Chemical Engineering Journal 262 (2015) 640–647

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Chemical Engineering Journal

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

Kinetics of Jojoba oil methanolysis using a waste from fish industry

as catalyst
Marcos Sánchez a, Jorge M. Marchetti b, Noureddin El Boulifi a, José Aracil a, Mercedes Martínez a,⇑
a
Chemical Engineering Department, Faculty of Chemistry, Complutense University, 28040 Madrid, Spain
b
Department of Mathematical Science and Technology, Norwegian University of Life Sciences, Drøbakveien 31, 1432 Ås, Norway

h i g h l i g h t s

 The catalyst obtained after calcination is mainly CaO and it is macroporous.

 The optimum calcination temperature is 800 °C.
 The catalyst is easily contaminated by H2O and CO2.
 The kinetic mechanism fits a sigmoidal curve because mass transfer limitations.

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

Article history: In this study, the kinetics of the heterogeneous methanolysis of Jojoba oil using calcined shells of Mytilus
Received 11 August 2014 Galloprovincialis as catalyst has been studied at different temperatures (45–55–65 °C), methanol:oil ratios
Received in revised form 10 September (6:1–9:1–12:1) and catalyst percents (6–8–10%). The main products obtained are the jojobyl alcohols
2014
with pharmaceutical activity and Fatty Acid Methyl Ester (FAME) is produced as co-product. The catalyst
Accepted 25 September 2014
Available online 13 October 2014
was synthesized through calcination at 800 °C during 6 h. The catalyst was characterized by BET method,
X-ray diffraction analysis (XRD), inductively coupled plasma atomic emission spectrometry (ICP) and
transmission electron microscopy (TEM). The catalyst is mainly CaO which is macroporous, it has low
Keywords:
Jojoba oil
porosity and turns to Ca(OH)2 in the course of the reaction. The reaction was performed immediately
Kinetics after the calcination process in order to avoid the poisoning of the catalyst by H2O and CO2. The poisoning
CaO of the catalyst and its effect has also been object of this study. In addition, external and internal mass
Heterogeneous transfer limitations and the effect of different calcination temperatures on the process have been studied.
Biodiesel The proposed kinetic mechanism fits a sigmoidal curve because there are mass transfer limitations which
Methanolysis control the process at the beginning of the reaction whereas the chemical reaction is the limiting step
when a critical amount of FAME and jojobyl alcohols are formed. The chosen variables in this kinetic
study have been the temperature, the initial catalyst percent and the methanol:oil ratio. The kinetic study
describes the whole methanolysis process accurately.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction products and Fatty Acid Methyl Ester as co-product. The introduc-
tion of an environmentally-friendly catalyst derived from fish
Research is increasingly focused on producing Fine Chemicals industry (mussel shells) makes this process more profitable and
from inexpensive and environmentally-friendly raw materials. In even more interesting.
addition, the production of biodiesel has meant a significant Jojoba is a perennial shrub that grows naturally in deserts and
advance for limiting the use of fossil fuels in the last decade [1]. its interest is growing for industrial purposes in some countries,
These two concepts could be combined through a Jojoba biorefin- especially in cosmetics and pharmaceutical products. Today, Jojoba
ery where valuable long chain alcohols would be obtained as main crops are cultivated in the United States, Central and South Amer-
ica, South Africa and many other countries. Jojoba oil is obtained by
a solvent extraction or cool pressing with a yield about 50% [2–4].
⇑ Corresponding author. Tel./fax: +34 91 394 4167. The composition of the Jojoba oil has particularities regarding the
E-mail addresses: marcosan@pas.ucm.es (M. Sánchez), Jorge.mario.marchetti rest of vegetable oils [5] because it has no glycerides in their struc-
@nmbu.no (J.M. Marchetti), nboulifi@quim.ucm.es (N. El Boulifi), jam1@quim.ucm.es ture but a long straight ester chain [6]. It is composed of fatty acids
(J. Aracil), mmr1@quim.ucm.es (M. Martínez).

http://dx.doi.org/10.1016/j.cej.2014.09.088
1385-8947/Ó 2014 Elsevier B.V. All rights reserved.
 M. Sánchez et al. / Chemical Engineering Journal 262 (2015) 640–647 641

Table 1
Composition and properties of Jojoba oil.

