Chemical Engineering Journal 242 (2014) 136–143

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Characterization and environmental applications of clay–biochar

composites
Ying Yao a,b, Bin Gao b,⇑, June Fang b, Ming Zhang b, Hao Chen b, Yanmei Zhou b,c, Anne Elise Creamer b,
Yining Sun b,d, Liuyan Yang d
a
School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, China
b
Department of Agricultural and Biological Engineering, University of Florida, Gainesville, FL 32611, United States
c
Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
d
School of the Environment, Nanjing University, Nanjing 210046, China

h i g h l i g h t s

 A clay–biochar composite material has been successfully developed.

 Clay particles dramatically increase biochars’ adsorption ability.
 Clay–biochar composites could be recycled and reused after dye adsorption.

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

Article history: A novel engineered biochar with clay particles distributed on carbon surfaces within the biochar matrix
Received 4 November 2013 has been successfully developed as a low-cost adsorbent for environmental applications. Three biomass
Received in revised form 18 December 2013 feedstocks were pretreated with montmorillonite or kaolinite suspensions and then pyrolyzed at 600 °C
Accepted 20 December 2013
for 1 h in a N2 environment. Physicochemical characterizations including microscopy and X-ray analyses
Available online 2 January 2014
confirmed clay particles were present on the surface of biochar during the annealing process. Laboratory
adsorption experiments indicated that the presence of clay particles on carbon surfaces had dramatically
Keywords:
increased (about 5 times) the biochars’ adsorption ability to methylene blue (MB). In addition, the clay–
Engineered carbon
Biochar
biochar composites could be recycled and reused after dye adsorption with a stable capacity of around
Methylene blue 7.90 mg g1. The experimental results also showed that the sorption of MB on the clay–biochar compos-
Clay ites is mainly controlled by the ion exchange (with clay) and electrostatic attraction (with biochar) mech-
Montmorillonite anisms. Findings from this work indicate that engineered biochar, prepared from two low-cost materials
Kaolinite (clay and biochar), is a valuable adsorbent for removing contaminants from aqueous solutions.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction In recent years, clay minerals have been widely applied in agri-
culture, in industrial engineering, and in the discovery, recovery,
Biochar, pyrogenic carbon produced from agricultural and for- and refining of petroleum. A few of the important physical and
est residues, has received much attention recently because of its chemical properties that make clay minerals valuable include par-
potential application as a soil amendment as well as a carbon fixer ticle size, surface chemistry, particle shape, and surface area [14].
to benefit the environment. When it is amended into soils, biochar Due to their lamellar structure, high surface area, and high ion ex-
may improve soil fertility, enhance agricultural productivity, in- change capacity, clay minerals have great potential to fix various
crease soil nutrients and water holding capacity, and reduce emis- pollutants, such as heavy metals, dyes, and organic compounds
sions of other greenhouse gases [1–4]. Recent studies also suggest [15,16]. Montmorillonite and kaolinite are among the most studied
that biochar can be used as an alternative low-cost sorbent to re- clays that can potentially be used as low-cost adsorbents. Mont-
move various contaminants from water [4–9]. In addition, several morillonite with expandable-layered silicates consists of two tetra-
engineering methods have been developed to modify biochar and hedral and one octahedral unit forming a platelet approximately
enhance its sorption ability to various contaminants in aqueous 10 Å thick [17]. One important property is that the layers are neg-
solutions [10–13]. atively charged; the charge is normally balanced by hydrated cat-
ions placed in the interlayer spaces [15]. Kaolinite is also a layered
⇑ Corresponding author. Tel.: +1 (352) 392 1864x285. silicate mineral with one tetrahedral sheet linked through oxygen
E-mail address: bg55@ufl.edu (B. Gao). atoms to one octahedral sheet of alumina octahedral. The exchange

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.12.062
 Y. Yao et al. / Chemical Engineering Journal 242 (2014) 136–143 137

