Optimization of a Fe-Al-Ce nano-adsorbent granulation process that used spray coating in a fluidized bed for fluoride removal from drinking water

A coating granulation technology comprising the spraying of a Fe-Al-Ce nano-adsorbent suspension onto glass beads in a fluidized bed was developed. An acrylic-styrene copolymer latex was used as a binder. The granulated adsorbent was used in a packed bed for fluoride removal from drinking water. The effects of coating temperature, latex/Fe-Al-Ce ratio, and coating amount on granule compressive strength and adsorption capacity were investigated. With increased coating temperature, cross linking in the polymer in the coated layer increased, which resulted in increased granule strength but decreased adsorption capacity. With increased latex/Fe-Al-Ce ratio, more active sites were covered by the polymer, which also resulted in increased granule strength but decreased adsorption capacity. The optimal parameters for making high performance adsorbent granules were for the granules to be coated at 65 °C using a latex/Fe-Al-Ce ratio of 0.5:1 and a coating amount of 27.8%. These granules had a fluoride adsorption capacity of 2.77 mg/g (coated granules) for water with an initial fluoride concentration of 0.001 M that was treated at pH 7.     

颗粒化铁-铝-铈纳米吸附剂的除氟性能

采用在流化床中喷雾包覆方法将纳米吸附剂包覆在玻璃珠表面制备颗粒化吸附剂,考察了所制颗粒化纳米铁-铝-铈复合氧化物吸附剂在含氟水中的除氟性能. 结果表明,含氟初始浓度为10 mg/L时,颗粒化吸附剂的吸附速率符合拟一级反应动力学模型,吸附等温线符合Langmuir吸附模型,饱和吸附量达5.9 mg/g. 吸附容量随含氟水初始pH值升高而降低,吸附过程中溶液pH值逐渐趋近于中性;含氟水中其他阴离子对F-的吸附存在不同程度的竞争,竞争离子的影响顺序为NO3-"Cl-相似文献   

Effluent organic matter removal from reverse osmosis feed by granular activated carbon and purolite A502PS fluidized beds

Applying pre-treatments to remove dissolved organic matter from reverse osmosis (RO) feed can help to reduce organic fouling of the RO membrane. In this study the performance of granular activated carbon (GAC), a popular adsorbent, and purolite A502PS, an anion exchange resin, in removing effluent organic matter (EfOM) from RO feed collected from a water reclamation plant located at Sydney Olympic Park, Australia were evaluated and compared through adsorption equilibrium, kinetics and fluidized bed experiments. The maximum adsorption capacity (Q_max) of GAC calculated from the Langmuir model with RO feed was 13.4 mg/g GAC. The operational conditions of fluidized bed columns packed with GAC and purolite A502PS strongly affected the removal of EfOM. GAC fluidized bed with a bed height of 10 cm and fluidization velocity of 5.7 m/h removed more than 80% of dissolved organic carbon (DOC) during a 7 h experiment. The average DOC removal was 60% when the bed height was reduced to 7 cm. When comparing GAC with purolite A502PS, more of the later was required to remove the same amount of DOC. The poorer performance of purolite A502PS can be explained by the competition provided by other inorganic anions present in RO feed. A plug flow model can be used to predict the impact of the amount of adsorbent and of the flow rate on removal of organic matter from the fluidized bed column.     

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.     

The defluoridation of water by acidic alumina

Fluoride is considered as a major inorganic pollutant present in drinking water. To remove this excess fluoride, defluoridation was done by alumina. In the present study, alumina used was acidic in nature and hence considered as a good fluoride removing adsorbent. Characterization of the adsorbent was done by XRD, SEM, BET and FTIR with BET surface area of 144.27 m²/g. Systematic adsorption experiments were carried out with different process parameters such as contact time, adsorbent mass, pH, temperature and stirring speed. Fluoride adsorption by alumina was highly pH dependent. Maximum fluoride was removed from water at pH 4.4. At very low and very high pH, fluoride removal efficiency was affected. The study of thermodynamic parameters inferred that physical adsorption was dominant with activation energy of 95.13 kJ/mol and endothermic behavior of the process. The kinetics study concluded that pseudo second order kinetics was followed by the adsorption process. Adsorption equilibrium was studied with Langmuir and Freundlich isotherm models. The adsorption process followed Langmuir isotherm with an adsorption capacity of 8.4 mg/g. A regeneration study was proposed in order to reuse the adsorbent for better economy of the process. Finally, a process design calculation was reported to know the amount of adsorbent required for efficient removal of fluoride from aqueous medium.     