Esters Percent
Composition
C34-C36 0.2
C38 6.6
C40 30.2
C42 50.9
Fig. 1. Scheme of the transesterification of Jojoba oil.
C44 9
C46-C50 0.9

bound directly to fatty alcohols. Jojoba oil and its derivatives have Properties
Melting point (°C) 9
many applications in different fields such as cosmetics, pharma- Density (g/ml) 0.862
ceuticals and lubricants. Also, Jojoba oil is used as lubricant in high Iodine value (g/100 gr) 83
speed machinery, tool work, and metal cutting in the automotive Acid value 0.36
industry [7]. Viscosity (cSt) 26.6
Moisture (%) 0.03
Biodiesel is a nontoxic, biodegradable and renewable biofuel
Flash point (°C) 225
derived from vegetable oils or animal fats and it is one of the most CFPP (°C) 10
promising alternative fuels [8–10]. Biodiesel is usually produced by Oxidation stability (h) 41.3
a catalytic transesterification and it is completely miscible with
conventional diesel [11]. The catalysts used in the transesterifica-
tion can be homogeneous, heterogeneous or enzymes. The use of
a mortar and were calcined in a furnace chamber with embedded
homogeneous catalysts implies tedious steps of purification of
ceramic muffle at 500, 700, 800 and 900 °C for 6 h in order to con-
the biodiesel obtained. This drawback is even more worrying when
vert the CaCO3 to CaO. Finally the product obtained by calcination
the methanolysis of Jojoba oil (Fig. 1) is conducted because, unlike
was sieved at different diameters (3, 1 and 0.25 mm). The reactions
the rest of the vegetable oils, there is not a partial removal of the
were immediately performed after the calcination process in order
homogenous catalysts because of the glycerol decantation [3].
to prevent the poisoning of the catalyst by water and CO2 [14–17].
The washing step of the product obtained in the transesterification
of the Jojoba oil requires a huge amount of a strong acid agent
which makes the overall process unaffordable. In this case, the con- 2.3. Catalyst characterization
ventional washing agents such as distilled water or citric acid solu-
tion are substituted for a strong acid agent such as hydrochloric The crystalline phases of mussel shell catalyst were character-
acid. Therefore, heterogeneous catalysts can be removed easily ized by BET method, X-ray diffraction analysis (XRD), inductively
from the product, making the overall purification much more fea- coupled plasma atomic emission spectrometry (ICP) and transmis-
sible. Moreover, there are more advantages when a heterogeneous sion electron microscopy (TEM). The results of the BET method and
catalyst is used in the transesterification: catalyst reusability [12], ICP analysis are charted in Table 2. According to the results of the
easy separation of glycerol and much simpler handling and man- BET method the solid used for the transesterification of Jojoba oil is
agement of waste [13]. a macroporous catalyst (Fig. 2). The ICP results show that the fresh
The main objective of the present work is to determine the catalyst is mainly CaO (>99.5%) with a low content in MgO. Regard-
kinetics of Jojoba oil methanolysis using a heterogeneous catalyst ing the XRD patterns and TEM analysis, there is a clear difference
derived from fish industry. The mathematical model to obtain between the fresh and the used catalyst in its structures. The
the kinetic parameters is a multiparametric non-linear regression XRD patterns (Fig. 3) show that the fresh catalyst is CaO and after
based on the Marquardt algorithm. Calculations were performed
using experimental data obtained at different temperatures, cata-
Table 2
lysts contents and methanol:oil ratios. Initially, the study of the
BET method and ICP results.
behavior of the internal and the external diffusion was carried
out together with the assessment of the influence of the calcination Total surface area (m2/g) 2.16
Micropore volume (cm3/g) 0.00011
temperature on the reaction yield and the poisoning of the calcined
Ca content (lg/m) 678000 ± 22000
shells by water and CO2. Mg content (lg/m) 2427 ± 514