sites of kaolinite are located on the surface and it has no interlayer with the same pyrolysis conditions. All the biochar samples were
exchange sites [18]. Both montmorillonite and kaolinite have washed with DI water several times to remove impurities, oven
relatively high cation exchange capacity (CEC), have good dried, and sealed in a container for further testing. The resulting
adsorption properties, and can effectively remove some inorganic clay-modified and pristine biochar samples were henceforth
and organic pollutants from aqueous solutions [19,20]. Neverthe- referred to as BB-MMT, BG-MMT, HC-MMT, BB-KLN, BG-KLN,
less, because montmorillonite and kaolinite are very fine HC-KLN, BB, BG, HC, respectively.
particles (i.e., colloids/nanoparticles), they are unsuitable as
fixed-bed media or flocculation additives in water treatment 2.2. Characterizations
facilities.
Engineering methods, such as surface modification, have been The N2 surface areas of the engineered biochar were obtained
used to create biochar-based materials, particularly biochar-based using NOVA 1200 surface area analyzer. C, H, and N analyses were
composites with enhanced functions for environmental applica- conducted using a CHN Elemental Analyzer (Carlo-Erba NA-1500)
tions [21–23]. In these composites, the biochar serves as a good via high-temperature catalyzed combustion followed by infrared
porous structure to support and host the distribution of the nano- detection of the resulting CO2, H2 and NO2 gases, respectively.
particles within its matrix. This characteristic can be exploited for Major elements of biochars were determined by acid digestion of
the development of a new type of engineered biochar with clay the samples followed by inductively-coupled plasma atomic emis-
particles distributed within the biochar matrix to take advantage sion spectroscopy (ICP-AES) analysis. Biochar oxygen contents
of the recent development of the biochar technology and the good were determined by a mass balance assuming the total weight of
sorption ability of clay particles. To our knowledge, however, none all measured elements sum up to 1. Scanning electron microscope
of the previous studies have attempted to combine the advantages (SEM) imaging analysis of the biochars was conducted using a JEOL
of two low-cost materials (biochar and clay) into new engineered JSM-6400 Scanning Microscope. Surface elemental analysis was
materials with enhanced value and functions. also conducted simultaneously with the SEM at the same surface
The overarching objective of this work was to develop a simple locations using energy dispersive X-ray spectroscopy (EDX, Oxford
method to prepare clay–biochar composites for environmental Instruments Link ISIS). X-ray diffraction (XRD) analysis was carried
applications. Various engineered biochars were made in laboratory out using a computer-controlled X-ray diffractometer (Philips Elec-
from plant biomass (i.e., bamboo, bagasse, hickory chips) pre- tronic Instruments) equipped with a stepping motor and graphite
treated with clay (montmorillonite and kaolinite) suspension crystal monochromator. Thermogravimetric analysis (TGA) of
through slow pyrolysis. The physicochemical properties of these biochars was conducted with a Mettler Toledo’s TGA/DSC1 ana-
engineered biochars were characterized. In addition, the potential lyzer under a stream of air/nitrogen atmosphere, with heating from
environmental applications of the engineered biochars were eval- 30 °C to 750 °C (10 °C/min).
uated by measuring their sorption characteristics to methylene
blue (MB), which has long been used as a ‘‘model’’ compound to 2.3. Methylene blue sorption
represent the adsorption of contaminants, particularly organic
dyes, onto carbon materials [24]. The specific objectives of this The MB sorption ability of the biochars was examined using
work were as follows: (1) develop a novel approach for preparing 68 mL digestion vessels (Environmental Express) at room temper-
clay–biochar composites, (2) characterize their physicochemical ature (22 ± 0.5 °C) with a 1:500 (0.1 g biochar in 50 ml solution)
properties, (3) assess their ability to remove MB from aqueous biochar/solution (20 mg/L MB) ratio for 24 h. This sorbent dosage
solutions, and (4) determine the governing mechanisms of MB was commonly used in the literature for testing the sorptive prop-
sorption on the clay–biochar composites. erties of biochar/carbon based materials [27–29]. The samples
were withdrawn from a mechanical shaker and immediately fil-
tered through 0.22 lm pore size nylon membrane filters (GE cellu-
2. Experimental lose nylon membrane) to determine adsorbed methylene blue
concentrations by a UV–Vis spectrophotometer (Thermo Scientific
2.1. Biochar production EVO 60).

Montmorillonite (MMT), Kaolinite (KLN) and methylene blue

(C16H18ClN3S, molecular weight, 319.9 g/mol) were purchased 2.4. Adsorption kinetics and isotherm
from Southern Clay Products, Inc., Thiele Kaolin Co., and Sigma–
Aldrich, respectively. Adsorption kinetics and isotherm of MB onto BG-MMT were
A stable clay suspension was prepared by adding 2 g montmo- examined using a similar method to the one described above.
rillonite and/or Kaolin powder to 500 ml deionized (DI) water fol- 20 mg/L MB solutions and time intervals of 5 min, 30 min, 1, 2, 6,
lowed by sonication of the mixture for 30 min with ultrasonicator 12, 24, 36, and 48 h were used for adsorption kinetics study. The
(3510R-DTH, Bransonic Ultrasonics Corporation). The obtained adsorption isotherm was determined with different MB solution
clay suspensions were first modified on three biomass feedstocks: concentrations ranging from 1 to 150 mg/L for 48 h. The initial
bamboo (BB), bagasse (BG), and hickory chips (HC). Each was pH of all the solutions used in the sorption experiments was
milled into powders of 2 mm prior to use. 10 g of the feedstocks around 5.7. The samples were withdrawn from a mechanical
were dipped into the clay suspensions and stirred for 1 h. The feed- shaker and immediately filtered to determine adsorbed methylene
stocks were then separated from the mixture and oven dried at blue concentrations by UV–Vis spectrophotometer. All the experi-
80 °C. The clay treated biomass feedstocks were placed in a quartz mental treatments were performed in duplicate and the average
tube inside a tube furnace (MTI, Richmond, CA) to produce the values are reported. Additional analyses were conducted whenever
composites through slow pyrolysis in a N2 environment at temper- two measurements showed a difference larger than 5%.
atures of 600 °C for 1 h. These conditions were used in several pre-
vious studies that successfully produced biochar-based composite 2.5. Regeneration experiments
materials [21,25,26]. Untreated raw materials (bamboo, bagasse,
hickory chips) were also used as feedstocks to produce biochars Adsorbent regeneration studies were carried out by using
without clay modification (i.e., pristine biochars) in the furnace the MB saturated BG-MMT biochar obtained from isotherm
138 Y. Yao et al. / Chemical Engineering Journal 242 (2014) 136–143

