Article

pubs.acs.org/IECR

Kinetic Study on the Acid Hydrolysis of Cenchrus ciliaris Particles for

the Production of Xylose and Other Monosaccharides
Kareen K. Encinas-Soto, Abraham R. Martin-Garca, and Manuel Perez-Tello*
Department of Chemical Engineering and Metallurgy, University of Sonora, Blvd. Luis Encinas & Rosales, Hermosillo, Sonora,
Mexico
ABSTRACT: An experimental study on the acid hydrolysis of Cenchrus ciliaris particles was conducted. Input variables included
particle size of the raw material (<0.053 mm and 0.16 mm), sulfuric acid concentration (0.05 and 0.15 M), and reaction
temperature (120150 C). Output variables included the concentrations of xylose, glucose, arabinose, and furfural in the
aqueous solution. Five chemical reactions involving the hydrolysis of the Cenchrus ciliaris particles and the decomposition of the
monosaccharides were proposed, and a pseudohomogeneous model consisting of ve ordinary dierential equations was
developed. By means of numerical techniques, the values of the parameters of the Arrhenius equation for all chemical reactions
were determined. Good agreement between the model predictions and the experimental data was obtained. The hemicellulose in
the Cenchrus ciliaris particles was represented by an empirical formula containing 55 units of xylan, 25 units of glucan, and 19
units of arabinan oligomers.

INTRODUCTION
As a result of increasing concerns regarding the impact of
greenhouse gas emissions on the environment in the near
future, a current trend is the search for alternative fuels to
substitute for fossil fuels in the transportation industry. This is
because the processes by which fossil fuels are typically
produced and combusted also produce signicant amounts of
greenhouse gases such as carbon dioxide, methane, and nitrous
oxides which absorb infrared radiation emitted by the earth and
thus contribute to the global warming of the lower
atmosphere.13 Examples of this approach include the
commercial scale production of ethanol by biotechnological
routes in the United States4 and Brazil.5 Such technologies are
aimed at substituting gasoline in internal combustion
automobiles.
From a social perspective, a number of organizations have
criticized the processing of crops traditionally intended for
human consumption, such as corn and sugar cane, to produce
ethanol for the transportation industry.6 An alternative
approach consists of processing feedstocks which are not
intended for human consumption, such as lignocellulosic
materials, to produce ethanol. A review on the subject has
been reported recently.7 The processing of lignocellulosic
materials for this purpose typically involves four steps:7,8 (1)
hydrolysis of hemicellulose in the raw material to preferentially
release xylose to the aqueous solution, (2) hydrolysis of
cellulose in the remaining solid to release glucose to the
aqueous solution, (3) fermentation of glucose and xylose in the
liquid phase to produce ethanol, and (4) distillation of the
fermented mixture to obtain high-purity ethanol. Step 1 in the
above sequence is critical because the selective production of
xylose to leave a solid in which cellulose remains unreacted is
dicult. In addition to xylose, the hydrolysis of hemicellulose
typically produces other carbohydrates such as glucose and
arabinose. The hydrolysis of cellulose may also occur
simultaneously to produce additional glucose which is released
to the aqueous phase.
2015 American Chemical Society

From a process engineering approach, the goal of step 1 is to

produce an aqueous solution containing mostly xylose, leaving
behind a hemicellulose-free solid in which cellulose is ready for
further treatment. As the yields of steps 24 are strongly
dependent upon the eciency at which step 1 is conducted, it
is of interest to investigate the conditions at which the
production rate of xylose is maximized while keeping the
concentrations of the other products in the aqueous solution as
low as possible. A number of investigations regarding the
processing of lignocellulosic materials914 have focused on the
kinetics of step 1 to characterize the main features of the
complex chemical reactions taking place during the acid
hydrolysis of hemicellulose. The kinetics of the sulfuric acid
hydrolysis of a number of lignocellulosic materials has been
reported in the literature. Such studies include corn stover,
poplar, and switchgrass;15 hazelnut shells;16 sweet sorghum
bagasse;17 timber varieties and switchgrass;4 and forest residues
of Eucalyptus grandis5 as raw materials. These studies have
shown the potential of lignocellulosic materials as an alternative
to replace corn and sugar cane for the production of ethanol.
In this study, Cenchrus ciliaris, also known as buelgrass, is
proposed as a potential raw material for the production of
ethanol. Cenchrus ciliaris and other varieties of buelgrass grow
in the northwestern Mexican state of Sonora, as well as Arizona
and Texas in the United States. The grass was introduced into
Texas from the African savannah in the late 1940s18 and spread
quickly throughout the Sonoran desert. It is now considered a
threat to native plants in the area because it competes for water.
Also, its roots and soil coverage prevent the germination of
seeds of native vegetation. When dry, the grass burns quickly
and thus increases the risk of wildres.19 In the state of Sonora,
Received:
Revised:
Accepted:
Published:
436

