Equilibrium,kinetic and thermodynamic studies on the adsorption of 2-nitroaniline onto activated carbon prepared from cotton stalk fibre

Activated carbon prepared from cotton stalk fibre has been utilized as an adsorbent for the removal of 2-nitroaniline from aqueous solutions. The influence of adsorbent mass, contact time and temperature on the adsorption was investigated by conducting a series of batch adsorption experiments. The equilibrium data at different temperatures were fitted with the Langmuir, Freundlich, Tempkin, Redlich–Peterson and Langmuir–Freundlich models. The Langmuir–Freundlich isotherm was found to best describe the experimental data. The adsorption amount increased with increasing temperature. The maximum adsorption capacity of 2-nitroaniline was found to be 383 mg/g for initial 2-nitroaniline concentration of 200 mg/L at 45 °C. The kinetic rates were modeled by using the Lagergren-first-order, pseudo-second-order and Elovich models. The pseudo-second-order model was found to explain the adsorption kinetics most effectively. It was also found that the pore diffusion played an important role in the adsorption, and intraparticle diffusion was the rate-limiting step at the first 30 min for the temperatures of 25, 35 and 45 °C. FTIR and ¹³C NMR study revealed that the amino and isocyanate groups present on the surface of the adsorbent were involved in chemical interaction with 2-nitroaniline. The negative change in free energy (ΔG°) and positive change in enthalpy (ΔH°) indicated that the adsorption was a spontaneous and endothermic process.     

Adsorption of phosphorus on sediments from the Three-Gorges Reservoir (China) and the relation with sediment compositions

The adsorption of phosphorus (P) on four sediment samples (CunTan, XiaoJiang, DaNing and XiangXi) from the Three-Gorges Reservoir on the Yangtze River in China was studied systematically in batch experiments. A sequential chemical extraction experiment was conducted to clarify the effect of sediment composition on P adsorption. The results showed that P adsorption on four sediment samples mainly occurred within 6 h. P adsorption kinetics can be satisfactorily fitted by both power function and simple Elovich model. A modified Langmuir model may describe well the P adsorption on all the samples in our study. Theoretically, the maximum adsorption amount (Q_max) was 0.402 mg-P/g for XiaoJiang sediment, 0.358 mg-P/g for DaNing sediment, 0.165 mg-P/g for CunTan sediment, and 0.15 mg-P/g for XiangXi sediment. The sediment compositions such as organic matter, metal hydroxides, calcium and clay content showed influences on the P adsorption. Wherein, organic matter and metal hydroxides were the main factors affecting the P adsorption. The maximum P adsorption capacity (Q_max) enhanced with the increase of the content of (Fe + Al + Ca). Compared the zero-equilibrium P concentration (EPC₀) values obtained by the modified Langmuir models with actual P concentrations in water, all the sediments studied in this paper except for XiaoJiang showed a trend of releasing P as a source role, which could enhance the risk of eutrophication occurrence in the Three-Gorges Reservoir.     

棉秸秆活性炭吸附水溶性有机污染物研究

以棉花秸秆为原材料,采用"炭化-活化"工艺制备了高活性活性炭。研究了活性炭对苯酚、苯胺和苯甲酸等3种芳香族有机污染物的吸附过程动力学及热力学;测定了不同温度下该活性炭对3种污染物的吸附等温线。研究结果表明棉秸秆活性炭对苯酚、苯胺和苯甲酸的吸附过程均符合Lagergren二级吸附动力学方程;表观吸附活化能分别为Ea(苯酚)=15.91kJ/mol、Ea(苯甲酸)=12.56kJ/mol、Ea(苯胺)=11.16kJ/mol;吸附过程为自发的放热熵减过程;吸附等温模型符合Freundlich等温式;棉秸秆活性炭对苯酚、苯胺和苯甲酸的静态饱和吸附容量分别为450、321和298mg/g。棉秸秆活性炭制备简便、成本低廉,对水溶性有机污染物去除效果较好,可用于芳香族有机污染物的吸附治理。     

