Bioresource Technology 71 (2000) 103112

Surface properties of granular activated carbons from agricultural

by-products and their eects on raw sugar decolorization
M. Ahmednaa,1, W.E. Marshallb, R.M. Raoc,*
a
Technology International Inc., 429 West Airline Hwy, Suite S, LaPlace, LA 70068, USA
USDA-ARS-Southern Regional Research Center, P.O. Box 19687, New Orleans, LA 70179, USA
Department of Food Science, LAES, Louisiana State University Agricultural Center, Baton Rouge, LA 70803-4200, USA
b

Received 3 March 1999; received in revised form 30 April 1999; accepted 2 May 1999

Abstract
Granular activated carbons (GACs) were produced from sugarcane bagasse combined with one of two binders (corn syrup, coal
tar) by physical activation and from pecan shells by physical and chemical activation. GACs were evaluated for their physical
(hardness, bulk density), chemical (ash, pH), surface (surface area, pore size distribution, surface chemistry), and adsorption
properties (molasses color removal, sugar decolorization) and compared with two commercial reference carbons. Results showed
that larger surface area, a well-developed macro- and mesoporosity, and a minimal surface charge were desirable in GACs designed
for sugar decolorization. Steam activation of pecan shells carbon was the only by-product-activation combination that produced
GAC with all the above three desirable characteristics of a good sugar decolorizer. Chemical activation of pecan shells yielded
GACs with high surface area and adequate pore size distribution but with large surface charge. In contrast, sugarcane bagasse-based
GACs exhibited low surface areas and unsatisfactory physical/chemical properties. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Sugar decolorization; Activated carbons; Agricultural by-products; Surface properties; Surface chemistry

1. Introduction
The adsorption capacity of activated carbon is determined, not only by its total surface area, but also by
its internal porous structure and the presence of functional groups on the pore surface. Carbon surfaces have
a pore size that determines its adsorption capacity, a
chemical structure that inuences its interaction with
polar and nonpolar adsorbates, and active sites that
determine the type of chemical reactions with other
molecules (Bansal et al., 1988). For instance, carbons
with small pore size will not trap large adsorbate molecules and those, with large pores may not be able to
retain small adsorbate molecules. The electrical charge
of the surface groups may also enhance or hinder the
adsorption of the target molecules on the carbon surface. If the adsorbate has the same electrostatic charge
as that of the carbon surface, repulsion will occur,

*
Corresponding author. Tel.: +1-225-388-5189; fax: +1-225-3885300; e-mail: rrao@unix1.sncc.lsu.edu
1
Former student in the Department of Food Science, Louisiana
State University.

thereby inhibiting the process of adsorption. However,

the adsorption of such molecules will be enhanced if
they and the carbon surface carry opposite charges.
Thus, the adsorption behavior of activated carbon
cannot be interpreted on the basis of the surface area
alone. Carbons having equal surface areas but having
been prepared by dierent methods or given dierent
activation treatments often show markedly dierent
adsorption characteristics (Bansal et al., 1988). As a
result, an eective carbon should have a large surface
area with the proper pore size to trap the targeted species and a surface charge opposite that of the adsorbate.
Since surface properties of GACs are a function of
the precursor and pyrolysis and activation conditions, it
is essential to characterize them with respect to the
number and type of the chemical groups on the surface,
the polarity of the surface, pore size distribution and
total surface area. Many investigators have studied the
porous structure (Wigmans, 1989; Rodriguez-Reinoso
and Molina-Sabio, 1992; Mackay and Roberts, 1982;
Atkins, 1965; Rodriguez-Reinoso et al., 1985, 1989;
Dubinin, 1985; McEnaney, 1988) and surface chemistry
(Contescu et al., 1997; Morterra and Low, 1985; Reed
and Matsumoto, 1991; Arico et al., 1989; Bandoz et al.,

0960-8524/00/$ see front matter 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 0 - 8 5 2 4 ( 9 9 ) 0 0 0 6 9 - 3