experiment after discarding the supernatant dye solution. The montmorillonite, as Al(III) could be exchanged with Fe(II), resulting
resulting sorbent was then washed three times with DI water to re- in a negative charged. Mestdagh et al. [35] reported that varying
move non-adsorbed dye, and agitated with 50 ml of 0.50 mol l1 amounts of iron can be accommodated within the octahedral sheet
KCl solution for 2 h. The regenerated biochar was separated and of kaolinite. Montmorillonite modification also increased the bio-
oven dried at 80 °C for further MB sorption test with the same pro- char’s content of sodium (a typical element of montmorillonite).
cedure described above. This sorption-regeneration procedure was The significantly increased aluminum and iron contents of engi-
repeated multiple times. Because MB sorption on clay minerals is neered biochars suggested both montmorillonite and kaolinite
mainly through ion exchange [30], the use of KCl solution as the were successfully added onto the biochars. All other elements con-
desorption agent would also reveal the effect of MMT on the sorp- tents within the nine biochar samples were relatively low and
tion of MB on the composite adsorbent. comparable with each other (Table 1).
All nine biochars had large surface areas (Table 1). The order
of surface area was as follows: bagasse category > bamboo
3. Results and discussion category > hickory category (Table 1). Raw material treated with
clays decreased the surface area especially with kaolinite, probably
3.1. Elemental analysis and surface area because clays may cover/clog the pores on the biochars.

CHN analysis indicated that all nine biochar samples prepared

and used in this work were carbon rich with carbon content rang- 3.2. Thermogravimetric analysis
ing from 70.2% to 83.3% (mass based) (Table 1), which is typical of
pyrolyzed biomass [31,32]. The carbon contents of the bagasse- The TGA under air atmosphere showed that the clay–biochar
based biochars (i.e., BG-MMT, BG-KLN, and BG) were lower than composites had similar and comparable thermal stability to that
that of bamboo/hickory-based biochars, and they corresponded of the unmodified samples (Fig. 1a–c). Although the onset decom-
to their raw materials instead of clay categories, which showed position temperatures of the clay–biochar composites for all three
that the biochars’ carbon level wasn’t changed by clay modification types of raw materials were slightly decreased, the new engineered
and raw material type was the determinant. Previous studies have samples were still thermally stable as clay has long been used to
suggested that the chemical constituents, such as cellulose, lignin, improve materials’ thermal properties [36]. In addition, the resi-
and hemicellulose contents, of the feedstock may control the yield dues of all the clay–biochar composites were higher than that of
as well as quality of the pyrogenic carbons (biochars) [33,34]. The untreated samples. The kaolinite-modified sample’s residue is
hydrogen and nitrogen contents of all the samples were compara- slightly higher than the montmorillonite-modified one, due to
ble with each other and ranged from 2.12.9% and 0.20.8%, the presence of large amount of silicon within both of the clays
respectively, some of which are likely as surface functional groups, (Fig. 1a–c, Table 2). Clay contents of the modified biochars were
which are commonly found on biochar surfaces [32]. The oxygen calculated based on TGA results:
contents of biochars from the same type of raw material were com- wc  w0
parable to each other; however, that of kaolinite modified biochars Clay content ¼  100% ð1Þ
1  w0
was slightly elevated, which is probably due to the high oxygen
level in kaolinite. The level of oxygen in 3 raw material categories where wc and wo are residue contents of original biochar and corre-
was: bagasse > hickory > bamboo, which means biochar oxygen sponding clay–biochar composites, respectively. The bagasse based
level is based on the raw material type, while clay modification biochars had the highest montmorillonite and kaolinite contents of
only slightly alters it. 13.13% and 18.09%, respectively, probably resulted from its highest
Both montmorillonite and kaolinite are layered silicate miner- surface area as discussed above (Table 2). Kaolinite contents of the
als, with the chemical compositions (Na, Ca)0.33(Al, Mg)2(Si4O10) engineered biochars were slightly higher than montmorillonite con-
(OH)2nH2O and Al2Si2O5(OH)4, respectively. Hence, modification tents, and resulted in higher residue contents (Table 2). The TGA of
of the minerals could change the metal contents of the engineered the engineered and untreated biochars further indicated that the
biochars. Element analysis showed that both montmorillonite and simple slow-pyrolysis method successfully produced clay–biochar
kaolinite modification dramatically increased the biochars’ alumi- composites from pretreated biomass.
num content (Table 1), which is a main element of the clays. Also, Under nitrogen atmosphere, TGA of pretreated and untreated
the iron contents of the clay–biochar composites were higher than bagasse feedstocks was conducted with a heating rate of 10 °C/
that of the pristine biochars due to varying amounts of iron ele- min from 30 °C to 600 °C and staying at 600 °C for 1 h to simulate
ment in both clays (Table 1). It is consistent with the literature, biochar production process. Fig. 1d showed TGA curves were
as Segad et al. [17] indicated that iron is a common substitute in comparable to each other, suggesting that the clay pretreatment

Table 1
Surface area and elemental analysis of the nine biochars produced in this study. BG–MMT, BB–MMT, HC-MMT, BG-KLN, BB-KLN, HC-KLN, BG, BB, HC are biochars produced from
clay-pretreated and untreated feedstocks, respectively.