Converter slag–coal cinder columns for the removal of phosphorous and other pollutants

A mixture of converter slag and coal cinder as adsorbent for the removal of phosphorous and other pollutants was studied in the paper. The maximum P adsorption capacity, pH of solution, contact time and initial phosphate concentration were evaluated in batch experiments for the two materials firstly. The data of P sorption were best fitted to Langumir equation, and the maximum adsorption capacities of converter slag and coal cinder were 2.417 and 0.398 mg P/g, respectively. The pH of solutions with converter slag and coal cinder changed dramatically with time and closed to 8 in 8 h, and the influence of initial pH on phosphate removal by coal cinder was more significant than by converter slag. Phosphate removal rate by converter slag decreased with increase of initial phosphate concentrations. Subsequently, two flow-through columns (Column 1#, V_{converter slag}:V_{coal cinder} = 1:5; Column 2#, V_{converter slag}:V_{coal cinder} = 1:3) were operated for the removal of phosphorous and other pollutants from the effluents of a vermifilter for nearly eleven months. Results indicated the average removal efficiency of total phosphorus, dissolved phosphorus, COD and NH₄⁺–N by Column 1# were 44%, 56%, 31% and 67%, and by Column 2# were 42%, 54%, 24% and 57%, respectively. Column 1# had higher removal efficiency for P and other pollutants.     

Biosorption of cadmium (II) and lead (II) from aqueous solutions using mushrooms: A comparative study

Sorption capacity of oyster mushroom (Pleurotus platypus), button mushroom (Agaricus bisporus) and milky mushroom (Calocybe indica) were evaluated on biosorption of heavy metals, viz. cadmium (II) and lead (II) from aqueous solutions. The optimum sorption conditions were studied for each metal separately. The desired pH of the aqueous solution was found to be 6.0 for the removal of cadmium (II) and 5.0 for removal of lead (II) for all the mushrooms. The percent removal of both the metals was found to increase with the increase in biosorbent dosage and contact time. The fitness of the biosorption data for Langmuir and Freundlich adsorption models was investigated. It was found that biosorption of cadmium (II) and lead (II) ions onto the biomass of the three mushrooms were better suitable to Langmuir than Freundlich adsorption model. P. platypus showed the highest metal uptake potential for cadmium (q_max 34.96 mg/g) whereas A. bisporus exhibited maximum potential for lead (q_max 33.78 mg/g). Milky mushroom showed the lowest metal uptake capacity for both the metals. The present data confirms that mushrooms may be used as efficient biosorbent for the removal of cadmium (II) and lead (II) ions from aqueous solution.     

Preparation and properties of cotton stalk carbon/gold nanoparticles composite

In this paper, cotton stalk is used as a low-cost raw material source to prepare activated carbon with a unique porous structure with the assistance of chemical treatment. Gold nanoparticles as a multifunction building block were in situ assembled onto the carbon material, endowing this hybrid more promising applications. The as-fabricated CS carbon/AuNPs hybrid materials have been demonstrated to behave with catalytic and photothermal conversion properties, indicating that AuNPs successfully functionalise the activated carbon. The catalytic activity of the hybrid showed a glucose concentration-dependent effect (as low as 5 × 10^?6 M). The water temperature of the sample containing the CS carbon/Au NPs increased rapidly, and even reached 55 °C, only exposed to light for 5 min. When used as catalyst of reduction of p-nitrophenol, the hybrid showed a good reusability up to10 cycles.     

Sorption of nitrate onto amine-crosslinked wheat straw: characteristics, column sorption and desorption properties

The nitrate removal process was evaluated using a fixed-bed column packed with amine-crosslinked wheat straw (AC-WS). Column sorption and desorption characteristics of nitrate were studied extensively. Solid-state (13)C NMR and zeta potential analysis validated the existence of crosslinked amine groups in AC-WS. Raman shift of the nitrate peaks suggested the electrostatic attraction between the adsorbed ions and positively charged amine sites. The column sorption capacity (q(ed)) of the AC-WS for nitrate was 87.27 mg g(-1) in comparison with the raw WS of 0.57 mg g(-1). Nitrate sorption in column was affected by bed height, influent nitrate concentration, flow rate and pH, and of all these, influent pH demonstrated an essential effect on the performance of the column. In addition, desorption and dynamic elution tests were repeated for several cycles, with high desorption rate and slight losses in its initial column sorption capacity.     