2. Materials and methods

2.1. Reagents and materials 12

Adsorbed Volume (cm3/g STP)

10
Jojoba oil is supplied by Jojoba Israel (Israel). The characteristics
of the Jojoba oil are determined according to AOCS official method 8
and UCM method. The main properties and the composition of the
oil used as raw material can be found in Table 1. Certified methanol 6
of 99.8% purity is supplied by COR (Madrid, Spain). GC standards
were supplied by Sigma Aldrich. The catalyst is produced by the 4
calcination of mussel shells (Mytilus galloprovincialis specie) from
2
Galicia (Spain).
0
2.2. Catalyst preparation 0 0.2 0.4 0.6 0.8 1 1.2
P/P0
First of all, mussel shells were carefully washed and dried in
oven at 100 °C for 1 h. Secondly, the shells were grounded using Fig. 2. Nitrogen isotherm for the fresh catalyst.
642 M. Sánchez et al. / Chemical Engineering Journal 262 (2015) 640–647

per to remove samples. The diameter of the blade used is 6 cm. The
reaction temperature was achieved immersing the reactor into a
thermostatic bath (HETO) with an electrical device connected to
a PID controller which allows a temperature control of ±0.1 °C [18].
Experiments have been performed according to the following
procedure: Jojoba oil is added to the reactor. When the set temper-
ature is reached the catalyst and the methanol are poured in the
reactor, and just at that moment the reaction time is considered
zero. During the experiments the pressure and impeller speed
are maintained constant. After the reaction, the solid catalyst is
removed by filtration. Finally, the methanol is eliminated from
the product through a vacuum distillation at 10 mmHg [18]. Sam-
ples have been taken according to the prepared experiments for
determining the kinetics of the methanolysis and analyzed by
gas chromatography.

2.5. Product analysis

Fig. 3. XRD patterns of fresh and used catalysts. Red Line: Fresh Catalyst, Blue Line:
Used catalyst. (For interpretation of the references to color in this figure legend, the 2.5.1. GC (gas chromatography)
reader is referred to the web version of this article.) Fatty Acid Methyl Esters (FAME), monoglycerides, diglycerides
and triglycerides were monitored using a Hewlett–Packard 5890
series II chromatograph, connected to a Hewlett–Packard 3396SA
integrator, equipped with a flame ionization detector (FID) using
a fused silica capillary column The injection system was split-split-
less and the carrier gas was helium at a flow of 1 ml/min. The injec-
tor and detector temperatures were 275 and 325 °C, respectively. A
temperature program was used starting with a 1 min hold at
130 °C; followed by a ramp rate, firstly, of 2 °C min1 to 160 °C
and secondly of 30 °C min1 to 320 °C. The analysis of the stan-
dards and the reaction products were prepared dissolving the sam-
ples in CS2 and 1 ll was injected into the GC equipment. The used
procedure to characterize the samples was the internal standard.
N-Octyl octanoate was used as internal standard.

2.5.2. Acid value

Fig. 4. TEM of the fresh catalyst.
Acid value for the soybean biodiesel obtained in this study was
determined following the method specified in ASTM Method D
664, using a Metrohm Swiss model 702 SM Titrino.

2.5.3. Iodine value

Iodine value in this study was determined following the method
specified in AOCS Official Method Cd 1-25, using a Metrohm Swiss
model 702 SM Titrino.

2.5.4. Kinematic viscosity

The kinematic viscosity of the soybean oil was determined by
the method ASTM D445 using a Cannon–Fenske Viscosimeter.