October 27, 2015

December 22, 2015
December 28, 2015
December 28, 2015
DOI: 10.1021/acs.iecr.5b04034
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sulfuric acid solution and 10 g of 0.16 mm particles were placed

in the reactor at room temperature. The reactor was
hermetically closed, the mechanical stirrer was turned on, and
the stirring speed was set. The system was heated to 120 C,
and the temperature was held constant for 50 min. When the
target temperature was reached, 5 mL samples of the aqueous
solution were collected every 10 min for a total of ve samples.
The samples were ltered, centrifuged, and further analyzed by
high-performance liquid chromatography (HPLC) to determine the concentration of xylose as a function of time. This
procedure was followed in two separate experiments in which
the stirring speed was set to 500 and 600 rpm. Upon
comparison, the values of xylose concentration measured in
both experiments showed no signicant dierences. Therefore,
it was concluded that mass transfer eects around the solid
particles in both cases were negligible compared to overall
reaction kinetics. Thus, for convenience, a stirring speed of 600
rpm was set in all the experiments. As will be discussed later in
this paper, the minimization of the external mass transfer
resistance does not guarantee a reaction control regime in this
type of system. This is because the hydrolysis reactions cause
signicant changes in particle porosity; thus, internal diusion
may become signicant as the reactions proceed.
In a typical run, 1 L of a sulfuric acid solution with a
prespecied concentration and 10 g of sieved, dried particles of
Cenchrus ciliaris were placed into the reactor at room
temperature and the reactor was hermetically closed. The
mechanical stirrer was turned on, and the system was heated by
means of an electrical jacket surrounding the reaction vessel.
The prespecied temperature for the experiment was achieved
within 2427 min, after which the rst 5 mL sample of the
aqueous solution was collected by means of a sampling port
tube connected to the reactor. Successive 5 mL samples of the
aqueous solution were collected every 10 min during the
following 60 min under isothermal conditions. Upon collection,
the samples were kept in tapped essay tubes and cooled by
running tap water to interrupt the chemical reactions. The
liquid samples were ltered by means of a 0.22 mm Millipore
lter to remove any suspended particles. The ltered solutions
were poured into glass vials and centrifuged for 20 min in a
Beckman ETM centrifuge unit. The clear solutions thus
obtained were chemically analyzed by HPLC to determine
the concentrations of the reaction products as functions of
time. The HPLC unit used a Varian Hi-Plex H column
containing 711 m diameter particles of a cation exchange
resin of sulfonated styrene copolymer cross-linked with
divinylbenzene. The unit was operated at 75 C using water
as the mobile phase at a ow rate of 0.6 mL/min. The refractive
index detector was a Varian Star 9020 model operated at 35 C
and a range of 2.56 104 units index of refraction. The
ultravioletvisible detector was a Varian ProStar and was
operated at a wavelength of 254 nm to detect furfural.
The selection of the experimental conditions tested in this
work was based on similar studies reported in the
literature4,5,912 for the dilute acid hydrolysis of lignocellulosic
materials. Previous works5,15,16 showed that the amount of
degradation products tends to increase as the acid concentration and temperature increase. For a given set of
experimental conditions, the same eect is observed if the
reaction time is extended beyond a practical limit. Because the
goal of the dilute acid hydrolysis of lignocellulosic materials is
to obtain as much monosaccharides as possible with a
minimum amount of degradation products, such a situation is

Mexico, buelgrass covers about 150 000 hectares throughout

the year and is typically used by local ranchers as pasture to
feed the livestock, especially ruminants.18
A recent report20 showed that the chemical composition of
wild Cenchrus ciliaris grass varies with the seasons of the year.
This is attributed to the natural uctuations in weather
conditions, especially temperature and rainfall. It was also
found that the chemical composition of the plant is not
uniform, i.e., its components distribute unevenly in stem and
leaves. The average content of the plant considered in this
study21 was 88% organic matter other than protein, 10% crude
protein, and 2% acid-insoluble ash. The organic matter included
5.3% lignin, 35.3% cellulose, 31.8% hemicellulose, and 15.6% of
undetermined species other than protein. Cenchrus ciliaris is
thus classied as a lignocellulosic material because its
composition is similar to those of others reported in the
literature.4,5,912 Based on the above information and assuming
full hydrolysis of the hemicellulose and cellulose in Cenchrus
ciliaris grass to produce monosaccharides, the theoretical yield
of ethanol per ton of Cenchrus ciliaris grass was calculated. A
production of 0.51 kg of ethanol per kilogram of monosaccharides consumed was considered. The result was 332 L of
ethanol produced per ton of Cenchrus ciliaris grass processed.
This theoretical value is similar to those of sugar cane bagasse22
(400 L/ton), forest residues23 (282 L/ton), and several types of
wheat24 (368447 L/ton) and conrms the potential of
Cenchrus ciliaris as a feedstock to produce ethanol.
The goal of this investigation was to study the kinetics of the
dilute acid hydrolysis of Cenchrus ciliaris particles under
controlled laboratory conditions. For that purpose, an
experimental program was conducted to collect relevant data.
Also, a mathematical formulation was developed to represent
the time evolution of the concentrations of the main reaction
products, as described below.