ZnCl2活化茄子秸秆制备活性炭及表征

以茄子秸秆为原料、ZnCl2为活化剂制备活性炭。通过正交实验方法确定了制备活性炭的最佳工艺条件,采用低温氮气吸附、BET、Langmuir和BJH理论对其孔结构进行了表征,利用红外光谱分析样品的表面官能团,扫描电镜观察表面形貌。结果表明以茄杆活性炭的最佳工艺条件:浸渍比为2,浸渍时间为8h,活化温度为550℃,活化时间为60min,所得的活性炭的碘吸附值为1270.06mg/g,亚甲基蓝吸附值为17.4mL/g;BET和Langmuir比表面积分别为1649.615和1851.649m2/g,吸附总孔容为0.488cm3/g,吸附平均孔径为2.241nm。     

Adsorption of mercury cation on chemically modified clay

A montmorillonite clay (M) sample from the Amazon region, Brazil, was intercalated with pyridine (Py), dimethyl sulfoxide (DS) and 3-aminopropyltriethoxysilane (APS). The chemically modified montmorillonite (M_P/APS) sample showed modification of its physical-chemical properties including: specific area 41.39 m² g⁻¹ (M) to 198.45 m² g⁻¹ (M_P/APS). Solid-state ²⁹Si CPMAS/NMR of the silylated montmorillonite samples showed Q² and Q³ signals as well as T² and T³ signals. The appearance of T² and T³ signals can be attributed to the grafting of APS to the interlayer surface silanol groups. The natural and modified clays were used for mercury cation adsorption from aqueous solutions at room temperature and pH 3.0. The energetic effects (Δ_intH°, Δ_intG° and Δ_intS°) caused by mercury cation adsorption were determined through calorimetric titrations.     

Arsenic (III,V) removal from aqueous solution by ultrafine α-Fe2O3 nanoparticles synthesized from solvent thermal method

Ultrafine iron oxide (α-Fe₂O₃) nanoparticles were synthesized by a solvent thermal process and used to remove arsenic ions from both lab-prepared and natural water samples. The α-Fe₂O₃ nanoparticles assumed a near-sphere shape with an average size of about 5 nm. They aggregated into a highly porous structure with a high specific surface area of ∼162 m²/g, while their surface was covered by high-affinity hydroxyl groups. The arsenic adsorption experiment results demonstrated that they were effective, especially at low equilibrium arsenic concentrations, in removing both As(III) and As(V) from lab-prepared and natural water samples. Near the neutral pH, the adsorption capacities of the α-Fe₂O₃ nanoparticles on As(III) and As(V) from lab-prepared samples were found to be no less than 95 mg/g and 47 mg/g, respectively. In the presence of most competing ions, these α-Fe₂O₃ nanoparticles maintained their arsenic adsorption capacity even at very high competing anion concentrations. Without the pre-oxidation and/or the pH adjustment, these α-Fe₂O₃ nanoparticles effectively removed both As(III) and As(V) from a contaminated natural lake water sample to meet the USEPA drinking water standard for arsenic.     

Biosorption of chromium species by aquatic weeds: kinetics and mechanism studies

In this paper, we have presented the results of Cr(VI) and Cr(III) removal from aqueous phase by different aquatic weeds as biosorbents. Batch kinetic and equilibrium experiments were conducted to determine the adsorption kinetic rate constants and maximum adsorption capacities of selected biosorbents. In most of the cases, adsorption followed a second-order kinetics. For Cr(III), maximum adsorption capacity was exhibited by reed mat (7.18mg/g). In case of Cr(VI), mangrove leaves showed maximum removal/reduction capacity (8.87mg/g) followed by water lily (8.44mg/g). There was a significant difference in the concentrations of Cr(VI) and total chromium removed by the biosorbents. In case of Cr(VI) removal, first it was reduced to Cr(III) with the help of tannin, phenolic compounds and other functional groups on the biosorbent and subsequently adsorbed. Acid treatment significantly increased Cr(VI) removal capacity of the biosorbents whereas, alkali treatment reduced the Cr(VI) removal capacities of the biosorbents. FTIR spectrum showed the changes in functional groups during acid treatment and biosorption of Cr(VI) and Cr(III). Aquatic weeds seem to be a promising biosorbent for the removal of chromium ions from water environment.     