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M. Ahmedna et al. / Bioresource Technology 71 (2000) 103112

1993; Papirer et al., 1991; Molina-Sabio et al., 1991;

Coughlin and Esra, 1968; Matsumura et al., 1976; Rositani et al., 1987) of activated carbons made from a
variety of precursors and activation conditions. This
extensive research eort has led to the development of
several methods for the determination of the surface
properties of activated carbons and demonstrated the
importance of surface properties in the commercial use
of activated carbons. Among the accepted techniques,
the Brunauer, Emmet and Teller (BET) method (Rodriguez-Reinoso and Solano, 1989) and titration with
bases of dierent alkalinities or Boehm method (Boehm,
1966) remain the most popular techniques used to
quantify an activated carbon's surface area and surface
oxides, respectively.
The objectives of this work were to (1) determine the
surface properties (surface area, pore size distribution,
surface functional groups) of granular activated carbons
prepared from sugarcane bagasse and pecan shells, (2)
determine the eciency of these carbons in removing
sugar colorants compared to the selected commercial
carbons and (3) study the relationship between carbons'
surface properties and their ability to remove sugar
colorants from aqueous solutions.
2. Methods
2.1. Materials
Sugarcane bagasse (SB) was provided by the
Audubon Sugar Institute, Louisiana State University Agricultural Center, Baton Rouge, LA and pecan
shells (PS) by Sun Diamond of New Mexico, Las
Cruces, NM. Corn syrup (CS) was supplied by A.E.
Staley Manufacturing Company, Decatur, IL, and coal
tar pitch (CT) by Koppers Industries, Follarsbee, WV.
The reference carbons were Calgon CPG-LF and
Cane Cal from Calgon Carbon, Pittsburgh, PA. The
commercial GACs were made from bituminous coal
with coal tar as a binder and were selected on the basis
of manufacturer recommendations as excellent decolorizers of organic liquids such as raw sugar liquors
(Calgon, 1987).
2.2. Methods
2.2.1. Preparation of granular activated carbons
Sugarcane bagasse and pecan shells were milled to
1012-mesh size (US standard sieve) with a hammercutter mill (Glen Mills, Clifton, NJ).
Briquettes for subsequent pyrolysis and activation
were prepared from sugarcane bagasse by combining
with one of two binders (corn syrup or coal tar) in two
binder/by-product ratios (1:1 and 1:2), according to the
procedure described by Pendyal et al. (1999a). Sug-

arcane bagasse with binder and milled pecan shells was

subsequently pyrolyzed and activated by either physical
activation or chemical activation, as described in Table 1, using an inert atmosphere furnace with retort.
After activation, the GACs were cooled overnight in the
furnace under nitrogen gas. The chemically activated
carbons were washed in a soxhlet extractor until no residual phosphoric acid was present as shown by the
absence of a precipitate when 10 drops of 0.01M lead
acetate was added to 100 ml of the nal wash water. The
physically activated carbons were washed with room
temperature water, and all GACs were then dried
overnight at 50C before use. Final yield for chemically
activated pecan shells was 39%, and nal yields for the
physically activated bagasse-based and shell-based carbons were 1426%.
2.2.2. Measurement of physical, chemical and adsorption
properties
Physical (bulk density, hardness, surface area) and
chemical (ash, pH, conductivity) properties were determined according to the procedures of Ahmedna et al.
(1997). Adsorption properties (percent molasses color
removed and percent sugar decolorization) were also
performed as described by Ahmedna et al. (1997); the
only modication was the use of a carbon dosage of 4%
(weight per volume, w/v) instead of 1% (w/v).
2.2.3. Determination of surface properties
Total surface area and pore size distribution. Granular
activated carbons were dried under vacuum at 110C for
3 h to remove moisture from carbon pores. 250 mg of
dry carbon were then placed in a Micrometrics Gemini
2375 Surface Area Analyzer (Micrometrics, Norcross,
GA), and nitrogen adsorption isotherms were run at 77
K. From these isotherms, micro-, meso- and macropore
volumes were calculated using the BJG model; and pore
surface areas were calculated using t-plots (Gregg and
Sing, 1982).
Surface chemistry. Two methods were used to study
the nature of the oxygen groups on the surface of activated carbons. These methods were titration with bases
of varying strength and Fourier Transform Infrared
Spectroscopy (FTIR).
Titration method. One-tenth N solutions of sodium
bicarbonate, sodium carbonate, sodium hydroxide and
sodium ethoxide were prepared along with a 0.1N solution of HCl. 50 ml of each base were placed in a 250
ml Erlenmeyer ask and 0.5 g of carbon was introduced
into each ask with a teon stirring bar. A blank (base
with no carbon) was run in parallel with the carbon
samples. Flasks containing 1% (w/v) carbon slurries
along with the blanks were sealed and continuously
stirred for 24 h. At the end of 24 h, carbon was separated from the solution using 0.45 lm lters. 10 ml of