2.5.5. Oxidation stability

Oxidation Stability in this study was determined following the
method specified in AOCS Official Method Cd 12b-92, using a
model 743 Rancimat instrument.
Fig. 5. TEM of the used catalyst.

2.5.6. CFPP (cold filter plugging point)

the transesterification process is converted to Ca(OH)2. This fact is Soybean biodiesel CFPP was determined by the method ASTM
also seen in the change of the cubic structure of CaO solid (Fig. 4) to D6371, using a CFFP tester (ISL CPP 97-2).
a hexagonal structure of Ca(OH)2 (Fig. 5).
2.5.7. CP (cloud point)
2.4. Experimental setup Soybean biodiesel CP was determined by the method ASTM
D2500, using a CFFP tester (ISL CPP 97-2).
Experiments have been carried out in a 250 cm3 three necked
batch reactor, where the total volume of Jojoba oil is 85 cm3. The 2.5.8. PP (pour point)
reactor is equipped with a reflux condenser to return the evapo- Soybean biodiesel PP was determined by the method ASTM
rated methanol back to the reactor, a mechanical stirrer and a stop- D97, using a CFFP tester (ISL CPP 97-2).
 M. Sánchez et al. / Chemical Engineering Journal 262 (2015) 640–647 643

2.5.9. Water content 0.0020

Water content in this study was determined following the
method specified in ISO EN12937, using a Metrohm Swiss model 0.0018
702 SM Titrino.

-r A(mol/lmin)
0.0016
2.5.10. Flash point
Flash point in this study was determined following the method 0.0014
specified in ASTM D93, using a Petrotest PM4 (Instrumentación
Analítica S.A.). 0.0012

2.5.11. Cetane number 0.0010

Cetane number in this study was determined following the 0 0.5 1 1.5 2 2.5 3 3.5
method specified in ASTM D613, using an automatic IROX DIESEL Catalyst particle diameter (mm)
(Grabner Instruments).
Fig. 7. Study of internal diffusion limitations. Operation conditions: T = 65 °C;
catalyst percent = 8% and methanol:Jojoba oil ratio = 9:1.
3. Results

For obtaining the kinetic modeling of the transesterification of impact over the yield of the reaction due to the fact that the cata-
Jojoba oil using a waste from the fish industry 27 experiments lyst used is macroporous and the micropore volume is insignifi-
were conducted. In addition, the influences of the temperature, cant. Therefore, the same yields are obtained when the catalyst
catalyst percent and the methanol:Jojoba oil ratio were deter- particle diameter used varies from 0.25 mm to 3 mm. Nevertheless,
mined. However, some previous experiments were carried out to the catalyst particle diameter chosen to carry out the kinetic mod-
determine the possibility of avoiding the external and internal eling experiments was 1 mm in order to perform all the experi-
mass limitations on the reaction, the suitable calcination tempera- ments at the same conditions.
ture and the study of the possible poisoning of the catalyst with the
time. 3.1.3. Influence of the calcination temperature
The catalytic activity of the calcined mussel shells obtained at
3.1. Preliminary experiments different calcination temperatures for 6 h under the same reaction
conditions (65 °C of reaction temperature, methanol:Jojoba oil
3.1.1. Influence of stirring speed ratio of 9:1, catalyst percent of 8% and reaction time from 0 to
Preliminary experiments were carried out at stirring speeds 600 min) has been studied. The calcination temperatures tested
between 1.37 and 17.5 Np (Power Number). The experiments were on the mussel shells in this experimentation were 500, 700, 800
conducted at the same operation conditions: 65 °C, reaction time and 900 °C. The results obtained in this part of the study are
of 600 min, catalyst concentration of 8% and methanol:Jojoba oil reflected in Fig. 8. As seen in Fig. 7, there is a negligible catalyst
ratio of 9. Under these conditions, the way the external diffusion activity when the waste is calcined at 500 °C. Nevertheless there
limitations could be evaluated. As seen in Fig. 6, at a lower values is no difference in the catalytic activity when calcination is per-
of 2 in the Power Number mass transfer limitations is not detected. formed at 800 or 900 °C [19] and it is quite lower at 700 °C, espe-
Following the results obtained in Fig. 5, the value chosen for the cially at initial stages of the reaction. This fact is because all the
Power Number to conduct the kinetic modeling was 1.37 for avoid- amount of shells were not converted to CaO and mass transfer lim-
ing external diffusion limitations throughout the reaction. itations appeared throughout the process.