Synthesis,characterization and kinetic of a surfactant-modified bentonite used to remove As(III) and As(V) from aqueous solution

In this study, organobentonites were prepared by modification of bentonite with various cationic surfactants, and were used to remove As(V) and As(III) from aqueous solution. The results showed that the adsorption capacities of bentonite modified with octadecyl benzyl dimethyl ammonium (SMB3) were 0.288 mg/g for As(V) and 0.102 mg/g for As(III), which were much higher compared to 0.043 and 0.036 mg/g of un-modified bentonite (UB). The adsorption kinetics were fitted well with the pseudo-second-order model with rate constants of 46.7 × 10⁻³ g/mg h for As(V) and 3.1 × 10⁻³ g/mg h for As(III), respectively. The maximum adsorption capacity of As(V) derived from the Langmuir equation reached as high as 1.48 mg/g, while the maximum adsorption capacity of As(III) was 0.82 mg/g. The adsorption of As(V) and As(III) was strongly dependent on solution pH. Addition of anions did not impact on As(III) adsorption, while they clearly suppressed adsorption of As(V). In addition, this study also showed that desorbed rates were 74.61% for As(V) and 30.32% for As(III), respectively, after regeneration of SMB3 in 0.1 M HCl solution. Furthermore, in order to interpret the proposed absorption mechanism, both SMB3 and UB were extensively characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) analyses.     

Adsorption of Cr(VI) using silica-based adsorbent prepared by radiation-induced grafting

Silica-based adsorbent was prepared by radiation-induced grafting of dimethylaminoethyl methacrylate (DMAEMA) onto the silanized silica followed by a protonation process. The FTIR spectra and XPS analysis proved that DMAEMA was grafted successfully onto the silica surface. The resultant adsorbent manifested a high ion exchange capacity (IEC) of ca. 1.30 mmol/g and the Cr(VI) adsorption behavior of the adsorbent was further investigated, revealing the recovery of Cr(VI) increased with the adsorbent feed and the equilibrium adsorption could be achieved within 40 min. The adsorption capacity, strongly depended on the pH of the solution, reached a maximum Cr(VI) uptake (ca. 68 mg/g) as the pH was in the range of 2.5–5.0. Furthermore, even in strong acidic (4.0 mol/L HNO₃) or alkaline media (pH 11.0), the adsorbent had a sound Cr(VI) uptake capacity (ca. 22 and 30 mg/g, respectively), and the adsorption followed Langmuir mode. The results indicated that this adsorbent, prepared via a convenient approach, is applicable for removing heavy-metal-ion pollutants (e.g. Cr(VI)) from waste waters.     

Preparation of adsorbent for phosphate recovery from aqueous solutions based on condensed tannin gel

We have synthesized an iron-loaded tannin gel as an adsorbent for phosphate recovery in aqueous solutions. The use of the tannin gel prepared from condensed tannin, which is a ubiquitous and inexpensive natural polymer, is not only cost effective and environment-friendly, but interesting because the phosphate-adsorbed gel can be expected to use directly as a fertilizer. The amount of iron loaded into the tannin gel oxidized by nitric acid was much larger than that into the non-oxidized tannin gel. This increase in the amount of the loaded iron resulted in the significant increase in the adsorption amount of phosphate onto the gel. Mössbauer spectroscopy indicated that the morphology of iron in the gel is a mono-type complex, which is formed as a result of the reaction between Fe(III) and the oxidized tannin gel with carbonyl groups. The iron-loaded tannin gel showed the adsorption selectivity for phosphate over other anions and the pH independence of phosphate adsorption in the wide range of initial pH 3-12. The phosphate adsorption isotherm for the iron-loaded tannin gel followed the Freundlich equation with constants of K_F = 2.66 and 1/n = 0.31, rather than the Langmuir equation. The adsorption amount of phosphate on iron weight basis for the iron-loaded tannin gel is 31.3 mg-P/g-Fe, which indicates that iron in the gel was efficiently used for the phosphate adsorption compared with other phosphate adsorbents, such as iron hydroxides.     

