Summary of test conditions for esterification experiments.
Abstract
This work investigated the role of mass-transfer interfacial area in the biodiesel production using the acid-catalyzed esterification process. The interfacial area between alcohol and oil feedstock was determined by conducting acid-catalyzed esterification experiments using methanol and oleic acid (as free fatty acid) under ranges of five process parameters: reaction temperature (45–65°C), agitation speed (200–400 rpm), methanol-to-oil ratio (3:1–9:1 mol/mol), catalyst concentration (0.5–2.0%), and concentration of free fatty acid (5–30%). Effects of these parameters on the biodiesel conversion rate and the interfacial area were quantified. An empirical correlation for the interfacial area was developed as a function of process parameters. Results show that the enhancement of biodiesel production rate is attributed to reaction kinetics and/or interfacial area. The interfacial area is the sole contributor to the increase in biodiesel production rate due to the increase in methanol-to-oil ratio and agitation speed. Both kinetics and interfacial area contribute to the increase in biodiesel production rate due to the reaction temperature and catalyst concentration. The interfacial area plays negligible role in the change in biodiesel production rate due to the free fatty acid content.
Keywords
- biodiesel
- esterification
- mass-transfer interfacial area
- reactor design
- hydrodynamics
- parametric effects
1. Introduction
Energy use is considered to be the most fundamental requirement for various human activities, especially in the industrial, transportation, and agricultural sectors. Among different kinds of fuels, petroleum constitutes the majority of the world’s energy supply. However, petroleum is a finite and nonrenewable energy source, which has already caused serious environmental pollution. Therefore, a sustainable, affordable, and environmentally friendly alternative to petroleum is urgently needed.
Biodiesel is considered to be an important alternative to conventional petroleum-based diesel [1]. It is nontoxic, and biodegradable, offers lower emissions of a number of air pollutants, can be used in typical diesel engines without any major modifications, and has greater lubricity than conventional diesel, thus reducing corrosion in diesel engines [2]. Biodiesel can be used in its pure form called B100 (100% biodiesel) or in a blend with different proportions of conventional diesel fuels. Common blends include B20 (20% biodiesel and 80% conventional diesel), which are much closer to diesel fuel properties than B100 and B5 (5% biodiesel and 95% conventional diesel).
In the typical biodiesel production process, the catalyzed transesterification or esterification reaction is carried out in a multiphase reactor where the two immiscible chemical reactants (oil feedstock and alcohol-containing catalyst) are brought into contact using different agitation or mixing mechanisms. Because the cost of biodiesel production depends heavily on the cost of raw materials, using low-quality feedstocks such as waste cooking oils or nonedible oils instead of high-quality feedstocks will significantly reduce the biodiesel production cost. However, low-quality feedstocks have high content of free fatty acids (FFAs), which can react with the alkaline catalyst and produce soaps. This side reaction in the alkali-catalyzed transesterification process will reduce the catalyst efficiency and the biodiesel conversion rate. Additionally, the formation of soaps will make the later purification process difficult. As a result, the undesired side reactions caused by FFAs will increase the cost of biodiesel production. Therefore, when using low-quality feedstocks for biodiesel production, the content of FFAs must be reduced to an acceptable level (typically below 1% according to references [3–5]) before the alkali-catalyzed transesterification process. One efficient method for removing the FFAs from feedstocks is esterification, where the FFAs react with alcohol to form ester and water as products.
Due to the nature of the multiphase reaction, the efficiency or rate of biodiesel production relies heavily on two primary factors: (i) the kinetics of catalyzed transesterification or esterification reactions and (ii) the hydrodynamics of liquid-liquid mixing promoted by reactor design and operation. In order to arrive at a high-efficiency and optimized biodiesel reactor, these two fundamental features must be understood. To date, a large quantity of biodiesel research works has been carried out in many different aspects, such as production rate and the quality of biodiesel products derived from different feedstocks, kinetic studies to find optimal reaction conditions for achieving higher yields, and use of enzyme and heterogeneous catalysts as an alternative to the conventional homogeneous catalysts [6–11]. Most kinetic works reported biodiesel conversion profiles as a function of reaction time under specific reaction conditions and for specific types of reactor design and operation. As such, the reported kinetic data essentially reflect the combined performance of both reaction kinetics and hydrodynamics of liquid-liquid reaction systems.
