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Fuel 89 (2010) 36–42

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Fuel journal homepage: www.else vier.com/locate/fuel Optimization of the transesterification reaction in

Optimization of the transesterification reaction in biodiesel production

F. Ferella a, * , G. Mazziotti Di Celso b , I. De Michelis a , V. Stanisci c , F. Vegliò a

a Department of Chemistry, Chemical Engineering and Materials, University of L’Aquila, Monteluco di Roio, 67040 L’Aquila, Italy b Department of Food Science, University of Teramo, Via C.R. Lerici 1, 64023 Mosciano Sant’Angelo (TE), Italy c Fox Petroli S.p.A., Via Osca 74, 66054 Vasto (CH), Italy

article info

Article history:

Received 7 December 2008 Received in revised form 21 January 2009 Accepted 23 January 2009 Available online 14 February 2009

Keywords:

Biodiesel

Rapeseed oil

Transesterification

ANOVA

abstract

In this paper response surface methodology (RSM) was used to study the transesterification reaction of rapeseed oil for biodiesel production. The three main factors that drive the conversion of triglycerides into fatty acid methyl esters (FAME) were studied according to a full factorial design at two levels. These factors were catalyst concentration (KOH), temperature and reaction time. The range investigated for each factor was selected taking into account the process of Fox Petroli S.p.A. Analysis of variance (ANOVA) was used to determine the significance of the factors and their interactions which primarily affect the first of the two transesterification stages. This analysis evidenced the best operating conditions of the first transesterification reaction performed at Fox’s plant: KOH concentration 0.6% w/w, temperature 50 C and reaction time 90 min with a CH 3 OH to KOH ratio equal to 60. Three empirical models were derived to correlate the experimental results, suitable to predict the behavior of triglyceride, diglyceride and monoglyceride concentration. These models showed a good agreement with the experimental results, demonstrating that this methodology may be useful for industrial process optimization. 2009 Elsevier Ltd. All rights reserved.

1. Introduction

The problems that nowadays affect fossil fuels are well known:

increasing price that makes petroleum no longer economically sus- tainable, emission of very dangerous pollutants for human health, emission of carbon dioxide that is the main reason of the global warming. Moreover fossil fuels are non-renewable resources, so they will last for a limited period of time. In this scenario vegetable oils are more attractive, because of their renewable nature and environmental benefits. Biodiesel is said to be carbon neutral, as biodiesel yielding plants absorb more carbon dioxide than that added to the atmosphere when used as fuel [1–4] . It is highly bio- degradable in fresh water as well as in soil. The best part of biodie- sel (90–98%) is mineralized in 21–28 days under aerobic or anaerobic conditions [5–7] . Furthermore, the use of biodiesel in diesel engines reduces the emissions of hydrocarbons, carbon monoxide, particulate matter and sulphur dioxide. Only nitrogen oxides emission increases: this behavior is due to the oxygen con- tent of biodiesel [8–14] . However, vegetable oils have some disad- vantages. First of all, the direct use in internal combustion engines is problematic. Due to their high viscosity (about 11–17 times greater than diesel fuel) and low volatility, they do not burn com- pletely and form deposits in the fuel injectors of diesel engine [15,16]. An improvement on viscosity can be obtained with transe-

* Corresponding author. Tel.: +39 0862 43 4265; fax: +39 0862 43 4203. E-mail address: francesco.ferella@univaq.it (F. Ferella).

0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved.

doi:10.1016/j.fuel.2009.01.025

sterification, which seems to be the process that assures best re- sults in terms of lowering viscosity and improving other characteristics [3] . Besides these technical difficulties, there are some social problems to be considered, as the extensive use of veg- etable oils may cause starvation in poor and developing countries. As regards catalyst, potassium hydroxide has been successful in producing biodiesel at industrial level [17] . Nevertheless, potas- sium hydroxide produces soaps by neutralizing the free fatty acid in the oil or by triglyceride saponification. Thus, biodiesel and glyc- erine have to be purified by washing with hot distilled water two or three times, resulting in a high consumption of both time and water [3] . Unfortunately, due to their polarity, soaps dissolve in glycerol phase during the separation stage after the reaction, but they may be separated by means of a simple centrifugation. Forma- tion of soaps decreases biodiesel yield obtained after the clarifica- tion and separation stages. In addition, the dissolved soaps increase the methyl ester solubility in glycerol, an additional cause of yield loss [4] . Several types of vegetable oils can be used for the biodiesel production. In this paper rapeseed oil was studied, but there are no technical restrictions to the use of other kinds of veg- etable oils, although biodiesels coming from some vegetable oils may not fulfil quality standards [18–22]. In Italy diesel fuel consumption was about 26 million tons in 2007 [23] . Considering that from every hectare of rape is possible to obtain around 1.1–1.2 tons of oil [24] , the possibility of total substitution of diesel fuel with biodiesel is unlikely. However, veg- etables oil can represent a small contribution, if biodiesel and die-

