Optimization of Extraction Process and Kinetics of Sterculia foetida

Jun 11, 2012 - Department of Chemical Engineering, Anna University, Chennai 600 025, Tamil Nadu, India. ‡. Climate Change Technology Division, Korea...
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Optimization of Extraction Process and Kinetics of Sterculia foetida Seed Oil and Its Process Augmentation for Biodiesel Production Pandian Sivakumar,† Karuppiah Subramanian Parthiban,† Padmanaban Sivakumar,† Mari Vinoba,‡ and Sahadevan Renganathan*,† †

Department of Chemical Engineering, Anna University, Chennai 600 025, Tamil Nadu, India Climate Change Technology Division, Korea Institute of Energy Research, Yuseong-gu, Daejeon 305-343, Korea

‡

S Supporting Information *

ABSTRACT: This article reports optimization and kinetic studies on extraction of Sterculia foetida seed oil and process optimization for biodiesel production from the same. The oil extraction follows first-order kinetics, and the yield was found to reach a maximum of 55.58 wt % for a 1:12 seed-to-hexane weight ratio. The activation energy and activation thermodynamic parameters at 338 K were determined as Ea = 69.441 kJ mol−1, ΔH‡ = 66.63 kJ mol−1, ΔS‡ = −238.07 J mol−1 K−1, and ΔG‡ = 147.09 kJ mol−1. Complete physicochemical properties of the oil were analyzed using standard methods. The low acid value of 0.42 mg of KOH g−1 for fresh oil enables alkali catalytic transesterification. Different biodiesel production parameters including methanol-to-oil molar ratio, catalyst concentration, and reaction temperature were examined. An optimum yield of 95.4 wt % with a conversion of 98.91% was achieved at values of 6:1, 0.9 wt %, and 338 K, respectively. The fuel properties of the produced biodiesel were compared with the ASTM D6751 biodiesel standard.

1. INTRODUCTION Fossil fuels as energy resources are of vital importance to sustainable development. Because of the recent crisis with petroleum based diesel and the continually increasing demand, there is a need to find an appropriate solution.1 Alternative fuel sources being developed around the globe include biodiesel, biomass, biogas, and synthetic fuels. Among these alternatives, biodiesel can be used directly, whereas the others need some sort of modification before they can be used as substitutes for conventional fuels.2,3 Biodiesel exhibits performance and combustion characteristics similar to those of petroleum derived diesel.4−6 As an alternative for petroleum based diesel in the transportation sector, biodiesel leads to the easiest and most crucial solution for environmental problems such as reductions in greenhouse gas emissions. Biodiesel is biodegradable, nontoxic, and renewable, and its use in diesel engines also shows a decrease in the emissions of CO, SOx, unburned hydrocarbons, and particulate matter.7 It can be produced through many different processes, involving thermal and chemical methods, but production based on the transesterification reaction, whereby vegetable oil or fat reacts with alcohol by using a catalyst to form alkyl esters, is most attractive.8 One of the main advantages of the transesterification process is that production can be carried out at almost any scale (from laboratory scale using a few liters of oil to large industrial scale capable of producing thousands of liters of biodiesel per year).9 A homogeneous basic catalyst is used in conventional biodiesel production that is known for its high conversion rate process. Among these catalysts, NaOH is preferred for its effectiveness in this process. The amount of catalyst used depends on the acid number of the oil. Methanol is the most common alcohol because of its properties and low cost.10 Biodiesel can also be used in home heating, marine and © 2012 American Chemical Society