M. Ahmedna et al. / Bioresource Technology 71 (2000) 103112

105

Table 1
Precursors, pyrolysis and activation conditions of agricultural by-product-based granular activated carbons
Carbon labels Precursor (P)

Binder (B) P/B ratio Pyrolysis conditions

Activation Conditions

SBCS11
SBCS21
SBCT11
SBCT21
PS23
PS9
PS63
PS10

Corn syrup 1/1

Corn syrup 2/1
Coal tar
1/1
Coal tar
2/1
None
N/A
None
N/A
None
N/A
None
N/A

Physical: 900C for 4 h under 13% CO2

Physical: 900C for 4 h under 13% CO2
Physical: 900C for 20 h under 13% CO2
Physical: 900C for 20 h under 13% CO2
Physical: 800C for 6 h under 75% CO2
Physical: 800C for 8 h under 13% CO2
Physical: 850C for 6 h under steam
Chemical: 1 h at 450C under N2

Sugarcane bagasse
Sugarcane bagasse
Sugarcane bagasse
Sugarcane bagasse
Pecan shells
Pecan shells
Pecan shells
Pecan shells

700C for 1 h under N2

700C for 1 h under N2
750C for 1 h under N2
750C for 1 h under N2
700C for 1 h under N2
700C for 1 h under N2
700C for 1 h under N2
2 h soak in 50% H3 PO4 1/2 h at 170C

the ltrate were pipeted into a 50 ml beaker and 15 ml of

0.1N HCl were added to it. Excess HCl was subsequently determined by titration with 0.1N NaOH. Titrations were carried out using a PC Titrate Autotitrator
(Man-Tech Associates, Tonawanda, New York) equipped with a 50 ml burette and a Corning pH Meter probe.
The titrant volume was automatically controlled at 0.3
pH unit increments. This option allowed good control of
the volume of titrant around inexion points of the titration curves, where pH change is most rapid, thereby
ensuring accurate detection of the inexion points. The
volume of NaOH necessary to reach the equivalent
point was recorded for the blank and the carbon samples. The dierence in volume of NaOH consumed by
the blank and by the carbon sample was calculated and
converted into H equivalents neutralized by standard
base per gram of carbon.
FTIR method. Each carbon was mixed with an appropriate amount of KBr (analytical grade IR) in order
to prepare a 0.5% (w/w) dispersion of carbon in KBr.
The dispersions were dried overnight in a vacuum oven
at 100C. To prevent contamination with water, KBrcarbon disks were made in a glove bag under nitrogen
atmosphere. Disks were prepared using a Delta Press
(Tetragon Scientic, Elbridge, New York). Infrared
spectra of the disks were determined using a Prospect
FTIR (Midac, Irvine, CA) and automatically corrected
for an air background. For each run, 32 scans were taken at a resolution of 4 cm1 . During the scans, the FT
IR chamber was continuously purged with a ow of
nitrogen to remove moisture.
Statistical analysis. Analysis of variance (ANOVA)
was used to compare the mean values of physical,
chemical, and adsorption properties among various
GACs. Multiple regression was used to select models
relating carbon surface properties to the decolorization
eciency of GACs (SAS, 1988). The selected models
were employed to generate 3-D plots of the decolorization capacity as a function of carbon surface
properties. Finally, principal component and cluster
analyses (SAS, 1989) served as tools by which the experimental and commercial carbons were grouped based
on their similarities in terms of all the properties investigated.