F. Ferella et al. / Fuel 89 (2010) 36–42

37

sel were blended together. In 2007 469,707 tons of biodiesel were produced in Italy, of which 202,035 tons were used in domestic market [25] . Biodiesel is blended at 5% and up to 25% with diesel in some petrol stations, while it is used unblended for heating pur- poses. Fox Petroli S.p.A. is one of the most important Italian com- panies amongst those operating in the production of biodiesel. The plant is situated in Vasto, Central Italy, and in 2007 it produced around 130,000 tons of biodiesel [26] . The raw rapeseed oil under- goes first transesterification, and then a settler lets the glycerine separate from supernatant, which reaches a reactor for the second transesterification: the final triglyceride conversion is 98–99%. Fur- ther glycerine is separated in another settler. A heat exchanger re- moves part of methanol, whereas the other part is dried off by vacuum distillation. The raw biodiesel is then washed by water and centrifuged for removal of last traces of glycerine and soaps. Water is dried off in an evaporator and a vacuum dryer; finally, the biodiesel (named BIOFOX) is stored to be distributed and sold. The glycerine is refined and sold as by-product. Several parameters affect the transesterification: catalyst concentration, methanol concentration, temperature, reaction time, pressure and the type of oil because of different content of triglycerides and phospholip- ids. In this study three of the most important parameters which af- fect the yield of the first transesterification reaction were tested, i.e. catalyst concentration, temperature and time of reaction. More- over, these are the easiest factors which can be carefully controlled during the industrial production. All the tests were performed by using rapeseed oil at atmospheric pressure, since the transesterifi- cation proceeds very fast even at low pressure: this avoids the in- crease of costs both in terms of equipment and energy consumption. As alkaline metal hydroxides are easily the most ac- tive, KOH is used for the biodiesel manufacturing. The compound which really reacts with triglycerides is methylate, hence the amount of methanol also affects the transesterification. The CH 3 OH:KOH ratio (w/w) was fixed at 60 for all the tests performed during the experimental campaign: changing the amount of KOH, the concentration of methanol automatically changes in different tests. The total reaction between triglycerides and methanol to give biodiesel is a sequence of three sequential reactions:

Triglyceride þ CH 3 OH ! Diglyceride þ FAME Diglyceride þ CH 3 OH ! Monoglyceride þ FAME Monoglyceride þ CH 3 OH ! Glycerol þ FAME

ð

ð

ð

1Þ

2Þ

3Þ

From a stoichiometric point of view three moles of methanol are required for each mole of triglyceride: however, in order to maximize ester production, a greater molar ratio is employed, usu- ally the double [27,28]. The aim of the present work is the determi- nation of the best operating conditions for the first reaction of the two-stage transesterification industrial process developed by Fox Petroli S.p.A.

2. Materials and methods

2.1. ANOVA and regression analysis

The experimental tests were carried out according to a full 2 3 factorial design where factors (low and high level in parentheses) were: KOH concentration (0.2%; 0.6% w/w), temperature (50 C; 60 C) and reaction time (30 min; 90 min). Each test was replicated twice. The above values were chosen taking into account economic considerations: the range of KOH concentration (percentage by weight referred to the oil weight) and the reaction time have been selected around the typical value used in the industrial production of the company. The higher tem- perature level was determined by considering the boiling point of methanol (65 C), whereas the lower value is 50 C, since previous

tests carried out by the authors demonstrated unsatisfactory con- version rates of triglycerides. Moreover at lower temperatures mis- cibility of methoxide and oil is scarce: this behaviour is due to the greater polarity of the methoxide molecule with respect to the tri- glyceride one, which is non-polar and determines the hydrophobic performance of the oil itself. As a matter of fact, the greater the temperature, the greater the miscibility of that mixture. Responses selected to test the yield of the transesterification were triglycer- ide, diglyceride and monoglyceride concentration (hereafter TC, DC, MC, respectively). Experimental results were worked out using ANOVA, which allows to evaluate whether the effect and the inter- action among the investigated factors are significant with respect to the experimental error. Yates’ algorithm is a simple technique for estimating the main effects and interactions among them. The significance of the main factors and their interactions was assessed by F -test method with a confidence level of 95% [29,30]. Response surface methodology (RSM), a mathematical–statistical tool, was used for modelling TC, DC and MC. These responses of interest are influenced by the three tested factors and RSM allows the opti- mization of all these responses. For example, TC can be expressed as:

TC ¼ f ð A; B; C Þ þ e

ð 4Þ

where e represents the error observed in the response TC. A low-or- der model is usually employed, like a first-order model, but if a cur- vature in the surface is present, a polynomial of higher order must be used. In this study three second-order polynomials were used to describe the response surface for TC, DC and MC; the general struc- ture of that polynomial is the following:

k

Y ¼ b 0 þ X b i x i þ X b ii x þ X

2

i

i¼1

i

i <j

X b ij x i x j þ e

j

ð 5Þ

where Y is the yield of the reaction, b i are the regression coefficients and x i are the coded factors. Obviously a polynomial can not approximate all the space of the independent variables, but it usu- ally fits the real response for a relatively small region. The model parameters can be estimated by using proper experimental designs while collecting data. The experimental design for fitting the sec- ond-order models was orthogonal and rotatable. Orthogonality is the optimal design property as it minimizes the variance of the regression coefficients. Rotability is another important property which implies that the variance of a response at a certain point is

that the variance of a response at a certain point is Fig. 1. Central composite design

Fig. 1. Central composite design for three factors at two levels.

38

Table 1 Test conditions of the full factorial design.

F. Ferella et al. / Fuel 89 (2010) 36–42

Test

Treatment

Coded factors

A

B

C

combination

A

B

C

KOH (% w/w)

Temperature ( C)

Time (min)

1

(1)

1

1

1

0.2

50

30

2

a

1

1

1

0.6

50

30

3

b

1

1

1

0.2

60

30

4

ab

1

1

1

0.6

60

30

5

c

1

1

1

0.2

50

90

6

ac

1

1

1

0.6

50

90

7

bc

1

1

1

0.2

60

90

8

abc

1

1

1

0.6

60

90

9

0

0

0

0

0.4

55

60

10

0

0

0

0

0.4

55

60

11

0

0

0

0

0.4

55

60

12

0

1.68

0

0.4

46.6

60

13

0

1.68

0

0.4

63.4

60

14

1.68

0

0

0.064

55

60

15

1.68

0

0

0.736

55

60

16

0

0

1.68

0.4

55

9.5

17

0

0

1.68

0.4

55

110.5

only a function of the distance of the point from the design centre

and does not depend on direction [30,31]. The central composite de-

sign carried out in this study is shown in Fig. 1 . This central composite design can be rotatable by the choice of

a ; its general formula is:

a ¼ ðn f Þ 1=4

ð 6Þ

where n f is the number of points used in the factorial portion of the design. In this case, considering eight points, a is equal to 1.68. Table 1 gives the conditions of all the tests developed by the full factorial design, both in terms of coded and non-coded variables. The central point test was replicated three times (tests 9–11, Table 1), in order to have a good estimation of the experimental error. Furthermore, six axial tests (12–17, Table 1) were also carried out to better under- stand the shape of the response surfaces. The regression analysis was used to build three quantitative models, in which only the significant factors were taken into ac- count. These models were built in order to predict TC, DC and

MC for many operating conditions that were not directly tested.

It should be noted that the use of the models outside the investi- gated range is not allowed, since it would lead to wrong results.

2.2. Experimental procedure

The experimental tests were carried out using a 500 ml jacketed stirred reactor tank. The temperature of oil was controlled by a thermometer and regulated by an electrically heated water bath (Colora WK16). The reactor was mechanically stirred at 600 rpm to assure a good mixing of the reactants.

Table 2 Quality control of the rapeseed oil.

Parameter

Unit

Value

Method

Acidity (as oleic acid) Cloud point Density at 20 C Iodine number Lecithin (as phosphorus) Erucic acid Sulphur content Total contamination Viscosity at 20 C Water content

% C kg/m 3 gI 2 /100g ppm % ppm % m m 2 /s %

<0.10

NGD C10-1976 EN 23015 EN ISO 3675 ISO 5508 UNI 22038-2001 ISO 5508 EN ISO 20846 NGD C7-1976 EN ISO 3104 KARL FISHER

3.8

0.92

113

<10

<0.20

<2

<0.05

77.5

<0.10

For each test 200 ml of rapeseed oil (quality control reported in Table 2 ) were heated at the required temperature, according to the experimental plan shown in Table 1 ; in the meantime, KOH (flakes, assay > 90%, Sigma–Aldrich) was dissolved in a certain volume of methanol (anhydrous 99.8%, Sigma–Aldrich), in order to have a fixed ratio CH 3 OH:KOH equal to 60 (w/w). As said before, this ratio was kept constant for all the tests. For example, in test 1, 0.37 g of KOH were dissolved in 22.1 g of methanol, considering the oil den- sity of 0.92 kg/m 3 . Once KOH was completely dissolved, methoxide was added to the hot solution, and the reaction took place for the required time. After that, 10 ml of solution were withdrawn and 2 ml of citric acid were added to stop the transtesterification. Hence, the biodiesel was separated from glycerine by centrifugation (Thermo Scientific IEC CL30) and the sample was then ready for analysis.

