Modeling the mass transfer in biosorption of Cr (VI) y Ni (II) by natural sugarcane bagasse

Modeling the mass transfer in biosorption of Cr (VI) y Ni (II) by natural sugarcane bagasse The Cr (VI) and Ni (II) ion biosorption process by natural sugarcane bagasse in a fixed bed column was investigated. The characteristic removal parameters such as retention capacity, removal percent and unused bed length were experimentally determined at different operating conditions. Overall mass transfer coefficient was investigated and reported for the stud - ied biosorption system. The breakthrough curves were simulated using Matlab2010a software to check the validity of the obtained overall mass transfer coefficients. Experimental data fitted well with predicted data ( R = 0.94). A statistical analysis was performed using the software Statgraphics Centurion-X 15.2.06 to compare the simulated and experimental data. No significant differences were observed between experimental and simulated data. The best operating conditions for Cr (VI) removal were 15 mg/L of inlet concentration and 1.5 g of biosorbent. For Ni (II) removal the best results were obtained with 25 mg/L of inlet concentration and 1.5 g of solid. The results obtained through the breakthrough curve showed high removal percentages (94.70 and 97.90% for chromium and nickel, respectively). Moreover, results indicated that sorption of these metals was irreversible and it was controlled by the mass transfer at the external film. Keywords Biosorbent · Heavy metals · Pollution · Wastewaters Nomenclature t Break-point time (min) V Effectiv e volume (ml) t Satur ated point time (min) ef s F V olumetric flow (mL/min) C Initial concentration (mg/L) t Time (min) C Concentr ation in the time to the exit of the column (mg/L) C Concentration of retained metal (mg/L) * M. Calero de Hoces m T otal amount of heavy metal sent to column (g) total mcaleroh@ugr.es m Total amount of heavy metal retained in column ads I. L. Rodríguez Rico (g) ivanl@uclv.edu.cu m Total mass of the adsorbate (g) R. J. Cabrera Carrazana u Superficial velocity of fluid (cm/min) rjcabrera@nauta.cu H Bed length (cm) N. Kumar Karna H Length of unused bed (cm) UNB n.karna@udt.cl H Longitude of saturated bed (cm) sat I. Iáñez-Rodríguez N Ov erall number of transfer units ireneir@ugr.es W Adsorbate amount in equilibrium with the fluid sat (mg/g) Central University “Marta Abreu” of Las Villas, Carretera a K Overall volumetric mass transfer coefficient Camajuaní Km 5 1/2, Santa Clara, Villa Clara, Cuba ca −1 (min ) Central University “Marta Abreu” of Las Villas, Calle Danielito entre Central y San Miguel, Santa Clara, Greek letters Villa Clara, Cuba τ Dimensionless time Technological Development Unit, University of Concepción, ε Bed porosity Concepción, Chile ρ Bulk density (g/L) Department of Chemical Engineering, University of Granada, ρ Particle density (g/L) 18071 Granada, Spain Vol.:(0123456789) 1 3 55 Page 2 of 8 Applied Water Science (2018) 8:55 the adsorption kinetics were studied through a mathemati- Introduction cal model that takes into account both the external and internal mass transfer resistances, nonideal plug flow Nowadays, pollution of wastewaters by heavy metals along the column, and the variation of fluid velocity along caused by anthropogenic activities is a problem to be the column. solved (Martín-Lara et al. 2017). Chromium and nickel are Tan and Spinner (1994), developed a more complete heavy metals that are considered as very dangerous pol- model for ionic exchange that includes the limitation of lutants in wastewaters because they are persistent as they total transference. This model can predict the breakthrough do not degrade to harmless compounds. They are toxic curves for any species removed by the biosorbent and elution substances known to cause multiple organ damage, even curves obtained during regeneration. However, the solution at low concentrations. Moreover, they are human carcino- of the model is extremely complex and the values of the gens and they cause long-term health problems in human mass transfer coefficients for all ionic species present in the population (Iqbal 2016; Tchounwou et al. 2012). system is required. Different technologies have been tested for heavy metal The values of these coefficients can be estimated or deter - removal from wastewater such as chemical precipita- mined by fitting the model to experimental data (Yang and tion, ion exchange, reverse osmosis, electro-flotation and Volesky 1996; Hatzikioseyian et al. 2001; Borba et al. 2006; bioremediation among others. These methodologies pre- Escudero et al. 2013; Gu et al. 2013; Sulaymon et al. 2014). sent some drawbacks like the production of toxic sludge, The main advantage of the model is that it can simulate and high energy and chemical requirements and low efficiency predict the performance of a column under various condi- (Mushtaq et al. 2016; Rashid et al. 2016). tions including different flow rates, feed compositions, col- Biosorption is an interesting alternative for metal umn size, bed porosities and ionic forms of the biosorbent. removal which overcomes the disadvantages of the afore- mentioned methods. It is low cost and it has a high effi- ciency and selectivity for particular contaminants. Moreo- Materials and methods ver, the use of chemicals is minimum and no sludge is generated. Furthermore, regeneration of the biosorbents Biosorbent and metal recovery are possible (Bhatti et al. 2016). Many agricultural and forestry waste materials have been tested Sugar cane bagasse samples were collected from the Sugar for biosorption such as rice husk, pine bark, sawdust, pea- Power Station located in the Central University “Marta nut and orange peels among others (Nadeem et al. 2016; Abreu” of Las Villas, in Santa Clara, Cuba. The bagasse Tahir et al. 2017). was sieved in a sieve machine Model MLW with a group of Use of adsorption systems for industrial and municipal sieves (Tyler Series). The fraction between 0.5 and 1 mm wastewater treatment has become more prevalent during was selected. the recent years (Babu and Gupta 2004). An adsorption process is often used at the end of a treatment sequence Preparation of standards and reagents for pollution control as high degree of purification can be achieved. Adsorption is an important step in indus- Preparations of Cr (VI) and Ni (II) solutions was carried trial downstream processing. It is important to stop the out using analytical grade reagents. Potassium dichromate adsorption stage before the adsorbent is saturated which (K Cr O ) and nickel sulfate (II) hexahydrate (NiSO ·6H O) requires a thorough understanding of adsorption character- 2 2 7 4 2 ACS 99% supplied by J. T. Baker were used for preparing istics (Bautista et al. 2003). At industrial scale, the break- the synthetic wastewater. through time of the operation must be determined through Solutions were prepared by diluting the analytical rea- an economic and, eventually, environmental evaluation of gents with distilled water to desired concentrations. The the process. solutions of nickel were prepared at concentrations of 15 The adsorption kinetics can be described by various and 25 mg/L. Chromium solutions were prepared at a con- models depending upon the mechanism of transport (pore centration of 10 and 15 mg/L. diffusion, solid diffusion, and both mechanisms in parallel) The pH of the solution is a key parameter for the evalu- assumed inside