3.1.2. Influence of particle size 3.1.4. Difference in the catalytic activity between commercial CaO and
Experiments at the same conditions as the external diffusion calcined mussel shells and poisoning of the catalyst
limitations study but at different catalyst particle diameter (from The catalytic activity of the commercial CaO has been compared
0.25 mm to 3 mm) were conducted. The Power Number was fixed to the calcined mussel shells and the results are presented in Fig. 9.
at 1.37 for avoiding external mass transfer limitations. As pre- As seen in Fig. 9, the catalytic activity of the calcined mussel shells
sented in Fig. 7, the catalyst particle diameter has a negligible is almost a 20% higher than the case of the commercial CaO. There

100
0.0018 90
0.0016 80
0.0014 70
0.0012 60
500ºC
-r A(mol/lmin)

xa(%)

0.001 50
700ºC
0.0008 40
800ºC
0.0006 30
900ºC
0.0004 20
0.0002 10
0 0
0 5 10 15 20 0 200 400 600 800
Power Number (Np) Time (min)

Fig. 6. Study of external diffusion limitations. Operation conditions: T = 65 °C; Fig. 8. Study of calcination temperature of the mussel shells. Operation conditions:
catalyst percent = 8% and methanol:Jojoba oil ratio = 9:1. T = 65 °C; catalyst percent = 8% and methanol:Jojoba oil ratio = 9:1.
644 M. Sánchez et al. / Chemical Engineering Journal 262 (2015) 640–647

100 Table 3
Experimentation performed for the kinetic study and Jojoba oil conversion at
90
600 min.
80
70 Experiment Temperature MeOH:Jojoba Catalyst Jojoba oil
(°C) oil percent (%) conversion (%)
60
1 45 6 6 52.4
xa(%)

50
Commercial 2 45 6 8 68.4
40 3 45 6 10 68.3
Calcination of shells 4 55 6 6 74.0
30
5 55 6 8 71.1
20
6 55 6 10 74.6
10 7 65 6 6 72.4
0 8 65 6 8 66.1
0 200 400 600 800 9 65 6 10 59.9
Time (min) 10 45 9 6 59.5
11 45 9 8 59.6
12 45 9 10 79.6
Fig. 9. Evaluation of the catalytic activity of the commercial CaO and calcined 13 55 9 6 77.9
mussel shells. Operation conditions: T = 65 °C; catalyst percent = 8% and metha- 14 55 9 8 92.7
nol:Jojoba oil ratio = 9:1. 15 55 9 10 88.5
16 65 9 6 82.3
are two possible reasons to this fact: (i) the poisoning of the com- 17 65 9 8 93.3
mercial catalyst with water and CO2 and (ii) the presence of MgO in 18 65 9 10 90.3
the calcined waste used as catalyst [20]. 19 45 12 6 78.3
20 45 12 8 70.8
In addition, the effect of possible poisoning on the catalyst has
21 45 12 10 81.4
been also evaluated through three different reactions under the 22 55 12 6 78.3
same reaction conditions: 65 °C of reaction temperature, metha- 23 55 12 8 90.5
nol:Jojoba oil ratio of 9, catalyst percent of 10% and reaction time 24 55 12 10 87.7
from 0 to 600 min. The first reaction was performed immediately 25 65 12 6 92.7
26 65 12 8 95.0
with the calcined catalyst, the second reaction was conducted with 27 65 12 10 93.2
the same catalyst but 4 days after the calcination process and
finally the third reaction was carried out again with the same cat-
alyst but 21 days after calcination. As seen in Fig. 10, there is
almost a 35% of difference in the Jojoba oil conversion between 100
using the catalyst immediately or 21 days after the calcination pro- 90
cess because of the poisoning by water and carbon dioxide on the 80
calcined shells. 70
60
45ºC
xA (%)

