Removal of Copper Ions and Methylene Blue from Aqueous Solution

Article pubs.acs.org/IECR

Removal of Copper Ions and Methylene Blue from Aqueous Solution Using Chemically Modified Mixed Hardwoods Powder as a Biosorbent Yi-Zhuan Zhang, Yan-Qiao Jin,* Qiu-Feng Lü,* and Xian-Su Cheng College of Materials Science and Engineering, Fuzhou University, 2 Xueyuan Road, Fuzhou 350116, China ABSTRACT: Citric acid modified mixed hardwoods powder (CMH) was prepared as a biosorbent to remove copper ions and methylene blue (MB) from aqueous solution by batch techniques. FT-IR and XRD were used to characterize the biosorbent. The effects of initial pH value, biosorption temperature, contact time, and initial adsorbate concentration on the biosorption capacities and adsorptivity of Cu2+ and MB onto CMH were investigated. The results showed that CMH exhibited excellent biosorption characteristics for Cu2+ and MB. The maximal biosorption capacity of Cu2+ and MB onto CMH was 165.0 and 237.4 mg/g at 20 °C, respectively. The biosorption kinetics studies indicated that Cu2+ and MB biosorption followed the pseudo-second-order model. The biosorption may be controlled by external intraparticle diffusion mass transfer during the whole biosorption process. Furthermore, the biosorption-equilibrium can be well described by Langmuir and Freundlich isotherm models.

1. INTRODUCTION Wastewater from industries contains pathogenic microorganisms, dyes, suspended particles, and heavy metal ions.1−3 Dyes and heavy metal ions are considered some of the most toxic water pollutants, causing environmental pollution and biological problems to human health and other life forms.4−6 Therefore, the removal of dyes and heavy metal ions from wastewater has been a challenging task in environmental industries. Conventional methods for removal of metals and dyes include chemical precipitation, chemical oxidation7 or ion exchange, reverse osmosis, electrochemical treatment, filtration, evaporation recovery, and membrane technologies.8−12 These methods have some significant disadvantages, such as insufficient metal and dye removal, high energy requirements, high cost, and generation of toxic chemicals or other waste byproducts that require further disposal.13 Thus, developing appropriate low-cost and efficient technologies for effluent treatment is vital. Recently, activated carbon, which has large porous surface area, micropore character, and acidic functional groups, has been recognized as an attractive method to remove heavy metals and dyes from wastewater.14,15 Despite its prolific use in adsorption processes, its high cost and the difficulties associated with regeneration make it less economically available as an adsorbent. Taking these criteria into consideration, the search for a low cost and easily available adsorbent has led many researchers to seek more economical and efficient techniques to use agricultural wastes and industrial byproducts as adsorbents.7,16−20 Biomass wastes are abundant, low-cost, renewable, readily available materials;21 they contain hydroxyl, phenolic hydroxyl, carbonyl, carboxylic, and other functional groups that can bind heavy metals and dyes by physicochemical interactions.22 Complex processes such as ion exchange, complexation, and chelation are involved in heavy metals and dyes adsorbtion by biomass wastes.23 However, biosorption capacities of untreated biomass wastes are rather low. To enhance the biosorption capacity of biomass wastes, they need © 2014 American Chemical Society

to be modified or treated before use. Chemical modification has shown great promise in improving the adsorption capacity and adding value to the agricultural byproducts.24,25 Because the affinity of the carboxylic functional groups for metal ions and dyes is very high, incorporation of acidic groups onto the hydroxyl of polysaccharide matrix of cellulosic waste materials will increased binding with positively charged metal ions and dyes.15 Citric acid (CA) is a low-cost material that enriches carboxylic groups. Biomass wastes (such as soy, corn, and protein products) modified by CA have shown increased biosorption capabilities for metal ions and dyes.26,27 Mixed hardwoods (MH) is an abundant byproduct of the forestry and paper industry, and it is either used as solid fuel for cooking or abandoned directly. It contains various organic compounds (lignin, cellulose, hemicelluloses, ash, and pectin) with polyphenolic, hydroxyl, and carboxyl functional groups that might be useful for binding ions and dyes. The immobilization of citric acid on MH will introduce more surface adsorptive sites (mainly carboxylic functional groups from citric acid) into MH, and change the nature of MH from hydrophobic to hydrophilic, which facilitates the access of copper ions and MB to surface adsorption sites. The objective of the present work is to prepare a new environmentally friendly and low-cost biosorbent, CMH, i.e., mixed hardwoods powder modified by using citric acid. Then, CMH was used to remove Cu2+ ions and methylene blue (MB) from an aqueous solution by static biosorption in the batch method. Optimal biosorption conditions were investigated as a function of CMH concentration, initial pH value, biosorption temperature, contact time, and initial concentration. The pseudo-first-order and pseudo-second-order kinetic models, Langmuir and Freundlich isotherm models were used to Received: Revised: Accepted: Published: 4247

