Optimization of biodiesel production

In the world economic context, the optimization of industrial processes is a tool that has been applied frequently in order to reduce the consumption of raw materials, with the main objective of reducing production costs. Response surface methodology (RSM) is a powerful tool for the optimization of chemical reactions and/or industrial processes. The main advantages of this method include: (1) an understanding of how the test variables (process variables) affect the selected process response; (2) the determination of any possible interrelationship among the test variables; and (3) the characterization of the combined effect that all test variables may have on the process response (Myers & Montgomery, 1995). There are only few examples in the literature involving optimization of transesterification of vegetable oils to produce biodiesel, even knowing that the costs of biofuel production are high (Domingos et al., 2008).

Pinzi et al. (2011) evaluated together with the process variables, how raw material fatty acid composition affects the biodiesel production. The authors applied a factorial design to determine how the operation conditions affected the transesterification process (reaction temperature, initial catalyst concentration by oil mass and methanol concentration), while the reaction yield was considered as the response variable. The vegetable oils studied were maize (MME), sunflower (SFME), olive (OOME), coconut (CME), linseed (LME) and palm (PME). A different range of temperature (from 40 oC to 60 oC) was selected for coconut oil and palm oil, since these oils are rich in unsaturated fatty acids. Molar ratio methanol:oil ranged from 4.2:1 to 5.4:1 and catalyst concentration from 0.8 to 2.1% Optimized conditions for each of the raw materials are shown in Table 1.

A complementary study aimed to define the optimum time of reaction based on a study of reaction kinetics. During the transesterification reaction carried out at the optimized condition, samples were taken at 30s, 1, 2, 5, 10, 35, 60, 90 and 120 min. Kinetic curves showed that every transesterification reaction presents similar performance curve, with the exception of coconut that exhibits the lowest yield of fatty acid methyl esters (FAME). After 20-min reaction oils with longer fatty-acid chains (olive, corn, linseed and sunflower) achieve the optimal yield of FAME, but on the other hand palm oil and coconut oil show the best performance after 40-min reaction. The authors observed that the effect of catalyst concentration was influenced by fatty-acid composition. Vegetable oils composed by unsaturated fatty acids show a directly proportional dependence between the concentration of catalyst and yield, up to a maximum. Whereas, considering vegetable oils with (mono) saturated fatty acids, amounts of catalyst greater than the optimal value lead to soap production. Fatty acids chain length also seems to influence biodiesel conversion. Oils with longer fatty-acid chains need half of the reaction time requested by oils comprising shorter fatty-acid chains to achieve maximum yield.

Silva et al. (2011) discussed in their paper the production process optimization for biodiesel by transesterification of soybean oil with ethanol, where several parameters, including catalyst, alcohol/vegetal oil molar ratio, and temperature would influence the transesterification. The authors’ main objective was to study how the process variables (ethanol-to-oil ratio, catalyst concentration, reaction time and temperature) affecting the yield of biodiesel and then optimize this process. The levels of process variables studied were: ethanol/oil ratio (i. e., 3:1, 6:1, 9:1, 12:1 and 15:1), catalyst concentration (0.1%, 0.5%, 0.9%, 1.3% and 1.7% w/v of NaOH), reaction time (40, 60, 80, 100, and 120 min) and temperature (40, 50, 60, 70 and, 80 °C). Optimum values of the process parameter for maximum efficiency (95% of ethyl esters) were molar ratio ethanol: soybean oil 9:1, catalyst concentration 1.3% w/v, temperature 40 oC and reaction time 80 minutes. The analysis of the effects of process variables on yield in ethyl esters showed that the molar ratio, catalyst concentration and reaction time had a positive effect while the temperature had a negative effect. A positive effect means that the larger the values of process variables, the greater the yield of biodiesel.