3.2. Kinetic experiments 50

40 55ºC
For obtaining the kinetic model 27 different experiments have 30 65ºC
been conducted. As shown in Table 3, temperature, methanol:oil 20
ratio and catalyst percent have been the chosen variables to per- 10
form this study. The Jojoba oil conversion charted in Table 3 is at 0
600 min of reaction time. In addition to the kinetic model study, 0 200 400 600 800
the effect of these three variables on the process has been Time (min)
discussed.
Fig. 11. Study of the effect of the temperature operation conditions: catalyst
percent = 8% and methanol:Jojoba oil ratio = 9:1.
3.2.1. Effect of temperature
The effect of the temperature has been studied by setting the
catalyst percent at 8% and the methanol:Jojoba oil ratio at 9. The The temperature has a positive effect on the oil conversion (xA)
results are shown in the Fig. 11. [7]. There is an important difference in the results obtained for
100
45 °C, 55 °C and 65 °C, respectively, though there is almost no dif-
ference between performing the reaction at 55 °C or 65 °C. The
90
effect of the temperature is quite similar for all catalyst concentra-
80
tions and methanol:Jojoba oil ratios.
70
60
xa(%)

50 Immediately 3.2.2. Effect of the methanol:oil molar ratio

40 4 days The effect of the methanol:Jojoba oil ratio has been studied by
30 setting the temperature at 65 °C and the catalyst percent at 8%.
21 days
20 The results are shown in the Fig. 12.
10 As expected, the methanol:oil ratio has a positive influence in
the reactor and therefore, the more methanol:Jojoba oil ratio in
0
0 200 400 600 800 the reaction the more Jojoba oil conversion is obtained. However,
Time (min) the is not an important difference between carrying out the reac-
tion at 9:1 or 12:1 methanol:Jojoba oil.
Fig. 10. Evaluation of the effect of the contamination on the catalyst. Operation The effect of the methanol:Jojoba oil ratio is quite similar for all
conditions: T = 65 °C; catalyst percent = 10% and methanol:Jojoba oil ratio = 9:1. Temperatures and catalyst percent tested.
 M. Sánchez et al. / Chemical Engineering Journal 262 (2015) 640–647 645

100 concluded that the thermal catalysis is negligible because the oil
90 conversion was within the experimental error measurements after
80 10 h of reaction time. Therefore, it is necessary the presence of a
70 catalyst to conduct the reaction.
60
3.2.5. Effect of calcium methoxide concentration
xA (%)