jet applications, furnaces, boilers, and oil-fueled lighting equipment.11 Edible oils, such as soybean, sunflower, palm, and sesame oils, are being used for the production of biodiesel.12,13 However, in the past few years, concerns have arisen about the use of these food grade oils for transportation purposes. Use of such edible oils to produce biodiesel is not feasible in view of the significant gap between demand and supply for such oils as foods and that fact that they are far too expensive to be used at present. Obviously, the use of nonedible vegetable oils compared to edible oils is preferable. The high cost of biodiesel is the major barrier for its commercialization.14,15 Researchers have determined that the majority (85−95%) of the total cost of biodiesel production is the cost of the raw material.16 One way of reducing biodiesel production costs is to use low-cost raw material. Most nonedible oil crops grow well on wastelands, can tolerate drought and dry conditions, and do not need intensive care.17 Many studies have been conducted on biodiesel production from nonedible oils, such as Jatropha curcas oil,18,19 karanja seed oil, rubber seed oil,20 castor oil, and mahua oil.21 However, other nonedible oils have not been investigated as raw materials for the production of biodiesel, including Sterculia foetida oil. The S. foetida plant belongs to the Sterculiaceae family, which has 2000 types of species. It is a wild plant, is well-adapted to tropical and subtropical areas, and has an average plant life span of more than 100 years. S. foetida is a large, straight, deciduous tree growing up to 40 m in height and 3 m in girth with branches arranged in whorls.22 It can easily be raised from seed Received: Revised: Accepted: Published: 8992

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and ripe cuttings. The fruit is large, woody, red, nearly smooth, and about 10 cm long. It contains from 10 to 15 seeds, which are initially white in color and later turns black when ripe and about 2 cm long. S. foetida gives about 200−350 kg of seed per tree per year. The kernel of the seeds yields 50−60 wt % bland, light-yellow fatty oil. The major purpose of this study was to investigate extraction and biodiesel production from the S. foetida oil. The extraction was established to determine the appropriate solvent, seed-tosolvent ratio, kinetic parameters, thermodynamic parameters, and activation energy. The effects of three important parameters, namely, methanol-to-oil molar ratio, catalyst concentration, and reaction temperature, on the biodiesel yield were studied. The physical and chemical properties of S. foetida oil and biodiesel were determined by standard methods.

The fatty acid profile of the S. foetida oil was quantified and qualified using gas chromatography on a CHEMITO GC 8610 instrument with a flame ionization detector and nitrogen as the carrier gas. Hydrogen and oxygen were used for ignition purposes. The column was packed with BPX-70 phase (50% cyanopropyl, 50% methylsiloxane). The injection port was maintained at 250 °C, and the detector port was maintained at 260 °C. The temperature of the oven was initially 160 °C and was increased by 7.5 °C per minute to a final oven temperature of 240 °C. The data obtained were collected by Win-Chrom software and compared with standards. The mean molecular weight of the oil was calculated from the fatty acid profile using the equation

2. MATERIALS AND METHODS 2.1. Materials. S. foetida seeds were collected from Anna University campus, Chennai, India. Solvents such as n-hexane (99%), petroleum ether (bp 313−323 K), tetrahydrofuran (99.5%), methanol (99.5%), and chloroform (99.4%) were supplied by Merck, Mumbai, India. NaOH (99%) and anhydrous sodium sulfate (99%) were purchased from Sisco Research Laboratories, Mumbai, India. The reagents and chemicals were used as received without any further purification. 2.2. Soxhlet Extraction. The collected seeds were dried in sunlight for 1 week. They were then dehulled to obtain the kernels for extraction. Thirty grams of kernels was macerated and packed in a thimble for Soxhlet extraction with 250 mL of five different solvents. The extraction time was maintained for a maximum of 16 h at a rate of 8 cycles per hour. After extraction, the extract was filtered using Whatman 40 filter paper to remove particles that were entrained during the process. Solvent present was recovered by simple distillation. The oil yield obtained was expressed in terms of mass percentage of the samples and calculated as

