LX-92树脂对硫酸体系低浓度镓离子的动态吸附

研究了粉煤灰模拟硫酸浸出液中的镓在聚苯乙烯树脂(LX-92)上吸附分离的可能性,采用固定床吸附装置考察了树脂动态吸附?脱附镓的行为,利用Thomas, Yoon-Nelson和Adam-Bohart经验模型对动态吸附过程进行了分析和预测。结果表明,降低流速(F)、增加床层高度(Z)、减小镓(Ш)初始浓度(C0)有助于提高固定床吸附效率和平衡吸附容量;在C0为260 mg/L, Fad为5.0 mL/min、吸附温度为55℃的条件下,树脂的最大动态平衡吸附容量为56.65 mg/g;用3.0 mol/L H2SO4在1.0 mL/min流速的最佳洗脱条件下,洗脱率达到94.40%;树脂在硫酸体系中对低浓度镓离子的吸附?脱附具有良好的循环使用性,经过吸附?脱附镓离子可富集10倍以上;树脂吸附镓的动态行为满足Yoon-Nelson动态吸附模型,建立了动态吸附速率常数KYN和半穿透时间τ值常数与初始离子浓度、流速、床层高度的对应方程,为低浓度镓离子的吸附法提取工程化提供了理论基础。     

聚氨酯泡沫塑料法从粉煤灰中回收镓研究

基于在酸性溶液中镓可形成酸根阴离子并可和复杂阳离子形成离子缔合物的性质,研究了以聚氨酯泡沫塑料(PU)为吸附材料,在盐酸介质中吸附富集镓的性能和条件。结果表明,在6 mol/L的HCl溶液中,PU对镓有良好的吸附性能,在含镓10 mg/L,液固比50 mL/g下,吸附率可达98%以上,静态饱和吸附容量为46.7 mg/g-PU。实验证实,除Fe3+外,溶液常见共存离子对吸附无影响;获得了一种新的有应用价值的从粉煤灰中吸附回收镓的工艺方法。     

改性Zr-Na/Zeolite双功能沸石脱除水溶液中氨氮和磷性能研究

采用氯化钠离子交换和氯氧化锆沉积沉淀两步法改性天然沸石,得到具有脱除水中氨氮和磷的双功能锆钠改性天然沸石（Zr-Na/Zeolite）,考察了不同pH、溶液初始质量浓度和温度下Zr-Na/Zeolite对氨氮溶液、含磷溶液及氮磷共存溶液的吸附情况。结果表明,Zr-Na/Zeolite能够在保持Na改性沸石（Na/Zeolite）优良的吸附氨氮性能的基础上,极大地提高吸附磷的能力。在不同pH下,Zr-Na/Zeolite 吸附氨氮和磷的效果呈现不同的规律。对于氨氮,水溶液pH在4~8时具有最佳吸附性能,最高吸附量达到4.5 mg/g。对于含磷阴离子,脱磷能力随pH的升高而降低,吸附容量从pH=2时的4.71 mg/g降到pH=10时的2.20 mg/g。溶液初始质量浓度从10 mg/L提高到200 mg/L时,氨氮和磷的单位吸附容量分别从1.42和2.46 mg/g提高到11.6和11.8 mg/g,去除率分别从57.0%和98.2%降低到23.2%和23.6%。溶液温度从25 ℃升高到45 ℃,氨氮的吸附容量提高了10%,磷的吸附容量提高了11%。磷和氨氮的吸附过程符合准二级动力学模型。0.1 mol/L NaOH和1.0 mol/L NaCl混合溶液可以再生Zr-Na/Zeolite,循环吸附14次,吸附效率几乎保持不变。     

Adsorption behavior of fluoride ions using a titanium hydroxide-derived adsorbent