50 6:1
Although CaO is practically insoluble in methanol [15,23,24]
40 9:1
some calcium methoxide can be formed and consequently, a
30 12:1 homogeneous contribution could have significance on the process
20
[25]. Therefore, the highest percent of the catalyst together with
10
the highest volume of methanol used in the experimentation were
0 added in a flask and the mixture was stirred during 10 h at 65 °C in
0 100 200 300 400 500 600 700
Time (min)
order to know the rate of the homogeneous contribution on the
process. After this mixing process, the product obtained was fil-
Fig. 12. Study of the effect of the methanol:Jojoba oil ratio operation conditions: tered and was used to perform the transesterification reaction at
temperature = 65 °C; catalyst percent = 8%. 65 °C. The oil conversion obtained was 1.84% and the homoge-
neous contribution was considered negligible as Kouzu et al. [15]
and Veljković et al. [21] also showed in their works.
3.2.3. Effect of the initial catalyst concentration
The effect of the catalyst percent has been studied by setting the
3.2.6. Kinetic model
temperature at 65 °C and the methanol:Jojoba oil ratio at 9:1. The
The proposed model has been based on previous literature
results are shown in the Fig. 13.
[21,24]. As many authors have reported, oxide metal used as cata-
As expected, the catalyst percent has a slightly positive influ-
lyst in the transesterification reaction gives sigmoidal curves oil
ence over reaction rates [7]. However, the optimum catalyst per-
conversion vs time [21,24,26,27]. The kinetic mechanism assumes
cent is 8% because a higher concentration of catalyst has a
that the initial stages of the reaction, mainly at lower temperatures
negative impact over the transesterification. A 10% catalyst percent
and low methanol:oil ratios, there are mass transfer limitations
implies an amount of catalyst in the reactor which impede to reach
which control the process. As the FAME and the jojobyl alcohols
the turbulence inside the reactor and that makes the yield of the
are produced they improve the solubility of the reaction mixture
reaction lower because external diffusion limitations [21]. How-
because they act as cosolvents [28]. When a critical point regarding
ever, there are also other parameters which affect the turbulence
FAME and jojobyl alcohols compositions is reached the chemical
inside the reactor such as the shape of the mixer, the ratio between
process becomes the limiting step of the process. This effect can
the diameter of the agitator and the diameter of the reactor, the
be seen in the sigmoidal form in the Jojoba oil conversion vs time
ratio between the height of the impeller and that of the liquid,
plots.
the diameter of the catalyst particles, etc, but they have not been
The kinetic mechanism proposed fits the whole methanolysis
the aim of this study.
process accurately. For determining the kinetics, the following
The effect of the catalyst amount is quite similar for all temper-
assumptions were considered [24]:
atures. However, the effect of the catalyst percent on the methan-
olysis changes at different methanol:Jojoba oil ratios. On one hand, (a) The methanolysis takes place between the methoxide ions
the more catalyst in the reactor the more likely the appearance of absorbed on the solid Surface and the Jojoba oil which is
mass transfer limitations. On the other hand, the methanol is present in the methanol phase.
absorbed on the surface of the solid [22] and at high methanol:oil (b) As shown before, homogeneous contribution and thermal
ratios and catalyst percentages the production of CH3O- and catalysis are negligible.
thereby the catalytic activity increases. Therefore, there are two (c) There are mass transfer limitations which have influence in
opposing effects when the transesterification is carried out at the the first stages of the reaction.
highest level of catalyst percent (10%) and methanol:oil ratio (d) The chemical equilibrium is reached in the last stage of the
(12:1). transesterification.
(e) The Jojoba oil methanolysis using CaO as catalyst can be
3.2.4. Effect of the non-catalyzed process described using a first order reaction kinetics.
A reaction was performed in order to know which the effect of (f) There are no internal mass limitations because of the main
the thermal catalysis is in the transesterification process. It can be characteristics of the catalyst (low porosity and surface
area).
100
(g) The mass transfer limitations at the beginning of the process
90
do not limit the overall process rate.
80
(h) The reactor used is a CSTR (Continuous Stirred Tank Reactor)
70 and therefore, temperature and composition inside the reac-
60 tor are maintained constant throughout the process.
xA (%)

50 6%
40 8% Assuming a first order reaction and the mass transfer limita-
30 10% tions the Jojoba oil conversion vs time has been calculated from
20 the following expressions, which are derived from Kesić et al. [24]:
10 1 a0
0
¼ ð1Þ
kmt;A a  ðkmt;A Þ0
Time (min)
a
¼ ð1 þ a  xbA Þ ð2Þ
Fig. 13. Study of the effect of the catalyst percent. Operation conditions: temper- a0
ature = 65 °C; methanol:Jojoba oil ratio = 9:1.
646 M. Sánchez et al. / Chemical Engineering Journal 262 (2015) 640–647

1.000 1.200
0.900
1.000
0.800
0.700
Exp 45ºC 0.800 Exp 6:1

Ca(mol/L)
0.600
Ca(mol/L)