where MWoil is the average molecular weight and MWi and Xi represent the molecular weight and mass fraction, respectively, of the ith fatty acid. 2.5. Transesterification Setup. The transesterification reaction was carried out in a 250 mL double-necked round flat bottom flask, equipped with a thermometer, condenser, and magnetic stirring system. To prevent the loss of methanol during reaction, a water-cooled condenser was used to condense and reflux the vapors it back into the reactor. To achieve perfect contact between the reagents and the oil during transesterification, they must be stirred well at a constant rate. The reactor containing 100 mL of S. foetida oil was immersed in a water bath, heated by a hot plate to a predetermined temperature at 600 rpm to promote sufficient agitation. The required amount of catalyst previously dissolved in methanol was charged into the reactor. After the reaction was completed, heating and stirring were stopped. The reaction mixture was transferred into a decanter and left for 4 h to separate into two distinct phases, namely, the ester phase (biodiesel) and the glycerol phase. It took approximately 10 min for phase separation, but the biodiesel layer was translucent. After 4 h, the ester phase became transparent, and the separation was completed. Further reaction might happen during the settling time, but the process is slow because of the low temperature, the lack of stirring, and the presence of low amounts of catalyst and methanol. However, it is said that an even longer settling time is favorable for the separation.24 The lower glycerol layer was decanted. The ester phase was washed five times with 100 mL of warm distilled water. The water wash removes impurities such as the residual catalyst, methanol, glycerol, and soaps. Experiments were performed in triplicate, and the error bars that are shown in the figures represent standard deviations from the means of three independent experiments. The ester phase was then dried using anhydrous sodium sulfate. The final product yield was determined gravimetrically as

MWoil = 3∑ (MWiXi) + 38

oil yield (wt %) = [mass of oil extract (g) /mass of seed kernel (g)] × 100

2.3. Batch Extraction. Laboratory-scale extraction was carried out in a batch process. Seed and solvent were taken by weight ratio in a 250 mL screw-cap conical flask and kept inside a temperature-controlled shaker. The oil distributes between the two phases (seed and solvent) depending on its partition coefficient. The rate at which the transfer of solute takes place from the feed to the extracting solvent depends on the process parameters. The mixing rate was kept constant at 250 rpm. Once the required time (10, 20, 30, 40, and 50 min) was attained, the mixing was stopped, the mixture was cooled, and the liquid and solid phases were separated. The mass of oil extracted at each time interval was determined gravimetrically after the solvent had been removed by distillation. 2.4. Oil Characterization. The important physical and chemical properties of the extracted oil were determined in the fuels and combustion laboratory. The acid value, saponification value, and iodine value were determined by titrimetry according to AOCS Official Methods.23 Determinations of the density, viscosity, and flash point were carried out using a hydrometer, Redwood viscometer, and Pensky−Martin open-cup apparatus, respectively.

biodiesel yield (wt %) = [mass of biodiesel (g)/mass of oil (g)] × 100

2.6. Biodiesel Characterization. The conversion of S. foetida oil to biodiesel was estimated using 1H NMR spectroscopy. Analysis was performed on a Bruker AVANCE III 500 MHz spectrometer (AV 500), at 300 K using a 5 mm probe head and CDCl3 as the solvent. The protons of the methylene group adjacent to the ester moiety in triglyceride and the protons in the alcohol moiety of the product methyl 8993

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esters were used to calculate the conversion of oil to biodiesel.25 The conversion was calculated using the equation 2AME × 100% conversion (%) = 3Aα‐ME where AME is the integration value of the methoxy protons of the methyl esters and Aα‑ME is the integration value of methylene protons. Biodiesel properties including kinematic viscosity, cetane number, saponification value, flash point, cloud point, and pour point were obtained according to ASTM standard methods.26 S. foetida biodiesel properties were then compared with ASTM D6751 standards. Figure 1. Effect of seed-to-n-hexane weight ratio.

3. RESULTS AND DISCUSSION 3.1. Effects of Different Solvents on Oil Yield. In this experiment, five different solvents were chosen to extract the S. foetida oil. The maximum oil content was estimated by Soxhlet extraction. The solvent was selected on the basis of oil yield and unsaponifiable matter. As reported in Table 1, the yield of oil

is, the extracted oil represents 96.49 wt % of the maximum available oil, which is 57 wt % (Soxhlet method), The percentage yields of oil for n-hexane at various temperatures are given in Table 2. A rate equation for oil extraction from S. foetida seeds can be written as