3. Results and discussion

3.1. Physical and chemical properties
The physical and chemical properties of GACs may
not relate directly to their eectiveness in removing
sugar colorants, but they are important for their commercial utilization. As a result, they are usually given as
a part of the commercial specication of industrial
carbons.
GACs prepared from sugarcane bagasse and corn
syrup had relatively low bulk density, low hardness,
similar pH and high ash contents when compared with
the reference carbons (Table 2). Sugarcane with coal tar
as binder had similar bulk density and hardness but
lower pH and higher ash content than the reference
GACs. Physical activation of pecan shells produced
carbons with physical and chemical characteristics (bulk
density, hardness, pH and ash) that were generally
similar to the reference carbons. Chemical activation of
pecan shell (PS10) appeared to reduce bulk density and
hardness. The observed dierences in physical and
chemical characteristics among the experimental carbons are attributable to the precursors and activation
conditions used in their manufacture. For instance, the
low ash and high hardness values of pecan shell-based
carbons can be explained by high lignin and low ash
contents of the shells in comparison to sugarcane bagasse and the absence of high ash binders.
3.2. Surface area and pore size distribution
In comparison to the reference carbons, sugarcane
bagasse-based carbons, especially with coal tar as
binder, exhibited limited surface area, while the GACs
derived from pecan shells showed relatively larger surface area (Table 3). The highest surface area (1200 m2 /g)
among pecan shell-based carbons was achieved by
chemical activation (PS10) and the lowest surface area
(522 m2 /g) by carbon dioxide activation (PS9). Steam
activation yielded a carbon (PS63) with the closest surface area (852 m2 /g) to the reference carbons. The proportion of meso- plus macropore/total surface area
ranged from 8% to 50% of the total surface area. Pecan

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M. Ahmedna et al. / Bioresource Technology 71 (2000) 103112

Table 2
Physical and chemical properties of experimental granular activated carbons
Activated carbons
SBCS21
SBCS11
SBCT11
SBCT21
PS23
PS9
PS63
PS10
CCAL b
CPG-LF
a
b

Bulk density (g/cm3 )

0.25
0.25
0.47
0.47
0.42
0.44
0.38
0.34
0.48
0.54

0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.02
0.01
0.01

Hardness (% survival)

74.25
70.00
93.25
83.25
91.50
91.50
92.00
70.75
83.25
94.00

g
bc
b
d
cd
e
f
b
a

cd

4.99
10.60 d
2.75 ab
1.50 bc
1.29 ab
1.29 ab
1.15 ab
2.75 d
3.59 cb
1.41 a

pH
8.26
8.07
6.60
6.44
8.10
8.11
7.74
7.66
8.25
7.38

Ash (%)

0.22
1.16
0.24
0.25
0.53
0.22
0.13
0.41
0.15
0.19

a
a
c
c
a
a
ab
ab
a
b

26.96 1.14 a
26.88 2.87 a
17.79 1.37 c
23.39 0.62 b
7.33 1.49 de
3.61 1.41 f
1.70 0.27 f
3.30 1.72 f
9.08 0.52 d
4.70 0.45 ef

Means with dierent letters are signicantly dierent at 5% signicance level.

Commercial Carbons, manufactured by Calgon.

