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International Journal of Development Research

ISSN: 2230-9926 Vol. 12, Issue, 11, pp. 60260-60265, November, 2022
https://doi.org/10.37118/ijdr.25715.11.2022

RESEARCH ARTICLE OPEN ACCESS

COBALT CATALYST FOR BIODIESEL PRODUCTION FROM ACIDIC RAW MATERIALS

Neyda de la Caridad Om Tapanes1*; Ana Isabel de Carvalho Santana1; Roberta Gaidzinski1;
Wilma Clemente de Lima Pinto1, Rodolfo Salazar Perez2, Daphne Costa Pacheco Aguiar1,3
and Donato Alexandre Gomes Aranda2
1State University of Rio de Janeiro, UERJ, Rio de Janeiro-RJ, Brasil 23070200; 2Federal University of Rio de
Janeiro, UFRJ, Rio de Janeiro - RJ, 23560-352; 3Fábrica Carioca de Catalisadores, FCC

ARTICLE INFO ABSTRACT

The use of raw materials with high acidity is one of the options to reduce the production cost of
Article History: biofuels, such as biodiesel. The reaction commonly used to produce biodiesel is basic
Received 14th August, 2022 transesterification, in which the triglyceride feedstock reacts with an alcohol, in the presence of a
Received in revised form catalyst, producing biodiesel and glycerol. This reaction requires raw materials with low fatty acid
20th September, 2022 content, such as soybean, canola, corn and sunflower vegetable oils, to avoid soap formation, emulsions
Accepted 29th October, 2022
and reduced process efficiency. Currently, the cost of these vegetable oils is high, especially after the
Published online 30th November, 2022
pandemic period, leading companies to look for lower cost solutions, and therefore higher acidity, such
KeyWords: as residual oils, which seriously impairs the reaction yield. In this sense, a solution that would make it
possible to obtain good yields in the production of biodiesel from raw materials with high acidity could
Cobalt catalyst; Biodiesel;
be the use of suitable catalysts, which together with the transesterification of triglycerides, allow the
Acidic raw material.
esterification of the fatty acids present. The present study proposes the use of cobalt spinel metal
*Corresponding author: oxides, which are considered bifunctional catalysts for having a structure with acidic and basic active
Neyda de la Caridad Om Tapanes sites, being able to simultaneously catalyze the transformation of triglycerides and fatty acids. Model
samples of vegetable oil of different acidity were tested and the catalysts were synthesized using the
combustion method. The full factorial design methodology in blocks was applied to evaluate the
relationship between the reaction yield and the operational parameters catalyst concentration and
alcohol/oil molar ratio and temperature. In the reactions catalyzed by CoAl2O4, the variable of greatest
statistical significance was the catalyst concentration, followed by the interaction of catalyst
concentration with temperature. It was statistically proven that fatty acid contents up to 20% in the raw
material do not affect the transesterification yield.

Copyright©2022, Neyda de la Caridad Om Tapanes et al. This is an open access article distributed under the Creative Commons Attribution License, which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Citation: Neyda de la Caridad Om Tapanes; Ana Isabel de Carvalho Santana; Roberta Gaidzinski; Wilma Clemente de Lima Pinto, Rodolfo Salazar Perez,
Daphne Costa Pacheco Aguiar and Donato Alexandre Gomes Aranda. “Cobalt catalyst for biodiesel production from acidic raw materials”, International
Journal of Development Research, 12, (11), 60260-60265.

