Biochemical Engineering Journal 105 (2016) 27–35

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Biochemical Engineering Journal

journal homepage: www.elsevier.com/locate/bej

Functionalized agricultural biomass as a low-cost adsorbent:

Utilization of rice straw incorporated with amine groups for the
adsorption of Cr(VI) and Ni(II) from single and binary systems
Yunhai Wu a,b,∗ , Yiang Fan b , Meili Zhang b , Zhu Ming b , Shengxin Yang b , Aynigar Arkin b ,
Peng Fang b
a
Key Laboratory of Integrated Regulation and Resources Development of Shallow Lakes, Ministry of Education, Hohai University, 1st Xikang Road, Nanjing
210098, China
b
College of Environment, Hohai University, 1st Xikang Road, Nanjing 210098, China

a r t i c l e i n f o a b s t r a c t

Article history: The adsorption of Cr(VI) and Ni(II) applying amine-functionalized modified rice straw (MRS) as an adsor-
Received 19 February 2015 bent in single and binary systems was investigated. The MRS was characterized by Fourier transform
Received in revised form 17 July 2015 infrared spectroscopy (FTIR), Thermo-gravimetric Analysis (TG), Brunauer–Emmett–Teller (BET) anal-
Accepted 30 August 2015
ysis, Scanning Electron Microscope (SEM) and the Energy Dispersive Spectrometer (EDS) analysis. The
Available online 1 September 2015
adsorption study was conducted systematically by varying adsorbent dosage, initial pH value, tempera-
ture and initial metal ion concentration. The results showed that the maximum adsorption capacity for
Keywords:
Cr(VI) was 15.82 mg/g with MRS dosage 10 g/L at pH 2.0, temperature 318 K and initial metal ion concen-
Modified rice straw
Binary systems
tration 200 mg/L, and 3.95 mg/g for Ni(II) at pH 7.0, temperature 318 K and initial metal ion concentration
Adsorption 80 mg/L with MRS dosage 10 g/L, respectively. The adsorption data were suitable for Langmuir isotherm
Waste treatment model better both in single and binary systems. The pseudo-second-order model could better describe
Kinetic parameters the adsorption process in single and binary systems. In binary systems, the existence of Ni(II) hindered
Environmental preservation the adsorption of Cr(VI) but the removal of Ni(II) was enhanced with the existence of Cr(VI) ions. Ther-
modynamic constant values (G0 < 0, H0 > 0, S0 > 0) illustrated that the adsorption of Cr(VI) and Ni(II)
onto MRS were spontaneous and endothermic.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction membrane filtration [9] and ion exchange [10–12]. Compared with
treatment methods listed above, adsorption is considered as an effi-
In recent years, with the rapid development of modern industry, cient method for the removal of heavy metals from wastewater
the discharge of metals such as nickel and chromium are ecological with several advantages like no chemical sludge, easy to operate
threats, even at low concentration [1–4]. Cr(VI) and Ni(II) ions are [13] and the process appears to be inexpensive [13–15].
widely used in leather tanning, electroplating, cement manufactur- Rice straw is comprised of cellulose, hemicellulose and lignin
ing and dye industries [5,6], the concentration of which can reach that can adsorb heavy metals in aqueous solutions validly [6]. Hence
hundreds of milligrams per liter in high-concentration electroplat- the adsorption of heavy metal ions with waste agricultural materi-
ing wastewater [5]. Therefore, environmental regulations require als could provide a novel treatment of both crop residues and heavy
the treatment of wastewater to remove and recover heavy metals metal pollution.
[7]. In several previous reports, many authors have documented
Various methods for heavy metal removal have been proposed, the use of rice straw for the adsorption of heavy metals [16–18].
demonstrated and applied, such as chemical precipitation [8], Whereas, a lot of previous researchers simply modified rice straw
by acid or alkali washing, which just improved the adsorption
capacity inconspicuously. The amine-functionalized modified rice
straw, however, with the incorporation of amine groups, showed
∗ Corresponding author at. Key Laboratory of Integrated Regulation and Resources the prominent ability in the removal of metal ions [19,20] due to
Development of Shallow Lakes, Ministry of Education, Hohai University, 1st Xikang the fact that amine groups are easily to be protonated in acid envi-
Road, Nanjing 210098, China. Fax: +86 25 83786697. ronment and the metal ions could be adsorbed onto the adsorbent
E-mail address: [email protected] (Y. Wu).