EXPERIMENTAL WORK
Samples of Cenchrus ciliaris grass were collected manually in the
town of Banamichi, Mexico during February and March, 2008.
The town of Banamichi is located at 3001 N and 11013 W
with an average altitude of 1300 m above sea level. The climate
is typically dry and semiarid, with an annual mean temperature
of 21.4 C. The collection of grass samples was conducted
randomly at dierent locations in the vicinity of the town, after
which the samples were stored at room temperature for 1 week.
The samples were dried at 80 C for 24 h in a laboratory oven.
Batches of 100 g of the dried material were ground in a 200
Pulvex mill for about 10 min. The ground material was sieved,
and the size fractions corresponding to <0.053 and 0.147
0.173 mm were collected. In this paper, such fractions are
referred to as <0.053 mm and 0.16 mm, respectively, the latter
of which indicating the mean size of the sieved fraction. The
sieved particles were transferred into plastic bags, and the bags
were labeled and sealed for storage at room temperature. The
experimental program took about ve months, during which
the particles were taken from the plastic bags as needed.
The hydrolysis of the sieved Cenchrus ciliaris particles was
conducted in a 2 L stainless steel, high-pressure Parr cylindrical
reactor, model 4850. The reactor is capable of operating
isothermally within a variation of 1 C by means of a
temperature controller. Preliminary experiments were conducted in this reactor to nd the value of the stirring speed
under which the mass transfer resistance around the solid
particles becomes negligible. With that purpose, 1 L of a 0.05 M
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kX ,H+

undesirable and oers no practical interest for the processing of

such materials. On the other hand, concentrated acid hydrolysis
methods7 typically operate at temperatures lower than 100 C
with high production of monosaccharides and thus high ethanol
yields. However, they are highly corrosive and energyconsuming.
In this study, a full factorial, 2 2 3 experimental design
with repetitions at the center of the array25 was used. Input
variables tested in the experiments included particle size
(<0.053 and 0.16 mm), sulfuric acid concentration (0.05 and
0.15 M), and reaction temperature (120, 135, and 150 C).
Output variables measured in the experiments included the
concentrations of xylose, glucose, arabinose, and furfural in the
aqueous solution as functions of time up to 90 min. To
determine the uncertainty of the experimental data, a series of
four repetitions were conducted at the following experimental
conditions: 0.0530.16 mm size fraction, 0.1 M acid
concentration, and 135 C. Such conditions correspond to
the mean values of the input variables tested in the experiments.
Based on the experimental data obtained from the repetition
experiments, the error bars for all species concentrations were
obtained.25 A selected number of reacted particles were
observed in a JEOL 5410LV scanning electron microscopy
(SEM) instrument to determine its morphology.

X(aq) F(aq)
k G ,H+

G(aq) P(aq)
kA ,H

(5)

The hydrolysis of the Cenchrus ciliaris particles is represented

by reactions 1 and 2 which are generally accepted to be
catalyzed by the acid species.30 Reactions 35 involve the
decomposition of the monosaccharides produced by the acid
hydrolysis. Symbols H and C represent hemicellulose and
cellulose, respectively; similarly, symbols X, G, and A indicate
xylose, glucose, and arabinose; F stands for furfural; P and Q
are the degradation products from glucose and arabinose; (s)
and (aq) indicate solid and aqueous phases, respectively.
Symbols GH and GC are stoichiometric coecients which
indicate the molar amount of glucose produced per mole of
reacting hemicellulose and cellulose, respectively. Similarly,
symbols XH and AH are the molar amounts of xylose and
arabinose produced per reacting mole of hemicellulose. Finally,
symbols m and n indicate the molar amounts of water
consumed per mole of reacting hemicellulose and cellulose in
reactions 1 and 2, respectively. Based on the chemical formulas
of the monosaccharides and oligomers, it is found that m and n
may be obtained from the following relationships:

FORMULATION OF THE KINETIC MODEL

The details of the reaction mechanisms governing the acid
hydrolysis of lignocellulosic materials are still uncertain. Also,
they have been found to be dependent upon the specic raw
material being treated and the experimental conditions. A
number of mathematical formulations have been reported in
the literature to represent the acid hydrolysis of a variety of
lignocellulosic materials.915 A detailed discussion of the several
types of models is beyond the scope of the present paper. A
review on the subject up to the year 2000 is available.26 Most of
the mathematical formulations915 are based on a pseudohomogeneous approach in which the mathematical complexity
depends on the number of reaction steps considered in the
formulation. The models have been used with two primary
goals: (1) the prediction of the kinetics of concentrations of
xylose and other monosaccharides upon hydrolysis of the raw
materials1012,15 and (2) the optimization of the operating
conditions for the hydrolysis of cellulose and hemicellulose by
means of statistical techniques.27,28 In the pseudohomogeneous
approach, the eect of the acid concentration on the overall
reaction rate is typically included in the pre-exponential term of
the Arrhenius expression for the apparent rate constant, ki.
Recently, a new model for the acid hydrolysis of sugar cane
bagasse was developed by Greenwood et al.29 The model takes
into account the heterogeneous nature of the hydrolysis
reactions, internal diusion, and particle properties such as
shape and porosity. The goal of the present formulation was to
provide a reasonable quantitative representation of the major
chemical changes observed during the acid hydrolysis of the
Cenchrus ciliaris particles studied in this work. The model was
based on the following overall chemical reactions

m = XH + GH + AH 1 and n = GC 1

It is noted that reactions 1 and 2 are heterogeneous because

they involve the contact of Cenchrus ciliaris particles with the
aqueous solution, whereas reactions 35 are liquid-phase
homogeneous reactions. In the present formulation, reactions 1
and 2 were treated according to a pseudohomogeneous
approach similar to that used by other authors.912 This is
justied because the reaction mechanisms governing the
hydrolysis of lignocellulosic materials are complex and still
uncertain. The following assumptions were made: (a) the
system under study is a batch, perfectly mixed reactor; (b) the
volume of the liquid phase is constant; and (c) all reactions are
irreversible and obey a rst-order kinetics with respect to the
reactants. From the above considerations, the mass balance
equations for the species involved in reactions 15 are written
as

kH ,H+

H(s) + mH 2O XH X(aq) + GHG(aq) + AH A(aq)