Table 3
Surface properties of experimental and commercial GACs

Activated
carbons

TSA b
(g/m2)

MSA c
(g/m2 )

MMSA/
TSA d

TSC e
(meq H /g)

SBCS21
SBCS11
SBCT11
SBCT21
PS23
PS9
PS63
PS10
CCALf
CPG-LFf

314
337
78
180
641
522
852
1203
920
904

261
267
39
120
588
477
645
942
783
802

0.17
0.21
0.50
0.34
0.08
0.09
0.24
0.22
0.15
0.11

0.29
0.19
0.07
0.12
0.34
0.22
0.31
1.12
0.47
0.49

a
Values are means of duplicate determinations where the standard
deviations are less than 10% of the mean values.
b
Total surface area.
c
Micropore surface area.
d
Ratio of macro- plus mesopore surface area to total surface area.
e
Total surface charge.
f
Commercial carbons, manufactured by Calgon.

shells activated with carbon dioxide (PS9, PS23) were

predominantly microporous, while carbons from sugarcane bagasse and coal tar had the highest meso- plus
macroporosity. Both the type of precursor and the
method of activation appear to aect pore size distribution. Carbon dioxide activation produced larger
meso- plus macropore surface area when applied to
sugarcane bagasse chars (1750%) than when used to
activate pecan shell chars (89%). The latter showed
more meso- plus macropore development when activated with either steam or phosphoric acid. These observations can be explained by the fact that steam is
more reactive than carbon dioxide at a given temperature (Rodriguez-Reinoso and Molina-Sabio, 1992). The
water molecule has a smaller molecular dimension than
carbon dioxide, which leads to faster diusion into the
porous structure of the char, and therefore, a faster reaction rate. The reaction rate of steam is approximately
three times faster than the reaction of carbon dioxide at
800C (Gergova et al., 1992). Phosphoric acid, on the
other hand, is impregnated into the raw material to

inuence the pyrolysis such that the tar formation and

volatilization are kept to a minimum (Pollard et al.,
1992). The bubbling of phosphoric acid through the byproduct matrix and the reduction of tar formation result
in a well developed surface area.
3.3. Surface chemical groups
The titration method revealed that many, but not all,
of the carbons evaluated contained four classes of surface oxides (surface groups): carboxyls, lactones, phenols and carbonyls (Fig. 1). The concentration of
surface groups varied depending on the precursor and
activation conditions. Among the 10 carbons investigated, chemically activated pecan shell (PS10) showed
the highest concentration of surface groups. In contrast,
GACs prepared from sugarcane bagasse and coal tar
exhibited the lowest concentrations. Phenols and carbonyls were the dominant surface oxides for most of the
GACs. Carboxyls were absent in one of the commercial
carbons (CCAL) as well as in the steam activated pecan
shell-based carbon.
The results of FTIR studies were generally consistent with those of the titration method as shown by the
representative examples of FTIR spectra given in
Figs. 2 and 3. For instance, the carbon derived from
pecan shells through chemical activation (PS10) had the
most intense peaks among all the experimental carbons
(Fig. 3). These peaks covered the absorption bands
corresponding to all the functional groups revealed by
titration. The two commercial carbons (Fig. 2) and the
steam activated pecan-based carbon (Fig. 3) exhibited
relatively weak FTIR absorption peaks, indicating a
low concentration of oxides on their surface. Approximate FTIR band assignments indicated the presence of
carbonyls, carboxyls, lactones and phenols. The 1800
1540 cm1 band (Band 1) was associated with the C O
stretching mode in carbonyls, carboxylic acids and lactones, while the 14401000 cm1 band (band 2) was
assigned to the CO stretching and OH bending
modes, such as in alcohols and carboxylic acids,

M. Ahmedna et al. / Bioresource Technology 71 (2000) 103112

107

Fig. 1. Concentration of surface oxides for GACs. SBCS and SBCT Sugarcane Bagasse with Corn Syrup and Coal Tar, respectively; and PS
Pecan Shells; CCAL and CPGLF are the commercial reference carbons. SBCS and SBCT Sugarcane Bagasse with Corn Syrup and Coal Tar,
respectively; and PS Pecan Shells; CCAL and CPGLF are the commercial reference carbons. Bars represent the means of two replications, where
the standard error for each measurement was less than 5%.