http://dx.doi.org/10.1016/j.bej.2015.08.017
1369-703X/© 2015 Elsevier B.V. All rights reserved.
28 Y. Wu et al. / Biochemical Engineering Journal 105 (2016) 27–35

Fig. 1. FTIR spectra of RS and MRS (A) and SEM photographs of RS (a, b) and MRS (c, d) (B).

by electrostatic and ion exchange [21,22], which could improve the (SEM). The kinetic and thermodynamic parameters were calculated
adsorption efficiency. Furthermore, industrial wastewater usually and the equilibrium data were fitted to some isotherm models to
contains several species of metals, and so the metallic sorption determine the adsorption mechanism.
behaviors become more intricate [23]. Thus, a sorption study for
multiple metals is realistic. 2. Materials and methods
The purpose of this work is to investigate the capabil-
ity of amine-functionalized modified rice straw (MRS) for the 2.1. Preparation of modified rice straw
removal of Cr(VI) and Ni(II) from single and binary component
systems. The adsorbent was characterized by Fourier trans- Rice straw (RS) was collected from a cultivated area in Jiangsu
form infrared spectra (FTIR), Thermo-gravimetric Analysis (TG), province, China. RS was washed with distilled water and then dried
Brunauer–Emmett–Teller (BET) and Scanning Electron Microscope for 24 h at 373 K. Next, the oven-dried rice straw was crushed,
 Y. Wu et al. / Biochemical Engineering Journal 105 (2016) 27–35 29