Therefore, it can be said that the catalytic activity is associated with

INTRODUCTION the geometric area that presents the material and not with its mass.
The synthesis of biodiesel through heterogeneous catalysis offers
Catalysis is the phenomenon in which a relatively small amount of a technical and environmental advantages as it facilitates the
material, called a catalyst, increases the rate of a chemical reaction purification of the biodiesel produced, reducing the cost and time
without being consumed in the process (SCHMAL, 2011). Catalysts used in the washing and drying stages of the products, it also enables
are widely found in nature, in industry and in laboratories, it is the recovery and reuse of the solid catalyst throughout its useful life,
estimated that they contributed 1/6 of the value of all industrialized minimizing the generation of effluents and residues. Together, it
products. Catalysts can be divided into homogeneous or facilitates the recovery and purification of glycerin. Another problem
heterogeneous, depending on the way they act, restricted to a single in the biodiesel industry is the need to use raw materials with low
phase or distributed at the interface present between the phases of the acidity, which makes the process more expensive and the type of raw
reaction system. In heterogeneous catalysis, object of this study, material to be used. In Brazil, several studies are being carried out
several combinations of phases are possible, however, in general, the with the objective of expanding the use of raw materials with high
catalyst is a solid, and the reactants and products are distributed in acidity, mainly industrial waste (Tavares, 2020; Moura, 2021).
one or more gaseous or liquid phases. These materials have large Several heterogeneous catalysts have been proposed as catalysts for
surface areas mainly associated with high microporosity where active the synthesis of biodiesel, but what stands out in the use of spinel-
sites that can be acidic or basic are located. type catalysts is related to the nature of the acidic and basic sites
60261 Neyda de la Caridad Om Tapanes et al. Cobalt catalyst for biodiesel production from acidic raw materials

found in these materials (DI SERIO, 2008; Semwal, 2011). Spinel

oxides have a regular structure with a face-centered cubic compact RESULTS AND DISCUSSION
packing of oxygen at the vertices and faces. They have 8 cubes that
form a unit cell, totaling 56 atoms (32 anions and 24 cations). Response measured for the Reaction Yield of the experiments were
Although they contain 96 interstices between the anions of the cubic represented in Table 2. From the results obtained, showed in table 2, a
unit cell (64 tetrahedral and 32 octahedral), only 8 of the tetrahedral statistical analysis was performed to obtain 1st and 2nd order
and 16 of the octahedral cations are occupied by them. Greater regression models. Analysis of variance (ANOVA) was used to
occupancy of these sites is not possible, due to the short distances and define the process parameters that significantly influence the reaction
the coulombic interactions between the guest ions in interstitial sites yield. The ANOVA results for the response variable and its
and the ions in the A and B sites (Sickafus, 1999). The oxides with corresponding F and P statistics are shown in Tables 3 and 4.
typical AB2O4 spinel structure, when used as heterogeneous catalysts
in the production of biodiesel, in addition to having high selectivity, Table 1. Variables employed in the experimental design
have the advantage of being able to esterify free fatty acids and at the
same time transesterify triglycerides (Nuñez, 2022). Thus, aimed to Factor Factor Values
evaluate Cobalt metal oxides (cobalt aluminate) as catalysts in the levels
production of biodiesel from the transesterification of model mixtures C, %m/m Catalyst concentration* 2 1; 10
based on vegetable oil with different fatty acid contents. T, °C Temperature 2 50; 150
AG, % m/m Added of oleic acid* 3 0; 10; 20