(1)

C(s) + nH 2O GCG(aq)

(4)

A(aq) Q(aq)

k C ,H+

(3)

dH
= kHH
dt

(6)

dC
= k CC
dt

(7)

dX
= XHkHH kXX
dt

(8)

dG
= GHkHH + GCk CC k GG
dt

(9)

dA
= AHkHH kAA
dt

(10)

dF
= kX X
dt

(11)

Equations 611 were subject to the initial conditions (IC)

IC:

(2)
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t = 0, H = H0 ; C = C0 ; X = G = A = 0
DOI: 10.1021/acs.iecr.5b04034
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where H, C, X, G, A, and F refer to the molar amounts of the
corresponding species per unit volume of aqueous solution at
time t, and symbols ki are the reaction rate parameters dened
in reactions 15. It is noted that t = 0 corresponds to the time
at which the heating of the solidliquid suspension in the
reactor started. Equations 6 and 7 state that the rate of
consumption of hemicellulose and cellulose in the reactor is
proportional to their instantaneous amounts in the reactor.
Equation 8 indicates that the accumulation rate of aqueous
xylose in the reactor results from two competing processes;
namely, its production from reaction 1 and its consumption to
produce furfural according to reaction 3. Equations 911 may
be interpreted similarly for the accumulation rate of glucose,
arabinose, and furfural in the reactor, respectively. The reaction
rate parameters ki at time t were computed from the Arrhenius
equation
E
ki = ki0 exp i
RT

i = H, C, X, G, A

Figure 1. Typical time evolution of the system temperature during the

acid hydrolysis of Cenchrus ciliaris particles. The continuous lines
represent the linear ts of the experimental data indicated by the
symbols.

composition of Cenchrus ciliaris21 and the amount of solid used

in the experiments (10 g), it was found that H0 = 0.23 mmol/L
and C0 = 0.19 mmol/L.
The values of the model parameters ki0, Ei, and ij were
obtained from the following procedure. First, an initial set of
parameter values was established and eqs 611 were solved
numerically by means of the Eulers method.34 A time step: t =
5 103 min was used up to a total time of 82 min. During the
calculations, the values of ki at time t were computed from eq
12 by using the calculated values of T according to the
procedure described previously. The numerical integration of
eqs 611 coupled to eq 12 was performed for all the
experimental runs simultaneously, after which the objective
function, OF, was computed from

(12)

where ki0 is the pre-exponential term, Ei the apparent activation

energy, and R the ideal gas constant. It is of interest to note the
implications of the pseudohomogeneous approach used in this
work. For a given elementary reaction, the pre-exponential
elem
term, kelem
, are constant values.
i0 , and activation energy, Ei
They are referred to in the literature as intrinsic kinetic
parameters.31 Because the reaction mechanisms governing the
hydrolysis of Cenchrus ciliaris particles are uncertain, reactions
15 cannot be considered as elementary reactions; instead,
they are overall reactions that involve a number of elementary
steps. The elucidation of the elementary steps governing the
hydrolysis of lignocellulosic materials is currently a challenge in
this area. This is mostly due to the complexity of the solid
structure of plants,32,33 which is strongly dependent upon the
plant species under consideration and makes the analysis of the
reacting system dicult.
On the other hand, the reaction system involves the contact
of a reactant solid and a liquid phase. Therefore, typical factors
that aect the rate of heterogeneous reactions31 may also play a
signicant role in this type of system. Such factors include
particle properties such as size, morphology, and chemical
composition and physical phenomena such as internal diusion.
The simultaneous eects of all chemical and physical factors
relevant to the system result in the overall reaction kinetics
measured in the experiments. Furthermore, symbols ki0 and Ei
used in this paper are overall parameters, the values of which in
general depend upon the input variables tested in the
experiments. In this work, they are termed apparent or
empirical values to distinguish from the intrinsic values
mentioned previously.
During the experiments, the system temperature, T,
increased mostly linearly prior to reaching the target temperature, as shown in Figure 1. The temperature-versus-time data
was tted to a series of straight lines within selected time
intervals. The calculated values from such a procedure are
represented in Figure 1 by the continuous lines. Overall, good
agreement between the calculated and the experimental values
was obtained. The calculated values were further used during
the numerical algorithm described next.
From a mathematical standpoint, eqs 611 coupled with eq
12 is a set of nonlinear, ordinary dierential equations. They
may be solved once the model parameters ki0, Ei, and ij and the
initial conditions (IC) are specied. Based on the chemical