The removal behavior of fluoride ions was examined in aqueous sodium fluoride solutions using a titanium hydroxide-derived adsorbent. The adsorbent was prepared from titanium oxysulfate (TiOSO₄·xH₂O) solution, and was characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry-differential thermal analysis, Fourier transform infrared spectrum and specific surface area. Batchwise adsorption test of prepared adsorbent was carried out in aqueous sodium fluoride solutions and real wastewater containing fluoride ion. The absorbent was the amorphous material, which had different morphology to the raw material, titanium oxysulfate, and the specific surface area of the adsorbent (96.8 m²/g) was 200 times higher than that of raw material (0.5 m²/g). Adsorption of fluoride on the adsorbent was saturated within 30 min in the solution with 200 mg/L of fluoride ions, together with increasing pH of the solution, due to ion exchange between fluoride ions in the solution and hydroxide ions in the adsorbent. Fluoride ions were adsorbed even in at a low fluoride concentration of 5 mg/L; and were selectively adsorbed in the solution containing a high concentration of chloride, nitrate and sulfate ions. The adsorbent can remove fluoride below permitted level (< 0.8 mg/L) from real wastewaters containing various substances. The maximum adsorption of fluoride on the adsorbent could be obtained in the solution at about pH 3. After fluoride adsorption, fluoride ions were easily desorbed using a high pH solution, completely regenerating for further removal process at acidic pH. The capacity for fluoride ion adsorption was almost unchanged three times after repeat adsorption and desorption. The equilibrium adsorption capacity of the adsorbent used for fluoride ion at pH 3 was measured, extrapolated using Langmuir and Freundlich isotherm models, and experimental data are found to fit Freundlich than Langmuir. The prepared adsorbent is expected to be a new inorganic ion exchanger for the removal and recovery of fluoride ions from wastewater.     

Ion‐exchange adsorption of calcium ions from water and geothermal water with modified zeolite A

The modified zeolite A was prepared by a two‐step crystallization method to remove scale‐forming cations from water and geothermal water. The adsorption kinetics, mechanism and thermodynamics were studied. The calcium ion adsorption capacity of the modified zeolite A was 129.3 mg/g (1 mg/g = 10^?3 kg/kg) at 298 K. The adsorption rate was fitted well with pseudo‐second‐order rate model. The adsorption process was controlled by film diffusion at the calcium ion concentration less than 250 mg/L (1 mg/L = 10^?3 kg/m³), and it was controlled by intraparticle diffusion at the concentration larger than 250 mg/L. The calculated mass‐transfer coefficient ranged from 2.23 × 10^?5 to 2.80 × 10^?4cm/s (1 cm/s = 10^?2m/s). Dubinin–Astakhov isotherm model could appropriately describe the adsorption thermodynamic properties when combined with Langmuir model. The adsorption process included not only ion exchange but also complexation between calcium and hydroxyl ions. The adsorption was spontaneous and endothermal. The high adsorption capacity indicates that the modified zeolite A is a suitable adsorption material for scale removal from aqueous solution. © 2014 American Institute of Chemical Engineers AIChE J, 61: 640–654, 2015     

Comparison of Basic Dye Crystal Violet Removal from Aqueous Solution by Low-Cost Biosorbents

Abstract

The removal of basic dye crystal violet by low-cost biosorbents was investigated in this study using a batch experimental system. The adsorption of crystal violet onto various adsorbents was solution pH-dependent and the maximum removal occurred at basic pH 10.0. The kinetic experimental data were analyzed using pseudo-first-order and pseudo-second-order equations to examine the adsorption mechanism and the intraparticle diffusion model to identify the potential rate controlling step. These results suggested that the adsorption of crystal violet onto various adsorbents was best represented by the pseudo-second-order equation. The suitability of the Langmuir and Freundich adsorption isotherms to the equilibrium data was also investigated at various temperatures for all four sorbents and the adsorption isotherms exhibited Freundlich behavior. The Freundlich constant K_f was 1.55 for alligator weed, 2.33 for Laminaria japonica, 9.59 for rice bran and 5.38 (mg/g)/(mg/L)^1/n for wheat bran, respectively at adsorbent concentration 5 g/L, pH 10.0 and 20°C. The thermodynamic parameters (ΔH, ΔG, and ΔS) were calculated and the results showed that the adsorption process for various adsorbents was spontaneous, endothermic, with an increased randomness, respectively. The particle size and the reaction temperature exhibited an insignificant impact on the adsorption equilibrium of crystal violet. The adsorbents investigated could serve as low-cost adsorbents for removing the crystal violet from aqueous solution.     

