comparing surface area-normalized adsorption data and adsorbent pore size distributions with and without the presence of adsorbed antibiotics. The findings indicate that efficient adsorption of bulky pharmaceuticals to AC can be achieved by enlarging the adsorbent pore size through suitable activation treatments.