OF =

{|Xkje Xkjc | + |Gkje Gkjc | + |Akje Akjc |

k=1 j=1

+ |Fkje Fkjc |}

(13)

where superscripts e and c indicate the experimental and

calculated values, respectively, of the concentrations of the
corresponding monosaccharides and furfural at the jth value of
time; N is the total number of experimental points in the kth
experiment; and M is the total number of experimental runs. In
the present case, N and M took on the values of 7 and 12,
respectively. Equation 13 represents the summation of the
absolute errors in the calculation of the species concentration
under all experimental conditions.
The goal of the numerical algorithm was to minimize the
value of OF so that the calculated values in the right-hand side
of eq 13 approached the experimental values. If the value of OF
did not achieve a prespecied convergence criterion, a new set
of ki0, Ei, and ij values was established and the procedure was
repeated as many times as necessary. For the optimization step,
the generalized reduced gradient method built within the
framework of the Solver algorithm in Excel 2007 was used.
During the calculations, care was taken to restrict the values of
Ei so that they were dependent upon the chemical reactions
only. Therefore, the value of Ei for a given chemical reaction
was set to be a constant value in all runs. This is a simplication
of the pseudohomogeneous approach to keep the number of
adjustable parameters as low as possible. A similar approach was
used for the stoichiometric coecients ij. As a result, the
numerical algorithm was aimed at calculating 60 values of ki0, 5
values of Ei, and 4 values of ij, for a total of 69 parameter
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experiments. In the second group shown in Figures 2b, 3a,

3b, and 4b, the monosaccharides concentrations increased

values. Finally, a quantitative estimation of the accuracy of the

present formulation was obtained from the following expression
ek =

100
4N

j=1

Fkjc

+ 1 e
Fkj

Gkjc
Gkje

+ 1

Xkjc
Xkje

+ 1

Akjc
Akje

(14)

where ek is the average error in percentage obtained from the

calculation of the species concentrations in the kth run relative
to the mean experimental values, and other symbols have been
dened previously.

DISCUSSION OF RESULTS
Figures 24 show the predicted and the experimental values of
the species concentrations in the aqueous phase during the acid

Figure 3. Predicted and experimental values of species concentration

during the acid hydrolysis of Cenchrus ciliaris particles. Experimental
conditions: 0.05 M H2SO4, 135 C (a) < 0.053 mm; (b) 0.16 mm.
Glucose experimental, ; glucose calculated, solid line; xylose
experimental, ; xylose calculated, dashed line; arabinose experimental, ; arabinose calculated, ; furfural experimental, ;
furfural calculated, .

gradually with time and eventually approached an asymptotic

value or reached a maximum and further decreased. In these
cases, the concentration of furfural was low and increased
linearly with time. The shape of all curves shown in Figures
24 may be explained in terms of reactions 15. For all the
experimental conditions, reactions 1 and 2 initiated the
production of the monosaccharides; thus, xylose, glucose, and
arabinose concentrations increased steadily at short reaction
times without signicant formation of the degradation products
F, P, and Q from reactions 35. Once the monosaccharides
were incorporated into the solution, they began decomposition
according to reactions 35. As of this time, the concentrations
of the monosaccharides increased, decreased, or remained
constant over time depending on the rate of the competing
reactions. For instance, Figures 2a and 4a show experiments in
which the rate of formation of the monosaccharides was
substantially higher than their rate of decomposition at all
times. In contrast, Figures 2b, 3a, 3b, and 4b show experiments
in which the rate of formation of the monosaccharides was of
similar order of magnitude to their rate of decomposition. In
the latter cases, the rate of decomposition eventually became
higher than the rate of formation of the monosaccharides, and
the monosaccharides concentrations reached a maximum and
further decreased. The gradual increase of the furfural
concentration with time in such cases is the evidence of the
decomposition reactions.

Figure 2. Predicted and experimental values of species concentration

during the acid hydrolysis of Cenchrus ciliaris particles. Experimental
conditions: 0.16 mm, 0.05 M H2SO4; (a) 120 C and (b) 150 C.
Glucose experimental, ; glucose calculated, solid line; xylose
experimental, ; xylose calculated, dashed line; arabinose experimental, ; arabinose calculated, ; furfural experimental, ;
furfural calculated, .

hydrolysis of Cenchrus ciliaris particles. The experimental values

are represented by the discrete symbols, whereas the values
predicted by eqs 811 are indicated by the continuous curves.
For the sake of brevity, a selected number of experimental
conditions are shown as examples. Prior to the discussion of the
kinetic model results, the general trends observed in the
experimental data are presented.
A general inspection shows two types of behavior. In the rst
group shown in Figures 2a and 4a, the monosaccharide
concentrations increased mostly linearly with time, while
furfural concentration remained negligible throughout the
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ides increased linearly with time. The largest concentration of