the particles or in the external film (Bajpai ation of biosorption performance, specifically in the metal et al. 2004, 2007; Dizge et al. 2009; Gupta and Babu 2009; speciation (Guzman et al. 2003). In the case of heavy metals, Plazinski and Rudzinski 2010). biosorption studied in this work, the speciation of the metals In the present study, the effect of various operating vari- is not changed with the pH (constant in the process), there- ables (bed height and inlet adsorbate concentration) on the fore, the main effect will be explained by the impact of this process of fixed-bed biosorption was studied. Furthermore, parameter on the functional groups of the biomass. It was 1 3 Applied Water Science (2018) 8:55 Page 3 of 8 55 studied that the most reactive groups (carboxylic groups) on – Effluent volume, V (mL), can be calculated using ef the biomass are generally found under charge point zero (pH Eq. (1): 6). (Vicente 2011; Bermúdez et al. 2011). V = F ∗ t ef b (1) Castro et al. 2004, reported that the pKa of carboxylic where F is the volumetric flow rate circulating through groups on alginate fraction in the biomass is generally found the column expressed in mL/min and t represents the between 2 and 4. total flow time in min. Then, the pH of the solution was adjusted by adding the – Total amount of metal which entered in the column, m total appropriate quantity of 0.1 M hydrochloric acid (HCl). The in mg, can be calculated as follows: initial pH of solutions was fixed at 2 and 5 for dichromate solutions and nickel sulfate, respectively. C × F × t o b m = (2) total Hydraulic tests and selection of the operation where C represents the metal inlet concentration in mL/ parameters o min. – Total amount or metal retained by the column, m in The column (diameter: 1 cm, height: 20 cm) was filled with ads mg, is represented by the area under the breakthrough natural sugar cane bagasse and water was circulated with the curve. It can be calculated by the following expression: purpose of determining the most appropriate flows for the t=t established operation conditions. Ko et al. (2001) suggested for the processes on the mac- m = C dt (3) ads R roscopic level, that if the flow rate increases, the residence t=0 time of the fluid in the bed decreases, resulting in a low use of the biosorption capacity of the bed. On the other hand, where C denoted the concentration of metal removal for the processes on the microscopic level, the change of the in mg/L. volumetric flow rate affects only the diffusion of the ions in the liquid film, but not the one in the bioadsorbent. Accord- Estimation of mass transfer parameters ing to this author, high volumetric flow rates result in small resistances in the liquid film and high values of the external The concentration in the fluid and the solid phase change with mass transfer coefficient. Based on these considerations, time as well as with position in a x fi ed bed. The transfer process the best flow allows a non-fragmenting stable bed and no is described by the overall volumetric mass transfer coefficient draining occurrence at the end of the operation. Besides, an (K a) obtained from a solute material balance in the column appropriate flow gives a proper drop pressure. As a result, considering irreversible isotherms (McCabe et al. 1993). the selected feed flow was of 2 mL/min. The selected bed u N height was six times the internal diameter of the column K a= (4) (Khalid et al. 1998; Treybal 1993). Once studied, the biosorption of Cr (VI) and Ni (II) using N is defined as: one fixed bed column, several models were applied to the experimental data of the breakthrough curves for carrying N( − 1) = 1 + ln (5) out the fitting and the determination of the mass transfer o parameters. The samples were collected every 5 min for the The parameter τ is defined as: first 100 min and then each 10 min, until the biosorbent was saturated. u C t − H o o The chromium and nickel concentrations were determined (6) (1 − )HW by atomic absorption spectrophotometry using Pye Unicam s sat SP9 PHILIPS Atomic Absorption Spectrophotometer, Chro- where H is the time to displace fluid from the bed voids mium Analytical Line: 357.9 nm and Nickel Analytical Line: 232.0 nm to calculate the metal removal percent in a column. (normally negligible); u C t is the total solute fed to a unit o o cross-section of bed up to time t; and  (1 − )HW is the s sat Data analysis capacity of the bed, or the amount of the solute exchanged if the entire bed came to equilibrium with the feed. To analyze the dynamic Cr (VI) and Ni (II) removal in up- The solid line in Fig. 1 represents the predicted break- flow fixed bed column, breakthrough curves were drawn and through curve (McCabe et al. 1993). The slope increased the data were evaluated with the following equations. with time and C/C becomes 1 for N(τ−1) = 1. 1 3 55 Page 4 of 8 Applied Water Science (2018) 8:55 −K a H − H C c sat ln = (8) C u o o The longitude of saturated bed (H ) it is the product of sat the speed of the mass transfer section for the time since the area begins to move and it can be calculated using Eq. (9) (1 − )W u C p sat o o H = t − (9) sat (1 − )W K aC p sat c o And W , which is adsorbate amount in equilibrium with sat the fluid (mg/g) can be calculated as: ads W = sat (10) To check the validity of the obtained results, the K a val- Fig. 1 Breakthrough curves for irreversible adsorption ues determined from the experimental data were used to simulate the breakthrough curves using Matlab2010a soft- If the diffusion in the pores control the rate of adsorption, ware. Simulations were limited to C/Co ≈ 0.5, as the con- the breakthrough curve has an opposed form to that of the sidered margin is enough to contain the breakthrough point corresponding to the control of the external film. The break - under all the experimental conditions. The disposal limits of through curve is S-shaped when both internal and external Ni (II) and Cr (VI) according to Cuban Norm NC 27-12 are resistance are significant, as shown in dashed line. 2.0 and 0.5 mg/L, respectively. Calculation of the unused bed surface Statistical analysis of the data Calculation of the unused bed surface is a method to evalu- ate the adsorption capacity of biosorbents in continuous flow- A statistical analysis was performed using the software Stat- packed columns. graphics Centurion-X 15.2.06 to compare the simulated Hence, for a full bed length (H), the length of unused bed and experimental data. R squared coefficient, standard devia- (H ) is: tion and F tests were calculated to determine the reliability UNB of the data calculated by mathematical models compared to H = 1 − (7) experimental data. UNB where t represents the saturation time of the biosorbent in min. Small values of this parameter mean that the break- Results and discussion through curve is close to an ideal step with negligible mass- transfer resistance. Then, minimum H quantities are UNB The breakthrough curves for adsorption of Cr (VI) and Ni desirable in optimized operational conditions. (II) were determined experimentally in a packed column It is important to set the breakthrough point considering the with sugarcane bagasse. All the experiments were performed concentration according to the limit fixed by environmental at 25 °C. standards that sets discharge concentration limits for heavy Figure  2 shows the plot of the mean data from three metal ions, or other process conditions. experiments