Table 1. Effects of Different Solvents on the Extraction of S. foetida solvent

yield (wt %)

unsaponifiable matter (wt %)

n-hexane petroleum ether tetrahydrofuran methanol chloroform

57 59.2 61.5 45.4 47

2 4 6.5 10 8

dY = kY n dt

where Y is the percentage yield of oil, t is the time of extraction, k is the rate constant, and n is the reaction order. Because the percentage yield of oil increased with time, the expression for dY/dt has a positive sign.27 Using the values in Table 2 and applying the differential method, plots of ln(dY/dt) versus ln Y were drawn and were found to be linear by means of equation fitting. First-order kinetics was found from the values of n obtained from the slopes of the straight lines, and the reaction rate constants (k) were calculated. 3.4. Calculation of Thermodynamic Parameters. The rate constant k was found to increase with increasing temperature, and this trend is obvious in Table 2. The changes can be described by the Arrhenius type equation28

extracted by tetrahydrofuran was high, and the oil contained a significant amount of unsaponifiable matter. The extractive value in n-hexane was not much different from that in petroleum ether, but the unsaponifiables and filtrate color were quite different from those obtained with petroleum ether as the extractive solvent. The methanol extraction yield was poor because of the polar nature of this solvent, which conceivably destroys intracellular compartmentalization in the S. foetida seeds, allowing solubilization of more unsaponifiable matter. Among the solvents tested, chloroform extracted less matter from the seeds and provided filtrate with a different color than the other solvents. Because n-hexane contains less unsaponifiable and provides a higher yield, it was identified as being a good solvent for the extraction. From these considerations, n-hexane was selected as the solvent for extraction. 3.2. Effect of Solvent Ratio on Oil Extraction. The seedto-hexane weight ratio was used to find the optimum solvent quantity for extraction in a batch study. Different solvent ratios of 1:6, 1:8, 1:10, 1:12, and 1:14 were studied. The extraction was carried out at 250 rpm and 338 K for 80 min in a shaker. Figure 1 shows the yield of oil for different seed-to-hexane weight ratios. The solvent ratio of 1:12 provided the optimum oil yield of 55 wt %. A further increase in seed-to-hexane ratio of 1:14 did not show any significant increase in oil yield. It was observed that the yield increased with increasing solvent ratio until equilibrium was reached. 3.3. Kinetics and Thermodynamics of Oil Extraction. Batch extraction was performed at different time intervals of 10, 20, 30, 40, and 50 min in a 250 mL screw-cap conical flask. From these results, it is obvious that the maximum amount of oil extracted reached 55 wt % of seeds at 338 K, in 50 min; that

k = Ae−Ea / RT where k is the rate constant, A is the Arrhenius constant or frequency factor, Ea is the activation energy, R is the universal gas constant, and T is the absolute temperature. A plot of ln k versus 1/T (Figure 2) should give a straight line whose slope represents the activation energy of extraction, −Ea/R and whose intercept is ln A. Thus, the activation energy and the Arrhenius constant were calculated as Ea = 69.441 kJ mol−1 and A = 2.589 s−1, respectively. The activation thermodynamic parameters were calculated according to the transition state theory29 as Rt ΔS ⧧ /R e A= Nh ΔH ⧧ = Ea − RT ΔG⧧ = ΔH ⧧ − T ΔS ⧧

where N is Avogadro’s number, h is the Planck's constant, ΔS⧧ is the activation entropy, ΔH⧧ is the activation enthalpy, and ΔG⧧ is the activation free energy or Gibb’s energy. These activation thermodynamic parameters are listed in Table 3 for each temperature. 8994

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Table 2. Percentage Yields of Oil at Various Extraction Temperatures and Values of the Reaction Rate Constants time (min) temperature (K)

10

20

30

40

50

308 318 328 338

43.39 45.03 46.90 49.23

44.17 45.94 47.99 50.54

44.99 46.91 49.17 51.93

45.78 47.94 50.42 53.42

46.78 49.02 51.74 55

k (min−1) 1.67 1.75 3.06 2.14

× × × ×

R2

10−6 10−6 10−6 10−5

0.9982 0.9864 0.9827 0.9857

Figure 2. Plot of ln K versus 1/T for oil extraction.

Figure 3. Plot of ln YT versus 1/T for oil extraction.