xylose was 5.6 mmol/L and was obtained at the end of the
experiment. Also, no substantial presence of furfural was
detected. In contrast, when the temperature was increased to
150 C (lower plot), the reaction rate of all reactions also
increased and became of the same order of magnitude. As a
result, the concentrations of all monosaccharides and furfural
were higher than those observed at 120 C. Thus, xylose
concentration reached a maximum of 11.8 mmol/L at t = 20
min and further decreased to 8.4 mmol/L at t = 60 min. The
concentration of furfural steadily increased with time and
reached the highest value of 2.6 mmol/L at the end of the
experiment. The trends observed in Figure 2 are expected
because temperature is known to increase the reaction rate by
increasing the velocity of the reacting molecules. However, a
relevant nding from Figure 2 is that a temperature change of
30 C may substantially aect the reaction kinetics during the
acid hydrolysis of Cenchrus ciliaris particles, which has practical
implications on the system operation.
Figure 3 shows the eect of particle size on the reaction
kinetics at 135 C when the particles were contacted with a
0.05 M sulfuric acid solution. As expected, < 0.053 mm particles
(upper plot) were more reactive than 0.16 mm particles (lower
plot). This is noted by the higher concentration values of both
xylose and glucose obtained with <0.053 mm particles than
those obtained with 0.16 mm particles. The hydrolysis reactions
in the <0.053 mm particles initiated prior to reaching the
isothermal stage, as the concentrations of all species in the rst
sample collected at t = 18 min were not zero. The
decomposition of xylose to produce furfural from reaction 3
also initiated early in the experiment. A distinctive feature in
Figure 3 concerns the concentration of arabinose, which is of
similar order of magnitude in both upper and lower plots.
Arabinose is produced from reaction 1 only, whereas glucose is
produced from reactions 1 and 2. Figure 2 shows that arabinose
production was not substantially aected by the change in
particle size from <0.053 to 0.16 mm, whereas glucose
production was indeed aected by such a change. This suggests
that a signicant amount of glucose released from the <0.053
mm particles was produced from the hydrolysis of cellulose,
reaction 2. A possible explanation for this behavior is that
grinding to ne sizes left a signicant number of particles in
which cellulose was exposed to the acid solution. In contrast, in
the 0.16 mm particles, most of the cellulose was not initially
exposed to the acid solution. Because a detailed analysis of the
composition and morphology of the reacting particles was
beyond the scope of this investigation, the clarication of this
point deserves further research.
The eect of acid concentration on the reaction kinetics of
<0.053 mm particles at 120 C is shown in Figure 4. When a
dilute 0.05 M acid solution was used, the reactions were slow
and the concentrations of the monosaccharides increased
linearly with time. Also, degradation of xylose was negligible as
no furfural was detected in the aqueous phase throughout the
experiment. In contrast, when the acid concentration was
increased to 0.15 M, the reaction rate increased substantially
and low concentrations of furfural were detected. Although the
reaction mechanisms of the hydrolysis of lignocellulosic
materials are still under debate, it is generally accepted30 that
hydrogen ions act as catalysts in the hydrolysis of hemicellulose
by attacking the chemical bonds of the oligomers making up
the hemicellulose matrix, namely, xylan, glucan, and arabinan.
The resulting compounds are then suitable for reacting with

Figure 4. Predicted and experimental values of species concentration

during the acid hydrolysis of Cenchrus ciliaris particles. Experimental
conditions: <0.053 mm, 120 C; (a) 0.05 M H2SO4; (b) 0.15 M
H2SO4. Glucose experimental, ; glucose calculated, solid line; xylose
experimental, ; xylose calculated, dashed line; arabinose experimental, ; arabinose calculated, ; furfural experimental, ;
furfural calculated, .

It is expected that the experiments shown in Figures 2a and

4a will eventually exhibit a behavior similar to those shown in
Figures 2b, 3a, 3b, and 4b should the reaction time be extended
longer than 60 min at the selected temperature. This trend was
observed in the hydrolysis of other lignocellulosic materials
such as switchgrass,11 sugar cane bagasse,13 and corncob.14 In
general, if the reaction time is increased without limit, reactions
35 will eventually deplete the monosaccharides and the
aqueous phase will contain the degradation products F, P, and
Q only. Because such a situation is undesirable, the length of
the reaction time was restricted within a range in which the
experimental data may be of practical interest; namely, the
preferential release of xylose from reaction 1 while keeping
furfural concentration values as low as possible.35 An overall
analysis of the experimental data showed that the maximum
concentration of xylose measured in the experiments was 11.9
mmol/L and was obtained at t = 56 min in the experiment
conducted with <0.053 mm size particles, 0.15 acid
concentration, and temperature of 150 C. Under such
conditions, the concentration of furfural was 1 mmol/L. As
far as the maximization of the xylose concentration is
concerned, such conditions represent the optimum values.
Figures 24 are aimed at illustrating the eects of the test
variables on the overall kinetics of the reacting system. The test
variables included temperature, particle size, and sulfuric acid
concentration. Figure 2 shows the species concentrations in the
aqueous phase when 0.16 mm particles were contacted with a
0.05 M solution of sulfuric acid in the reactor. The eect of
temperature is noted by comparing the upper and lower plots.
At 120 C (upper plot), the rate of the hydrolysis reactions was
signicantly higher than the rate of decomposition of the
monosaccharides, and the concentrations of the monosacchar441

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Table 1. Numerical Values of the Pre-exponential Terms of Equation 12 and Errors Obtained from Equation 14
run no. (k) target temperature (C)
1
2
3
4
5
6
7
8
9
10
11
12

120
120
120
120
135
135
135
135
150
150
150
150

[H2SO4] M mean particle size (mm)

0.05
0.05
0.15
0.15
0.05
0.05
0.15
0.15
0.05
0.05
0.15
0.15

kH0 (min1)