for each operation conditions. Table 1 shows characteristic parameters of the removal Breakthrough curve simulation of Cr (VI) and Ni (II). It is observed that the best operat- ing conditions for the removal of Cr (VI) are C = 15 mg/L Simulation is a modern technique that uses mathematical mod- and m = 1.5 g, while for the Ni (II) are C = 25  mg/L and els to predict the behavior of a system. o m = 1.5 g, with a removal percentage of 94.70 and 97.90%, To predict the breakthrough point in biosorption systems, respectively. The maximum retention capacities of natural Eq. (8) can be applied (McCabe et al. 1993). sugarcane bagasse were similar to that reported by Karna 1 3 Applied Water Science (2018) 8:55 Page 5 of 8 55 (2013). However, Mishra et al. (2016), who studied biosorp- this work. They found that a higher adsorbate concentration tion process of Ni and Cr with Hydrilla verticillata, found a gave a higher driving force for biosorption process. higher removal percentage for chromium than for nickel (96 On the other hand, Manikandan et  al. (2016) studied and 92%, respectively) which is in contrast with the obtained Cr (VI) adsoption by waste litchi peels. They found that results. when inlet concentration increased, the breakthrough time Sharma and Singh (2013) observed that the percentage Ni decreased which is in accordance with the results obtained absorbed by rice straw increased with increasing inlet con- in this work. centration, which is in accordance with the results found in 0255075100 125150 175200 020406080 100 120 140 160 180 200 Time (min) Time (min) (a) (b) 6 10 3 5 0 0 04080 120 160 200 240 280 320 0306090120 150180 210 Time (min) Time (min) (c)(d) Fig. 2 Breakthrough curves of Cr (VI) and Ni (II) on natural (filled circle) represents the breakpoint in each case. The data plot- sugar cane bagasse at different experimental conditions: a Co ted represent the mean of three experimental runs for each operating (Cr) = 10  mg/L and m = 1.5  g; b Co (Cr) = 15  mg/L and m = 1.5  g; c condition Co (Ni) = 15 mg/L and m = 1.5 g; d Co (Ni) = 25 mg/L and m = 1.5 g. Table 1 Characteristic Metal C (mg/L) m (g) t (min) V (ml) m (g) m (g) % removal o b ef total ads parameters of the removal of Cr (VI) and Ni (II) in fixed bed Cr(VI) 10 1.5 5 10 0.1 0.096 96.00 columns filled with sugarcane 15 1.5 35 70 1.05 1.020 97.50 bagasse Ni (II) 15 1.5 130 260 3.90 3.750 96.20 25 1.5 70 140 3.50 3.430 97.90 Table 2 Mass transfer −1 Metal C (mg/L) H (cm) Ka (min ) N H (cm) W (mg/g) o c UNB sat parameters for the dynamic runs Cr(VI) 10 20 0.302 2.10 19.44 1.07 15 20 0.437 3.62 17.62 1.99 Ni (II) 15 20 0.587 2.65 11.61 3.43 25 20 0.644 4.46 12.22 3.58 1 3 Concentration (mg/L) Concentration (mg/L) Concentration (mg/L) Concentration (mg/L) 55 Page 6 of 8 Applied Water Science (2018) 8:55 The mass transfer parameters were estimated from the of the results obtained in the simulation compared to the breakthrough data of Cr (VI) and Ni (II) in solutions and are experimental ones. Table 3 shows the obtained results. enlisted in Table 2. It is observed that the Cr (VI) and Ni (II) It is clear that the breakthrough curves presented good increase significantly the parameters with increasing initial agreement with the experimental data (R is always above concentration of the solution, indicating that the biosorption 0.94). In addition, the F tests demonstrated that in all the process was fast and very favorable. cases there was no significant difference between the simu- This process was considered as irreversible adsorp- lated data and the experimental data because the significance tion because the mass transfer rate was proportional to level was always bigger than 0.05. the initial concentration of the fluid. As a result, it could Other authors like Chao et  al. (2014) and Chen et  al. be concluded that initial metal concentration influenced (2012) applied other mathematical models like Thomas significantly the driving force that governs all process of model and Yoon–Nelson models, obtaining good agreement mass transfer. between experimental and predicted results (R values above In the biosorption of Cr (VI), the height of unused bed 0.90). In future works, different models could be applied to (H ) varied with operating conditions in the column. experimental data obtained for sugarcane bagasse to deter- UNB However, this behavior is less marked in the removal of Ni mine which of the models give the best fitting. (II). The plot of N(τ−1) versus C/C for the biosorption of Cr (VI) and Ni (II) on natural sugar cane bagasse showed that Conclusions the rate-controlling step of the process was the external film, which proved that the biosorption of these metals were irre- It can be concluded that the use of sugarcane bagasse for versible. Figure 3 shows the behavior described above and Cr (VI) and Ni (II) removal from wastewater is suitable as explained in Sect. “Calculation of the unused bed surface” the metal retention values obtained in this work were high. corresponding to different operation conditions. Hence, it can be considered as a low-cost and efficient alter - Figure 4 shows the simulated curves using the model that native for the removal of those metals. Results showed that include the calculated values of K a. metal retention was higher when inlet metal concentrations A statistical analysis was carried out using the software were 15 and 25 mg/L for chromium and nickel, respectively. Statgraphics Centurion-X 15.2.06 to check the reliability 1.0 1.0 0.8 0.8 0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0 -3.0 -2.0 -1.0 0.01.0 -3.0 -2.0 -1.0 0.01.0 N(τ-1) N(τ-1) (a) (b) 1.0 1.0 0.8 0.8 0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0 -3.0 -2.0 -1.0 0.01.0 -3.0 -2.0 -1.0 0.01.0 N(τ-1) N(τ-1) (c) (d) Fig. 3 Breakthrough curves for irreversible adsorption of Cr (VI) and Ni (II) natural sugar cane bagasse at different experimental conditions: a Co (Cr) = 10 mg/L and m = 1.5 g; b Co (Cr) = 15 mg/L and m = 1.5 g; c Co (Ni) = 15 mg/L and m = 1.5 g; d Co (Ni) = 25 mg/L and m = 1.5 g 1 3 C/Co C/Co C/Co C/Co Applied Water Science (2018) 8:55 Page 7 of 8 55 0.5 0.5 0.4 0.4 0.3 0.3 0.2 0.2 0.1 0.1 0.0 0.0 020406080100 020406080100 120 Time (min) Time (min) (b) (a) 0.5 0.5 0.4 0.4 0.3 0.3 0.2 0.2 0.1 0.1 0.0 0.0 050100 150 200 020406080100 120 Time (min) Time (min) (c) (d) Fig. 4 Breakthrough curves of Cr (VI) and Ni (II) on natural (Cr) = 15  mg/L and m = 1.5  g; c Co (Ni) = 15  mg/L and m = 1.5  g; d sugar cane bagasse experimental (o) and simulates (-) at different Co (Ni) = 25  mg/L and m = 1.5  g. Filled circle represents the break- experimental conditions: a Co (Cr) = 10  mg/L and m = 1.5  g; b Co point in each case Future work will focus on the study of the use of sug- arcane bagasse for the removal from wastewater of other Table 3 Statistical analysis carried out to check the reliability of the heavy metals or other kind of contaminants such as emer- results obtained in the simulation gent pollutants. Metal C (mg/L) R Standard devia- F tests tion Acknowledgement The authors thank the Central University “Marta Abreu” of Las Villas, Cuba, for providing the means to carry out this Cr(VI) 10 0.98 0.157 0.985 work. 15 0.94 0.150 0.427 Open Access This article is distributed under the terms of the Crea- Ni (II) 15 0.99 0.127 0.826 tive Commons Attribution 4.0 International License (http://creat iveco 25 0.98 0.145 0.782 mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- tion, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. Values of mass transfer coefficients were reported for References the removal of Cr (VI) and Ni (II) with sugarcane bagasse as biosorbent. Through the estimation of the mass transfer Babu BV, Gupta S (2004) Modeling and Simulation for Dynamics of parameters, it was possible to establish that the biosorp- Packed Bed Adsorption. In: Proceedings of International Sym- tion of Cr (VI) and Ni (II) by sugarcane bagasse was fast posium and 57th Annual Session of IIChE in association with AIChE (CHEMCON-2004), Mumbai and irreversible. The controlling stage was mainly gov- Bajpai J, Shrivastava R, Bajpai AK (2004) Dynamic and equilibrium erned by the resistance in the external film. The K a val- studies on adsorption of Cr (VI) ions onto binary bio-polymeric ues determined from the experimental data were used to beads of cross linked alginate and gelatin. Colloid Surf A simulate the breakthrough curves. The statistical analysis 236:81–90 Bajpai J, Shrivastava R, Bajpai AK (2007) Binary biopolymeric beads of experimental and theoretical data showed no significant of alginate and gelatin as potential adsorbent for removal of toxic differences between both data. 1 3 C/Co C/Co C/Co C/Co 55 Page 8 of 8 Applied Water Science (2018) 8:55 Ni2+ ions: a dynamic and equilibrium study. J Appl Polym Sci Manikandan NA, Alemu AK, Goswami L, Pakshirajan K, Pugaz- 103:2581–2590 henthi G (2016) Waste litchi peels for Cr (VI) removal from Bautista L, Martinez M, Aracil J (2003) Adsorption of ALPHA-amyl- synthetic wastewater in batch and continuous systems: sorben ase in a fixed bed: operating efficiency and kinetic modeling. characterization, regeneration and reuse study. J Environ Eng AIChE J 49:2631–2641 142(9):C4016001 Bermúdez YG, Rico ILR, Bermúdez OG, Guibal E (2011) Nickel Martín-Lara MA, Iáñez-Rodríguez I, Blázquez G, Quesada L, Pérez biosorption using Gracilaria caudata and Sargassum muticum. A, Calero M (2017) Kinetics of termal decomposition of some Chem Eng J 166:122–131 biomasses in an inert environment. An investigation of the Bhatti HN, Zaman Q, Kausar A, Noreen S, Iqbal M (2016) Efficient effect of lead loaded by biosorption. Waste Manag. https ://doi. remedation of Zr (IV) using citrus peel waste biomass: kinetic, org/10.1016/j.wasma n.2017.09.021 equilibrium and thermodynamic studies. Ecol Eng 95:216–228 McCabe WL, Smith JC, Harriott P (1993) Unit operations of chemical Borba CE, Guirardello R, Silva EA, Veit MT, Tavares CRG (2006) engineering, 5th edn. McGraw-Hill, New Delhi Removal of Ni (II) ions from aqueous solution by biosorption in Mishra A, Tripathi BD, Rai AK (2016) Packed-bed column biosorption a fixed bed column: experimental and theoretical breakthrough of Cr (VI) and Ni (II) onto fenton modified Hydrilla verticillata curves. Biochem Eng J 30:184–191 dried biomass. Ecotoxicol Environ Saf 132:420–428 Castro C, Herrero R, Vicente MES (2004) Gibbs–Donnan and spe- Mushtaq M, Bhatti N, Iqbal M, Noreen S (2016) Eriobotrya japonica cific-ion interaction theory descriptions of the effect of ionic seed biocomposite efficiency for copper adsorption: isoterms, strength on proton dissociation of alginic acid. J Electroanal Chem kinetics, thermodynamic and desorption studies. J Environ Manag 564:223–230 176:21–33 Chao H-P, Chang C-C, Nieva A (2014) Biosorption of heavy metals on Nadeem R, Manzoor Q, Iqbal M, Nisar J (2016) Biosorption of Pb (II) Citrus maxima peel, passion fruit shell, and sugarcane bagasse in onto immobilized and native Mangifera indica waste biomass. J a fixed-bed column. J Ind Eng Chem 20:3408–3414 Ind Eng Chem 35:185–194 Chen S, Yue Q, Gao B, Li Q, Xu X, Fu K (2012) Adsorption of hexa- Plazinski W, Rudzinski W (2010) A novel two-resistance model for valent chromium from aqueous solution by modified corn stalk: a description of the adsorption kinetics onto porous particles. Lang- fixed-bed column study. Bioresour Technol 113:114–120 muir 26:802–808 Dizge N, Keskinler B, Barlas H (2009) Sorption of Ni(II) ions from Rashid A, Bhatti HN, Iqbal M, Noreen S (2016) Fungal biomass com- aqueous solution by Lewatit cation-exchange resin. J Hazard posite with bentonite efficiency for nickel and zinc adsorption: a Mater 167:915–926 mechanistic study. Ecol Eng 91:459–471 Escudero C, Poch J, Villaescusa I (2013) Modelling of breakthrough Sharma R, Singh B (2013) Removal of Ni (II) ions from aqueous solu- curves of single and binary mixtures of Cu (II), Cd (II), Ni (II) and tions using modified rice straw in a fixed bed column. Bioresour Pb (II) sorption onto grape stalks waste. Chem Eng J 217:129–138 Technol 146:519–524 Gu T, Iyer G, Cheng KSC (2013) Parameter estimation and rate model Sulaymon AH, Yousif SA, Al-Faize MM (2014) Competitive biosorp- simulation of partial breakthrough of bovine serum albumin on a tion of lead mercury chromium and arsenic ions onto activated column packed with large Q Sepharose anion-exchange particles. sludge in fixed bed adsorber. J Taiwan Inst Chem E 45:325–337 Sep Purif Technol 116:319–326 Tahir N, Bhatti HN, Iqbal M, Noreen S (2017) Biopolymers composites Gupta S, Babu BV (2009) Modeling, simulation, and experimental with peanut hull waste biomass and application for crystal violet validation for continuous Cr (VI) removal from aqueous solutions adsorption. Int J Biol Macromol 94:210–220 using sawdust as an adsorbent. Bioresour Technol 100:5633–5640 Tan HKS, Spinner IH (1994) Multicomponent ion exchange column Guzman J, Saucedo I, Revilla J, Navarro R, Guibal E (2003) Copper dynamics. Can J Chem Eng 72:330–341 sorption by chitosan in the presence of citrate ions: influence of Tchounwou PB, Yedjou CG, Patlolla AK, Sutton DJ (2012) Heavy metal speciation on sorption mechanism and uptake capacities. metals toxicity and the environment. EXS 101:133–164 Int J Biol Macromol 33:57–65 Treybal RE (1993) Mass transfer operations, 2nd edn. McGraw-Hill, Hatzikioseyian A, Tsezos M, Mavituna F (2001) Application of simpli- New Delhi fied rapid equilibrium models in simulating experimental break - Vicente IA (2011) Tecnología sostenible para la obtención de un through curves from fixed bed biosorption reactors. Hydrometal- biosorbente de metales pesados a partir del bagazo de caña de lurgy 59:395–406 azúcar. PhD Thesis, Universidad Central “Marta Abreu” de Las Iqbal M (2016) Vicia faba bioassay for environmental toxicity monitor- Villas, Santa Clara ing: a review. Chemosphere 144:785–802 Yang J, Volesky B (1996) Intraparticle diffusivity of Cd ions in a new Karna NK (2013) Modelación matemática del proceso de biosorción biosorbent material. J Chem Technol Biotechnol 66:355–364 +6 +2 de Cr y Ni : estudios en serie en columnas de lecho fijo con Bagazo de Caña de Azúcar. Trabajo de Diploma, Universidad Publisher’s Note Springer Nature remains neutral with regard to Central “Marta Abreu “de Las Villas, Santa Clara jurisdictional claims in published maps and institutional affiliations. Khalid NRA, Ahmad S, Kiani SN, Ahmed J (1998) Adsorption of cadmium from aqueous solutions on rice husk. Radiochim Acta 83:157–162 Ko DCK, Poter JF, Mckay G (2001) Film-pore diffusion model for the fixed bed sorption of copper and cadmium onto bone char. Water Res 36:3786–3886 1 3 http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Applied Water Science Springer Journals

Modeling the mass transfer in biosorption of Cr (VI) y Ni (II) by natural sugarcane bagasse

Free
8 pages
Loading next page...