(Morterra and Low, 1983, 1985; Zawadski, 1981; Laine

et al., 1989). The assignment of a specic wave number
to a given functional group was not possible because the
absorption bands of various functional groups overlap
and shift, depending on their molecular structure and
environment. Shifts in absorption position may be
caused by factors such as intramolecular and intermolecular hydrogen bonding, stearic eect and degree of

Fig. 2. FTIR spectra of the reference carbons (a) CPGLF and (b)
CCAL. Band assignments: Band 1: Stretching of C@O in carbonyls
(aldehyde and ketones), carboxylic acids, and lactones. Band 2: CO
stretching and OH bending in alcohols (phenols, lactones), and carboxylic acids.  Absorption of each group may shift within each band
depending on molecular structure and environment.

conjugation. For instance, within its given range, the

position of the C@O stretching band (common to carbonyls, carboxylic acids and lactones) is determined by
many factors. These include: (1) the physical state, (2)
electronic and mass eects of neighboring substituents,
(3) conjugation, (4) hydrogen bonding and (5) ring
strain (Kendall, 1966; Smith, 1979). The IR absorption

Fig. 3. FTIR spectra of granular activated carbons from pecan shells

produced by (a) chemical activation (PS10), (b) carbon dioxide activation (PS23) and (c) steam activation (PS63).

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M. Ahmedna et al. / Bioresource Technology 71 (2000) 103112

bands of oxygen groups on the surface of solid GACs

are likely to be aected by some or all of the factors
listed above. The presence of peaks in Band 1 is indicative of the presence of carbonyls and/or lactones.
Coexistence of peaks in both Band 1 and 2 are indicative
of carboxylic acids (C O stretching, CO stretching
and OH in-plane bending), phenols (OH bending),
lactones and carbonyls (C@O stretching). The absence
of distinct peaks in one or two bands indicates absence
of the corresponding surface oxides. Most of the carbons activated at high temperature (800900C) showed
absorption peaks in Band 1 and no peaks in Band 2
suggesting a predominance of carbonyls and lactones.
Chemical activation of pecan shells (PS10) showed
strong absorption peaks in both bands, indicating the
presence of carboxylic acids and phenols along with
carbonyls and lactones. The same pattern was also revealed by titration (Fig. 1). These results are in agreement with the ndings of many investigators (Bansal et
al., 1988; Molina-Sabio et al., 1991; Zawadski, 1981)
who reported that carbons produced at lower temperature have a variety of surface oxides, including carboxylic acids; but the majority of these surface structures,
especially carboxylic acids and lactones decompose in
the temperature range 600800C.
3.4. Adsorption properties of GACs and their relationship
to surface properties
Based on both molasses color removed and sugar
decolorization, GACs made from sugarcane bagasse
using corn syrup as a binder (SBCS 21 and 11) and two
pecan shell-based carbons (PS63, steam activated and
PS10, chemically activated) were as eective as the
commercial carbons in removing sugar colorants
(Figs. 4 and 5). GACs produced from sugarcane bagasse
with coal tar as a binder and those prepared from pecan
shells using CO2 activation were the least eective decolorizers. The superior decolorization eciency of the
carbons produced with corn syrup is probably due to
their relatively well developed surface area compared
with carbons made with coal tar. The limited surface
area of coal-tar carbons may be attributed to the fact
that coal tar has a higher carbon content than corn
syrup, and therefore, would be volatilized to a much
lesser extent (Pendyal et al., 1999a), yielding less developed surface area.
Overall, three characteristics of activated carbon can
be used to explain the observed dierences in molasses
and raw sugar color adsorption among the carbons.
These properties include total surface area, pore-size
distribution (relative proportion of micro-, meso- and
macropores), and chemical reactivity, which depends on
the types and concentrations of the surface oxides on the
carbon surface (Mattson and Mark, 1971; Dubinin,
1987). Large surface area is generally a requirement for