July 24, 2013 February 22, 2014 February 26, 2014 February 26, 2014 dx.doi.org/10.1021/ie402370d | Ind. Eng. Chem. Res. 2014, 53, 4247−4253

Industrial & Engineering Chemistry Research

Article

Cu2+ ions and MB in working solutions were measured using a Varian Cary50 Conc spectrometer at a λmax of 805 and 665 nm, respectively. Standard calibration curves, fitted by the Beer− Lambert’s law, were prepared from Cu2+ ions or MB solutions with different concentrations that yielded absorbance ranging from 0.1 to 1. The above experiments were repeated several times. The biosorption capacity and adsorptivity were calculated by eqs 1 and 2, respectively:

analyze the biosorption processes of metal ions and MB onto CMH.

2. EXPERIMENTS 2.1. Materials. The mixed hardwoods powder (MH) was obtained from a paper mill in Hangzhou, Zhejiang Province, China. It is mainly composed of hemicellulose (15.7%), lignin (35.6%), cellulose (35.5%), ash and pectin (13.2% totally). Cellulose contains a large number of hydroxyl groups, and lignin contains carboxylic and phenolic groups; these function groups have strong interactions with metal ions and dyes. The immobilization of citric acid on MH will introduce carboxylic functional groups into the cellulose of MH. So maybe cellulose plays the most important role in biosorption processes of Cu2+ ions and MB onto CMH, lignin plays the second role, and hemicelluloses are less potent. Ash and pectin have few active groups, so they have no effect on the adsorption process. Mixed hardwoods powder was dried in an oven at 60 °C for 24 h, and then ground and screened to get a geometrical size of 120 mesh. Citric acid (CA), copper nitrate, methylene blue trihydrate, and other reagents were purchased from Sinopharm Chemical Reagent Co., Ltd., and used without further treatment. 2.2. Preparation of CMH. Twenty g of mixed hardwoods powder was pretreated with a 0.1 mol/L NaOH aqueous solution at room temperature, followed by washing with a large amount of distilled water to remove excess NaOH. The pretreated mixed hardwoods powder was mixed with CA (0.6 mol/L, 0.2 L) for 1 h at room temperature. The supernatant of the mixture was discarded and the remainder was dried at 50 °C overnight; thermo-chemical esterification was then carried out at 120 °C for 3 h. The esterified mixed hardwoods powder was washed with hot distilled water repeatedly until no turbidity was observed when 0.1 mol/L lead nitrate was added. The esterified mixed hardwoods powder was filtered and suspended in 0.1 mol/L NaOH aqueous solution for 2 h, and then washed with distilled water to remove the excess sodium hydroxide. Finally, the product was dried in an oven at 60 °C for 24 h, and then ground and screened through a sieve of 120 mesh. The resulting product was labeled as CMH. 2.3. Characterization. The characteristic functional groups on the surface of biosorbents were analyzed by a Nicolet 5700 FTIR spectrophotometer in KBr pellets. Wide angle X-ray diffraction patterns of samples were obtained using an Ultima III X-ray model diffractometer (Rigaku, Japan) with Cu Kα radiation at a scanning rate of 10°/min in a reflection mode over a 2θ range from 5° to 80°. Morphology was characterized using a Hitachi S-3000N scanning electron microscopy (SEM), and determination of the Brauner−Emmett−Teller (BET) surface area of the samples was carried out by physical adsorption of N2 at 77 K on a Micromeritics ASAP 2020 apparatus (Norcross, GA). The MH and CMH were degassed at 120 °C for 8 h under vacuum prior to measurement. 2.4. Biosorption Experiments. The biosorption tests were conducted by a series of batch experiments in single system using 25-mL conical flasks at a certain temperature. To explore the optimal experimental conditions, the batch studies were performed for biosorbent concentrations, initial pH value, biosorption temperatures, contact time, and different initial adsorbate concentrations. The pH value of the solution was adjusted with 0.1 mol/L HNO3 or 0.1 mol/L NaOH solutions. The mixed liquor was filtered through a 0.1-μm membrane filter paper to collect the supernatant. The concentrations of