 
/lp/springer_journal/modeling-the-mass-transfer-in-biosorption-of-cr-vi-y-ni-ii-by-natural-c2DtKytDjY
Publisher
Springer Berlin Heidelberg
Copyright
Copyright © 2018 by The Author(s)
Subject
Earth Sciences; Hydrogeology; Water Industry/Water Technologies; Industrial and Production Engineering; Waste Water Technology / Water Pollution Control / Water Management / Aquatic Pollution; Nanotechnology; Private International Law, International & Foreign Law, Comparative Law
ISSN
2190-5487
eISSN
2190-5495
D.O.I.
10.1007/s13201-018-0692-z
Publisher site
See Article on Publisher Site

Abstract

The Cr (VI) and Ni (II) ion biosorption process by natural sugarcane bagasse in a fixed bed column was investigated. The characteristic removal parameters such as retention capacity, removal percent and unused bed length were experimentally determined at different operating conditions. Overall mass transfer coefficient was investigated and reported for the stud - ied biosorption system. The breakthrough curves were simulated using Matlab2010a software to check the validity of the obtained overall mass transfer coefficients. Experimental data fitted well with predicted data ( R = 0.94). A statistical analysis was performed using the software Statgraphics Centurion-X 15.2.06 to compare the simulated and experimental data. No significant differences were observed between experimental and simulated data. The best operating conditions for Cr (VI) removal were 15 mg/L of inlet concentration and 1.5 g of biosorbent. For Ni (II) removal the best results were obtained with 25 mg/L of inlet concentration and 1.5 g of solid. The results obtained through the breakthrough curve showed high removal percentages (94.70 and 97.90% for chromium and nickel, respectively). Moreover, results indicated that sorption of these metals was irreversible and it was controlled by the mass transfer at the external film. Keywords Biosorbent · Heavy metals · Pollution · Wastewaters Nomenclature t Break-point time (min) V Effectiv e volume (ml) t Satur ated point time (min) ef s F V olumetric flow (mL/min) C Initial concentration (mg/L) t Time (min) C Concentr ation in the time to the exit of the column (mg/L) C Concentration of retained metal (mg/L) * M. Calero de Hoces m T otal amount of heavy metal sent to column (g) total mcaleroh@ugr.es m Total amount of heavy metal retained in column ads I. L. Rodríguez Rico (g) ivanl@uclv.edu.cu m Total mass of the adsorbate (g) R. J. Cabrera Carrazana u Superficial velocity of fluid (cm/min) rjcabrera@nauta.cu H Bed length (cm) N. Kumar Karna H Length of unused bed (cm) UNB n.karna@udt.cl H Longitude of saturated bed (cm) sat I. Iáñez-Rodríguez N Ov erall number of transfer units ireneir@ugr.es W Adsorbate amount in equilibrium with the fluid sat (mg/g) Central University “Marta Abreu” of Las Villas, Carretera a K Overall volumetric mass transfer coefficient Camajuaní Km 5 1/2, Santa Clara, Villa Clara, Cuba ca −1 (min ) Central University “Marta Abreu” of Las Villas, Calle Danielito entre Central y San Miguel, Santa Clara, Greek letters Villa Clara, Cuba τ Dimensionless time Technological Development Unit, University of Concepción, ε Bed porosity Concepción, Chile ρ Bulk density (g/L) Department of Chemical Engineering, University of Granada, ρ Particle density (g/L) 18071 Granada, Spain Vol.:(0123456789) 1 3 55 Page 2 of 8 Applied Water Science (2018) 8:55 the adsorption kinetics were studied through a mathemati- Introduction cal model that takes into account both the external and internal mass transfer resistances, nonideal plug flow Nowadays, pollution of wastewaters by heavy metals along the column, and the variation of fluid velocity along caused by anthropogenic activities is a problem to be the column. solved (Martín-Lara et al. 2017). Chromium and nickel are Tan and Spinner (1994), developed a more complete heavy metals that are considered as very dangerous pol- model for ionic exchange that includes the limitation of lutants in wastewaters because they are persistent as they total transference. This model can predict the breakthrough do not degrade to harmless compounds. They are toxic curves for any species removed by the biosorbent and elution substances known to cause multiple organ damage, even curves obtained during regeneration. However, the solution at low concentrations. Moreover, they are human carcino- of the model is extremely complex and the values of the gens and they cause long-term health problems in human mass transfer coefficients for all ionic species present in the population (Iqbal 2016; Tchounwou et al. 2012). system is required. Different technologies have been tested for heavy metal The values of these coefficients can be estimated or deter - removal from wastewater such as chemical precipita- mined by fitting the model to experimental data (Yang and tion, ion exchange, reverse osmosis, electro-flotation and Volesky 1996; Hatzikioseyian et al. 2001; Borba et al. 2006; bioremediation among others. These methodologies pre- Escudero et al. 2013; Gu et al. 2013; Sulaymon et al. 2014). sent some drawbacks like the production of toxic sludge, The main advantage of the model is that it can simulate and high energy and chemical requirements and low efficiency predict the performance of a column under various condi- (Mushtaq et al. 2016; Rashid et al. 2016). tions including different flow rates, feed compositions, col- Biosorption is an interesting alternative for metal umn size, bed porosities and ionic forms of the biosorbent. removal which overcomes the disadvantages of the afore- mentioned methods. It is low cost and it has a high effi- ciency and selectivity for particular contaminants. Moreo- Materials and methods ver, the use of chemicals is minimum and no sludge is generated. Furthermore, regeneration of the biosorbents Biosorbent and metal recovery are possible (Bhatti et al. 2016). Many agricultural and forestry waste materials have been tested Sugar cane bagasse samples were collected from the Sugar for biosorption such as rice husk, pine bark, sawdust, pea- Power Station located in the Central University “Marta nut and orange peels among others (Nadeem et al. 2016; Abreu” of Las Villas, in Santa Clara, Cuba. The bagasse Tahir et al. 2017). was sieved in a sieve machine Model MLW with a group of Use of adsorption systems for industrial and municipal sieves (Tyler Series). The fraction between 0.5 and 1 mm wastewater treatment has become more prevalent during was selected. the recent years (Babu and Gupta 2004). An adsorption process is often used at the end of a treatment sequence Preparation of standards and reagents for pollution control as high degree of purification can be achieved. Adsorption is an important step in indus- Preparations of Cr (VI) and Ni (II) solutions was carried trial downstream processing. It is important to stop the out using analytical grade reagents. Potassium dichromate adsorption stage before the adsorbent is saturated which (K Cr O ) and nickel sulfate (II) hexahydrate (NiSO ·6H O) requires a thorough understanding of adsorption character- 2 2 7 4 2 ACS 99% supplied by J. T. Baker were used for preparing istics (Bautista et al. 2003). At industrial scale, the break- the synthetic wastewater. through time of the operation must be determined through Solutions were prepared by diluting the analytical rea- an economic and, eventually, environmental evaluation of gents with distilled water to desired concentrations. The the process. solutions of nickel were prepared at concentrations of 