Despite its importance to the development of high-performance reactors, the knowledge of hydrodynamics or mass-transfer interfacial area (
Therefore, the objectives of this work are: (i) to extend knowledge of interfacial area formed between immiscible reactants during the acid-catalyzed esterification reaction which can be used for the design of a high-efficiency reactor, (ii) to investigate the role of process parameters on interfacial area in the esterification process, and (iii) to develop an empirical correlation for interfacial area estimation as a function of process parameters. To achieve these objectives, a series of esterification experiments were performed using a stirred reactor operated under variable ranges of reaction conditions (Table 1). The experimental results were obtained in forms of free fatty acid (FFA) conversion profiles which were subsequently used for determining the interfacial area values.
Process parameter | Range |
---|---|
Reaction temperature (°C) | 45–65 |
Agitation speed (rpm) | 200–400 |
Methanol-to-oil ratio (mol:mol) | 3:1–9:1 |
Catalyst concentration (wt%) | 0.5–2.0 |
Free fatty acid concentration (%) | 5–30 |
Type of free fatty acid | Oleic acid |
Type of catalyst | Sulfuric acid |
2. Methods
2.1. Materials
Two sets of chemicals were used in the experiments: (i) reactants and an acid catalyst for the esterification reaction and (ii) supporting chemicals for liquid sample analysis. For esterification experiments, canola oil was used as the base ingredient of oil feedstock. Oleic acid (90%) from Sigma-Aldrich (Oakville, Ontario) was used as the representative of free fatty acids (FFAs) commonly found in the feedstock. A predetermined amount of oleic acid was added to the base canola oil in order to simulate low-quality feedstock. Sulfuric acid (98%) was used as the acid catalyst, and methanol (99.98%) was chosen to represent the alcohol reactant. Both sulfuric acid and methanol were purchased from Fisher Scientific (Ottawa, Ontario). For liquid sample analysis, toluene (99.9%), isopropyl alcohol (99.9%), and potassium hydroxide (0.1 N) were used for titrations to determine the acid number or FFA content of the oil phase.
2.2. Experimental setup
The mass-transfer interfacial area (
2.3. Experimental procedures
The experiments were conducted in two different modes: (i) esterification tests with a well-defined interfacial area between oil feedstock and methanol, and (ii) esterification tests with the complete mixing between the two reactants. The first mode of experiments provided the true kinetic features of the esterification reaction, while the second gave the reaction performance that integrates both kinetic and hydrodynamic effects of the reaction system.
For the experiments with a fixed interfacial area (first mode), the canola oil was mixed with oleic acid to simulate a low-quality feedstock containing different levels of FFA. A 250 mL of the prepared feedstock was then transferred into the 500-mL glass reactor and maintained at a desired reaction temperature. An impeller or agitator was placed in the middle of this oil phase and set at a particular mixing speed in order to keep the oil phase homogenized but yet the oil-surface undisturbed. Meanwhile, a predetermined amount of H2SO4 (catalyst) was mixed with methanol to form a catalyst/methanol mixture with a desired catalyst concentration. For each experimental run, a 93 mL of catalyst/methanol mixture was used to ensure an excessive amount of methanol (more than 40 mol/mol ratio) available for reacting with FFA in the oil phase. Prior to the reaction, the catalyst/methanol mixture was heated to the desired reaction temperature in a water bath. Once the reaction temperature was reached, the methanol mixture was transferred into the glass reactor to start the esterification reaction. In order to keep the interface between the oil phase and the methanol phase undisturbed, a separating funnel was used to smoothly transfer the preheated catalyst/methanol mixture into the reactor. For each experiment, the reaction temperature was controlled by the water bath. The reaction was timed until it reached its equilibrium. During the experiment, a series of samples were collected from the oil phase at different time intervals. Each sample was transferred into a test tube and then immersed in cold water at 4°C to quench the reaction immediately. For better separation of the final mixture, the samples were centrifuged for 5 min at 3000 rpm, and then, the top layer sample was collected and sent for analysis.
For the experiments with the complete mixing (second mode), each esterification experiment also began with the preparation of low-quality feedstock by mixing canola oil and oleic acid at a specific ratio. The FFA content of the prepared feedstock was analyzed in terms of acid number in accordance with the ASTM D974-04 standard, the details of which are provided in the next subsection. Following the preparation, a known amount of feedstock was charged to the reactor and heated to the desired reaction temperature with an accuracy of ±1°C. The feedstock was also stirred by the agitator at a fixed speed. Once the reaction temperature was reached, a predetermined amount of methanol/sulfuric acid mixture (with a given catalyst concentration) was rapidly injected into the reactor to start the esterification reaction. Prior to injection, this alcohol/catalyst mixture was preheated to the reaction temperature in order to avoid unwanted fluctuation in reaction temperature, especially at the beginning of the test. Each experimental run was carried out for at least 70 min at the desired temperature and agitation speed. A series of liquid samples (3 mL) were collected from the reactor at a regular time interval during the experiment. These liquid samples were then analyzed for their acid number so as to determine the depletion of FFA as a function of time.