Multi-component granulation in a fast fluidized bed

The granulation of multi-component particles was conducted in a fast fluidized bed with an atomizing binder solution. The effects of gas velocity and binder droplet diameter on granulation rate, granule size distribution and granule composition were studied. The granulation rate and granule yield were determined by the balance between the agglomeration rate of feed particles and the disintegration rate of granules because there was no secondary granulation. With the increase in gas velocity and the reduction in binder droplet size, the agglomeration rate of feed particles decreased but the disintegration rate of granules increased, resulting in a reduced granule yield. Despite the larger fraction of small particles in the granules, the homogenous granulation of multi-component particles was achieved.     

Cationic polymer chain tethered on the pore-wall of 3-D ordered macroporous resin for the removal of hexavalent chromium from aqueous solution

A novel 3-D ordered macroporous (3DOM) adsorbent with a cationic polymer chain (poly(N,N-dimethylaminoethyl methacrylate), PDMAEMA) tethered on the pore wall was prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) for the removal of toxic Cr(VI) ions from aqueous solution. In comparison with recently reported adsorbents, the adsorbent remarkably stands out owing to large adsorption capacity, relatively fast kinetics, and high stability in the regeneration process. The adsorption capacity significantly depended on the solution pH and there was a wide working pH range that is much convenient in practical application. Kinetics of Cr(VI) adsorption by the 3DOM adsorbent was studied in batch experiments, in the temperature range 298–318 K. The equilibriums were arrived within 120–130 min and a pseudo-second order model can be described well. In the adsorption isotherm study, experimental data followed the Langmuir adsorption model. The maximum adsorption capacity increased with the increase of temperature, and reached the high value of 431.0 mg/g at 308 K. Thermodynamic parameters revealed spontaneous and endothermic adsorption processes. Furthermore, the 3DOM adsorbent remained high adsorption capacity (above 90% of the original Cr(VI) loading capacity) after 15 adsorption–desorption cycles by simply using sodium hydroxide solution as the desorption liquid, which ensured the reusability of 3DOM adsorbent.     

Granulation time in fluidized bed granulators

Size enlargement of particles in fluidized bed granulation involves mixing of particles with a binder liquid to form larger wet granules and drying them to form dry granules. Identification of the time for completion of granulation process is critical as further fluidization of dry granules is providing extra energy for their attrition. Monitoring the bed pressure drop and bed temperature of a batch fluidized bed granulator with time can provide information on the time for completion of the granulation process. Experimental observations on granulation time and size of granules in a lab-scale batch fluidized bed granulator are presented. Model based equations are developed for the estimation of granulation time and size of granules.     

Fluoride ions adsorption from water by CaCO3 enhanced Mn–Fe mixed metal oxides

Novel CaCO₃-enhanced Mn–Fe mixed metal oxides (CMFC) were successfully prepared for the first time by a simple-green hydrothermal strategy without any surfactant or template combined with calcination process. These oxides were then employed as an adsorbent for adsorptive removal of excess fluoride ions. The adsorbent was characterized by SEM, XPS, XRD, FTIR, and BET analysis techniques. The adsorption property of CMFC toward fluoride ion was analyzed by batch experiments. In fact, CMFC exhibited adsorption capacity of 227.3 mg∙g^‒1 toward fluoride ion. Results showed that ion exchange, electrostatic attraction and chemical adsorption were the main mechanism for the adhesion of large amount of fluoride ion on the CMFC surface, and the high adsorption capacity responded to the low pH of the adsorption system. When the fluoride ion concentration was increased from 20 to 200 mg∙L^‒1, Langmuir model was more in line with experimental results. The change of fluoride ion adsorption with respect to time was accurately described by pseudo-second-order kinetics. After five cycles of use, the adsorbent still maintains a performance of 70.6% of efficiency, compared to the fresh adsorbent. Therefore, this material may act as a potential candidate for adsorbent with broad range of application prospects.     

Performance evaluation of alumina cement granules in removing fluoride from natural and synthetic waters

Of late, the ground water sources of many countries remain fragile due to fluoride attack. The intensity and scale of the human stress effects associated with this issue, prompts global research for sustainable solutions. This paper examines and compares the potential of a newly developed adsorbent alumina cement granules (ALC) in removing fluoride from natural ground water, and synthetic water prepared using conditions and concentrations relevant to natural freshwater environments. The batch sorption profiles appeared similar in natural and synthetic systems. The fluoride removal was concentration dependent in synthetic system as the equilibrium adsorption capacity was found to be 4.75 and 3.91 mg g⁻¹ corresponding to initial concentrations of 20 and 8.65 mg l⁻¹ at optimal conditions. ALC exhibited reduced fluoride adsorption capacity in treating natural water compared to synthetic systems in both batch and column studies. The sorption process is found to be unaffected in the pH range of 3.0–11.5. Though the presence of ions like nitrates, chlorides, sulfates, and bicarbonates did not offer any interference to fluoride sorption, silicates and phosphates at higher concentrations reduced fluoride uptake by ALC. The natural organic matter in ground water appears to play a role in reducing the adsorption capacity of ALC. Thermodynamics of sorption confirms that the process is spontaneous and endothermic in both natural and synthetic systems.     