ground and then sieved to desired mesh size (150–250 ␮m) for use. (the molar concentration of Cr(VI) and Ni(II) were 1.154 mM and
Ten-gram pretreated RS fractions were firstly reacted with 10 mL 1.017 mM, respectively) and the molar concentration ratio of Cr(VI)
epichlorohydrin and 9 mL N,N-dimethylformamide in a three-neck and Ni(II) were 1.1:1. Cr(VI) – Ni(II) solution was mixed with 1.0 g
round bottom flask (250 mL). Then the mixture was stirred for 1 h at MRS, varying initial pH from 2.0 to 9.0. The process for testing and
373 K. Secondly, 3 mL diethylenetriamine was added and the slurry analyzing was the same as in the single component systems. The
was stirred for 1 h at 373 K. Thirdly, 9 mL triethylamine was added effect of competitive metal ions in binary systems was also tested.
into the flask with stirring for 2 h at 373 K. The product was washed
with deionized water and filtered. Then the wet rice straw was 2.4. Isotherm experiments
dried for 24 h at 373 K and stored in a desiccator. The dried prod-
uct MRS would be used as the adsorbent in the following sorption In single component systems, isotherm experiments were con-
experiments. ducted by mixing 1 g adsorbent with 100 mL solutions, the initial
concentration of Cr(VI) was in the range 40–200 mg/L and Ni(II)
2.2. Characterization of RS and MRS ranged from 10 to 80 mg/L. Adjust the initial pH at 2.0 for Cr(VI)
and 7.0 for Ni(II). The isotherms were obtained using different tem-
Molecular structure and chemical properties of MRS before perature (298 K, 308 K and 318 K). In binary component systems,
and after the amine functionalization were studied by FTIR, TG, 100 mL solution containing Cr(VI) (100 mg/L), Ni(II) (10–80 mg/L)
BET and SEM. FTIR analysis with KBr discs containing the ground and another 100 mL solution containing Ni(II) (60 mg/L), Cr(VI)
sample was performed in an FTIR spectrometer (Spectrum 100, (40–200 mg/L) were prepared. Solutions were mixed with the MRS
PerkinElmer Corporation, America). The spectra were recorded (1.0 g) in two conical flasks and shaken at 308 K for 1 h and 5 h
in the region of 400–4000 cm−1 . A Thermo-gravimetric analyzer respectively to reach equilibrium and then the solutions were fil-
(Diamond TG/DTA6300, PerkinElmer Corporation, America) was tered and analyzed.
employed to investigate the mass loss of the adsorbent and the
velocity of the reaction. The samples were placed into the fur- 2.5. Adsorption kinetics study
nace and heated at a rate of 10 K/min within the temperature
range from room temperature (298 K) to 873 K, under nitrogen For the kinetics experiments, 1 g adsorbent were mixed with
as purge and protective gas [24,25]. The BET specific surface area 100 mL solution, the initial concentrations of Cr(VI) are 40 mg/L,
analyzer (MICROMERITICS, ASAP 2010, America) was used to ana- 100 mg/L and 200 mg/L. And the initial concentrations of Ni(II) are
lyze the specific surface area of RS and MRS. In order to observe 40 mg/L, 60 mg/L and 80 mg/L. Samples were withdrawn at the
the microstructure of MRS, the sample was examined by FE-SEM required intervals. In binary systems, on the one hand, 100 mL solu-
(S4800, Carl Zeiss AG, Germany). tion containing 100 mg/L Cr(VI) with the concentration of Ni(II)
range from 40 mg/L to 80 mg/L was prepared; on the other hand,
2.3. Adsorption experiments another 100 mL solution was provided with Ni(II) (60 mg/L) and