2.4. Sample analysis
A 3-mL liquid sample collected from the reactor was transferred to a test tube where 6 mL of de-ionized water was added. The tube was then capped and shaken vigorously to promote complete contact between water and the sample. This allowed the methanol and catalyst to combine with water, thus separating them from the sample. After being shaken, the test tube was placed in a centrifuge operating at 4000 rpm for 10 min. The centrifugal force helped develop two liquid layers, that is, the top layer for oil and the bottom layer for a mixture of water, methanol, and catalyst. The top layer was then withdrawn from the test tube for FFA content analysis by ASTM D974-04. A 2-mL sample was taken from the oil phase, weighed for its mass, and then dissolved in a 100-mL titration solvent (a mixture of toluene, water, and isopropyl alcohol with a volumetric mixing ratio of 100:1:99). Then, p-naphtholbenzein (the titration indicator) was added into the sample which was eventually titrated with 0.1 N potassium hydroxide (KOH) solution. Results from titration were then used for calculating the acid number (in mg KOH/g oil) based on the following equation:
where
2.5. Data analysis
Data obtained from each esterification experiment were composed of a set of FFA content values (or acid numbers) taken at different reaction times. These data were subsequently used for determining mass-transfer interfacial area (
The rate of esterification reaction is essentially the rate of FFA conversion into fatty acid methyl ester (FAME). With the stoichiometric ratio of 1:1, the conversion rate can be expressed as a function of reactant concentrations (i.e.,
where
where
where
Because the magnitude of constant
where
Integrating the above equation results in the following equation:
where
3. Results and discussion
3.1. Parametric effects on FFA conversion rate and mass-transfer interfacial area
3.1.1. Effect of reaction temperature
The effect of reaction temperature was observed from the experiments carried out at three different temperatures: 45°C, 55°C, and 65°C and for oil feedstock containing 5%, 15%, and 30% FFA. Other experimental conditions were fixed at 0.5 wt% H2SO4 catalyst, 6:1 methanol-to-oil ratio, and 300 rpm agitation speed. Results in Figure 2a, b show that the conversion of FFA proceeded rapidly at the beginning of the reaction period. As much as 80% conversion (based on initial FFA concentration) was observed within the first 20 min. Then, the conversion rate diminished significantly when FFA conversion approached the plateau. Both figures also show that the FFA conversion rate (or slope of FFA conversion profiles at the first reaction period) increased with reaction temperature regardless of the initial FFA concentration. The increasing conversion rate was quantified and presented in terms of percent improvement compared to the conversion rate at 45°C, as shown in Figure 3. It appears that the conversion rate could be enhanced as much as 160% when the reaction temperature was raised from 45 to 65°C. Both kinetic and hydrodynamic factors (
As for the role of temperature on
3.1.2. Effect of methanol-to-oil ratio
The effect of methanol-to-oil ratio was investigated under 0.5 wt% H2SO4, 300 rpm agitation speed, 45°C and 65°C reaction temperature, for three different FFA concentrations (5%, 15%, and 30%). It was found that methanol-to-oil ratio has a significant impact on FFA conversion performance. An increase in methanol-to-oil ratio enhances the conversion rate for all test conditions. From Figure 4a, b FFA conversion rate could be improved by as much as 30 - 35% when methanol-to-oil ratio increases from 3:1 to 9:1. The increasing conversion rate is due to a significant increase in interfacial area
Based on the analysis shown in Figure 5, the improvement in FFA conversion rate due to increasing methanol-to-oil ratio is primarily caused by
3.1.3. Effect of agitation speed
The effect of agitation speed on FFA conversion was investigated by varying the agitation speed from 200 to 300 rpm and further to 400 rpm. The investigation was done for three different FFA concentrations (5%, 15%, and 30%) at 0.5 wt% H2SO4, 6:1 methanol-to-oil ratio, and 45°C and 65°C. Results show that agitation speed has an impact on FFA conversion performance. As shown in Figure 6a, b, increasing agitation speed from 200 to 300 rpm leads to a significant increase in the conversion rate. For instance, the rate could be improved by 150% at the reaction temperature of 45°C for oil feedstock containing 5% FFA (Figure 7). However, it should be noted that raising agitation speed further from 300 to 400 rpm leads to only a small increase in the rate of FFA conversion. It is apparent that the improvement under fixed reaction conditions (excluding agitation speed) was solely caused by an increase in