Novel technique to regenerate activated alumina bed saturated by fluoride ions

A novel technique to regenerate adsorbent column is presented. The process used is based on the utilization of an electrochemical cell which regenerates several saturated adsorbent bed. This paper presents the regeneration of the activated alumina (AA) bed saturated by fluoride ions. The results obtained in this study demonstrated that desorption of fluoride from activated alumina is a rapid process. Most of the fluoride content desorbed within 6–15 min. The utilization of the electrochemical cell allows a complete desorption of the fluoride under optimum conditions. The reduction of about 90% of the sodium hydroxide amount was attained by the electrochemical process. A study of adsorption–regeneration cycles showed that the electrochemical technique was more efficient than current techniques. A 95%, recovery of the adsorption capacity was realized with the electroregeneration system. In addition, the volume of water used to regenerate the saturated bed was lower than for current regeneration techniques. The washing did not exceed 6% of the treated water volume. The electrodesorption operation was successfully applied for fluoride desorption from saturated activated alumina column by natural water with strong mineralisation.     

Synthesis and characterization of millimetric gamma alumina spherical particles by oil drop granulation method

An oil drop granulation process was developed to prepare porous meso-structured gamma (??) alumina (Al₂O₃) granules. The ??-Al₂O₃ granules prepared were 2?mm diameter spherical particles with low sphericity factor (0.02?±?0.01). The XRD results validated that the synthesized granule possesses crystallinity of ??-Al₂O₃ phase. The N₂ adsorption?Cdesorption isotherm and BJH pore size distribution of the synthesized granule elucidated the existence of mesoporous characteristic with unimodal pore in the mesopore region. The synthesized and characterized granules can be used as a potential support for catalyst in either moving or fluidized bed reactor.     

离子筛型锂吸附剂的吸附性能研究

研究了自制粒状离子筛型锂吸附剂的吸附容量、洗脱性能和重复吸附洗脱时的稳定性。结果表明，吸附剂在纯锃盐溶液中的锂离子吸附容量为15．63mg／g，在海水中的锂离子吸附容量为5．68mg／g；洗脱剂盐酸的浓度越高，对吸附剂中锂离子的洗脱率越高，但同时离子筛的溶损率加大；吸附剂循环吸附洗脱时，吸附与洗脱性能较稳定，并可重复使用。     

Chemically modified organic/inorganic nanoporous composite particles for the adsorption of reactive black 5 from aqueous solution

In the present work, we report a chemically modified polyacrylamide/silica nanoporous composite adsorbent for the removal of reactive black 5 (RB5) azo dye from aqueous solutions. The composite adsorbent was synthesized in a packed bed and modified by ethylenediamine (EDA). The adsorbent was characterized by Fourier transformation infrared (FT-IR), thermogravimetric analysis (TGA), thermoporometry, Brunauer, Emmett and Teller (BET) method and scanning electron microscopy (SEM). Mechanical stability of the adsorbent was examined in a packed bed by following the back-pressure of the column. Pore diameter of the composite adsorbent in dry and wet states was estimated to be about 18.71 nm and 12.61 nm, respectively. Adsorption experiments were performed in batch mode and effect of various operational parameters on the adsorption capability of the adsorbent was studied systematically. The maximum adsorption capacity of the modified composites was found to be 454.5 mg RB5/g of adsorbent. The equilibrium data were analyzed by Langmuir, Freundlich, Sips, BET and Redlich–Peterson isotherm models and found to fit well to the BET isotherm. The data kinetically followed the pseudo-second-order model. High adsorption capacity, fast removal mechanism, and good mechanical stability are three advantages of the presented composite for the removal of RB5.     

Manufacturing pharmaceutical granules: Is the granulation end-point a myth?

The moist agglomeration process by high-shear mixing/granulation, i.e. the wet massing, screening and subsequent drying is a wide spread but critical unit operation. Since for decades formulators are looking for the correct “end-point” of this important process, i.e. when do you need to stop massing or stop with the addition of granulating liquid? What is the correct amount of granulating liquid? A similar situation exists in case of the moist agglomeration in fluidized bed equipment. In the latter case the simultaneous drying of the still moist granules have to be taken into account. Recently a science-based virtual equipment simulator could be developed mimicking the granule size evolution in a fluidized bed granulator during the addition of granulating liquid. For the simultaneous drying the Mollier chart is used. With this virtual equipment simulator it is possible to simulate “crash situations”, i.e. by overwetting or by an incorrect use of the parameter setting. However the determination of the “end-point” depends only on the operator, who desires a certain granule size distribution and a well-defined final moisture content of the batch. Thus the existence of a process intrinsic “end-point” has to be questioned. The same situation can be reported in case of high-shear mixing/granulation based on many years of research. In fact nobody could clearly show the existence of an intrinsic “end-point”. However during the continuous addition of a granulating low viscous liquid a sudden increase in power consumption can be measured, which levels off. Such a measurement depends on the formulation and leads to an “early signal” not to the “end-point”. This signal can be used for a tight control of the granulation process and leads to a low batch to batch variability in the final granule size distribution. The latter is the goal of the PAT (Process Analytical Technology) Initiative emphasizing “Quality by Design”.     