Crack closure under high load-ratio conditions for Inconel-718 near threshold behavior

Fatigue-crack-growth (FCG) rate tests were conducted on compact specimens made of an Inconel-718 alloy to study the behavior over a wide range in load ratios (0.1 ? R ? 0.95) and a constant K_max test condition. Previous research had indicated that high R (>0.7) and constant K_max test conditions near threshold conditions were suspected to be crack-closure-free and that any differences were attributed to K_max effects. During a test at a load ratio of 0.7, strain gages were placed near and ahead of the crack tip to measure crack-opening loads from local load-strain records during crack growth. In addition, a back-face strain (BFS) gage was also used to monitor crack lengths and to measure crack-opening loads from remote load-strain records during the same test. The BFS gage indicated that the crack was fully open (no crack closure), but the local load-strain records indicated significant amounts of crack closure. The crack-opening loads were increasing as the crack approached threshold conditions at R = 0.7. Based on these measurements, crack-closure-free FCG data (ΔK_eff against rate) were calculated. The ΔK_eff-rate data fell at lower ΔK values and higher rates than the constant K_max test results. In addition, constant R tests at extremely high R (0.9 and 0.95) were also performed and compared with the constant K_max test results. The constant R test results at 0.95 agreed well with the ΔK_eff-rate data, while the R = 0.9 data agreed well with constant K_max test data in the low-rate regime. These results imply that the R = 0.7 test had a significant amount of crack closure as the threshold was approached, while the R = 0.9 and K_max test results may have had a small amount of crack closure, and may not be closure free, as originally suspected. Under the high load-ratio conditions (R ? 0.7), it is suspected that the crack surfaces are developing debris-induced crack closure from contacting surfaces, which corresponded to darkening of the fatigue surfaces in the near-threshold regime. Tests at low R also showed darkening of the fatigue surfaces only in the near-threshold regime. These results suggest that the ΔK_eff against rate relation may be nearly a unique function over a wide range of R in the threshold regime.     

The effect of perfusion culture on proliferation and differentiation of human mesenchymal stem cells on biocorrodible bone replacement material

Biocorrodible iron foams were coated with different calcium phosphate phases (CPP) to obtain a bioactive surface and controlled degradation. Further adhesion, proliferation and differentiation of SaOs-2 and human mesenchymal stem cells were investigated under both static and dynamic culture conditions. Hydroxyapatite (HA; [Ca₁₀(PO₄)₆OH₂]) coated foams released 500 μg/g iron per day for Dulbecco's modified eagle medium (DMEM) and 250 μg/g iron per day for McCoys, the unmodified reference 1000 μg/g iron per day for DMEM and 500 μg/g iron per day for McCoys, while no corrosion could be detected on brushite (CaHPO₄) coated foams. Using a perfusion culture system with conditions closer to the in vivo situation, cells proliferated and differentiated on iron foams coated with either brushite or HA while in static cell culture cells could proliferate only on Fe-brushite. We conclude that the degradation behaviour of biocorrodible iron foams can be varied by different calcium phosphate coatings, offering opportunities for design of novel bone implants. Further studies will focus on the influence of different modifications of iron foams on the expression of oxidative stress enzymes. Additional information about in vivo reactions and remodelling behaviour are expected from testing in implantation studies.     