It should be noted that the degree of rate improvement also depends on reaction temperature. This exhibits an interaction effect between agitation speed and temperature. The effect of agitation speed at a lower reaction temperature (45°C) is much greater than the effect at the higher temperature (65°C). This behavior can be explained by comparing the magnitude of interfacial area formed at these two temperatures. From Figure 6c, d it can be seen that the higher temperature (65°C) tends to offer a greater area,
As mentioned previously, raising agitation speed beyond 300 rpm does not have much impact on the conversion rate of FFA. This can be explained by considering the conventional power correlation for agitated reaction. According to McCabe et al. [18], the power number,
3.1.4. Effect of catalyst concentration
The effect of catalyst concentration was studied by varying H2SO4 concentration from 0.5 to 2.0 wt%. The effect was examined for three FFA concentrations (5%, 15%, and 30%) and two reaction temperatures (45°C and 65°C) at 6:1 methanol-to-oil ratio and 300 rpm agitation speed. Results in Figure 8a, b show that an increase in H2SO4 concentration leads to an enhancement of FFA conversion performance for all test conditions. For instance, the conversion rate can be improved by 70% when H2SO4 concentration increases from 0.5 to 2.0 wt% at 45°C. Both hydrodynamics and kinetics were found to contribute to such improvement as shown in Figure 9. The hydrodynamic contribution (or an increase in
3.1.5. Effect of FFA concentration in oil feedstock
The effect of FFA concentration was examined over ranges of operating conditions, that is, 45 - 65°C reaction temperature, 200 - 400 rpm agitation speed, 3:1 - 6:1 methanol-to-oil ratio, and 0.5 - 2.0 wt% catalyst concentration. The results in Figure 10 show that FFA concentration plays an important role in the FFA conversion performance. An increase in FFA concentration causes the conversion rate to decrease. However, it should be noted that the hydrodynamics of the reaction system in this case does not contribute to the changes in FFA conversion rate since the interfacial area,
3.2. Empirical correlation for mass-transfer interfacial area
The effects of process parameters on the interfacial area reported earlier were correlated in the form of an empirical equation that would facilitate the design of a biodiesel reactor. Development of the correlation was focused primarily on four important parameters controlling the interfacial area between methanol and oil feedstock, that is, reaction temperature, agitation speed, methanol-to-oil ratio, and catalyst concentration. Firstly, the effect of each process parameter was regressed individually to arrive at the best mathematical expression offering simplicity and the lowest data deviation. Four types of mathematical expressions were considered in this screening step: linear, exponential, logarithmic, and power forms. It was found that most parametric effects can be described by linear expressions, except for the effect of agitation speed, the nonlinear behavior of which can be expressed well by the logarithmic equation. Values of average absolute deviation (%AAD) and R2 derived from individual regressions are summarized in Table 2.
Based on the selected equations in the screening step, an overall empirical correlation that combines all four parametric effects was formulated and expressed in the following form:
where
Process parameter | Mathematical expression | %AAD | R2 |
---|---|---|---|
Temperature ( |
4.06 | 0.91 | |
Methanol-to-oil ratio ( |
13.34 (45°C) 14.68 (65°C) |
0.89 (45°C) 0.82 (65°C) |
|
Agitation speed ( |
16.81 (45°C) 3.64 (65°C) |
0.83 (45°C) 0.96 (65°C) |
|
Catalyst concentration ( |
11.09 (45°C) 11.09 (65°C) |
0.69 (45°C) 0.48 (65°C) |
Correlation constant | Value |
---|---|
3.85 | |
32.50 | |
198.04 | |
51.98 | |
53.01 | |
−1465.72 |
4. Conclusions
Mass-transfer interfacial area plays an important role in the performance of acid-catalyzed esterification-based biodiesel production. Increasing the interfacial area enhances rate of biodiesel production (or rate of free fatty acid conversion). The magnitude of the interfacial area varies with process parameters, except free fatty acid content in oil feedstock. The interfacial area increases with increasing reaction temperature, agitation speed, methanol-to-oil ratio, and catalyst concentration, thus resulting in the increase in biodiesel production rate.
The increase in the biodiesel production rate may or may not be solely attributed to the available interfacial area. It can be attributed to both reaction kinetics and interfacial area. The interfacial area is the exclusive contributor to the increase in the biodiesel production rate when the agitation speed or the methanol-to-oil ratio increases. Both interfacial area and kinetics contribute to the enhancement of biodiesel production rate when the reaction temperature or the catalyst concentration increases.