0.16
0.053
0.16
0.053
0.16
0.053
0.16
0.053
0.16
0.053
0.16
0.053

9.9
13.0
28.6
29.4
26.9
55.6
19.1
20.7
42.4
55.9
22.0
67.6

(Xylan)55 (Glucan)25 (Arabinan)19 + 98H 2O

Cellulose + 114H 2O 115Glucose

3.46
2.46
6.41
2.93
2.36
7.04
1.79
1.78
7.33
6.63
8.96
5.34

kG0 (min1)
49.5
21.7
32.8
1.1 108
3.1
5.8 102
1.4
0.6
4.4
0.42
108
0.14

kC0 (min1)
3

3.4 10
108
0.7
3.6
2 102
4.2
108
0.6
0.5
4.7
2.9
4.4

kA0 (min1)

ek (%)

5.2 102
108
3.4
4.6
2.9
4.1
0.4
1.4
3.5
0.4
108
3.3 102

42
33
36
39
38
11
33
31
18
13
30
10

from one run to another. In contrast, the values of kG0, kC0, and
kA0 spanned over several orders of magnitude. This may be a
result of the aforementioned phenomenon.
Because the rate of the degradation reactions was in general
lower than the rate of hydrolysis of hemicellulose, few
experimental data were collected in which the degradation
reactions substantially aected the concentrations of the
monosaccharides in the aqueous solution. This typically
occurred at the latest stages of the experiments. As a result,
the uncertainties in the calculation of kG0, kC0, and kA0 were
higher than those related to the calculation of both kH0 and kX0.
To improve the accuracy in the estimation of such quantities,
experiments longer than 90 min at the selected temperature are
required. During this work, attempts were made to correlate the
ki0 values shown in Table 1 with the operating conditions,
namely, temperature, particle size, and acid concentration.
However, such eorts were unsuccessful. The diculties
associated in nding a good correlation for ki0 were expected
because ki0 are empirical values. Furthermore, the apparent
kinetic parameters obtained in this work cannot be generalized
to other experimental conditions. This is a typical restriction of
the pseudohomogeneous approach. In addition to the
uncertainties in the ki0 values just discussed, the characteristics
of the reacting particles may have strongly aected the behavior
of the present system. This point is discussed further in this
paper.
The last column in Table 1 shows the values of ek computed
from eq 14 for all the experimental conditions tested. They
varied in the range of 1042% with an average value of 28%. It
is emphasized that ek represents the average error in the
calculation of the mean experimental values. Thus, it does not
take into account the variability of the experimental data.
Regarding the concentrations of glucose, arabinose, and
furfural, Figures 24 show that the predicted values in most
cases were within the bars representing the experimental
uncertainty. The largest discrepancies between the calculated
and the experimental values were obtained for xylose
concentration, in which the kinetic model underpredicted
some of the experimental values, as shown in Figures 2b, 3b, 4a,
and 4b. Overall, Figures 24 show that despite the
uncertainties in the reaction mechanisms and the diculties
associated with the experimental program discussed previously,
the present model was capable of reproducing the major
features observed in the experiments, and a good agreement
between the predicted and the experimental values was
obtained.

water molecules to release the monosaccharides to the aqueous

phase. The production of the monosaccharides also regenerates
the hydrogen ions and the process repeats itself. Figure 4
indicates that such a catalytic process is dependent upon the
acid concentration and thus the reaction rate of reactions 1 and
2 increased with acid concentration. This result is in good
agreement with other studies reported in the literature for
similar systems.30
Regarding the results of the kinetic model, Figures 24
showed that overall, a reasonable agreement between the
predicted and the experimental values was obtained. The
optimization algorithm described in the previous section
provided the following values for the stoichiometric coefcients: XH = 55, GH = 25, AH = 19, and GC = 115.
Therefore, the hemicellulose in the Cenchrus ciliaris particles
may be represented by an empirical formula consisting of 55
units of xylan, 25 units of glucan, and 19 units of arabinan
oligomers, and reactions 1 and 2 may be rewritten as

55Xylose + 25Glucose + 19Arabinose

kX0 (min1)

(15)
(16)

Table 1 shows the values of the pre-exponential terms ki0 as

well as the errors ek obtained from eq 13. The corresponding
values of the apparent activation energies were found to be EH
= 23, EX = 26, EG = 24, EC = 26, and EA = 20 kJ/mol. These
values are lower than others reported in the literature for
lignocellulosic materials11,14,15 which typically vary in the range
of 100200 kJ/mol. It is emphasized that both ki0 and Ei are
empirical quantities that include both physical and chemical
phenomena occurring within the particles. As will be discussed
later in this paper, the eect of internal diusion may be
signicant in the present system; this may explain the low
values of the apparent activation energies.
Because the units of the pre-exponential terms ki0 are the
same, their values can be compared to each other. A general
inspection of Table 1 shows that in most runs the value of kH0
was higher than other ki0 values at the same experimental
conditions. This indicates that the reaction rate for the
hydrolysis of hemicellulose (reaction 1) was in general higher
than the rate of reactions 25. From a practical perspective,
this is a good result because the goal of the acid treatment of
lignocellulosic materials is to maximize the production of the
monosaccharides while minimizing their degradation. It is also
noted that the values of kH0 and kX0 did not vary drastically
442

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components making up the Cenchrus ciliaris grass are dierent.