Cr(VI) (40–200 mg/L).
2.3.1. Adsorption in single component systems
Adsorption experiments in single systems were conducted by 2.6. Adsorption thermodynamics study
many researchers and the adsorption method is well known. The
adsorption method of this study consult some previous research The experiments were conducted by mixing 1 g adsorbent with
[26–28]. The dosage of MRS increased from 0.2 g to 1.4 g and batch 100 mL of solutions. The initial concentration of Cr(VI) was 40 mg/L,
experiments were carried out in conical flasks by agitating 1.0 g 100 mg/L and 200 mg/L, the concentration of Ni(II) was 40 mg/L,
adsorbent with 100 mL Cr(VI) or Ni(II) solutions (the concentration 60 mg/L and 80 mg/L, respectively. The thermodynamic parameters
of metal ions were both 60 mg/L). A series of experiments were were tested at different temperatures (298 K, 303 K, 308 K, 313 K
conducted by varying initial pH (2.0–9.0), within the temperature and 318 K).
range from 298 K to 318 K and different metal ion concentrations
(40–200 mg/L for Cr(VI) and 10–80 mg/L for Ni(II)) in order to inves- 3. Results and discussion
tigate the factors which influence the adsorption performance.
After adsorption, the mixture of adsorbent and solution was sep- 3.1. Characterization of the MRS
arated by centrifugation and the supernatant was analyzed by a
UV-spectrophotometer (UV1201 model). The MRS which adsorbed The FTIR spectra was applied to observe the changes of
Cr(VI) was analyzed at the wavelength of 540 nm and the MRS functional groups on the surface of RS before and after amine mod-
which adsorbed Ni(II) was analyzed at the wavelength of 530 nm, ification from the peaks of the Fig. 1. As shown in Fig. 1A, the
respectively. observed peak at 3415 cm−1 is related to the stretching vibration of
The removal efficiency and adsorption capacity (qe ) were calcu- O H groups. The spectrum of MRS in Fig. 1A shows that the peaks
lated from the following equations: at 1643, 1371 and 782 cm−1 are all corresponding to stretching and
Co − Ce bending vibration of N H groups [29,30]. As expected the −NH2
Removal(%) = × 100 (1) groups existed on the surface of RS, indicating that amine groups
Co
were grafted on the RS successfully.
(Co − Ce ) · V As shown in Fig. 1B, the SEM images of RS (Fig. 1B (a) and (b))
qe = (2)
M and MRS (Fig. 1B (c) and (d)) were under different magnifications. It
where Co (mg/L) and Ce (mg/L) are initial and equilibrium metal appears that after modification, the surface structure is smoother.
concentrations; V (mL) is the volume of solution and M (g) is the And small beads on RS are eliminated, which was ascribed to the
mass of MRS. reduction of most lignin, hemicellulose and other impurities.
The thermo-gravimetric analysis was shown in Fig. S1 (ESM),
2.3.2. Adsorption in binary component systems which indicated the weight loss of 29.39% and 40.55% for RS and
For adsorption of Cr(VI) and Ni(II) in binary systems, experi- MRS respectively in the temperature range from 473 to 623 K. The
ments were conducted with the mixture of Cr(VI) and Ni(II) ion weight losses of RS and MRS are related to physiabsorbed water
solutions. Both concentrations of two metal ions were 60 mg/L [31]. The maximum weight loss of the sample occurs at about 673 K
30 Y. Wu et al. / Biochemical Engineering Journal 105 (2016) 27–35