Acknowledgments
The authors would like to thank the Natural Sciences and Engineering Research Council of Canada (NSERC) and the City of Regina for their financial support and collaboration.
References
- 1.
Santacesaria E, Tesser R, Di Serio M, Guida M, Gaetano D, Garcia Agreda A. Kinetics and mass transfer of free fatty acids esterification with methanol in a tubular packed bed reactor: A key pretreatment in biodiesel production. Industrial and Engineering Chemistry Research. 2007; 46( : 5113–5121.15 ) - 2.
Bhatnagar A K, Kaul S, Chhibber V K, Gupta A K. HFRR studies on methyl esters of nonedible vegetable oils. Energy Fuels. 2006; 20 : 1341–1344. - 3.
Freedman B E H P, Pryde E H, Mounts T L. Variables affecting the yields of fatty esters from transesterified vegetable oils. Journal of the American Oil Chemists' Society. 1984; 61( : 1638–1643.10 ) - 4.
Liu K S. Preparation of fatty acid methyl esters for gas-chromatographic analysis of lipids in biological materials. Journal of the American Oil Chemists' Society. 1994; 71( : 1179–1187.11 ) - 5.
Ma F, Clements L D, Hanna M A.Biodiesel fuel from animal fat: ancillary studies on transesterification of beef tallow. Industrial and Engineering Chemistry Research. 1998; 37( : 3768–3771.9 ) - 6.
Sendzikiene E, Makareviciene V, Janulis P, Kitrys S. Kinetics of free fatty acids esterification with methanol in the production of biodiesel fuel. European Journal of Lipid Science and Technology. 2004; 106 : 831–836. - 7.
Berrios M, Siles J, Martin M A, Martin A. A kinetic study of the esterification of free fatty acids (FFA) in sunflower oil. Fuel. 2007; 86 : 2383–2388. - 8.
Aranda D A G, Santos R T P, Tapanes N C O, Ramos A L D, Antunes O A C. Acid-catalyzed homogeneous esterification reaction for biodiesel production from palm fatty acids. Catalysis Letters. 2008; 122 : 20–25. - 9.
Thiruvengadaravi K V, Nandagopal J, Bala V S S, Kirupha S D, Vijayalakshmi P, Sivanesan S. Kinetic study of the esterification of free fatty acids in non-edible Pongamia pinnata oil using acid catalyst. Indian Journal of Science and Technology. 2009; 2( : 20–24.12 ) - 10.
Berrios M, Martin M A, Chica A F, Martin A. Study of esterification and transesterification in biodiesel production from used frying oils in a closed system. Chemical Engineering Journal. 2010; 160 : 473–479. - 11.
Yadav P K S, Singh O, Singh R P. Palm fatty acid biodiesel: process optimization and study of reaction kinetics. Journal of Oleo Science. 2010; 59( : 575–580.11 ) - 12.
Stamenkovic O S, Lazic M L, Todorovic Z B, Veljkovic V B, Skala D U. The effect of agitation intensity on alkali-catalyzed methanolysis of sunflower oil. Bioresource Technology. 2007; 98 : 2688–2699. - 13.
Zhou L. Reaction kinetics of biodiesel production by using low quality feedstock [thesis]. University of Regina: Canada; 2013. - 14.
Ceriani R, Goncalves C B, Rabelo J, Caruso M, Cunha A C C, Cavaleri F W, Batista E A C, Meirelles A J A. Group contribution model for predicting viscosity of fatty compounds. Journal of Chemical Engineering Data. 2007; 52 : 965–972. - 15.
Ceriani R, Paiva F R, Goncalves C B, Batista E A C, Meirelles A J A. Densities and viscosities of vegetable oils of nutritional value. Journal of Chemical Engineering Data. 2008; 53 : 1846–1853. - 16.
Paul E L, Atiemo-Obeng V A, Kresta S M. Handbook of Industrial Mixing: Science and Practice. New Jersey: John Wiley & Sons Inc; 2004. - 17.
McCabe W L, Smith J C, Harriott P. Unit Operations of Chemical Engineering. 5th ed. New York: McGraw-Hill Inc; 1993. - 18.
McCabe W L, Smith J C, Harriott P. Unit Operations of Chemical Engineering. 7th ed. New York: McGraw-Hill Inc; 2005. - 19.
Kulkarni M G, Dalai A K, Bakhshi N N. Transesterification of canola oil in mixed methanol/ethanol system and use of esters as lubricity additive. Bioresource Technology. 2007; 98 : 2027–2033. - 20.
Zhou Z, Li M, Yan Y. Viscosity of oil and surfactant binary solution. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2000; 175 : 263–266.