Exp 55ºC Exp 9:1

0.500 0.600
Exp 65ºC Exp 12:1
0.400
Model 45ºC 0.400 Model 6:1
0.300
0.200 Model 55ºC Model 9:1
0.200
0.100 Model 65ºC Model 12:1
0.000 0.000
0 200 400 600 800 0 200 400 600 800
Time (min) Time (min)

Fig. 14. Experimental and predicted Jojoba oil concentration profile at different Fig. 15. Experimental and predicted Jojoba oil concentration profile at different
temperatures. Operation conditions: catalyst concentration 6%; methanol:oil methanol:Jojoba oil ratios. Operation conditions: catalyst concentration 6%; tem-
Ratio = 9:1. perature: 65 °C.

4. Conclusions
kmt;A ¼ ðkmt;A Þ0  ð1 þ a  xbA Þ ð3Þ
The transesterification of Jojoba oil using a waste from fish
industry was carried out at different operation conditions where
dxA kmt;A  k
¼ kapp  ð1  xA Þ ¼  ð1  xA Þ the variables have been the temperature, the catalyst concentra-
dt kmt;A þ k

tion and the methanol:oil ratio. The catalyst was synthesized by
ðkmt;A Þ0  1 þ a  xbA  k calcination at 800 °C of M. galloprovincialis shells and it was com-
¼
 ð1  xA Þ ð4Þ
ðkmt;A Þ0  1 þ a  xbA þ k pletely characterized. The temperature, the methanol:oil ratio
and the catalyst percent have a positive effect on the reaction yield.
Ea However, there are opposing effects at high methanol:oil ratios
k ¼ k1  eðRT Þ ð5Þ and catalyst percentages which affect the transesterification yield.
The internal mass limitations are negligible in this process because
ðkmt;A Þ0 ¼ A  g ccat  C dM;0  T e ð6Þ of the low micropore volume. The external mass limitations
throughout the process are avoided when the Power Number is
where xA is the conversion of the Jojoba oil during the transesterifi- set at 1.37. The catalyst should be used immediately after the cal-
cation process, k is the kinetic constant of the reaction, k1 is the cination process in order to avoid a reduction of the yield due to
pre-exponential factor (min1), Ea is the activation energy poisoning of the catalyst. The kinetic model proposed is a
(cal/mol), T is the temperature (K), gcat is the amount of catalyst pseudo-first order model reaction. This model has a sigmoidal form
added to the reactor (g), CM,0 is the concentration of methanol at because at the beginning of the reaction the mass transfer limita-
the beginning of the process (mol/L), kmt,A is the overall Jojoba oil tions control the process but when a critical concentration of cosol-
volumetric mass transfer coefficient (min1), (kmt,A)0 is overall vent is reached the chemical reaction becomes the limiting step.
Jojoba oil volumetric mass transfer coefficient at the beginning of The coefficients associated to this model proposed were deter-
the process (min1), a specific internal area (m1), a0 specific mined by multiparametric non-linear regression and the whole
internal area at the beginning of the process (m1) and a, b, c, d methanolysis process was fitted accurately.
and e are fitting parameters.
The mass transfer limitations depend on the temperature, the Acknowledgements
amount of catalyst present in the reaction and the methanol:Jojoba
oil ratio [20,23] as aforementioned. Therefore, for quantifying The authors gratefully acknowledge financial support of this
(kmt,A)0 it has been proposed an equation which takes into account work by the Ministry of Science and Technology, Madrid, Spain
these three factors, seen in Eq. (6). (PRI-PIBAR 2011-1375), NILS Mobility Grants (009-ABEL-CM-
According to the experimentation, the kinetic model proposed 2013) and the NMBU University (Ås, Norway).
seems to be consistent with the following expression:

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 7292:02  eð RT Þ
7 0:89 0 13158
dxA 3:302  10  g 0cat  C M;0  T  1 þ 59:7  x0:23
A
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