and the sample was carbonized with the temperature range from
773 K to 873 K. The higher weight loss of MRS confirmed that the
modification process eliminated large amounts of ash specifica-
tion and decreased the degree of crystallinity and polymerization
of fiber.
The BET surface area and pore size of RS and MRS was investi-
gated using N2 adsorption/desorption measurements at 77 K. The
pore size distribution of RS and MRS was demonstrated in Fig. S2
(ESM), which demonstrated that the BET surface area of RS and MRS
are 11.31 m2 /g and 5.52 m2 /g, respectively. The most probable pore
size of RS is 4.420 nm and 3.112 nm for MRS. The decrease of BET
specific surface area from RS to MRS can be attributed to the graft
of amino-groups. The most probable pore sizes of RS and MRS can
prove that the pores were blocked and pore size became narrow
when the amino-groups were grafted onto the rice straw surfaces.

3.2. Comparison of the adsorption of Cr(VI) and Ni(II) onto RS

and MRS

The removal percentage of Cr(VI) and Ni(II) onto RS and MRS

were compared and the results were depicted in Fig. S3 (ESM). The
concentration of Cr(VI) and Ni(II) were 60 mg/L, the dosage of RS
and MRS were both 1.0 g per 100 mL, the pH values of Cr(VI) and
Ni(II) were 7.0 and the temperature remained 303 K. As shown in
Fig. S3 (ESM), the RS have adsorption ability for Cr(VI) and Ni(II), the
removal percentage of Cr(VI) and Ni(II) is 25% and 22%, respectively.
As for MRS, the removal percentage of Cr(VI) and Ni(II) is 62% and
54%, respectively. The removal of Cr(VI) and Ni(II) onto MRS per-
form better than onto the RS due to the fact that the incorporation
of amine groups provides more binding sites compared with the RS
[32,33].

3.3. Effects of adsorption factors in single component systems

3.3.1. Effect of adsorbent dosage

After adsorption, the Energy Dispersive Spectrometer (EDS)
analysis was conducted and the energy spectra diagram was exhib-
ited in Fig. S4 (ESM), which demonstrated that Cr(VI) and Ni(II)
can be absorbed onto the MRS and the MRS can be regarded as
an effective adsorbent. The effect of adsorbent dosage on removal
percentage of Cr(VI) and Ni(II) was shown in Fig. 2A. The adsorp-
tion ratios of Cr(VI) and Ni(II) increased before the dosage reached
1.0 g per 100 mL solution, which was probably because of that the
adsorption sites and surface area increased with MRS dosage, the
percentage of removal is higher with higher adsorbent dosage. But
the concentration of metals is constant, the percentage of adsorp-
tion decreases when the adsorbent dosage exceeds 1.0 g, suggesting
that the saturation adsorption was reached and the optimum adsor-
bent dosage was selected as 1.0 g for other experiments.