Thermodynamic parameters (ΔH, ΔS, and ΔG) for the extraction of S. foetida oil using n-hexane as the solvent were estimated using the equations30

energy. In addition, the negative value of ΔG (ΔG < 0) at 338 K indicates that there is a decrease in the free energy; that is, the extraction process of S. foetida oil using n-hexane at 338 K is a spontaneous process. The system initially consists of the S. foetida seeds and n-hexane, whereas the oil molecules are extracted from the S. foetida seeds during the process, and therefore, the entropy of the mixture increases in the course of the extraction; that is, the positive value of entropy change (ΔS > 0) at 338 K indicates that the process is irreversible. 3.5. Properties of S. foetida Oil. Physicochemical properties of S. foetida oil were determined. The iodine value was found to be 104 mg of I2 g−1, which is lower than those for bitter almond and peanut oil.31 The acid value was 0.42 mg of KOH g−1, which is lower than those of mahua oil and rapeseed oil but close to the acid values of canola oils.14,32 This shows that no acid pretreatment is required for base catalyst production of biodiesel from the oils with the acid value lower than 2 mg of KOH g−1.33 The density of the S. foetida oil was relatively close to those measured for soybean and cottonseed oils, whereas the kinematic viscosity was quite low.34 3.6. Optimization of Biodiesel. 3.6.1. Effect of Catalyst Concentration. The catalyst concentration is another im-

K⧧ =

YT YU

ΔG 1 ΔH 1 ΔS =− + R T R T R ⧧ where K is the equilibrium constant, YT is the percentage yield of oil at temperature T, YU is the percentage unextracted oil, ΔH is the enthalpy change, ΔS is the entropy change, and ΔG is the change in free energy or Gibb’s energy. A plot of ln YT versus 1/T (Figure 3) at 50 min should give a straight line whose slope represents the enthalpy change of extraction, −ΔH. Thus, the enthalpy change was calculated to be ΔH = 0.063 kJ mol−1 for S. foetida seed oil extraction. The ΔH value obtained was indicating the physicochemical nature of the oil extraction process. Other thermodynamic parameters (ΔS and ΔG) and the equilibrium constant values for extraction at 50 min are included in Table 3 for each temperature. According to these results, the positive value of enthalpy indicates that the process is endothermic and requires ln K ⧧ = −

Table 3. Activation Thermodynamic Parameters, Thermodynamic Parameters, and Equilibrium Constants at Different Temperatures T (K)

ΔH⧧(kJ mol−1)

ΔS⧧ (J mol−1 K−1)

ΔG⧧ (kJ mol−1)

K⧧

ΔS (mol−1 K−1)

ΔG (kJ mol−1)

308 318 328 338

66.88 66.80 66.71 66.63

−237.29 −237.56 −237.83 −238.07

139.96 142.34 144.72 147.09

4.57 6.14 9.83 27.5

12.63 15.08 19.01 27.55

−3.89 −4.79 −6.23 −9.31

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vegetable oil interferes with separation of glycerin because there is an increase in solubility. When glycerin remains in solution, it helps to drive the equilibrium back toward the left and lowering the yield of esters.39 3.6.3. Effect of Reaction Temperature. Reaction temperature can influence the reaction rate and was found to significantly affect the yield of biodiesel. When the transesterification reaction was carried out at 318 K, the yield of biodiesel was only 68 wt %. However, the yield of biodiesel increased to 95.4 wt % when the reaction temperature was increased to 338 K. In other words, reaction temperature has a more significant effect on the yield at higher reaction temperature than at lower temperature. Figure 6 shows the

portant variable that affects the transesterification reaction, as well as hydrolysis and saponification reactions.35 Experiments were performed using NaOH concentrations in the range of 0.45−1.05 wt % (based on the weight of the S. foetida oil), with the methanol-to-oil molar ratio and reaction temperature set at 6:1 and 328 K, respectively, for a 1 h mixing time. From Figure 4, one can see that the reaction yield was low for catalyst

Figure 4. Effect of catalyst concentration.