Q = [(C0 − C)V ]/m

(1)

q = [(C0 − C)/C0] × 100%

(2)

where Q (mg/g) is the amount adsorbed per gram of adsorbent, q is the adsorptivity (%), C0 (mg/L) is the initial concentration, and C (mg/L) is the adsorbate concentration after biosorption. V (mL) is the volume of the adsorbate solution, and m (g) is the amount of biosorbent. 2.5. Model Fitting. The pseudo-first-order and pseudosecond-order kinetic models were applied for the mathematical description of the biosorption kinetic data using eqs 3 and 4, respectively:16 ln(Q e − Q t) = ln Q e − k1t

(3)

t /Q t = 1/(k 2Q e 2) + t /Q e

(4)

where k1 and k2 represent the pseudo-first-order rate constant (min−1) and the pseudo-second-order kinetic rate constant [g/ (mg min)], respectively. Qe is the biosorption capacity at equilibrium, and Qt is the biosorption capacity (mg/g) at any time. Herein, the initial biosorption rate v0 [mg/(g min)] is calculated as v0 = k2Qe2. Langmuir and Freundlich isotherm equations were applied to quantify the sorption equilibrium, as listed in eqs 5 and 6:28 Ce/Q e = Ce/Q m + 1/(KLQ m)

(5)

ln Q e = ln KF + (1/n)ln Ce

(6)

where Ce (mg/L) is the equilibrium concentration, Qe (mg/g) is the biosorption capacity, and Qm (mg/g) and KL (mL/mg) are saturated biosorption capacity and biosorption energy constants obtained by Langmuir model, respectively. KF and 1/ n are Freundlich constants related to biosorption capacity and biosorption intensity of the biosorbent, respectively.

3. RESULTS AND DISCUSSION 3.1. Characterization of Biosorbent. 3.1.1. FT-IR spectra. FTIR spectra serve as a useful tool to identify the presence of functional groups on the surface of biosorbents. FT-IR spectra of MH and CMH are shown in Figure 1a. The absorption peak at 3338 cm−1 is attributed to O−H and N−H hybrid stretching vibration of hydroxyl groups. The absorption peak at 2925 cm−1 is assigned to C−H stretching vibration of either methyl or methylene groups.29 The absorption peaks at 1593−1507 cm−1 are ascribed to CC vibration absorption peak of the benzene ring. The absorption peaks at 1000−1200 cm−1 correspond to characteristic main skeleton cellulose peak. The absorption peaks at 1462 and 1421 cm−1 are ascribed to C−H deformation vibration of lignin and carbohydrates. Compared with the FTIR spectrum of mixed hardwoods powder, the spectra of CMH typically exhibited a peak at 1736 cm−1, corresponding to characteristic stretching vibration 4248

dx.doi.org/10.1021/ie402370d | Ind. Eng. Chem. Res. 2014, 53, 4247−4253


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Figure 1. FT-IR spectra (a) and X-ray diffractograms (b) of CMH and MH.

adsorption band of carboxyl groups. This confirms the esterification between hydroxy of cellulose in mixed hardwoods powder and CA.30 3.1.2. X-ray Diffraction. X-ray diffraction was used to investigate patterns of CMH and MH. It can be seen from Figure 1b that sharp diffraction peaks corresponding to crystallinity of CMH cannot be observed. There are two diffraction peaks of cellulose I, at 2θ 17 and 22, which identified the amorphous form of CMH as compared with the X-ray diffraction of MH. The changes in the XRD pattern also may be due to the removal of impurities during the washing using NaOH. Besides, partial removal of lignin also may be one of the reasons for the increase of crystallinity of the MH. The amorphous form of CMH could provide more adsorption sites which are in favor of the penetration of adsorbates into the surface of CMH. 3.1.2. Pore Structure Characterization and Morphology. The BET surface areas of MH and CMH were 1.59 and 0.87 m2/g, respectively. The nitrogen adsorption−desorption isotherms of MH and CMH are demonstrated in Figure 2a and b. Clearly, the isotherms of MH and CMH exhibited typical type-II adsorption−desorption isotherms, indicating that MH and CMH are almost nonporous. Figure 2c, d, e, and f presents the SEM images of MH and CMH. It shows that MH has a wrinkled structure with some small cavities and particles on the surface. Comparison of these images presents that the citric acid modification does not significantly change the morphology of MH. However, the surface of CMH is more smooth, which shows that the cavities are clogged by the adsorbed citric acid molecules and particles were rinsed after modification.15 This also explains the reduction in the BET surface area of CMH as compared with that of MH. The SEM images of MH and CMH also show that porosities of CMH were very low. This result is consistent with the nitrogen adsorption−desorption isotherms and BET surface area. The low porosity clearly indicated that biosorption was dominated by chemical process rather than by physical adsorption. 3.2. Effect of Biosorbent Concentration. The biosorption capacity (Q) and adsorptivity (q) of Cu2+ ions and MB onto CMH and MH with the CMH and MH concentration ranging from 0.24 to 4 g/L are shown in Figure 3. It is observed that the adsorptivity of MB and Cu2+ increases with increasing biosorbent concentrations, whereas the biosorption capacity decreases. This can be explained by the fact that the surface per unit mass of biosorbents exposed to adsorbates decreases as the amount of biosorbents is decreased. The initial higher biosorption capacity can be due to increased