15 The adsorption kinetics can be described by various and 25 mg/L. Chromium solutions were prepared at a con- models depending upon the mechanism of transport (pore centration of 10 and 15 mg/L. diffusion, solid diffusion, and both mechanisms in parallel) The pH of the solution is a key parameter for the evalu- assumed inside the particles or in the external film (Bajpai ation of biosorption performance, specifically in the metal et al. 2004, 2007; Dizge et al. 2009; Gupta and Babu 2009; speciation (Guzman et al. 2003). In the case of heavy metals, Plazinski and Rudzinski 2010). biosorption studied in this work, the speciation of the metals In the present study, the effect of various operating vari- is not changed with the pH (constant in the process), there- ables (bed height and inlet adsorbate concentration) on the fore, the main effect will be explained by the impact of this process of fixed-bed biosorption was studied. Furthermore, parameter on the functional groups of the biomass. It was 1 3 Applied Water Science (2018) 8:55 Page 3 of 8 55 studied that the most reactive groups (carboxylic groups) on – Effluent volume, V (mL), can be calculated using ef the biomass are generally found under charge point zero (pH Eq. (1): 6). (Vicente 2011; Bermúdez et al. 2011). V = F ∗ t ef b (1) Castro et al. 2004, reported that the pKa of carboxylic where F is the volumetric flow rate circulating through groups on alginate fraction in the biomass is generally found the column expressed in mL/min and t represents the between 2 and 4. total flow time in min. Then, the pH of the solution was adjusted by adding the – Total amount of metal which entered in the column, m total appropriate quantity of 0.1 M hydrochloric acid (HCl). The in mg, can be calculated as follows: initial pH of solutions was fixed at 2 and 5 for dichromate solutions and nickel sulfate, respectively. C × F × t o b m = (2) total Hydraulic tests and selection of the operation where C represents the metal inlet concentration in mL/ parameters o min. – Total amount or metal retained by the column, m in The column (diameter: 1 cm, height: 20 cm) was filled with ads mg, is represented by the area under the breakthrough natural sugar cane bagasse and water was circulated with the curve. It can be calculated by the following expression: purpose of determining the most appropriate flows for the t=t established operation conditions. Ko et al. (2001) suggested for the processes on the mac- m = C dt (3) ads R roscopic level, that if the flow rate increases, the residence t=0 time of the fluid in the bed decreases, resulting in a low use of the biosorption capacity of the bed. On the other hand, where C denoted the concentration of metal removal for the processes on the microscopic level, the change of the in mg/L. volumetric flow rate affects only the diffusion of the ions in the liquid film, but not the one in the bioadsorbent. Accord- Estimation of mass transfer parameters ing to this author, high volumetric flow rates result in small resistances in the liquid film and high values of the external The concentration in the fluid and the solid phase change with mass transfer coefficient. Based on these considerations, time as well as with position in a x fi ed bed. The transfer process the best flow allows a non-fragmenting stable bed and no is described by the overall volumetric mass transfer coefficient draining occurrence at the end of the operation. Besides, an (K a) obtained from a solute material balance in the column appropriate flow gives a proper drop pressure. As a result, considering irreversible isotherms (McCabe et al. 1993). the selected feed flow was of 2 mL/min. The selected bed u N height was six times the internal diameter of the column K a= (4) (Khalid et al. 1998; Treybal 1993). Once studied, the biosorption of Cr (VI) and Ni (II) using N is defined as: one fixed bed column, several models were applied to the experimental data of the breakthrough curves for carrying N( − 1) = 1 + ln (5) out the fitting and the determination of the mass transfer o parameters. The samples were collected every 5 min for the The parameter τ is defined as: first 100 min and then each 10 min, until the biosorbent was saturated. u C t − H o o The chromium and nickel concentrations were determined (6) (1 − )HW by atomic absorption spectrophotometry using Pye Unicam s sat SP9 PHILIPS Atomic Absorption Spectrophotometer, Chro- where H is the time to displace fluid from the bed voids mium Analytical Line: 357.9 nm and Nickel Analytical Line: 232.0 nm to calculate the metal removal percent in a column. (normally negligible); u C t is the total solute fed to a unit o o cross-section of bed up to time t; and  (1 − )HW is the s sat Data analysis capacity of the bed, or the amount of the solute exchanged if the entire bed came to equilibrium with the feed. To analyze the dynamic Cr (VI) and Ni (II) removal in up- The solid line in Fig. 1 represents the predicted break- flow fixed bed column, breakthrough curves were drawn and through curve (McCabe et al. 1993). The slope increased the data were evaluated with the following equations. with time and C/C becomes 1 for N(τ−1) = 1. 1 3 55 Page 4 of 8 Applied Water Science (2018) 8:55 −K a H − H C c sat ln = (8) C u o o The longitude of saturated bed (H ) it is the product of sat the speed of the mass transfer section for the time since the area begins to move and it can be calculated using Eq. (9) (1 − )W u C p sat o o H = t − (9) sat (1 − )W K aC p sat c o And W , which is adsorbate amount in equilibrium with sat the fluid (mg/g) can be calculated as: ads W = sat (10) To check the validity of the obtained results, the K a val- Fig. 1 Breakthrough curves for irreversible adsorption ues determined from the experimental data were used to simulate the breakthrough curves using Matlab2010a soft- If the diffusion in the pores control the rate of adsorption, ware. Simulations were limited to C/Co ≈ 0.5, as the con- the breakthrough curve has an opposed form to that of the sidered margin is enough to contain the breakthrough point corresponding to the control of the external film. The break - under all the experimental conditions. The disposal limits of through curve is S-shaped when both internal and external Ni (II) and Cr (VI) according to Cuban Norm NC 27-12 are resistance are significant, as shown in dashed line. 2.0 and 0.5 mg/L, respectively. Calculation of the unused bed surface Statistical analysis of the data Calculation of the unused bed surface is a method to evalu- ate the adsorption capacity of biosorbents in continuous flow- A statistical analysis was performed using the software Stat- packed columns. graphics Centurion-X 15.2.06 to compare the simulated Hence, for a full bed length (H), the length of unused bed and experimental data. R squared coefficient, standard devia- (H ) is: tion and F tests were calculated to determine the reliability UNB of the data calculated by mathematical models compared to H = 1 − (7) experimental data. UNB where t represents the saturation time of the biosorbent in min. Small values of this parameter mean that the break- Results and discussion through curve is close to an ideal step with negligible mass- transfer resistance. Then, minimum H quantities are UNB The breakthrough curves for adsorption of Cr (VI) and Ni desirable in optimized operational conditions. (II) were determined experimentally in a packed column It is important to set the breakthrough point considering the with sugarcane bagasse. All the experiments