concentrations of 0.45−0.75 wt %. This is because not enough NaOH was present to catalyze the reaction. As the NaOH concentration was increased from 0.75 to 0.9 wt %, the biodiesel yield reached an optimum value of 90 wt %. Beyond the optimum value, there was a slight decrease in yield. This is because the excess catalyst will participate in saponification reaction to form soap and water that reduce the biodiesel yield.36 3.6.2. Effect of Methanol-to-Oil Molar Ratio. The molar ratio of alcohol to oil is one of the most important variable influencing the conversion into esters.37,38 The stoichiometric molar ratio of alcohol to triglyceride is 3:1, but transesterification is a reversible reaction, so higher molar ratios are typically used to shift the reaction toward the left. The average molecular weight depends on the molecular weight and the percentage concentration of fatty acids present in oil. The average molecular weight was determined to be 842 g mol−1 by gas chromatography. Experiments were carried out using methanol-to-oil molar ratios in the range of 3:1−9:1, with the NaOH concentration and reaction temperature set at 0.9 wt % and 328 K, respectively, for a reaction time of 1 h. Figure 5 shows the effect of the methanol-to-oil molar ratio in the yield of biodiesel. It can be observed that, as the methanol-to-oil molar ratio increased from 3:1 to 9:1, an optimum yield of 90 wt % was obtained at a 6:1 methanol-to-oil molar ratio. With further increase in the molar ratio, the yield remained more or less the same. However, a high molar ratio of alcohol to

Figure 6. Effect of reaction temperature.

effect of reaction temperature on biodiesel yield. At lower reaction temperatures, there is insufficient energy to promote extensive collisions among reactant particles. However, at higher reaction temperatures, the possibility of collisions among reactant particles becomes greater, and the necessary activation energy is easily reached.40 3.7. Fuel Properties of S. foetida Biodiesel. The fuel properties of the final product biodiesel obtained from S. foetida oil were determined using standard methods. The S. foetida biodiesel produced under optimum conditions yielded 95.4 wt % biodiesel. The conversion of biodiesel at this optimum yield was found to be 98.91% by 1H NMR spectroscopy. Clearly, the properties of biodiesel depend very much on the nature of the raw material, as well as the process used for its production. Inherent properties from S. foetida biodiesel have an effect on the performance of biodiesel as a diesel substitute. The biodiesel properties were compared to ASTM D6751standards.

4. CONCLUSIONS The extraction of oil from S. foetida seed was investigated using different solvents. It was found that n-hexane gave the best yield at an optimized 1:2 seed-to-hexane ratio. The kinetics data of extraction was obtained. It was found that extraction follows a first-order mechanism. The rate constant of extraction, the activation energy, and the activation thermodynamic parameters were calculated. The resulting oil was used for biodiesel production. The parameters affecting the biodiesel production were optimized as 0.9 wt % catalyst, 6:1 methanol-to-oil molar ratio, and 338 K. The physical and chemical properties of biodiesel were determined and compared with ASTM standards.

Figure 5. Effect of methanol-to-oil molar ratio. 8996

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ASSOCIATED CONTENT

S Supporting Information *

Physicochemical properties of S. foetida oil (Table S1) and fuel properties of S. foetida biodiesel (Table S2). This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Tel.: +919941613532. E-mail: rengsah@rediffmail.com. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge the Council of Scientific and Industrial Research, New Delhi, India, for financial support. Pandian Sivakumar thanks the Council of Scientific and Industrial Research, Human Resource Development Group (Extra Mural Research Division-1), New Delhi, India, for the award of a Senior Research Fellowship.

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REFERENCES

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dx.doi.org/10.1021/ie300882t | Ind. Eng. Chem. Res. 2012, 51, 8992−8998

Industrial & Engineering Chemistry Research

Article

(40) Meng, X.; Chen, G.; Wang, Y. Biodiesel production from waste cooking oil via alkali catalyst and its engine test. Fuel Process. Technol. 2008, 89, 851−857.

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dx.doi.org/10.1021/ie300882t | Ind. Eng. Chem. Res. 2012, 51, 8992−8998