Figure 2. (a, b) Nitrogen adsorption−desorption isotherms and (c−f) SEM images of MH and CMH.

Figure 3. Effect of biosorbent concentrations on the biosorption capacity (Q) and adsorptivity (q) of Cu2+ (other conditions: pH = 4.8, C0 = 640 mg/L, t = 4 h, T = 20 °C) and MB (other conditions: pH = 6.0, C0 = 200 mg/L, t = 4 h, T = 20 °C) onto CMH and MH.

surface area and the availability of more active biosorption sites.31,32 Apparently, CMH shows higher Cu2+ and MB removal capability than raw materials because CMH has more adsorption sites on its surface after modification, which confirms that the introduction of the hydroxyl and carboxyl functional groups into MH indeed enhance the adsorption of CMH for Cu2+ and MB. To obtain higher adsorptivity, the concentration of CMH was fixed at 2 g/L for MB and 4 g/L for Cu2+, respectively, in the following experiments. 3.2. Effect of Initial pH Value. The effect of the initial solution pH value on the biosorption of Cu2+ ions and MB on CMH is illustrated in Figure 4. It is found that the maximum biosorption capacities are achieved for Cu2+ and MB at pH 4.8 and 5.0, respectively. The Cu2+ biosorption capacity increases with increasing initial solution pH from 1.5 to 4.8, and then decreases significantly with the increase in pH, whereas the biosorption capacity of MB increases sharply with increasing 4249



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indicating an exothermic process of the biosorption.36 This may be due to the damage of active binding sites of the CMH surface available for biosorption at high temperatures, so the interaction between adsorbates (Cu2+ ions and MB) and active groups (hydroxyl and carboxyl groups) of the biosorbent is lower.37 However, the influence of temperature is to a limited extent and only in a certain temperature range, which indicates that the biosorption of CMH for MB was not dominated by physical adsorption and ion exchange is one of the mechanisms in the biosorption process.37 Clearly, low solution temperature is advantageous to the enhancement of biosorption capacity of Cu2+ and MB. 3.6. Effect of Contact Time and Biosorption Kinetics. The tendency of biosorption capacities and adsorptivity of Cu2+ and MB versus contact time is illustrated in Figure 6, which

Figure 4. Biosorption of Cu2+ and MB onto CMH and MH at different initial pH values.

the pH value from 1.0 to 5.0, and then keeps nearly constant from 5.0 to 10.0. Above pH 5.0, MB biosorption was favored. In other words, the CMH surface has a negative charge for all pH from 5.0 to 10.0. The reason might be attributed to the fact that the pH change in the solution resulted in the change in the surface charge of CMH. At lower pH, the concentration of H+ in sorption solution is higher,7 which competes with Cu2+ ions or MB for surface active sites, leading to low removal of Cu2+ ions and MB. For CMH, its functional groups are −OH and COO− (pKa from the interval of 3.5−4.0).33 At pH < 3.5, nonionic form of carboxyl group (i.e., −COOH) was presented, resulting in a low biosorption capacity of CMH. This is because the electrostatic interaction between the carboxyl groups and adsorbates was inhibited. With increasing pH, the negative charge density on the adsorbent surface increases due to the weakened protonation of carboxyl and hydroxyl groups and thus greatly improves the Cu2+ ions and MB biosorption. The increase in biosorption with the decrease of H + ion concentration (high pH) indicates that ion exchange is one major adsorption process for Cu2+ ions biosorption.34 When pH > 5, a part of Cu2+ ions exist as Cu(OH)+, Cu(OH)2, and Cu(OH)3− (precipitation), which present a larger size in solution and would not be adsorbed easily.35 Therefore, the Cu2+ ions binding should take place when pH value is between the pKa of deprotonation of the groups on CMH surface and metal precipitation. For MB, there is no significant change when pH is higher than 5.0. The surface of CMH in contact with water is negatively charged. Dissolved Cu2+ ions and MB are positively charged and will undergo attraction on approaching the anionic CMH surface. Therefore, Cu2+ and MB have a strong biosorption affinity for CMH. 3.3. Effect of Biosorption Temperature. Figure 5 presents the effect of biosorption temperature on the biosorption of Cu2+ ions and MB. It is found that the biosorption capacities of Cu2+ ions and MB onto CMH decrease with increasing temperature in the range of 15−40 °C,