Low cost adsorbents obtained from ash for copper removal

We investigated the utilization of ash and modified ash as a low-cost adsorbent to remove copper ions from aqueous solutions such as wastewater. Batch experiments were conducted to determine the factors affecting adsorption of copper. The influence of pH, adsorbent dose, initial Cu²⁺ concentration, type of adsorbent and contact time on the adsorption capacity of Cu²⁺ from aqueous solution by the batch adsorption technique using ash and modified ash as a low-cost adsorbent were investigated. The optimum pH required for maximum adsorption was found to be 5. The results from the sorption process showed that the maximum adsorption rate was obtained at 300 mg/L when a different dosage of fly ash was added into the solution, and it can be concluded that decreasing the initial concentration of copper ion is beneficial to the adsorption capacity of the adsorbent. With the increase of pH value, the removal rate increased. When the pH was 5, the removal rate reached the maximum of over 99%. When initial copper content was 300 mg/L and the pH value was 5, the adsorption capacity of the zeolite Z 4 sample reached 27.904 mg/g. The main removal mechanisms were assumed to be the adsorption at the surface of the fly ash together with the precipitation from the solution. The adsorption equilibrium was achieved at pH 5 between 1 and 4 hours in function of type of adsorbent. A dose of 1: 25 g/mL of adsorbent was sufficient for the optimum removal of copper ions. For all synthesized adsorbents the predominant mechanism can be described by pseudo-second order kinetics.     

柠檬皮渣对亚甲基蓝吸附性能研究

采用柠檬皮渣作为吸附剂对水溶液中亚甲基蓝进行吸附研究,考察了柠檬皮渣用量、溶液pH值、吸附时间、亚甲基蓝浓度、温度对吸附量的影响。结果表明:当柠檬皮渣用量为1 g/L,亚甲基蓝的初始质量浓度为100 mg/L,pH值为7,温度为30℃时,柠檬皮渣对亚甲基蓝吸附效果最好,吸附量为36.2 mg/g,吸附过程符合Langmuir等温吸附模型,吸附动力学遵从准二级动力学方程,热力学参数计算结果表明此吸附过程为自发的放热过程。     

壳聚糖超细纤维的制备及其铬离子吸附性能研究

利用静电纺丝和热交联技术,制备了良好形貌的交联壳聚糖/聚甲基丙烯酸(CS/PMAA)纤维膜,然后采用正丙醛化学改性得到改性CS/PMAA纤维膜。Cr(Ⅵ)离子吸附实验发现,铬元素浓度为6.50 mg/L时,CS/PMAA纤维膜的吸附量可以达到4.98 mg/g;而当铬元素浓度为3.75 mg/L时,铬的去除率可以达到81.0%;而且提高壳聚糖的含量有利于提高CS/PMAA纤维膜的吸附性能。改性CS/PMAA纤维膜吸附结果显示,正丙醛改性CS/PMAA纤维膜降低吸附性能,而进一步还原后的纤维膜的吸附性能优于未改性CS/PMAA纤维膜。实验结果表明,CS/PMAA纤维膜对铬离子具有良好的吸附性能;CS/PMAA纤维膜的吸附性能主要通过纤维氨基与Cr2O72-的相互作用进行,提高氨基的碱性和数量有利于提高纤维膜的吸附性能。     

Uniform macroporous amidoximated polyacrylonitrile monoliths for gallium recovery from Bayer liquor

Efficient recovery of gallium from aqueous solution remains a problem to be solved in industry. Here a novel crosslinked monolith based on polyacrylonitrile/dimethyl sulfoxide (C-PAN) was prepared by thermally induced phase separation and supercritical CO₂ extraction drying technology. The influences of dissolution temperature and exchange solvents with different solubility parameters on the pore structure of C-PAN were systematically studied. It was found that the pore diameter decreased with the decrease of dissolution temperature and the increase of Δδ between exchange solvent and PAN. Meanwhile, the C-PAN with a small and dense pore structure showed better mechanical strength. Thereafter, the Ga³⁺ adsorption ability of amidoximated monolith (C-PAO) in simulated Bayer liquor was determined by batch tests. In the case of using methanol as the exchange solvent, the kinetic and equilibrium inspection study illustrated that both physical and chemical adsorption are present due to the multiscale and interconnected structure and the amidoxime groups. The adsorption capacity of C-PAO monolith toward gallium was 15.8 mg/g, with the equilibrium time as fast as 140 min, which can meet the requirement for the rapid extraction of gallium from Bayer liquor. It is expected that our work can provide some new ideas for fabricating gallium adsorbents.     