Factor

Optimum value

MME

Yield: 98.67 (wt%)

Reaction temperature (oC)

47.53

Catalyst concentration (wt%)

1.92

Methanol/oil (molar ratio)

5.4

SFME

Yield: 99.70 (wt%)

Reaction temperature (oC)

59.82

Catalyst concentration (wt%)

1.81

Methanol/oil (molar ratio)

5.4

OOME

Yield: 98.02 (wt%)

Reaction temperature (oC)

45

Catalyst concentration (wt%)

1.6

Methanol/oil (molar ratio)

6.03

CME

Yield: 90.01 (wt%)

Reaction temperature (oC)

60

Catalyst concentration (wt%)

1.7

Methanol/oil (molar ratio)

6.6

LME

Yield: 97.71 (wt%)

Reaction temperature (oC)

53

Catalyst concentration (wt%)

1.8

Methanol/oil (molar ratio)

6.02

PME

Yield: 98.91 (wt%)

Reaction temperature (oC)

65

Catalyst concentration (wt%)

1.81

Methanol/oil (molar ratio)

6.15

Table 1. Optimization results according to Pinzi et al. (2011)

Another optimization study used Raphanus sativus (L. Var) crude oil in ethanolysis with sodium hydroxide as catalyst. Three process variables were used to develop the experimental design: the ethanol:oil molar ratio (MR of 6:1 and 12:1), the catalyst concentration in relation to oil mass (C of 0.4 and 0.8 wt% NaOH) and the alcoholysis temperature (T of 45 and 65 oC). This yield was expressed in relation to the oil mass used for ethanolysis, reason why some values were greater than 100%. Reaction temperature had no statistical significance over biodiesel yield. The highest biodiesel yield was 101.7% obtained at 65 oC with a MR of 12:1 and 0.4 wt% of C. Nevertheless, when the alcoholysis temperature was decreased to 45 oC, phase separation improved and lower levels of soap accumulation were obtained in the ethyl ester phase. The authors recommend the following procedure for the ethanolysis of Raphanus sativus crude oil: MR of 11.7:1, NaOH concentration of 0.4 wt%, 45 oC and vigorous agitation for 60 min as the first reaction stage, followed by a second stage in which MR and NaOH concentration can be reduced to 6:1 and 0.03 wt%, respectively (Domingos et al., 2008).

Heterogeneous catalysis optimization was studied by Marchetti & Errazu (2011). The reaction temperature’s effects (30, 45 and 55 oC), the initial amount of free fatty acid (2.8%, 9.9% and 19.5% w/w), the molar ratio of alcohol/oil (4.2:1, 5.01:1 and 6.1:1) and the type of catalyst (homogeneous — sulfuric acid or heterogeneous — Dowex monosphere 550A) over the main reaction are analyzed and their effects compared. Temperature and molar ratio had a positive effect over biodiesel production: when the temperature and molar ratio increase the final conversion increases as well. When the initial amount of free fatty acid was varied, experimental results show that the final conversion increases as the initial amount of free fatty acid increases. Therefore, this effect could also be seen on the total FAEE production since the final amount of biofuel will be produced from the triglycerides as well as from the fatty acids present in the reaction mixture. The last part of this paper, a comparative study was made between the production of esters using sulfuric acid and a base solid resin with ethanol anhydrous under similar operational conditions, such as T=55 oC, initial amount of FFA=9.9% w/w, 2.2% w/w of each catalyst, and a molar ratio of alcohol/mixture of 6.1:1. Sulfuric acid reaches its final conversion in about 3 days time, while base solid resin reaches almost 100% in 70 hours.

As can be seen by the results showed earlier, biodiesel production is influenced by several process variables. The ideal combination of these variables will result in a higher yield in esters as well as a final product of higher quality. In addition, production costs could be reduced, including the industrial level. It was observed that depending on the feedstock, the type of alcohol and catalyst, the optimum conditions change. Another relevant point is related to the diversification of oil sources, which also help to reduce costs and to produce a quantity of fuel that meets global demand. In this scenario come acid oils, such as waste frying, and the heterogeneous catalysts, which are being actively researched.

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