Figure 6. Effect of contact time on biosorption capacity and adsorptivity of Cu2+ ions and MB onto CMH.

shows that the equilibrium of both Cu2+ and MB is reached very quickly. The adsorbed amount of CMH for Cu2+ and MB increased sharply with increasing contact time before 50 min, and then becomes slower with the increase of contact time until equilibrium is achieved. This behavior may be due to the availability of an initially large number of vacant surface active sites on the surface of CMH and ions interacts rapidly,29 thus the amount of Cu2+ or MB accumulated on the CMH surface rapidly at the initial stage. With the contact time prolonging, filling of vacant sites becomes difficult due to repulsive forces between adsorbate adsorbed on CMH surface and adsorbate in solution.38 Two steps biosorption characteristics suggest that the biosorption may be due to the heterogeneity of the surface binding sites on biosorbents. For Cu2+, the biosorption equilibrium can be achieved when the contact time is about 1 h, faster than MB adsorption (about 3 h). The difference in diffusion processes of Cu2+ and MB may be due to the difference of molecular size of adsorbates. MB is an organic compound with a larger molecular size and takes more time to diffuse into the active sites of biosorbent. To investigate the mechanism of Cu2+ and MB sorption onto CMH, pseudo-first-order and pseudo-second-order models (Table 1) were used. It is also found that the calculated values of Qe (Cu2+ 116.7 mg/g, MB 105.0 mg/g) obtained from the pseudo-second-order model agreed better with the experimental Qe values (Cu2+ 111.0 mg/g, MB 99.60 mg/g). Moreover, the pseudo-second-order kinetic model provides much better correlation coefficients (R2) values and lower standard deviation (S2) than that of the pseudo-first-order kinetic model. So, the pseudo-second-order model is more suitable for predicting the kinetic process for Cu2+ and MB biosorption. This result is in accordance with the findings of many researchers.31,39,40 As the pseudo-second-order equation is successfully used to describe the adsorption kinetics based on

Figure 5. Biosorption of Cu2+ and MB on CMH at different temperature. 4250



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Table 1. Pseudo-First-Order and Pseudo-Second-Order Kinetic Parameters for Cu2+ and MB Biosorption onto CMH pseudo-first-order model

pseudo-second-order model

adsorbate

k1 (min−1)

R2

Qe (mg/g)

S2

v0 (mg/(g min))

R2

Qe (mg/g)

S2

Cu2+ MB

0.04881 0.02983

0.9301 0.8240

51.30 38.32

0.006015 0.0029

19.83 105.0

0.9800 0.9992

116.7 105.0

0.002939 0.001446

To investigate the biosorption isotherm, Langmuir and Freundlich sorption models are used. The parameters for Langmuir and Freundlich isotherms are presented in Table 2. It is observed that the Langmuir model is better fit for Cu2+ and MB biosorption process from values of R2 and S2. The biosorption of MB was found to be higher than Cu2+ ions, indicating more affinity of MB for CMH compared with Cu2+ ions. The maximum adsorption binding capacities obtained from Langmuir model for Cu2+ and MB are 168.6 mg/g and 238.7 mg/g, respectively. These results also show that the CMH has stronger ability to bind MB than Cu2+ ions. In addition, the obtained values of 1/n between 0 and 1 indicate good sorption of Cu2+ and MB on CMH. The values of Qm of Cu2+ and MB sorption onto CMH in this study are higher compared with other materials (Table 3), resulting from the introduction of carboxylic functional groups on CA into CMH.

the assumption that the rate-control step is a chemical sorption, indicating that the biosorption behavior of Cu2+ and MB onto CMH is a chemisorption process, especially an ion exchange process.41 The initial biosorption rate of MB is higher than that of Cu2+. It may be because MB has a better affinity for CMH than Cu2+, which was positively correlated with electronegative of metal ions. 3.7. Biosorption Isotherm. The results of biosorption isotherm experiments carried out at the initial Cu2+ ions concentrations from 64 to 6400 mg/L and MB concentrations from 1 to 800 mg/L are revealed in Figure 7. It indicates that