3.3.2. Effect of initial pH

The adsorptive removal of adsorbates mainly depends on pH
values of solution that influences both the ionization degree and
surface property of the adsorbents [34]. Fig. 2B shows the effect of
Fig. 2. Effect of adsorbent dosage (A), initial pH (B) and temperature (C) on adsorp-
initial pH on removal of Cr(VI) and Ni(II). The maximum adsorption tion of Cr(VI) and Ni(II) onto MRS.
capacity of Cr(VI) (3.503 mg/g) onto MRS was observed at pH 2.0.
The curve decreased sharply when the pH values increased from
2.0 to 9.0. For Ni(II) adsorption, the curve increased with the initial
pH (2.0–7.0), but decreased slowly when the pH values were above Lower pH could lead the surface of adsorbent to be protonated to
7.0. So the maximum adsorption capacity of Ni(II) was 2.68 mg/g higher extent and the adsorption of Cr(VI) would be more effective.
at pH 7.0. In fact, the Cr(VI) in solution exists in the form of oxyan- As pH values rising, the process of protonation became weakened
ions such as HCrO4 − , CrO4 2− and Cr2 O7 2− . The dominant form of and the adsorption decreased. The result has shown that the MRS
Cr(VI) is HCrO4 − at lower pH (1.0–3.0). As the pH rises, the domi- could act as a wonderful adsorbent for adsorbing Cr(VI) at low pH
nant species of Cr(VI) are CrO4 2− , Cr2 O7 2− , etc [31,35,36]. According in real application. The mechanism of the adsorption of Cr(VI) onto
to Li et al. [31], −NH2 groups were protonated into –NH3 + in acid the MRS was revealed in Fig. 3. The main component of the MRS is
environment, which can easily adsorb negative ions like HCrO4 − . cellulose, so we regard cellulose as the MRS.
 Y. Wu et al. / Biochemical Engineering Journal 105 (2016) 27–35 31

Fig. 3. The mechanism of adsorption of Cr(VI) onto MRS and deprotonation of the MRS.

In terms of Ni(II), its existences in solution were different with ing force became higher as well, the accessibility of the heavy metal
different pH values [37], which indicated that the dominant species ions to the binding sites of the MRS is relatively high with increased
are Ni2+ below pH 7.5. When the pH value ranges from 10.0 to 12.0, initial concentration, the ions exchange frequently and the uptake
the dominant species is Ni(OH)2 . And the main existence of Ni(II) is of heavy metals becomes more and more [4,20,39,40].
Ni (OH) 3 − when the pH value exceeds 12.0. At low pH values, H+ in
solutions competed with Ni2+ for adsorption. When pH increased
3.4. Effects of adsorption in binary component systems
from 2.0 to 7.0, the concentration of H+ reduced, Ni2+ became pre-
dominant ions and was absorbed onto MRS prior to other ions.
3.4.1. Effect of initial pH
The main form of Ni(II) was Ni(OH)2 sediments while Ni2+ was
Fig. S6a (ESM) represents that in binary component systems,
hydrolyzed after pH 7.0, the adsorption decreased because of the
the removal efficiency of Cr(VI) is lower than that in single com-
lessening concentration of Ni(II).
ponent systems due to the restraint of Ni(II), which can be mainly
attributed to the limited active binding sites, Ni(II) competes with
3.3.3. Effect of temperature Cr(VI) by occupying adsorption sites on the surface of MRS, which
The amount of adsorption as a function of temperature was contributes to the decrease of Cr(VI) adsorption. When the pH value
shown in Fig. 2C. Results indicate that the amount of Cr(VI) adsorp- is 3.0, the distance between two kinds of curves enlarged, which
tion increase from 8.21 mg/g to 9.37 mg/g and Ni(II) from 2.34 mg/g infers that the inhibition effect became more conspicuous.
to 2.57 mg/g when the temperature are in the range of 298–318 K, Fig. S6b (ESM) shows that in binary component systems, the
which might be due to the accelerated diffusivity of metal ions removal efficiency of Ni(II) is higher than that in single component
from the external layer into the micro pores of the biochar with systems because the existence of Cr(VI) promotes the adsorption
the increasing temperature [38]. of Ni(II). According to previous studies, −NH2 was protonated to
–NH3 + , negative charged Cr(VI) ions such as Cr2 O7 2− were absorbed
largely onto the MRS, then the surface of MRS become negative
3.3.4. Effect of initial metal ion concentration
charged gradually. Owing to the attraction of positive and negative
As shown in Fig. S5, the uptake of metal ions onto the MRS with
ions, the adsorption of Ni(II) was enhanced [36,37,41].
respect to a range of Cr(VI) (Fig. S5a) and Ni(II) (Fig. S5b) ion concen-
trations at optimum initial pH (the pH value for Cr(VI) is 2.0 and 7.0
for Ni(II)) were studied. The adsorption capacity of Cr(VI) increased 3.4.2. Effect of Cr(VI) adsorption in the presence of Ni(II) onto
from 3.76 mg/g to 15.82 mg/g with the increasing initial Cr(VI) con- MRS
centration from 40 mg/L to 200 mg/L. And the uptake of Ni(II) ions The coinstantaneous adsorption of Cr(VI) and Ni(II) ions from
increased from 0.74 mg/g to 3.95 mg/g with initial Ni(II) concentra- mixed solution was conducted at pH 5.0 and temperature of 303 K.
tion ranging from 10 mg/L to 80 mg/L. Different concentrations of The Cr(VI) and Ni(II) concentrations were both 60 mg/L (1.154 mM
Cr(VI) and Ni(II) were selected due to the fact that the concentration for Cr(VI) and 1.017 mM for Ni(II)). The solution has 0.1154 mmol
of Cr(VI) and Ni(II) are various in industrial wastewater. Actually, Cr(VI) and 0.1017 mmol Ni(II), the numbers of Cr(VI) and Ni(II) ions
as the initial concentrations of Cr(VI) and Ni(II) increased, the driv- were almost equal in the mixed solution. The result was shown in
32 Y. Wu et al. / Biochemical Engineering Journal 105 (2016) 27–35