Sample ID Surface area (m2/g) %, Mass based

C H N O K Na Mg Ca Cu Cr Fe Al As Cd Ag P Mn Pb Zn
BB–MMT 408.1 83.27 2.26 0.25 12.41 0.33 0.14 0.14 0.21 0.01 – 0.23 0.68 – – – 0.08 – – 0.01
BG–MMT 407.0 75.31 2.25 0.75 18.87 0.32 0.13 0.22 0.85 0.01 – 0.47 0.75 – – – 0.03 0.01 – 0.01
HC–MMT 376.1 80.93 2.21 0.28 15.14 0.11 0.04 0.19 0.57 0.01 – 0.15 0.32 – – – 0.00 0.04 – 0.00
BB–KLN 239.8 81.02 2.15 0.25 15.85 0.07 – 0.05 0.19 0.01 – 0.08 0.30 – – – 0.03 0.00 – 0.00
BG–KLN 328.6 70.20 2.44 0.74 24.44 0.06 – 0.16 0.88 0.02 – 0.46 0.53 – – – 0.03 0.05 – 0.00
HC–KLN 224.5 78.08 2.11 0.33 18.12 0.05 – 0.18 0.52 0.01 – 0.07 0.51 – – – 0.00 0.03 – 0.00
BB 375.5 80.89 2.43 0.15 14.86 0.52 0.01 0.23 0.34 0.00 – 0.00 0.04 – – – 0.54 0.00 0.00 0.01
BG 388.3 76.45 2.93 0.79 18.32 0.15 – 0.21 0.91 0.00 – 0.05 0.11 – – – 0.08 0.00 0.00 0.01
HC 401.0 81.81 2.17 0.73 14.02 0.24 – 0.13 0.82 0.00 – 0.01 0.06 – – – 0.02 0.01 0.00 0.00

‘–’: below detection limit.

 Y. Yao et al. / Chemical Engineering Journal 242 (2014) 136–143 139

Fig. 1. TGA of the biochars in air (a–c) and the feedstocks in nitrogen (d).

Table 2
Residue contents and clay contents of the nine biochars.

Sample Residue content (%) Clay content (%)

Original Char MMT-modified Char KLN-modified Char MMT-modified Char KLN-modified Char
Bamboo 5.88 11.50 12.94 5.97 7.50
Bagasse 14.22 25.48 29.74 13.13 18.09
Hickory 5.04 11.08 15.99 6.36 11.53

of biomass may not have any effect on biomass decomposition dur- mineral within biochars [12], was also found in clay–biochar com-
ing slow pyrolysis under nitrogen atmosphere. posites, which is consistent with the EDX results.

3.3. SEM-EDX and XRD 3.4. Methylene blue removal ability

SEM imaging of the clay–biochar composites (BG-MMT) The ability to remove MB from aqueous solution was tested for
showed that the sample surface was widely covered by thin film each of the nine biochars; the results are shown in Fig. 4. In gen-
structures (Fig. 2a and b). After zooming in at 8997 magnification, eral, the bagasse category biochars had a better MB removal rate
the films showed layered surfaces (Fig. 2c), a common clay struc- (i.e., amount removed by the sorbent/amount in the original solu-
tural morphology reported in literatures [37,38]. The surface cov- tion) than the other two categories, suggesting BG might be a bet-
erage with clay particles on the biochar was further confirmed ter feedstock for the production of biochar-based sorbents. All
by the EDX analysis. Both the EDX spectrum and SEM imaging of three biochars from untreated raw materials (i.e., BB, BG, and
the surface showed extremely high peaks for silicon, aluminum, HC) showed very low MB removal of about 9.0–25.6% (Fig. 4),
sodium, calcium, magnesium, and iron, all of which are typical of which is consistent with reported studies [39]. Surface modifica-
the elemental composition of clay minerals (Fig. 2d). tion with both clays did improve MB adsorption for bagasse and
XRD analysis of the clay–biochar composites (BG-MMT) also re- hickory biochars. However, it slightly reduced the removal of MB
vealed the presence of mineral crystals. In the spectrum, the four by the bamboo biochar, indicating that it not suitable to apply
strong peaks at 6.4° (d = 13.840 Å), 6.9° (d = 12.803 Å), 19.9° the clay–BB biochar composites for MB removal. Additional inves-
(d = 4.449 Å) and 35.1° (d = 2.555 Å) were identified as expansible tigations thus are still needed to explore the applications of the
phyllosilicates (i.e., montmorillonite) (Fig. 3). The XRD result con- clay–BB composites. For bagasse, the montmorillonite modifica-
curs to the SEM-EDX analyses that the simple production method tion improved the MB removal rate from 25.6% to 84.3%, while
in the work has successfully implanted montmorillonite onto the 30.0% for kaolinite modification. This dramatic improvement with
carbon surfaces of the biochar matrix. Quartz (SiO2), a common clay modification probably because the BG-MMT had the highest
140 Y. Yao et al. / Chemical Engineering Journal 242 (2014) 136–143

Fig. 2. SEM image (a–c) and EDX spectrum (d) of clay–biochar composites (BG–MMT).

1800
P
XRD spectrum of BG-MMT
1500
Intensity/Counts

PQ
1200
Q
900

600 P
Q
300

0
5 20 35 50 65 80
2θ
θ

Fig. 3. XRD spectrum of clay–biochar composites (BG–MMT).