an optimum adsorbent. However, the total surface area

has to possess adequate pore size distribution and surface chemistry to adsorb the targeted species. An activated carbon with large surface area may absorb very
rapidly, but its adsorptive capacity could be low because
it lacks the proper pore size to contain the adsorbed
material (Patrick, 1995). The presence of large and small
pores implies a favorable pore size distribution for adsorption of polydispersed colorants. The system of
macropores would serve as avenues for the rapid diusion of color bodies to the smaller pores where they are
adsorbed. These structures favorably enhance both the
adsorption and reactivation characteristics (Calgon,
1987). The presence of surface oxygen complexes also
imparts a polar character to the activated carbon surface, which can aect preferential adsorption of polar
organic solutes. Pore structure and chemistry of activated carbons made from agricultural by-products are
strongly dependent on pyrolysis temperature, composition and structure of the raw materials, and method of
activation (Girgis et al., 1994; Gergova et al., 1994;
Rodriguez-Reinoso and Molina-Sabio, 1992).
Since percent molasses color removed and percent
sugar decolorization did not seem to be directly proportional to surface area, pore size distribution as well
as total surface charge may have played a role in the
observed dierences.
Modeling of the percent molasses color removed as a
function of total surface area and pore ratio showed that
it followed a curvilinear relationship (Fig. 6). Such a
curvilinear relationship predicts that optimal decolorization by GACs would occur around a macro- plus
mesopore area/total surface area (MMSA/TSA) ratio of
0.25 and a total surface area between 1000 m2 /g and
1220 m2 /g. The low MMSA/TSA ratio of 0.080.09 for
carbons made from pecan shells activated with CO2
(PS9 and PS23) may, in part, explain why they failed to
achieve good decolorization eciency, despite their relatively high surface area. The high microporosity of
these carbons would make adsorption of larger molecules, as found in sugar colorants, problematic. These
large molecules would have diculty entering and navigating through the micropores with the possibility that
the micropores could become clogged, thereby eectively stopping further adsorption (Pendyal et al.,
1999b). According to Wigmans (1989), an activated
carbon with a high percentage of micropores will tend to
adsorb low molecular weight compounds, and as the
percentage of micropores decreases, the carbon can
adsorb compounds with a broader range of molecular
sizes. The presence of macro- and mesopores may help
adsorb the larger colorant molecules while allowing the
smaller molecules access to the micropores where they
are adsorbed.
The negatively charged surface formed by the dissociation of specic types of surface oxides appears to

M. Ahmedna et al. / Bioresource Technology 71 (2000) 103112

109

Fig. 4. Percent molasses color removed for experimental and commercial carbons. See Fig. 1 for carbon identication. Bars represent the means of
four replications where the standard error for each measurement was less than 5%. Bars with dierent letters are signicantly dierent at p < 0.05.

Fig. 5. Sugar decolorization eciency of experimental and commercial carbons. See Fig. 1 for carbon identication. Bars are means of four replications where the standard error for each measurement was less than 5%. Bars with dierent letters are signicantly dierent at p < 0.05.