Therefore, hemicellulose, cellulose, and lignin present in the
grass are likely to distribute unevenly in the particles upon
grinding. This hypothesis may explain the diculties found in
this work to correlate the values of ki0 with the operating
conditions. It may also explain the variability of the
experimental data shown in Figures 24.
Figure 6a shows a magnication of an unreacted 0.16 mm
particle, the surface of which is made up of bers distributed

Regarding particle morphology, Figure 5 shows scanning

electron microscopy images of the initial particles of the sieved

Figure 5. SEM images of Cenchrus ciliaris particles prior to the acid

hydrolysis experiments. General view of the sieved fractions: (a) <
0.053 mm and (b) 0.16 mm.

fractions. In both cases shown, the magnication was set to

allow a general view of the particle population. A wide range of
sizes is observed, especially in the sieved fraction 0.16 mm.
Overall, particle morphology varied signicantly and included
akes, long rods, thick cylinders, and particles with irregular
geometries. The surface of most particles was rough. In general,
the sieved fraction <0.053 mm contained a large number of
aked particles, whereas the sieved fraction 0.16 mm contained
a signicant amount of long rods and thick cylindrical particles.
This suggests that the origin of ne and coarse particles was
dierent during grinding,36 i.e., ne particles were likely
produced by abrasion of large chunks, whereas large particles
were mostly produced by fracture of the solid structures of the
plant by direct impact of the mill blades.37 As a result, it is likely
that grinding also produced particles with a variety of chemical
compositions. This is because physical properties relevant to
grinding38 such as the Youngs modulus and mass density of the

Figure 6. SEM images of the surface of 0.16 mm Cenchrus ciliaris

particles: (a) unreacted particle and (b) reacted particle at 120 C and
0.15 M acid concentration; reaction time, 85 min.

along its largest dimension. Fine particles with sizes less than 1
m are attached to the surface. Figure 6b shows that the reacted
particles of this size fraction retained their original geometry,
but their surface became highly porous and left the interior
bers exposed, thus indicating that dissolution of the exterior
layers occurred. The structures in the interior of the reacted
particles varied in both size and geometry. The porous structure
of the reacted particles suggests that internal diusion played a
signicant role in the rate of the hydrolysis reactions once the
external layer of the particles was consumed. The capture of
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(3) Wang, M. Q. GREET 1.5-transportation fuel-cycle model-Vol. 1:

methodology, development, use, and results; Argonne National Lab.:
Argonne, IL, 1999.
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dilute sulfuric acid hydrolysis of timber varieties and switchgrass.
Bioresour. Technol. 2008, 99 (9), 38553863.
(5) Canettieri, E.; Rocha, G.; Carvalho, J. A.; Silva, J. Evaluation of
the kinetics of xylose formation from dilute sulfuric acid hydrolysis of
forest residues of Eucalyptus grandis. Ind. Eng. Chem. Res. 2007, 46
(7), 19381944.
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D. R. Kinetic Characterization of Xylose Monomer and Oligomer
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autohydrolysis of lignocellulosic biomass for the production of
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sugarcane bagasse hemicellulose to produce xylose, arabinose, glucose
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Modeling and optimization of the dilute-sulfuric-acid pretreatment
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SEM images of reacted particles of the size fraction <0.053 mm

was not possible because of experimental diculties in the
sampling of the solid residue at the end of the experiments.
Because of their high reactivity and small size, it is likely that
most particles of this size fraction either were completely
consumed or remained suspended in the aqueous solution, thus
making its separation dicult by conventional methods.
The size, morphology, and chemical composition of the
reacting particles are relevant in the present context because
they are related to the rate of reactions 1 and 2, which are
intrinsically heterogeneous.31 In the present pseudohomogeneous model, it may aect the assumption that H0 and C0 are
equal for both size fractions studied. The role of particle
properties on the rate of acid hydrolysis of lignocellulosic
materials has received little attention in the literature and
deserves further investigation.

CONCLUDING REMARKS

AUTHOR INFORMATION

A combined approach involving an experimental program

coupled with the development of a pseudohomogeneous
mathematical model was conducted to elucidate the main
features of the acid hydrolysis of Cenchrus ciliaris particles under
controlled laboratory conditions. As a result of the present
methodology, the stoichiometry of the acid hydrolysis reactions
of hemicellulose and cellulose present in the particles was
obtained, as well as the values of the apparent kinetic
parameters. Overall, good agreement between the model
predictions and the experimental data was obtained in terms
of the concentrations of glucose, xylose, arabinose, and furfural
in the aqueous phase. Further research in this area should take
into account the properties of the reacting particles such as size
distribution, morphology, and chemical composition because
they may introduce uncertainties in both experimental and
model results.

Corresponding Author

*E-mail: mperezt@iq.uson.mx. Phone: +52(662)289-3784.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors express their gratitude to Dr. Francisco Brown,
Dept. of Research in Polymers and Materials, University of
Sonora, for his help in the capture of the SEM images shown in
this paper. Thanks are also due to Mr. Alejandro Murillo-Luke
for his help in the experimental work during the early stages of
this investigation. K.K.E.S. acknowledges CONACYT (National Council of Science and Technology, Mexico) for
providing the scholarship grant for her graduate studies during
this work. Funding for this research was provided by the
graduate program in engineering science, University of Sonora,
Mexico. The authors thank the reviewers for their valuable
comments to improve this paper.

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