Water vapor adsorption of CaCl2-impregnated activated carbon

Activated carbons (AC) impregnated with the hygroscopic salt CaCl₂ were synthesized to enhance the amount of water vapor adsorbed at low relative pressure (P/P₀). Possible applications for these materials are in adsorption heat pumps and desiccant air conditioners. The ACs were synthesized from tissue paper by chemical activation with K₂CO₃ and the porous properties were investigated of a number of materials prepared under a variety of activation conditions. The highest specific surface area (S_BET) (1820 m²/g) was obtained from the sample prepared with a K₂CO₃/sample ratio = 1/1 by mass, activated at 900 °C for 2 h under flowing N₂ (2 L/min). Impregnation with CaCl₂ was performed using 2.4-6.5 M CaCl₂ solutions and a solution volume equal to the pore volume of the AC. XPS surface chemical analysis revealed that the impregnated CaCl₂ was mostly successfully impregnated into the pores while the surface CaCl₂ increased gradually with increasing amount of impregnation. The adsorption of water vapor in the P/P₀ range 0.1-0.3 (ΔW_0.1-0.3) was dramatically increased by CaCl₂ impregnation, the ΔW_0.1-0.3 value reaching 0.52 g/g in the sample impregnated with 70 mass% CaCl₂; this value is much higher than previously reported ΔW_0.1-0.3 values.     

Potentiometric titration data on the enhancement of sorption capacity of surface-modified biosorbents: functional groups scanning method

In the present study, the relationship between the amount of anionic or cationic binding sites and adsorption capacities of biosorbents is discussed through potentiometric titration and mathematical model equations (proton-binding models). The poly(acrylic) acid-modified biomass (PAAB) and polyethylenimine-modified biomass (PEIB) derived from raw biomass (RB) Corynebacterium glutamicum (C. glutamicum) were used as cationic and anionic binding site-enhanced biosorbents, respectively. To obtain the sorption capacities of biomasses for anionic and cationic pollutants, isotherm tests were carried out using Basic Blue 3 (BB3, at pH 9) and Reactive Red 4 (RR4, at pH 2) as model anionic and cationic pollutants, respectively. The maximum sorption capacity (q_m) of PAAB was 1.28 times higher than RB for BB3. In the case of PEIB, the sorption capacity was found to be 3.27 times higher than RB for RR4. A quantitative information of functional groups could be estimated by the application of proton-binding models to potentiometric titration results. In addition, the buffering capacities of functional groups were obtained from the parameters of pK models. An increasing ratio of sorption capacities was similar to that of the buffering capacities of modified biosorbents obtained from all conditions of pK models. Therefore, the fact that the sorption capacity of modified biomass can be predicted by comparing it with the buffering capacity of biosorbents was confirmed.     

水分散苎麻麻骨饼的制备及其性能

为探索苎麻麻骨治理重金属废水的工业化应用可行性,首先,利用激光粒度仪、SEM和FTIR等表征手段对苎麻麻骨微粒进行微观表征,探明了苎麻麻骨的微观结构;然后在此基础上,将苎麻麻骨微粒与环境友好型天然润湿剂、黏结剂及崩解剂混合,按一定工艺流程加工成水分散苎麻麻骨饼（WDRSC）,在配方筛选过程中,测试了各种助剂质量分数对WDRSC性能的影响,并对苎麻麻骨与WDRSC吸附重金属Cu2+和Cd2+的能力进行了比较。结果显示:苎麻麻骨为具有多孔隙结构的天然物质,表面具有大量的吸附位点和官能团;当WDRSC配方中麻骨、润湿剂、黏结剂和崩解剂的质量比为75:13:2:10时,WDRSC入水后能迅速被水润湿（润湿时间小于60 s）并自动崩解（崩解时间小于60 s）,60 s内悬浮率达80%左右,各项性能均符合水分散颗粒剂的要求;润湿剂、黏结剂和崩解剂均能不同程度地影响WDRSC的相关性能;与苎麻麻骨相比,WDRSC对Cd2+与Cu2+的去除率分别提高了11%和4%。所得结论表明将苎麻麻骨制成WDRSC具有运输和使用方便、成本低廉、制作工艺简单且吸附后废渣处理方便等优点,为苎麻麻骨规模化利用的可行方法。