累托石/腐殖酸微球对水中蒽的吸附

采用累托石、腐殖酸、聚乙烯醇、海藻酸钠和氯化钙等材料制备微球状吸附剂去除水中多环芳烃蒽。考察了微球用量、蒽溶液初始浓度、吸附时间等因素对吸附效果的影响,测定了吸附等温线,采用Freundlich、Langmuir模式对等温吸附规律作了数学模拟,对吸附动力学及吸附机理进行了探讨。结果表明:在该研究条件下,微球用量、溶液初始浓度、吸附时间等因素对水中蒽的吸附效果有显著性影响。最优吸附条件为:微球用量=5 g/50 mL,初始浓度=10 mg/L,吸附时间=14 h。累托石/腐殖酸微球对水中蒽的等温吸附规律符合Freundlich和Langmuir模型,吸附动力学过程可用准一级、准二级动力学模式和双常数方程较好地模拟。吸附是靠微球与蒽的分子间作用力来实现的。     

H-103树脂处理含酚废水的实验研究

研究了H-103大孔吸附树脂对600~1000 mg/L苯酚水溶液中酚的吸附,考察了初始酚浓度、溶液pH值及温度对吸附性能的影响. 结果表明,在20 min内吸附达到平衡,吸附动力学可用拟二级动力学模型描述. 苯酚在大孔树脂上的吸附等温线很好地符合Langmuir吸附等温方程,在25℃下其饱和吸附量和Langmuir常数分别为86.00 mg/g和0.2719 L/mg.     

褐煤吸附MTBE(甲基叔丁基醚)的研究分析

MTBE(甲基叔丁基醚)作为一种汽油添加剂,在水环境中难降解并且不易被有机物吸附。采用颗粒状活性褐煤作为吸附剂去除水溶液中的MTBE,配制样品浓度范围为1.7μg/L~1.9 g/L。实验发现,pH值不影响吸附过程,MTBE的吸附更符合Freundlich吸附模型。在溶液起始浓度为1100 mg/L时,褐煤的最大吸附能力为21.5 mg/g。在MTBE起始浓度为74μg/L时,3 h后达到吸附平衡并且MTBE去除效率达到97.03%。由此可见,褐煤的吸附能力较高,吸附速度较快,可以作为从水溶液中去除MTBE的有效吸附剂。     

Cross-linked polyvinyl amidoxime fiber: a highly selective and recyclable adsorbent of gallium from Bayer liquor

Gallium, a scarce metal produced mainly from Bayer liquor, is widely used in semiconductors. Ion-exchange method is currently considered as the most effective method to recover gallium from Bayer liquor. In this article, fibrous amidoxime adsorbents are introduced to recover gallium from Bayer liquor. In addition, hydrazine cross-linked polyvinyl amidoxime (HPAO) fibers have been prepared. The structure of the as-prepared fibers was ascertained by FTIR, elemental analysis and weight gain rate. The adsorption kinetics, adsorption isotherm and recycling performance were investigated by batch method. Cross-linking duration was studied and it turned out to be an important factor to optimize the adsorption capacity and recycling performance. After 1.5 h cross-linking time, the fiber showed the highest gallium adsorption capacity of 14.83 mg/g in Bayer liquor. After 3 h cross-linking time, the fiber showed the best recycling performance, which retained 82.9% of the initial adsorption ability after four cycles. Adsorption capacity of vanadium was lower than 1 mg/g for all samples. HPAO displayed very fast adsorption kinetics with an equilibrium at 60 min. The EDS results confirmed the low extraction of aluminum and vanadium provided by HPAO fibers. The gallium-loaded fiber could be effectively eluted by acidified thiourea. With proper control of the cross-linking duration by hydrazine, HPAO fiber with high selectivity towards gallium, high adsorption capacity and good recycle performance could be obtained, which is promising for recovering gallium needed for industrial applications.     