MATERIALS AND METHODS *in fuel mixtures

Table 2. Experimental matrix used with response vectors

Preparation of the heterogeneous catalyst: The catalyst used in this
study was Cobalt Aluminate (CoAl2O4) synthesized by the Experiment AG C T Yield
combustion method at the Laboratory of Industrial Processes and 1 0 1 50 40.16± 0,05
Nanotechnology LPIN at the Universidade do Estado do Rio de 2 0 1 150 45.15± 0,02
Janeiro UERJ. The methodology started with the solubilization of 3 0 10 50 80.23± 0,13
nitrates in distilled and deionized water, in a porcelain crucible, on a 4 0 10 150 90.85± 0,03
plate at 150ºC. To the homogenized mixture, urea was added in 5 10 1 50 35.76± 0,24
stoichiometric amounts. The solution remained on the plate for partial 6 10 1 150 41.37± 0,3
evaporation of water, forming a solution of higher viscosity in the 7 10 10 50 81.83± 0,48
8 10 10 150 91.33± 0,37
form of a gel. It was immediately placed in a muffle furnace at 600°C
9 20 1 50 43.8± 0,38
to start the combustion reaction. After combustion, the product 10 20 1 150 43.87± 0,43
obtained is the catalyst that will be used in the reactions. The steps 11 20 10 50 74.91± 0,61
that finalize the catalyst and that are decisive to reach the activity of 12 20 10 150 89.41± 0,17
the active sites are the maceration until obtaining a powder and the
calcination in a muffle (Perez, 2017). The calcination of the catalyst, The mathematical model was developed to understand the effect of
which eliminates small amounts of carbon residues remaining from the variables studied and their interactions on the transesterification
the combustion, was carried out at 700ºC for 3 hours with a heating yield. ANOVA, illustrated in Tables3 and 4, is used to decide which
rate of 10ºCmin-1, under an air flow of 60 mL.min-1. model parameters significantly affect the response variable. These
tablesprovide the percentage of variance explained by the
Design of Experiments: In order to determine the suitable mathematical model compared to the variance contained in the
experimental conditions for obtaining biodiesel from highly acidic experimental results. The estimated regression coefficients for the
vegetable oil, the effect of some variables of the reaction system was first order model, Table 3, show that the only variable that is not
investigated using a factorial experimental design in blocks 23. The significant is the added fatty acid content. This result is important
independent variables selected in the study, called factors were because it demonstrates the potential of application of the spinel-type
catalyst concentration (C) and temperature (T). The alcohol/oil molar cobalt catalyst to transform acidic raw materials into biodiesel. The
ratio (R) was set at 6 and the reaction time at 60 minutes, the stirring significance of F (probability for ANOVA) was 3.32X10-7,
speed at 700 rpm and the alcohol used was anhydrous methanol from expressively smaller than 0.05, confirming the validity of the
TediaBrasil. The definition of these parameters, both fixed and suggested model. Similar results of these parameters were obtained in
variable, was carried out considering studies carried out previously the second order model (Montgomery, 2019). The confidence level
(Perez, 2017; Silva, 2014). The blocking variable was the fatty acid was specified at 95%, representing the degree of statistical reliability
content added to the vegetable oil (GA) mixture. The selected of the regression model, which infers a degree of uncertainty or risk
vegetable oil was soybean oil, and to prepare the model mixtures, 0, of up to 5% (Calado, 2003). If the P value of the factor is less than or
10 and 20% oleic acid were added to the vegetable oil, representing 3 equal to the degree of risk (0.05), it can be inferred that there is a
model mixtures each with 4 experiments with duplicates, totaling 24 significant correlation with the response variable, while P values
experiments. The response variable will be the Reaction Yield, which greater than 0.05 show that there is no adequate correlation. A
indicates how much of the raw material was transformed into marginal effect (p value = 0.09) was observed in the CT interaction
biodiesel. Table 1 displays the maximum and minimum levels for (Catalyst concentration- and temperature). Both 1st and 2nd order
each factor and the blocking variable. regression models have high values of R-Sq and adjusted R-Sq (adj),
97.36 and 97.93 % respectively, which shows that the model has good
Transesterification Reaction: All reactions were performed in a predictability. In the 2nd order model, the p values of C and the C-T
Parr® Instruments Inc. batch autoclave reactor, model 4836, in Interaction are below the accepted value of 0.05, demonstrating their
stainless steel, 450 mL capacity and 2,000 psi maximum working statistical significance on the response variable, Table 4.
pressure. The model mixture of vegetable oil was transesterified with
methanol in the presence of cobalt aluminate following the The model equation for the transesterification yield is shown in
experimental conditions defined in the design of experiments. The Equation 1.
temperature control was for 60 minutes, counting the reaction time
when the reaction temperature was reached. The progress of the Yield = 33.13 + 4.15*C + 0.0089 * C*T ± 3.32 ………………….. Eq.1
transesterification reaction was monitored by converting the fatty
acids to methyl esters in % w/w to determine the reaction yield. Residual analysis was performed to prove compliance with the
ANOVA assumptions and validate the regression model.
 60262 International Journal of Development Research, Vol. 12, Issue, 11, pp. 60260-60265, November, 2022

Table 3. ANOVA of factorial design for the Reaction yield (1th order model)

Sourceofvariation Degree of freedom (D.F) Sum ofsquares Meanssquares F Significanceof F

(SQ) (MQ)
Regression 3 5709.3675 1903.1225 136.1884 3.32 x 10-7
Residue 8 111.7935 13.9742
Total 11 5821.1610