Table 3. Comparison of Maximum Adsorption Capacity of Different Biosorbents Toward Cu2+ and MB adsorbent

Qm (mg/g)

refs

7.05 40.96 8.6 19.22 124.21 62 39.17 60.16 108.8 165.0

34 26 41 22 31 24 40 44 39 In this study

131.6 60.66 72.13 39.47 95.4 217.498 143 237.4

27 34 45 46 47 48 49 In this study

Cu2+

Figure 7. Effect of initial concentrations on biosorption capacity and adsorptivity of Cu2+ ions and MB onto CMH.

wheat straw citric acid modified soybean straw titania beads KOH treated pine cone powder rose petals waste biomass chemically modified sugar cane bagasse citric acid modified wheat straw citric acid treated wood sawdust fungal biomass with grafted poly(acrylic acid) mixed hardwoods powder MB citric acid modified kenaf core fibers wheat straw peanut husk palm-trees waste palm kernel fiber alkaline-treated cypress cone chips citric acid treated algae mixed hardwoods powder

the biosorption capacities increase with increasing the initial concentrations, and then reach maximum biosorption capacities of 165.0 and 237.4 mg/g for Cu2+ and MB, respectively. However, increasing the initial concentration causes a decrease in adsorptivity. The reason is that increasing the adsorbate concentration causes a larger competition of the adsorbates to reach the limited surface active sites of biosorbent.42 During the biosorption process of adsorbate on biosorbent, the ions in background electrolyte can compete with the adsorbate biosorption on the outer biosorption sites, whereas it does not compete for the inner sites.43 When the amount of binding sites is constant, at low concentration of adsorbate, an excess proton competes with Cu2+ and MB, resulting in a low level of Cu2+ and MB biosorption, whereas the adsorptivity was high. For MB, the adsorptivity was up to 100% when the initial MB concentration was lower than 30 mg/g. For Cu2+, the adsorptivity was up to 96.5% when the concentration was 64 mg/L. Generally, the initial heavy metal ions concentration is very low in most wastewater, hence high metal ions removal capacity at low concentration is of great importance for the development of adsorbents.41 Therefore, CMH could be used as an effective biosorbent to remove Cu2+ and MB from wastewater at lower adsorbates concentration.

4. CONCLUSIONS Citric acid modified mixed hardwoods powder (CMH) was successfully prepared as a biosorbent to remove Cu2+ and MB from aqueous solution. CMH exhibited excellent biosorption ability for Cu2+ and MB. The maximal biosorption capacities

Table 2. Langmuir and Freundlich Isotherm Parameters for Cu2+ and MB Biosorption onto CMH Langmuir isotherm model adsorbate 2+

Cu MB

2

Qm (mg/g)

KL (L/mg)

R

168.6 238.7

0.007535 0.09610

0.9994 0.9983

Freundlich isotherm model S × 10 2

−4

1.141 0.9625 4251

KF (mg/g)(L/mg) 20.44 116.9

1/n

1/n

R2

S2

0.2752 0.1157

0.9943 0.9961

0.01328 0.004389



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were up to 165.0 and 237.4 mg/g for Cu2+ and MB, respectively. The obtained data showed that the biosorption of Cu2+ and MB can be well fitted by the pseudo-second-order, and the Langmuir and Freundlich models. As an industrial biomass waste, the raw material, MH, is very cheap, and can be easily chemical modified. Therefore, it can be effectively used to remove Cu2+ and MB from wastewater.

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AUTHOR INFORMATION

Corresponding Authors

*Tel: +86 591 22 866 532. Fax: +86 591 22 866 539. E-mail: [email protected]. Mail: College of Materials Science and Engineering, Fuzhou University, 2 Xueyuan Road, Fuzhou 350108, P.R.China *Tel: +86 591 22 866 532. Fax: +86 591 22 866 539. E-mail: [email protected]. Mail: College of Materials Science and Engineering, Fuzhou University, 2 Xueyuan Road, Fuzhou 350108, P.R.China. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This project was supported by the Foundation for Development of Science and Technology of Fuzhou University (2012XQ-1) and the Scientific Research Project of Fuzhou University.

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REFERENCES

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Removal of Copper Ions and Methylene Blue from Aqueous Solution

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