Macroporous polymeric ion exchangers as adsorbents for the removal of cationic dye basic blue 9 from aqueous solutions

Two macroporous cation‐exchange resins, Purolite C145, a strongly acidic cation macroporous resin, and Purolite C107E, a weakly acidic cation‐exchange resin, were used to remove the dye Basic Blue 9 (BB9) from an aqueous medium. Batch adsorption experiments were carried out to analyze the effect of various parameters, such as the phase contact time, initial dye concentration, initial solution pH, resin dose, and temperature. The experimental equilibrium data were evaluated by the Langmuir, Freundlich, and Dubinin–Radushkevich (DR) adsorption models. The Freundlich model better described the adsorption processes of the BB9 dye onto both cation exchangers, and the monolayer adsorption capacities were established as 31.9846 mg/g (C145) and 27.77 mg/g (C107E) at 20°C. The values of the mean free adsorption energy (E) obtained from the DR model suggested a porous structure of the adsorbents and proposed ion exchange at the main mechanism of the adsorption process. The values of the thermodynamic parameters showed that the retention of the cationic dye was a spontaneous and endothermic process. Environmental scanning electron microscopy and Fourier transform infrared spectroscopy were used to characterize the sorbent and also to validate the adsorption mechanism as ion‐exchange ones. The desorption experiments by a batch method were performed with different solutions: 0.1 and 1 mol/L HCl, 2.5 mol/L H₂SO₄, CH₃OH, and a mixture between 1 mol/L HCl and CH₃OH. Desorption performed with sulfuric acid was shown to be most effective because more than 85% of the adsorbed dye was removed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39620.     

Adsorption behavior of cationic dyes on citric acid esterifying wheat straw: kinetic and thermodynamic profile

The kinetic and thermodynamic behaviors of cationic dye adsorption onto citric acid esterifying wheat straw (EWS) from aqueous solution were investigated. Two cationic dyes, methylene blue (MB) and crystal violet (CV) were selected as adsorbates. The kinetic and thermodynamic parameters of dye adsorption were examined with a batch system by changing various experimental factors (e.g. initial pH, EWS dosage, dye concentration, contact time, temperature). The MB and CV removal ratios came up to the maximum value beyond pH 4. The 2.0 g/L or up of EWS could almost completely remove MB and CV from 250 mg/L of dye solution. The adsorption percentages of MB and CV kept above 95% over a range from 50 to 350 mg/L of dye concentration when 2.0 g/L of EWS was used. The isothermal data followed the Langmuir model. The adsorption processes could be described by the pseudosecond-order kinetic model. The dual linear plots of intraparticle diffusion indicated that two intraparticle diffusion steps occurred in the dye adsorption processes. The thermodynamic study indicated that the adsorptions of dyes were spontaneous and endothermic. High temperatures favored the adsorption processes.     

Ammonia Removal from Aqueous Solutions by Iranian Natural Zeolite

Abstract

The capability of Iranian natural clinoptilolite for ammonia removal from aqueous solutions has been thoroughly studied. Both batch and continuous (column) experiments were carried out. The viability of this natural zeolite in reducing the leakage of ammonia to the environment through waste water streams was a main focus of this research. Through the batch experiments, the effect of process variables such as the size of zeolite particles, pH, and ammonia concentration of the feed solution on the kinetics of ammonia uptake were investigated. Ammonia removal occurred rapidly and within the first 15 minutes of contact time, a major part of ammonia was removed from the solution. An adsorption capacity about 17.8 mg NH₄ ⁺/g zeolite at feed ammonia concentration of 50 mg/L was obtained and the optimum range for pH was achieved about 5.5–7.6. The adsorption capacity of clinoptilolite in the continuous mode was about 15.16 and 15.36 mg NH₄ ⁺/g zeolite for the original and regenerated types of clinoptilolite, respectively, where feed ammonium concentration was 50 mg/L. Increasing the feed ammonium concentration to 100 mg/L did not reduce the capability of the column for its ammonium removal and up to a bed volume (BV) of 85, there was only less than 1 mg/L ammonium in the column outlet. Presence of cations such as Ca²⁺, Mg²⁺ and Na⁺ in the feed solution reduced the clinoptilolite adsorption capacity to about 11.68 mg NH₄ ⁺/g zeolite. Regeneration experiments were carried out using concentrated sodium chloride solutions, as well as tap water. Where tap water was used as the regenerant, gradual release of ammonium from exhausted clinoptilolite was observed.     