Cr(VI) preferentially, making the uptake of Ni(II) increase due to

the attraction existed between positive and negative charges [42].
This phenomenon demonstrated that the MRS could have great
adsorption effect in real industrial wastewater and the coexistence
of metals could change the efficiency of adsorption.

3.5. Adsorption isotherms in single and binary systems

When the adsorption is at the state of equilibrium, the results

were then fitted to the Langmuir [43] and Freundlich [44] isotherm
model. The Langmuir model is effective in monolayer adsorption on
surfaces and the Freundlich model is valid for non-ideal multilayer
adsorption. These two models can be expressed by the following
equation:

qm bCe
Langmuir : qe = (3)
1 + bCe
Ce
Freundlich : ln qe = ln + ln KF (4)
n
Fig. 4. Effect of Cr(VI) (60 mg/L) adsorption in the presence of Ni(II) (60 mg/L) onto
where qe (mg/g) is the amount of uptake at equilibrium time; qm
MRS.
(mg/g) is the maximum metal uptake of Langmuir isotherm; b is the
equilibrium coefficient, KF and n are constants related to adsorp-
tion.
As shown in Table 1, Figs. S7 and S8 (ESM), in single systems, the
data fitted to Langmuir and Freundlich models very well, the regres-
sion coefficients (R2 ) exceeded 0.90 for both two models, but the
Langmuir model can describe the adsorption process better with
higher R2 values, suggesting the adsorption of Cr(VI) and Ni(II) onto
MRS to be monolayer. The values of b in the Langmuir model sug-
gested whether the isotherm is unfavorable (b > 1), linear (b = 1),
favorable (0 < b < 1) or irreversible (b = 0) [45]. It can be seen from
the data that values of b were between 0 and 1 for Cr(VI) and Ni(II).
The parameters such as qm and b increased with the enhancement
of temperature, which indicated the adsorption of Cr(VI) and Ni(II)
was endothermic process.
Freundlich constant KF is related to temperature [43], value of
n is correlated with the favorability of adsorption. n > 1 indicates
favorable adsorption isotherm [46]. The results in Table 1 suggested
that KF increased as temperature increased, which indicated the
adsorption capability increased as well; values of n > 1 for Cr(VI)
Fig. 5. Effect of Ni(II) (60 mg/L) adsorption in the presence of Cr(VI) (60 mg/L) onto
MRS. and Ni(II) adsorption, which can be inferred that MRS has a nice
affinity for Cr(VI) and Ni(II) ions.
Fig. 4, indicating that the maximum amount of the uptake of Cr(VI) In binary systems, according to Figs. S9, S10 (ESM) and Table 2,
ions decreased from 7.23 mg/g to 5.85 mg/g when the Ni(II) ions the qm values of Cr(VI) were lower than those in single systems. But
were added into the solution. The adsorption of Ni(II) onto MRS has for Ni(II), the values of qm were higher than those in single systems.
the negative effect of Cr(VI) adsorption and inhibits the removal of The R2 of the Langmuir isotherm model were higher than those
Cr(VI) ions, which indicates that the binding affinity of Ni(II) on the of Freundlich isotherm model, which indicates the experimental
MRS may be higher than that of Cr(VI). data fitted to Langmuir isotherm model better, that is, the adsorbed
metal ions were on the active sites in the form of mono-molecules.
3.4.3. Effect of Ni(II) adsorption in the presence of Cr(VI) onto
MRS 3.6. Adsorption kinetic studies in single and binary systems
The simultaneous removal of Cr(VI) and Ni(II) ions from binary
component systems was investigated at 303 K and pH 5.0. The con- Kinetic data with different concentrations of Cr(VI) and
centrations of Ni(II) and Cr(VI) were both 60 mg/L, and the molar Ni(II) were investigated applying the pseudo-first-order [47] and
concentration for Cr(VI) and Ni(II) were 1.154 mM and 1.017 mM, pseudo-second-order [48] in order to determine the sorption effi-
respectively. The Cr(VI) ions numbers is almost the same as Ni(II) ciency of Cr(VI) and Ni(II). The pseudo-first-order model was
ions numbers in the solution. The result of adsorption of Ni(II) in the applied to depict the adsorption of liquid/solid system based on
absence and presence of Cr(VI) ions was presented in Fig. 5, indi- solid capacity [49], which can be expressed as follows:
cating that the maximum adsorption capability for Ni(II) increased
k1 t
from 2.94 mg/g to 3.42 mg/g with the presence of Cr(VI). There- ln(qe − qt ) = lnqe − (5)
2.303
fore, the existence of Cr(VI) ions promoted the adsorption of Ni(II).
According to previous literatures [31,37], Ni(II) presented as Ni2+ where qt (mg/g) are metal uptake at time t (min); K1 (min−1 ) is rate
ions and Cr(VI) existed as negatively charged at pH 5.0. In binary constant of pseudo-first-order equation.
component systems, the chemical bond between Cr(VI) and MRS The pseudo-second-order kinetic model was used for explain-
was stronger than that between Ni(II) and MRS. So MRS absorbed ing the adsorption mechanism of rate-controlling steps [50]. The
 Y. Wu et al. / Biochemical Engineering Journal 105 (2016) 27–35 33

Table 1
Langmuir and Freundlich adsorption parameters for Cr(VI) and Ni(II) adsorption in single systems.

Metal ions Isotherm parameters Temperature (K)

298 308 318

Cr(VI) Langmuir qm (mg/g) 21.8722 19.9956 21.3120

b (L/mg) 0.0401 0.0948 0.1311
R2 0.9401 0.9949 0.9685
Freundlich KF (mg/g) 1.9089 3.2915 4.1462
n 1.8999 2.3037 2.3771
R2 0.9762 0.9499 0.9085

Ni(II) Langmuir qm (mg/g) 6.1996 6.0723 6.2248

b (L/mg) 0.0364 0.0491 0.0540
R2 0.9981 0.9960 0.9954
Freundlich KF (mg/g) 0.4180 0.5563 0.6057
n 1.6771 1.8272 1.8395
R2 0.9837 0.9757 0.9891

Table 2
Binary adsorption isotherm model parameters for the removal of Cr(VI) and Ni(II).

Metal ions Langmuir Freundlich

2
qm (mg/g) b (L/mg) R KF (mg/g) n R2

Cr(VI) 18.6345 0.0760 0.9924 2.4692 2.0912 0.9553

Ni(II) 6.6606 0.0288 0.9822 0.3133 1.4952 0.9584

Table 3
Thermodynamic parameters for the removal of Cr(VI) and Ni(II).