Fig. 4. Comparison of MB adsorption ability of the biochars produced in this study.

amount of (13.13%) montmorillonite, which has superior ion
exchange ability for various cations, including MB [15,30,40,41].
Because BG-MMT demonstrated the highest MB removal ability, equilibrium reached in less than 48 h (Fig. 5a). Different mathe-
it was selected for further investigations, including adsorption matical models including pseudo-first-order, pseudo-second order,
kinetic and isotherm models, and identification of sorption the Ritchie nth-order, and the Elovich models were used to fit the
mechanisms, as shown below. kinetics data. The governing equations are listed below.
dqt
3.5. Sorption kinetics
¼ k1 ðqe qt Þ first-order ð2:1Þ
dt

Kinetics and isotherm studies were carried out and a number of dqt
¼ k2 ðqe  qt Þ2 second order ð2:2Þ
well-known sorption models were applied in order to better dt
understand the processes governing the adsorption of MB to the
engineered BG-MMT biochar. The kinetics experiment data dqt
¼ kn ðqe qt Þn Ritchie nth-order ð2:3Þ
shows a rapid initial uptake followed by smooth increase, with dt
 Y. Yao et al. / Chemical Engineering Journal 242 (2014) 136–143 141

Fig. 5. Adsorption kinetics data and modeling for MB onto BG–MMT biochar: (a) full and (b) pre-equilibrium adsorption versus square root of time. Symbols are experimental
data and lines are model results.

dqt 3.6. Sorption isotherm

¼ a exp ðbqt Þ Elovich ð2:4Þ
dt
The adsorption equilibrium isotherm is important for describ-
ing how the adsorbate molecules are distributed between the
where qt and qe are the amount of MB adsorbed at time t and equi- liquid and the solid phases under an equilibrium state [47]. The
librium, respectively; k1, k2, and kn are adsorption rate constants; a isotherm experiment results indicated montmorillonite modifica-
is the initial adsorption rate; and b is the desorption constant. The tion greatly enhanced the MB sorption ability of the BG-MMT with
best-fit kinetics models parameters are listed in Table 3. Among maximum MB sorption capacity of more than 10 mg g1 (Fig. 6),
the four kinetics models tested, the Ritchie nth-order and Elovich which is about 5 times of that of the BG (2 mg g1) as reported
models fit the experimental data better with coefficients of deter- in our previous study [25]. Hence, the clay surface modification
mination (R2) of 0.931 and 0.950, respectively, revealing that MB method in this study could be effectively used to promote adsor-
sorption to the engineered biochar BG-MMT could be controlled bent’s properties. The MB sorption capacities of the clay–biochar
by multiple mechanisms. composites tested in this work, however, were still lower than
Previous studies have suggested intraparticle diffusion pro- some activated carbons or engineered biochars, including bagasses
cesses as a dominant mechanism accounting for sorption contam- biochars obtained from vacuum pyrolysis [27,48]. Further
inants on carbon materials [42–44]. In this study, the linearized investigations thus are still need to optimize the synthesis of the
plots of Pre-equilibrium Qt (i.e., before 24 h) vs. t0.5 for the adsorp- clay–biochar composites to improve their sorptive properties.
tion of MB on BG-MMT biochar are shown in Fig. 5b. The high lin- Four well-known models that are essential to practical opera-
ear dependency on the square root of time (R2 = 0.983) revealed tion were used to fit the isotherm experimental data. The govern-
the sorption kinetics of MB on BG-MMT might be strongly affected ing equations are listed below [29,49].
by the intraparticle diffusion mechanism. The intraparticle diffu- KQC e
sion parameter Kid is defined as the slope of the plot, which was qe ¼ Langmuir ð3:1Þ
1 þ KC e
0.975 mg g1 h0.5 in this study (Fig. 5b). On the other hand, the
straight line did not pass through the origin; instead it had a signif- qe ¼ K f C ne Freundlich ð3:2Þ
icant intercept of 2.919 mg g1. This can be attributed to the wide
distribution of pore size for the engineered carbon studied [45]. K lf QC ne
This large intercept indicated the high contribution of the surface qe ¼ Langmuir—Freundlich ð3:3Þ
1 þ K lf C ne
sorption in the rate-controlling step, because the intercept of the
plot reflects the boundary layer effect (film diffusion) [46]. Hence, K r Ce
the rate-controlling parameter in the study is dominated by both qe ¼ Redlich—Peterson ð3:4Þ
1 þ aC ne
intraparticle and film diffusion mechanisms.

Table 3
Best-fit kinetics and isotherms models parameters for MB adsorption onto BG-MMT.

Parameter 1 Parameter 2 Parameter 3 R2

Adsorption kinetics
First-order k1 = 0.928 (h1) qe = 6.888 (mg g1) 0.769
Second-order k2 = 0.201 (g mg1 h1) qe = 7.265 (mg g1) 0.852
nth-order kn = 3.215 (gn1 mg1n h1) qe = 9.298 (mg g1) n = 5.000 0.931
Elovich b = 0.872 (g mg1) a = 160.019 (mg g1 h1) 0.950
Adsorption isotherms
Langmuir K = 0.373 (L mg1) Q = 11.940 (mg g1) 0.908
Freundlich Kf = 5.640 (mg(1n) Ln g1) n = 0.169 0.940
Langmuir–Freundlich Klf = 0.494 (Ln mgn) Q = 15.000 (mg g1) n = 0.449 0.928
Redlich–Peterson Kr = 3.211 (L g1) a = 20.000 (Ln mgn) n = 0.852 0.937
142 Y. Yao et al. / Chemical Engineering Journal 242 (2014) 136–143