reduce color removal by GACs. The highest percent

color removal was achieved by carbons having no carboxylic groups (or no negative charge at pH 7) (Fig. 7).
A carbon's eciency in removing sugar colorants decreased with increasing amount of negative charges on
the surface, probably because of charge repulsion of
sugar colorants which are predominantly negatively
charged. Electrostatic repulsion would explain why the
carbon made from pecan shells with chemical activation
(PS10) exhibited decolorization capacity lower than
expected, despite its extensive surface area (1200 m2 /g)
and its favorable pore size distribution (0.22). The
steam-activated pecan shell-based carbon was a good

sugar decolorizer because it possessed a good surface

area (850 m2 /g), an optimal pore size distribution (0.24),
and no carboxyls (negligible surface charge). This set of
surface properties appears to favor the adsoption of
sugar colorants and would, therefore, be recommended
for carbons designed for use in sugar reneries.
Carbons prepared from sugarcane bagasse and coal
tar exhibited low decolorization eciency mainly because
of their very low surface area (78180 m2 /g). The combination of sugarcane bagasse and corn syrup yielded
GACs with moderate surface area (300 m2 /g), good pore
size distribution, and a relatively low surface charge,
which explain their good sugar decolorizing capacity.

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M. Ahmedna et al. / Bioresource Technology 71 (2000) 103112

Fig. 6. Percent molasses color removed as a function of total surface area and pore ratio.

Fig. 7. Percent molasses color removed as a function of total surface area and surface charge (groups ionizable at neutral pH).

3.5. Grouping of experimental GACs based on similarities

to the commercial carbon references
The results of principal component analysis (Fig. 8)
and cluster analysis (Table 4) revealed that two byproduct-based carbons, namely PS10 (chemically activated pecan shells) and PS63 (steam-activated pecan
shells) were similar to the reference carbons in terms of
surface and adsorption properties. The two CO2 activated pecan shell-based carbons (PS9 and PS23) did not
cluster with the reference carbons mainly due to unfavorable pore size distribution. Carbons prepared with
coal tar (SBCT11, SBCT21), on the other hand, were
not classied with the reference carbons because of their

low surface area. GACs derived from sugarcane bagasse

with corn syrup (SBCS11, SBCS21) were close to being
included with the commercial carbons but were excluded
by their relatively low surface area. Otherwise, they
showed good sugar decolorization potential.
4. Conclusions
Raw sugar decolorization was favored in carbons
possessing high surface area, a preponderance of micropores, and low negative surface charge, as evidenced
by few carboxyl groups. Modeling of percent molasses
color removed as a function of surface area, pore ratio,

M. Ahmedna et al. / Bioresource Technology 71 (2000) 103112

111

Fig. 8. Grouping of GACs based on the rst two principal components. See Fig. 1 for carbon identication.

Table 4
Grouping of experimental GACs based on their surface and adsorption properties
Cluster 1

Cluster 2

Cluster 3

CCAL
CPGLF
PS63
PS10

SBCS105
SBCS11
SBCT21
SBCT11

PS23
PS9

and surface charge predicted that carbons with surface

areas above 300 m2 /g, pore ratios of 0.25, and no carboxylic groups were most eective in removing sugar
colorants. Even with a large surface area, carbons with
high negative surface charge and/or low pore ratio exhibited relatively poor decolorization eciency because
of charge repulsion between predominantly negatively
charged sugar colorants and the negatively charged
carbon surface and/or poor diusion of sugar liquor in
the carbon matrix. Pecan carbons produced by chemical
activation with phosphoric acid showed promise as
sugar decolorizers if their surface chemistry were altered
to reduce the amount of carboxyl groups and, therefore,
enhance their surface anity to sugar colorants. Steam
activation showed the best potential for producing activated carbons with high surface area, good pore ratio
and few carboxyl groups, which are good characteristics
for sugar decolorizers. Since GACs made from pecan
shells were very similar to the commercial carbons in
terms of raw sugar decolorization as well as most other
characteristics, they may provide a lower cost alternative
to the existing coal-based commercial carbons for use in
the sugar rening industry.

Acknowledgements
The authors gratefully acknowledge Dr. Willem
Kampen for generously providing laboratory space and
Dr. Christopher Toles for his assistance in carrying out
the surface area determinations. The research is in partial
fulllment of Doctor of Philosophy degree for one of us
(Mohamed Ahmedna) and was supported by USDAARS, Specic Cooperative Agreement #58-6435-3-121.
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