Adsorption characteristics of sericite for cesium ions from an aqueous solution

To efficiently remove cesium ions from aqueous solution, sericite was used as a novel adsorbent. The silanol (SiO₂) and aluminol (Al₂O₃) groups in sericite are likely to play an important role in adsorption process. The maximum adsorption capacity (q_m) and adsorption constant (K_L) for cesium ions obtained from the Langmuir isotherm model were 6.68 mg/g and 0.227 L/mg, respectively and regression curve fit well with the experimental data as the 0.965 of correlation coefficients (r²). However, when the Freundlich isotherm model was used correlation coefficient (r²) was 0.973. Therefore, it was concluded that Freundlich model fits equilibrium data better than Langmuir model. When the 6.0 g/L of sericie concentration was added to aqueous solution, cesium ions were removed by about 80% and the increase was not happened above 6.0 g/L of sericite concentration any more. The process was determined as exothermic reaction because the removal efficiency of cesium ions decreased as temperature increased. Furthermore, all adsorption was completed in 120 min and comparing the pseudo first and second-order kinetic models indicates that the adsorption of cesium ions using sericite follows well the pseudo-second-order kinetics.     

Simultaneous removal of Pb(II) and chemical oxygen demand from aqueous solution using immobilized microorganisms on polyurethane foam carrier

We studied the simultaneous removal of Pb(II) and chemical oxygen demand (COD) from synthetic solutions using immobilized microorganism. The immobilized microorganisms on polyurethane foam (IPUF) were successfully prepared by cultivating the microbe B350 in a mixture of culture medium and polyurethane foam (PUF). The adsorption of Pb(II) ion from aqueous solutions onto PUF and IPUF was studied by batch adsorption. IPUF exhibited high Pb(II) removal efficiency. When 0.12 g of IPUF was used to treat 50mL of 20mg/L P(II) solution at pH 7.0 and 25 °C for 120 mins, the removal ratio was 80%. The biosorption kinetics could be described by the pseudo-secondorder model, and the adsorption isotherms could be described by Langmuir and Freundlich equations. In addition, for synthetic wastewater containing Pb(II) and C₆H₁₂O₆, the removal ratios of Pb(II) and COD after being treated by IPUF for 8 hours were 92.0% and 84.2%, respectively. The removal ratio of COD clearly decreased with the increase of Pb(II) concentration, meaning that Pb(II) was toxic to the mobilized microorganisms and lower Pb(II) concentration was preferred.     

Adsorption characteristics of waste crab shells for silver ions in industrial wastewater

Waste crab shells were used as an adsorbent to efficiently adsorb silver ions in actual industrial wastewater. The functional groups like -NHCO or -NO₂ groups in crab shells play an important role in the adsorption of silver ions. The highest removal efficiency was about 96% obtained from the 30 g/L of adsorbent concentration at initial pH 6.0 of waste solution. Langmuir sorption model was chosen to estimate the maximum uptake capacity and affinity constant of waste crab shells for silver ions, and its value was 5.21mg/g-dry mass and 0.411 L/mg, respectively. Entire adsorption process was completed in 60 min, and removal efficiency of crab shells was higher than that of Amberlite IR 120 plus resin. The effect of temperature could be neglected in the range of 15.0–45.0 °C. Also, instrumental analysis such as SEM (scanning electron microscopy) photographs, EDX (energy dispersive X-ray) spectrum, and FT-IR spectrum were applied to investigate the surface condition and functional groups of crab shells.