14 69.65%, which is a good match with the regeneration study results

(70.11%). Hence, biochar itself is only capable of the uptake of a
12 small part of MB from solution, and the process might be nonre-
versible. The mechanism responsible for this part could be ex-
10 plained by the electrostatic interaction between the positively
charged MB and the surface of the biochar, which is usually nega-
Qt/(mg/g)

8 tively charged [50,51]. On the other hand, montmorillonite is the

Data
main factor for MB uptake (70.11%), which could be desorbed by
6 Freundlich KCl solution. The high CEC of montmorillonite (70–100 meq/
Langmuir 100 g) suggests that cation exchange could be the adsorption
4 Langmuir-Freundlich mechanism of montmorillonite [52–54]. When the montmorillon-
Redlich-Peterson ite content of BG–MMT was 13.13%, the MB sorption capacity of
2
the montmorillonite attached to the biochar matrix was
60.17 mg/g, which is comparable to the literature value of
0
0 30 60 90 120 150 58.2 mg/g [15]. After multiple cycle adsorptions, the BG–MMT
material is still stable, which is consistent with TGA results. The
Ce/(mg/l)
sorbent could be regenerated easily by KCl solution to recover most
Fig. 6. Adsorption isotherm data and modeling for MB on BG–MMT biochar. of its MB removal ability, revealing that the BG–MMT provides the
Symbols are experimental data and lines are model results. potential to be recycled and reused after MB dye adsorption.

4. Conclusions

For the first time, a novel engineered biochar with clay particles
implanted on carbon surfaces within the biochar pores has been
successfully developed. The resulting composites have unique
properties and functions inherited from both clay and biochar that
can be applied in large-scale applications because the feedstock
materials are abundant and inexpensive [15]. In addition, the
clay–biochar composites has a much higher sorption ability to
MB, a model contaminant, than the original char. Due to stability
and cycle performance, the engineered biochar can be regenerated
and reused for repeated MB sorption, giving it great potential to be
used as an innovative and low-cost adsorbent for environmental
applications, particularly with respect to removing contaminants
from aqueous solutions. In addition, because of the simple synthe-
sis and low-cost, the clay–biochar composites may also be used in
large-scale land application to improve soil quality and sequester
Fig. 7. Regeneration and cycle performance of BG–MMT sorbent. carbon.

Acknowledgment
where K, Kf, Klf, and Kr represents the four models’ coefficient,
respectively; Q (mg g1) denotes the maximum capacity; Ce This research was partially supported by the NSF through
(mg L1) is the sorbate concentration at equilibrium; and n and a Grant: CBET-1054405.
are constants for Freundlich and Redlich–Peterson models, respec-
tively [49]. All four tested isotherm models fit the experimental References
data fairly well and the parameters are also shown in Table 3.
[1] E. Marris, Putting the carbon back: black is the new green, Nature 442 (2006)
Freundlich and Redlich–Peterson models had slightly better fitting 624–626.
performance than the other two, with R2 of 0.940 and 0.937, respec- [2] O.R. Harvey, L.-J. Kuo, A.R. Zimmerman, P. Louchouarn, J.E. Amonette, B.E.
tively. Hence, MB sorption should be onto a heterogeneous surface, Herbert, An index-based approach to assessing recalcitrance and soil carbon
sequestration potential of engineered black carbons (Biochars), Environ. Sci.
and the process could be governed by multiple mechanisms, which Technol. 46 (2012) 1415–1421.
is consistent with kinetics study results. [3] D. Woolf, J.E. Amonette, F.A. Street-Perrott, J. Lehmann, S. Joseph, Sustainable
biochar to mitigate global climate change, Nat. Commun. 1 (2010).
[4] J. Lehmann, A handful of carbon, Nature 447 (2007) 143–144.
3.7. Regeneration and sorption mechanisms [5] C.L. Schelske, Eutrophication: focus on phosphorus, Science 324 (2009). 722-
722.
[6] D.J. Conley, H.W. Paerl, R.W. Howarth, D.F. Boesch, S.P. Seitzinger, K.E. Havens,
A regeneration study was carried out to evaluate the cyclic per- C. Lancelot, G.E. Likens, Controlling eutrophication: nitrogen and phosphorus,
formance of BG–MMT as an adsorbent by performing multiple cy- Science 323 (2009).
[7] L. Beesley, E. Moreno-Jimenez, J.L. Gomez-Eyles, E. Harris, B. Robinson, T.
cle adsorption experiments. At first, the MB adsorption capacity of Sizmur, A review of biochars’ potential role in the remediation, revegetation
BG–MMT was 11.26 mg g1. Multiple cycle dye adsorption re- and restoration of contaminated soils, Environ. Pollut. 159 (2011) 3269–3282.
vealed that the regenerated biochar continues to adsorb MB after [8] J. Lehmann, J. Gaunt, M. Rondon, Bio-char sequestration in terrestrial
ecosystems – a review, Mitig. Adapt. Strat. Global Change (2006) 403–427.
each adsorption–regeneration cycle, with a stable capacity of
[9] S.P. Sohi, E. Krull, E. Lopez-Capel, R. Bol, A review of biochar and its use and
around 7.90 mg g1 (Fig. 7), which account for 70.11% of initial function in soil, Adv. Agron. 105 (2010) 47–82.
capacity. Considering the MB sorption experiment results dis- [10] M. Zhang, B. Gao, S. Varnoosfaderani, A.F. Hebard, Y. Yao, M. Inyang,
cussed above, BG and BG–MMT removed 25.60% and 84.33% MB, Preparation and characterization of a novel magnetic biochar for arsenic
removal, Bioresour. Technol. 130 (2013) 457–462.
respectively (Fig. 4). In other words, BG biochar accounts for [11] Y. Xue, B. Gao, Y. Yao, M. Inyang, M. Zhang, A.R. Zimmerman, K.S. Ro, Hydrogen
30.35% dye sorption, while MMT explains for the remaining peroxide modification enhances the ability of biochar (hydrochar) produced
 Y. Yao et al. / Chemical Engineering Journal 242 (2014) 136–143 143