Term Coeficients Standart Error Stat t Value-P

intercept 29.9531 3.0511 9.8173 9.74 x 10-6
AG -0.0545 0.1322 -0.4124 0.6909
C 4.7735 0.2398 19.9057 4.23 x 10-8
T 0.0753 0.0216 3.4866 0.0082
S = 3,7382
R-sq= 98.08%
R-sq (adj) = 97.36%

Table 4. ANOVA of factorial design for the Reaction yield (2th order model)

Sourceofvariation Degree of freedom (D.F) Sum ofsquares (SQ) Meanssquares (MQ) F Significanceof F
Regression 6 5798.0511 966.3418 87.6839 6.68 x 10-5
Residue 5 55.1037 11.0207
Total 11 5853.1548
Term Coeficients Standart Error Stat t Value-P
intercept 33.1259 4.5164 7.3347 0.0007
AG 0.1103 0.2991 0.3689 0.7273
C 4.1524 0.5429 7.6479 0.0006
T 0.0293 0.0383 0.7648 0.4789
AG*C -0.0253 0.0261 -0.9713 0.3760
AG*T -0.0003 0.0023 -0.1108 0.9161
C*T 0.0089 0.0043 2.0826 0.0918
S = 3.3197
R-sq= 99.06%
R-sq (adj) = 97.93%

Figure 1. Residual plots for transesterification yield

For validation, the error terms must be normally and independently In the Normal probability plot, the residual is seen to be well
distributed with zero mean and constant variance. Residual analysis distributed along the midline and there is no possible outlier that
results are shown in Figure 1. Figure 1 presents the residual plots for reveals any non-normality in the distribution (Montgomery, 2019).
transesterification yield showing the accuracy of the model used. The Residues versus order plot is satisfactory, as there is no positive
60263 Neyda de la Caridad Om Tapanes et al. Cobalt catalyst for biodiesel production from acidic raw materials

correlation indicating violation of the independence assumption. The positively influences on the reaction yield, a logical result considering
residues versus Fitted value, Figure 1, configures an unstructured that the catalyst function is to increase the formation of products.
pattern demonstrating that the assumption of constant variance is Factorial design made it possible to analyze the influence of factors
answered. Figure 2 shows the Pareto diagram of the effects of factors on response variable. Considering the values presented in the
and interactions on the transesterification yield, in which the effects response surface analysis, it is possible to observe that to reach 70%
were plotted in descending order of their absolute values. of reaction yield it is necessary to use between 7 and 9% of catalyst in
the reaction mixture.Figure 4 confirms the non-influence of the oleic
acid content added in the reaction mixture on the transesterification
yield, up to additions of 20% m/m.

CONCLUSION
Currently, the use of metal oxides for heterogeneous catalysis has
been increasing due to the objective of finding catalysts with high
activity and selectivity, and which can, mainly, be easily separated
from the reaction mixture, allowing the reactor to operate
continuously.In the present study, the catalytic action of spinel-type
cobalt oxide, synthesized by combustion, was tested during the
transesterification of vegetable oil mixtures of different acidity
levels.The statistical study proved to be effective for evaluating the
parameters that exert the greatest influence on the biodiesel
Figure 2. Pareto diagram production process; conducting experimental designs allowed the
determination of the effect of the main process parameters on the
The reference line in the graph (in red) indicates which effects are reaction yield. The variable that had the greatest influence was the
significant, in this study the Lenth method was used to draw this line. catalyst concentration (C) followed by the interaction of catalyst
In Figure 2 it is possible to corroborate the results shown in Table 4, concentration with temperature (C-T).The analysis also showed that
the effects of the C factor and the CT interaction are located to the the variable Added of oleic acid (AG) has no significant influence on
right of the reference line and therefore it can be said that they are the reaction yield, when the maximum AG limit is 20% oleic acid.
statistically significant. Furthermore, it is seen that the greatest effect This result is important because it demonstrates the potential
is the concentration of the catalyst (C) because it extends the farthest. application of this cobalt compound as a catalyst in the production of
biodiesel.

Acknowledgements: This work was supported by Foundation Carlos

Chagas Filho Research Support of the State of Rio de Janeiro
(FAPERJ).

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