Metalions Co H0 S0 G0 (kJ mol−1 )

−1 −1
(mg/L) (kJ mol ) (kJ mol K ) 298 K 303 K 308 K 313 K 318 K

Cr(VI) 40 13.252 0.065 −6.296 −6.628 −6.953 −7.281 −7.601

100 45.231 0.165 −3.969 −4.794 −5.620 −6.445 −7.271
200 22.217 0.083 −2.636 −3.053 −3.470 −3.887 −4.304

Ni(II) 40 9.813 0.036 −0.945 −1.125 −1.306 −1.486 −1.667

60 9.356 0.037 −1.521 −1.704 −1.886 −2.069 −2.251
80 8.198 0.028 −0.206 −0.347 −0.488 −0.629 −0.770

pseudo-second-order kinetic equation can be described in its lin- 3.7. Adsorption thermodynamic studies
earized form:
The thermodynamic parameters such as G0 , H0 and S0
t 1 1 can better describe the adsorption mechanism. The relationship of
= + t (6) them can be expressed as follows:
qt k2 q2e qe

G0 = H 0 − TS 0 (8)

h= k2 q2e (7)
G0 = −RT ln Ko (9)

where K2 (g mg−1 min−1 ) is the rate constant of pseudo-second- Cad

Ko = (10)
order adsorption; h (mg g−1 min−1 ) is initial reaction rate. Ce
As shown in Fig. 6A and B, pseudo-second-order gave an excel-
S 0 H 0
lent adaption to the data. The parameters of two models were ln Ko = − (11)
R RT
summarized in Table S1 (ESM) for single systems. Higher values
of R2 in pseudo-second-order showed better fitting results to the where G0 (kJ/mol) is adsorption free energy, H0 (kJ/mol) is
adsorption than the pseudo-first-order kinetic model. In single sys- adsorption enthalpy, S0 (kJ mol−1 K−1 ) is adsorption entropy; R
tems, when the initial Cr(VI) and Ni(II) concentrations were higher, (8.314J/(mol K)) is universal gas constant, T (K) is temperature, Ko
the adsorption capability at equilibrium became higher, which is equilibrium constant; Cad (mg/L) is reduction of the concentra-
coule be explained that the adsorption process of Cr(VI) and Ni(II) tion after adsorption. H0 and S0 were slope and intercept of the
were mostly controlled by chemisorption behavior [51,52]. linear relationship of ln Ko versus 1/T.
The experimental data were found to be well fitted to the The results of the adsorption of Cr(VI) and Ni(II) onto MRS were
pseudo-second-order model in binary systems. When the concen- calculated according to Eqs. (10) and (11). Fig. S11 (ESM) illustrates
tration of Cr(VI) was fixed, the parameter h in pseudo-second-order the linear relationship between 1/T and ln Ko and Table 3 shows the
decreased with the increasing concentration of Ni(II) ions. How- parameters of thermodynamics.
ever, h increased with the increase of Cr(VI) concentration when Results indicated that G0 were all negative at different temper-
the Ni(II) concentration was fixed. The calculated values of kinetic atures, its absolute values increased with the rise of temperature,
parameters were listed in Table S2 (ESM), which suggested that the which suggested that the adsorption of Cr(VI) and Ni(II) could
existence of Ni(II) inhibited the absorption of Cr(VI) ions, but the happen spontaneously. H0 stayed positive values all the time,
existence of Cr(VI) promoted the removal of Ni(II). indicating that the reaction was endothermic and G0 also main-
34 Y. Wu et al. / Biochemical Engineering Journal 105 (2016) 27–35

Fig. 6. Kinetic models for Cr(VI) (a) and Ni(II) (b) removal in different concentrations. (A): pseudo-first-order kinetic model; (B): pseudo-second-order kinetic mode.

tained positive values, which inferred that the adsorbent had good Appendix A. Supplementary data
affinity for Cr(VI) and Ni(II).
Supplementary data associated with this article can be found, in
4. Conclusion the online version, at http://dx.doi.org/10.1016/j.bej.2015.08.017.

The results of the adsorption investigation illustrated that the

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