Removal of fluoride from drinking water by adsorption onto alum-impregnated activated alumina

The ability of the alum-impregnated activated alumina (AIAA) for removal of fluoride from water through adsorption has been investigated in the present study. All the experiments are carried out by batch mode. The effect of various parameters viz. contact time, pH effect (pH 2–8), adsorbent dose (0.5–16 g/l), initial fluoride concentration (1–35 mg/l) has been investigated to determine the adsorption capacity of AIAA. The adsorbent dose and isotherm data are correlated to the Bradley equation. The efficacy of AIAA to remove fluoride from water is found to be 99% at pH 6.5, contact time for 3 h, dose of 8 g/l, when 20 mg/l of fluoride is present in 50 ml of water. Energy-dispersive analysis of X-ray shows that the uptake of fluoride at the AIAA/water interface is due to only surface precipitation. The desorption study reveals that this adsorbent can be regenerated following a simple base–acid rinsing procedure, however, again impregnation of the regenerated adsorbent (rinsed residue) is needed for further defluoridation process.     

Adsorption of Reactive Blue 114 dye by using a new adsorbent: Pomelo peel

This paper describes the removal of Reactive Blue 114 dye from aqueous solutions by using pomelo (Citrus grandis) peel. Pomelo peel can be described as a new, low cost, abundantly available adsorbent. The optimum adsorbent mass, dye concentration, contact time and pH were determined in this study. The parameters of Langmuir, Freundlich and Temkin adsorption isotherms were also obtained using concentrations of the dyes ranging from 1.0 to 200 mg/L. Maximum adsorption capacity was obtained as 16 mg/g at pH 2 and 303 K solution temperature. The adsorption process was observed to be reaching equilibrium after about 90 min.     

Fluidized bed spray granulation: Investigation of the coating process on a single sphere

The coating and granulation of solid particles in a fluidized bed is a process which converts pumpable and atomizable liquids (solutions, slurries, melts) into granular solids in one step by means of drying. The solution to be processed is sprayed onto a fluidized bed. Particle growth can take place either via surface layering or agglomeration. In the case of surface layering the atomized droplets deposit a thin layer of liquid onto the seed particles. The solvent is then evaporated by the hot fluidizing, leaving behind the dissolved material on the surface. Although fluidized bed spray granulation and film coating have been applied in industry for several years, there is still a lack of understanding of the physical fundamentals and the mechanisms by which spherical granules are formed. Hence a new method was developed which allows the direct observation of the subsequent particle-forming mechanisms such as droplet deposition, spreading, wetting and drying. The authors present a laboratory scale apparatus in which a single freely suspended particle can be coated under well defined and constant coating and drying conditions. With this device, particle-growth-rate and the development of particle morphology were measured and investigated under various experimental conditions.     

Adsorption of fluoride from aqueous solution by magnesia‐amended silicon dioxide granules

BACKGROUND: A new kind of adsorbent, magnesia‐amended silicon dioxide granules (MAS), has been prepared by wet impregnation of silicon dioxide with magnesium chloride solution. The physicochemical properties were characterized using X‐ray diffraction (XRD), Fourier transform infrared (FT‐IR) and Brunauer, Emmett, Teller (BET) studies. The porous structure and high surface area of these granules make them suitable for sorption. The aim of this study was to show the possibility of defluoridation of water using MAS and to demonstrate the advantage of its use compared with silicon dioxide. RESULTS: XRD and FT‐IR analysis showed that amorphous magnesia was loaded on silicon dioxide after treating with magnesium chloride solution and calcining at 500 °C. Batch sorption experiments indicated that MAS is more effective than silicon dioxide for fluoride adsorption. The sorption capacities of MAS decreased as the solution pH rose. At pH 3, the maximum defluoridation capacity of MAS was 12.6 mg g^?1. The adsorption process fitted the Dubinin–Radushkevich isotherm and kinetic studies revealed that the adsorption followed second‐order rate kinetics. CONCLUSION: The results indicate that it is feasible to modify both the physical and chemical properties of silicon dioxide with magnesia so that it can be used as a potential adsorbent to adsorb fluoride from aqueous solution. Copyright © 2009 Society of Chemical Industry