from hydrothermal carbonization of peanut hull to remove aqueous heavy [33] A.H. Basta, V. Fierro, H. Saied, A. Celzard, Effect of deashing rice straws on their
metals: Batch and column tests, Chem. Eng. J. 200 (2012) 673–680. derived activated carbons produced by phosphoric acid activation, Biomass.
[12] Y. Yao, B. Gao, M. Inyang, A.R. Zimmerman, X. Cao, P. Pullammanappallil, L. Bioenerg. 35 (2011) 1954–1959.
Yang, Biochar derived from anaerobically digested sugar beet tailings: [34] A.H. Basta, V. Fierro, H. Ei-Saied, A. Celzard, 2-Steps KOH activation of rice
characterization and phosphate removal potential, Bioresour. Technol. 102 straw: an efficient method for preparing high-performance activated carbons,
(2011) 6273–6278. Bioresour. Technol. 100 (2009) 3941–3947.
[13] M. Inyang, B. Gao, P. Pullammanappallil, W. Ding, A.R. Zimmerman, Biochar [35] M. Mestdagh, L. Vielvoye, A. Herbillon, Iron in kaolinite: II. The relationship
from anaerobically digested sugarcane bagasse, Bioresour. Technol. 101 (2010) between kaolinite crystallinity and iron content, Clay. Miner. 15 (1980) 1–13.
8868–8872. [36] F. Gong, M. Feng, C. Zhao, S. Zhang, M. Yang, Thermal properties of poly (vinyl
[14] H.H. Murray, Overview, clay mineral applications, Appl. Clay Sci. 5 (1991) 379– chloride)/montmorillonite nanocomposites, Polym. Degrad. Stabil. 84 (2004)
395. 289–294.
[15] A. Gurses, C. Dogar, M. Yalcin, M. Acikyildiz, R. Bayrak, S. Karaca, The [37] L. Zhou, H. Chen, X. Jiang, F. Lu, Y. Zhou, W. Yin, X. Ji, Modification of
adsorption kinetics of the cationic dye, methylene blue, onto clay, J. Hazard. montmorillonite surfaces using a novel class of cationic gemini surfactants, J.
Mater. 131 (2006) 217–228. Colloid Interf. Sci. 332 (2009) 16–21.
[16] C. Bilgic, Investigation of the factors affecting organic cation adsorption on [38] S. Wang, Y. Hu, R. Zong, Y. Tang, Z. Chen, W. Fan, Preparation and
some silicate minerals, J. Colloid Interf. Sci. 281 (2005) 33–38. characterization of flame retardant ABS/montmorillonite nanocomposite,
[17] M. Segad, B. Jonsson, T. Akesson, B. Cabane, Ca/Na montmorillonite: structure, Appl. Clay Sci. 25 (2004) 49–55.
forces and swelling properties, Langmuir 26 (2010) 5782–5790. [39] A. Aygun, S. Yenisoy-Karakas, I. Duman, Production of granular activated
[18] D. Ghosh, K.G. Bhattacharyya, Adsorption of methylene blue on kaolinite, Appl. carbon from fruit stones and nutshells and evaluation of their physical,
Clay Sci. 20 (2002) 295–300. chemical and adsorption properties, Micropor. Mesopor. Mater. 66 (2003)
[19] A. Kaya, Characterization of clay particle surfaces for contaminant sorption in 189–195.
soil barriers using flow microcalorimetry, J. Environ. Eng-ASCE. 130 (2004) [40] Z. Klika, P. Pustkova, M. Dudova, P. Capkova, C. Klikova, T. Matys Grygar, The
918–921. adsorption of methylene blue on montmorillonite from acid solutions, Clay.
[20] J. Zhuang, G.R. Yu, Effects of surface coatings on electrochemical Miner. 46 (2011) 461–471.
properties and contaminant sorption of clay minerals, Chemosphere 49 [41] Y.-L. Ma, Z.-R. Xu, T. Guo, P. You, Adsorption of methylene blue on Cu (II)-
(2002) 619–628. exchanged montmorillonite, J. Colloid Interf. Sci. 280 (2004) 283–288.
[21] M. Zhang, B. Gao, Y. Yao, Y.W. Xue, M. Inyang, Synthesis of porous MgO– [42] J.J. Pignatello, B. Xing, Mechanisms of slow sorption of organic chemicals to
biochar nanocomposites for removal of phosphate and nitrate from aqueous natural particles, Environ. Sci. Technol. 30 (1995) 1–11.
solutions, Chem. Eng. J. 210 (2012) 26–32. [43] M.L. Brusseau, R.E. Jessup, P.S.C. Rao, Nonequilibrium sorption of organic
[22] M. Zhang, B. Gao, Y. Yao, M. Inyang, Phosphate removal ability of biochar/ chemicals: Elucidation of rate-limiting processes, Environ. Sci. Technol. 25
MgAl–LDH ultra-fine composites prepared by liquid–phase deposition, (1991) 134–142.
Chemosphere 92 (2013) 1042–1047. [44] R. Weerasooriya, H.J. Tobschall, W. Seneviratne, A. Bandara, Transition state