were performed concentration according to the limit fixed by environmental at 25 °C. standards that sets discharge concentration limits for heavy Figure  2 shows the plot of the mean data from three metal ions, or other process conditions. experiments for each operation conditions. Table 1 shows characteristic parameters of the removal Breakthrough curve simulation of Cr (VI) and Ni (II). It is observed that the best operat- ing conditions for the removal of Cr (VI) are C = 15 mg/L Simulation is a modern technique that uses mathematical mod- and m = 1.5 g, while for the Ni (II) are C = 25  mg/L and els to predict the behavior of a system. o m = 1.5 g, with a removal percentage of 94.70 and 97.90%, To predict the breakthrough point in biosorption systems, respectively. The maximum retention capacities of natural Eq. (8) can be applied (McCabe et al. 1993). sugarcane bagasse were similar to that reported by Karna 1 3 Applied Water Science (2018) 8:55 Page 5 of 8 55 (2013). However, Mishra et al. (2016), who studied biosorp- this work. They found that a higher adsorbate concentration tion process of Ni and Cr with Hydrilla verticillata, found a gave a higher driving force for biosorption process. higher removal percentage for chromium than for nickel (96 On the other hand, Manikandan et  al. (2016) studied and 92%, respectively) which is in contrast with the obtained Cr (VI) adsoption by waste litchi peels. They found that results. when inlet concentration increased, the breakthrough time Sharma and Singh (2013) observed that the percentage Ni decreased which is in accordance with the results obtained absorbed by rice straw increased with increasing inlet con- in this work. centration, which is in accordance with the results found in 0255075100 125150 175200 020406080 100 120 140 160 180 200 Time (min) Time (min) (a) (b) 6 10 3 5 0 0 04080 120 160 200 240 280 320 0306090120 150180 210 Time (min) Time (min) (c)(d) Fig. 2 Breakthrough curves of Cr (VI) and Ni (II) on natural (filled circle) represents the breakpoint in each case. The data plot- sugar cane bagasse at different experimental conditions: a Co ted represent the mean of three experimental runs for each operating (Cr) = 10  mg/L and m = 1.5  g; b Co (Cr) = 15  mg/L and m = 1.5  g; c condition Co (Ni) = 15 mg/L and m = 1.5 g; d Co (Ni) = 25 mg/L and m = 1.5 g. Table 1 Characteristic Metal C (mg/L) m (g) t (min) V (ml) m (g) m (g) % removal o b ef total ads parameters of the removal of Cr (VI) and Ni (II) in fixed bed Cr(VI) 10 1.5 5 10 0.1 0.096 96.00 columns filled with sugarcane 15 1.5 35 70 1.05 1.020 97.50 bagasse Ni (II) 15 1.5 130 260 3.90 3.750 96.20 25 1.5 70 140 3.50 3.430 97.90 Table 2 Mass transfer −1 Metal C (mg/L) H (cm) Ka (min ) N H (cm) W (mg/g) o c UNB sat parameters for the dynamic runs Cr(VI) 10 20 0.302 2.10 19.44 1.07 15 20 0.437 3.62 17.62 1.99 Ni (II) 15 20 0.587 2.65 11.61 3.43 25 20 0.644 4.46 12.22 3.58 1 3 Concentration (mg/L) Concentration (mg/L) Concentration (mg/L) Concentration (mg/L) 55 Page 6 of 8 Applied Water Science (2018) 8:55 The mass transfer parameters were estimated from the of the results obtained in the simulation compared to the breakthrough data of Cr (VI) and Ni (II) in solutions and are experimental ones. Table 3 shows the obtained results. enlisted in Table 2. It is observed that the Cr (VI) and Ni (II) It is clear that the breakthrough curves presented good increase significantly the parameters with increasing initial agreement with the experimental data (R is always above concentration of the solution, indicating that the biosorption 0.94). In addition, the F tests demonstrated that in all the process was fast and very favorable. cases there was no significant difference between the simu- This process was considered as irreversible adsorp- lated data and the experimental data because the significance tion because the mass transfer rate was proportional to level was always bigger than 0.05. the initial concentration of the fluid. As a result, it could Other authors like Chao et  al. (2014) and Chen et  al. be concluded that initial metal concentration influenced (2012) applied other mathematical models like Thomas significantly the driving force that governs all process of model and Yoon–Nelson models, obtaining good agreement mass transfer. between experimental and predicted results (R values above In the biosorption of Cr (VI), the height of unused bed 0.90). In future works, different models could be applied to (H ) varied with operating conditions in the column. experimental data obtained for sugarcane bagasse to deter- UNB However, this behavior is less marked in the removal of Ni mine which of the models give the best fitting. (II). The plot of N(τ−1) versus C/C for the biosorption of Cr (VI) and Ni (II) on natural sugar cane bagasse showed that Conclusions the rate-controlling step of the process was the external film, which proved that the biosorption of these metals were irre- It can be concluded that the use of sugarcane bagasse for versible. Figure 3 shows the behavior described above and Cr (VI) and Ni (II) removal from wastewater is suitable as explained in Sect. “Calculation of the unused bed surface” the metal retention values obtained in this work were high. corresponding to different operation conditions. Hence, it can be considered as a low-cost and efficient alter - Figure 4 shows the simulated curves using the model that native for the removal of those metals. Results showed that include the calculated values of K a. metal retention was higher when inlet metal concentrations A statistical analysis was carried out using the software were 15 and 25 mg/L for chromium and nickel, respectively. Statgraphics Centurion-X 15.2.06 to check the reliability 1.0 1.0 0.8 0.8 0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0 -3.0 -2.0 -1.0 0.01.0 -3.0 -2.0 -1.0 0.01.0 N(τ-1) N(τ-1) (a) (b) 1.0 1.0 0.8 0.8 0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0 -3.0 -2.0 -1.0 0.01.0 -3.0 -2.0 -1.0 0.01.0 N(τ-1) N(τ-1) (c) (d) Fig. 3 Breakthrough curves for irreversible adsorption of Cr (VI) and Ni (II) natural sugar cane bagasse at different experimental conditions: a Co (Cr) = 10 mg/L and m = 1.5 g; b Co (Cr) = 15 mg/L and m = 1.5 g; c Co (Ni) = 15 mg/L and m = 1.5 g; d Co (Ni) = 25 mg/L and m = 1.5 g 1 3 C/Co C/Co C/Co C/Co Applied Water Science (2018) 8:55 Page 7 of 8 55 0.5 0.5 0.4 0.4 0.3 0.3 0.2 0.2 0.1 0.1 0.0 0.0 020406080100 020406080100 120 Time (min) Time (min) (b) (a) 0.5 0.5 0.4 0.4 0.3 0.3 0.2 0.2 0.1 0.1 0.0 0.0 050100 150 200 020406080100 120 Time (min) Time (min) (c) (d) Fig. 4 Breakthrough curves of Cr (VI) and Ni (II) on natural (Cr) = 15  mg/L and m = 1.5  g; c Co (Ni) = 15  mg/L and m = 1.5  g; d sugar cane bagasse experimental (o) and simulates (-) at different Co (Ni) = 25  mg/L and m = 1.5  g. Filled circle represents the break- experimental conditions: a Co (Cr) = 10  mg/L and m = 1.5  g; b Co point in each case Future work will focus on the study of the use of sug- arcane bagasse for the removal from wastewater of other Table 3 Statistical analysis carried out to check the reliability of the heavy metals or other kind of contaminants such as emer- results obtained in the simulation gent pollutants. Metal C (mg/L) R Standard devia- F tests tion Acknowledgement The authors thank the Central University “Marta Abreu” of Las Villas, Cuba, for providing the means to carry out this Cr(VI) 10 0.98 0.157 0.985 work. 15 0.94 0.150 0.427 Open Access This article is distributed under the terms of the Crea- Ni (II) 15 0.99 0.127 0.826 tive Commons Attribution 4.0 International License (http://creat iveco 25 0.98 0.145 0.782 mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- tion, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. Values of mass transfer coefficients were reported for References the removal of Cr (VI) and Ni (II) with sugarcane bagasse as biosorbent. Through the estimation of the mass transfer Babu BV, Gupta S (2004) Modeling and Simulation for Dynamics of parameters, it was possible to establish that the biosorp- Packed Bed Adsorption. In: Proceedings of International Sym- tion of Cr (VI) and Ni (II) by sugarcane bagasse was fast posium and 57th Annual Session of IIChE in association with AIChE (CHEMCON-2004), Mumbai and irreversible. The controlling stage was mainly gov- Bajpai J, Shrivastava R, Bajpai AK (2004) Dynamic and equilibrium erned by the resistance in the external film. The K a val- studies on adsorption of Cr (VI) ions onto binary bio-polymeric ues determined from the experimental data were used to beads of cross linked alginate and gelatin. Colloid Surf A simulate the breakthrough curves. The statistical analysis 236:81–90 Bajpai J, Shrivastava R, Bajpai AK (2007) Binary biopolymeric beads of experimental and theoretical data showed no significant of alginate and gelatin as potential adsorbent for removal of toxic differences between both data. 1 3 C/Co C/Co C/Co C/Co 55 Page 8 of 8 Applied Water Science (2018) 8:55 Ni2+ ions: a dynamic and equilibrium study. J Appl Polym Sci Manikandan NA, Alemu AK, Goswami L, Pakshirajan K, Pugaz- 103:2581–2590 henthi G (2016) Waste litchi peels for Cr (VI) removal from Bautista L, Martinez M, Aracil J (2003) Adsorption of ALPHA-amyl- synthetic wastewater in batch and continuous systems: sorben ase in a fixed bed: operating efficiency and kinetic modeling. characterization, regeneration and reuse study. J Environ Eng AIChE J 49:2631–2641 142(9):C4016001 Bermúdez YG, Rico ILR, Bermúdez OG, Guibal E (2011) Nickel Martín-Lara MA, Iáñez-Rodríguez I, Blázquez G, Quesada L, Pérez biosorption using Gracilaria caudata and Sargassum muticum. A, Calero M (2017) Kinetics of termal decomposition of some Chem Eng J 166:122–131 biomasses in an inert environment. An investigation of the Bhatti HN, Zaman Q, Kausar A, Noreen S, Iqbal M (2016) Efficient effect of lead loaded by biosorption. Waste Manag. https ://doi. remedation of Zr (IV) using citrus peel waste biomass: kinetic, org/10.1016/j.wasma n.2017.09.021 equilibrium and thermodynamic studies. Ecol Eng 95:216–228 McCabe WL, Smith JC, Harriott P (1993) Unit operations of chemical Borba CE, Guirardello R, Silva EA, Veit MT, Tavares CRG (2006) engineering, 5th edn. McGraw-Hill, New Delhi Removal of Ni (II) ions from aqueous solution by biosorption in Mishra A, Tripathi BD, Rai AK (2016) Packed-bed column biosorption a fixed bed column: experimental and theoretical breakthrough of Cr (VI) and Ni (II) onto fenton modified Hydrilla verticillata curves. Biochem Eng J 30:184–191 dried biomass. Ecotoxicol Environ Saf 132:420–428 Castro C, Herrero R, Vicente MES (2004) Gibbs–Donnan and spe- Mushtaq M, Bhatti N, Iqbal M, Noreen S (2016) Eriobotrya japonica cific-ion interaction theory descriptions of the effect of ionic seed biocomposite efficiency for copper adsorption: isoterms, strength on proton dissociation of alginic acid. J Electroanal Chem kinetics, thermodynamic and desorption studies. J Environ Manag 564:223–230 176:21–33 Chao H-P, Chang C-C, Nieva A (2014) Biosorption of heavy metals on Nadeem R, Manzoor Q, Iqbal M, Nisar J (2016) Biosorption of Pb (II) Citrus maxima peel, passion fruit shell, and sugarcane bagasse in onto immobilized and native Mangifera indica waste biomass. J a fixed-bed column. J Ind Eng Chem 20:3408–3414 Ind Eng Chem 35:185–194 Chen S, Yue Q, Gao B, Li Q, Xu X, Fu K (2012) Adsorption of hexa- Plazinski W, Rudzinski W (2010) A novel two-resistance model for valent chromium from aqueous solution by modified corn stalk: a description of the adsorption kinetics onto porous particles. Lang- fixed-bed column study. Bioresour Technol 113:114–120 muir 26:802–808 Dizge N, Keskinler B, Barlas H (2009) Sorption of Ni(II) ions from Rashid A, Bhatti HN, Iqbal M, Noreen S (2016) Fungal biomass com- aqueous solution by Lewatit cation-exchange resin. J Hazard posite with bentonite efficiency for nickel and zinc adsorption: a Mater 167:915–926 mechanistic study. Ecol Eng 91:459–471 Escudero C, Poch J, Villaescusa I (2013) Modelling of breakthrough Sharma R, Singh B (2013) Removal of Ni (II) ions from aqueous solu- curves of single and binary mixtures of Cu (II), Cd (II), Ni (II) and tions using modified rice straw in a fixed bed column. Bioresour Pb (II) sorption onto grape stalks waste. Chem Eng J 217:129–138 Technol 146:519–524 Gu T, Iyer G, Cheng KSC (2013) Parameter estimation and rate model Sulaymon AH, Yousif SA, Al-Faize MM (2014) Competitive biosorp- simulation of partial breakthrough of bovine serum albumin on a tion of lead mercury chromium and arsenic ions onto activated column packed with large Q Sepharose anion-exchange particles. sludge in fixed bed adsorber. J Taiwan Inst Chem E 45:325–337 Sep Purif Technol 116:319–326 Tahir N, Bhatti HN, Iqbal M, Noreen S (2017) Biopolymers composites Gupta S, Babu BV (2009) Modeling, simulation, and experimental with peanut hull waste biomass and application for crystal violet validation for continuous Cr (VI) removal from aqueous solutions adsorption. Int J Biol Macromol 94:210–220 using sawdust as an adsorbent. Bioresour Technol 100:5633–5640 Tan HKS, Spinner IH (1994) Multicomponent ion exchange column Guzman J, Saucedo I, Revilla J, Navarro R, Guibal E (2003) Copper dynamics. Can J Chem Eng 72:330–341 sorption by chitosan in the presence of citrate ions: influence of Tchounwou PB, Yedjou CG, Patlolla AK, Sutton DJ (2012) Heavy metal speciation on sorption mechanism and uptake capacities. metals toxicity and the environment. EXS 101:133–164 Int J Biol Macromol 33:57–65 Treybal RE (1993) Mass transfer operations, 2nd edn. McGraw-Hill, Hatzikioseyian A, Tsezos M, Mavituna F (2001) Application of simpli- New Delhi fied rapid equilibrium models in simulating experimental break - Vicente IA (2011) Tecnología sostenible para la obtención de un through curves from fixed bed biosorption reactors. Hydrometal- biosorbente de metales pesados a partir del bagazo de caña de lurgy 59:395–406 azúcar. PhD Thesis, Universidad Central “Marta Abreu” de Las Iqbal M (2016) Vicia faba bioassay for environmental toxicity monitor- Villas, Santa Clara ing: a review. Chemosphere 144:785–802 Yang J, Volesky B (1996) Intraparticle diffusivity of Cd ions in a new Karna NK (2013) Modelación matemática del proceso de biosorción biosorbent material. J Chem Technol Biotechnol 66:355–364 +6 +2 de Cr y Ni : estudios en serie en columnas de lecho fijo con Bagazo de Caña de Azúcar. Trabajo de Diploma, Universidad Publisher’s Note Springer Nature remains neutral with regard to Central “Marta Abreu “de Las Villas, Santa Clara jurisdictional claims in published maps and institutional affiliations. Khalid NRA, Ahmad S, Kiani SN, Ahmed J (1998) Adsorption of cadmium from aqueous solutions on rice husk. Radiochim Acta 83:157–162 Ko DCK, Poter JF, Mckay G (2001) Film-pore diffusion model for the fixed bed sorption of copper and cadmium onto bone char. Water Res 36:3786–3886 1 3

Journal

Applied Water ScienceSpringer Journals

Published: Apr 4, 2018

References

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off