[23] Y. Yao, B. Gao, J. Chen, M. Zhang, M. Inyang, Y. Li, A. Alva, L. Yang, Engineered kinetics of Hg (II) adsorption at gibbsite, Äìwater interface, J. Hazard. Mater.
carbon (biochar) prepared by direct pyrolysis of mg-accumulated tomato 147 (2007) 971–978.
tissues: characterization and phosphate removal potential, Bioresour. Technol. [45] F.-C. Wu, R.-L. Tseng, R.-S. Juang, Initial behavior of intraparticle diffusion
138 (2013) 8–13. model used in the description of adsorption kinetics, Chem. Eng. J. 153 (2009)
[24] S. Chandrasekhar, P. Pramada, Rice husk ash as an adsorbent for methylene 1–8.
blue, effect of ashing temperature, Adsorption 12 (2006) 27–43. [46] M.H. Kalavathy, T. Karthikeyan, S. Rajgopal, L.R. Miranda, Kinetic and isotherm
[25] M. Inyang, B. Gao, A. Zimmerman, M. Zhang, Synthesis, characterization, and studies of Cu(II) adsorption onto H3PO4-activated rubber wood sawdust, J.
dye sorption ability of carbon nanotube–biochar nanocomposites, Chem. Eng. Colloid Interf. Sci. 292 (2005) 354–362.
J. 236 (2014) 39–46. [47] C. Almeida, N. Debacher, A. Downs, L. Cottet, C. Mello, Removal of methylene
[26] M. Zhang, B. Gao, Removal of arsenic, methylene blue, and phosphate by blue from colored effluents by adsorption on montmorillonite clay, J. Colloid
biochar/AlOOH nanocomposite, Chem. Eng. J. 226 (2013) 286–292. Interf. Sci. 332 (2009) 46.
[27] M. Zhang, B. Gao, Y. Yao, Y.W. Xue, M. Inyang, Synthesis, characterization, and [48] M. Carrier, A.G. Hardie, U. Uras, J. Gorgens, J. Knoetze, Production of char from
environmental implications of graphene-coated biochar, Sci. Total Environ. vacuum pyrolysis of South-African sugar cane bagasse and its characterization
435 (2012) 567–572. as activated carbon and biochar, J. Anal. Appl. Pyrol. 96 (2012) 24–32.
[28] M.D. Inyang, B. Gao, W.C. Ding, P. Pullammanappallil, A.R. Zimmerman, X.D. [49] C. Gerente, V.K.C. Lee, P. Le Cloirec, G. McKay, Application of chitosan for the
Cao, Enhanced lead sorption by biochar derived from anaerobically digested removal of metals from wastewaters by adsorption – mechanisms and models
sugarcane bagasse, Separ. Sci. Technol. 46 (2011) 1950–1956. review, Crit. Rev. Environ. Sci. Technol. 37 (2007) 41–127.
[29] Y. Yao, B. Gao, M. Inyang, A.R. Zimmerman, X.D. Cao, P. Pullammanappallil, L.Y. [50] F.A. Pavan, E.C. Lima, S.L. Dias, A.C. Mazzocato, Methylene blue biosorption
Yang, Removal of phosphate from aqueous solution by biochar derived from from aqueous solutions by yellow passion fruit waste, J. Hazard. Mater. 150
anaerobically digested sugar beet tailings, J. Hazard. Mater. 190 (2011) 501– (2008) 703–712.
507. [51] Y. Yao, B. Gao, M. Zhang, M. Inyang, A.R. Zimmerman, Effect of biochar
[30] P.T. Hang, Methylene blue absorption by clay minerals – determination of amendment on sorption and leaching of nitrate, ammonium, and phosphate in
surface areas and cation exchange capacities – (Clay-Organic Studies XVIII), a sandy soil, Chemosphere (2012).
Clay. Clay. Miner. 18 (1970) 203–212. [52] L. Wang, J. Zhang, A. Wang, Removal of methylene blue from aqueous solution
[31] A.R. Zimmerman, B. Gao, M.Y. Ahn, Positive and negative carbon using chitosan-g-poly (acrylic acid)/montmorillonite superadsorbent
mineralization priming effects among a variety of biochar-amended soils, nanocomposite, Colloid Surf. A 322 (2008) 47–53.
Soil Biol. Biochem. 43 (2011) 1169–1179. [53] G. Chen, J. Pan, B. Han, H. Yan, Adsorption of methylene blue on
[32] M. Inyang, B. Gao, W. Ding, P. Pullammanappallil, A.R. Zimmerman, X. Cao, montmorillonite, J. Dispersion Sci. Technol. 20 (1999) 1179–1187.
Enhanced lead sorption by biochar derived from anaerobically digested [54] A. Usuki, M. Kawasumi, Y. Kojima, A. Okada, T. Kurauchi, O. Kamigaito,
sugarcane bagasse, Separ. Sci. Technol. (2011), http://dx.doi.org/10.1080/ Swelling behavior of montmorillonite cation exchanged for x-amino acids by
01496395.01492011.01584604. e-caprolactam, J. Mater. Res. 8 (1993) 1174–1178.