2.3. Analytical methods

TC, DC and MC were measured by capillary column gas chroma- tography (Thermo TRACE GC Ultra) equipped with a cold on-col- umn injection and autosampler apparatus. Analyses were carried out according to the EN 14105 internal standard calibration; 100 mg of each biodiesel sample were mixed with 100 l l of 1,2,4-butanetriol (1 mg/ml, standard 1) and 100 l l of 1,2,3-Tricap- rinoylglycerol (8 mg/ml, standard 2). Other 100 l l of N -methyl-N - trimethylsilyltrifluoroacetamide (MTSFA, derivatization grade) were added to convert both free and total glycerol into volatile compounds. All reagents were supplied by Sigma–Aldrich. After 15 min, 8 ml of heptane were added as solvent. Final sample (0.5 l l) were injected into the gas chromatograph analyser for TC, DC, MC determination.

3. Results and discussion

3.1. ANOVA

The response of the factorial design is reported in Table 3 . Each result is expressed as arithmetic mean of two replications. Looking at Table 3 , test 6 gives the best simultaneous results in terms of triglycerides, diglycerides and monoglycerides, as their concentrations (0.05%, 0.09% and 0.36% w/w, respectively) are the lowest among those of the whole experimental plan. These results were obtained by 0.6% w/w of KOH, 50 C and 90 min of reaction. Comparing these values with the EN 14214 specifications (see

F. Ferella et al. / Fuel 89 (2010) 36–42

39

Table 3 Results obtained in terms of TC, DC and MC.

Test

Response

TC (% w/w)

DC (% w/w)

MC (% w/w)

1

16.42

11.28

6.74

2

1.45

0.87

0.72

3

18.50

12.48

7.17

4

0.43

0.33

0.80

5

14.10

10.58

5.57

6

0.05

0.09

0.36

7

16.34

12.44

6.73

8

0.01

0.09

0.84

9

3.32

2.07

0.93

10

2.47

1.46

0.90

11

2.95

1.80

1.09

12

6.65

3.63

1.26

13

2.50

1.51

1.02

14

96.71

3.23

0.07

15

0.01

0.04

0.60

16

6.84

4.58

2.72

17

2.74

1.63

0.83

Table 4 ), the biodiesel fulfils the quality requirements regarding TC, DC and MC. At the moment, the biodiesel produced by Fox Petr- oli after the first transesterification has the following composition:

TC 5.26%, DC 2.48%, MC 1.21% w/w; as expected, methanol and free glycerine content exceeds the limits indicated in the European specifications. Table 4 also shows the analysis of biodiesel pro- duced by that plant at the end of the process, as it is put on the market [26] . Fig. 2 shows the main effects and interactions among factors, which mainly influence the final concentration of triglycerides. Effects with a statistical significance lower than 95% were not reported, according to the F -test utilized. Catalyst concentration KOH, factor A, has a strong negative effect on the TC ( 16%): as ex- pected, increasing the amount of catalyst the concentration of tri- glycerides decreases. In this particular case, as the response variables (TC, DC, MC) represent the reactants, a negative effect

A B CAB AC 2 0 -2 -4 -6 -8 TC DC -10 MC -12
A
B
CAB
AC
2
0
-2
-4
-6
-8
TC
DC
-10
MC
-12
-14
-16
-18
Effect (%)

Fig. 2. Effect of factors and of their combinations on TC, DC and MC (A: KOH; B:

temperature; C: reaction time).

is advisable, because of a very low TC. This means that a greater amount of triglycerides reacts with methylate, increasing the yield of the transesterification. Reaction time, factor C, has a slight negative effect, so the yield of the process increases if the reaction time is prolonged from 30 to 90 min. The interaction AB has a slight negative effect too; if the amount of KOH increases together with temperature, the TC reduces, while the final conversion to FAME grows. Temperature, factor B, seems to have a small positive effect, even though it is not statistically significant with respect to the experi- mental error determined by replications of the central point test. Results of ANOVA for concentration of diglycerides are shown in Fig. 2 . As for TC, catalyst concentration has an important negative effect on DC in the range studied, whereas interaction AB between KOH and temperature is also negative but less determinant. Time is not significant: this could be explained by a greater reaction rate of the second reaction (Eq. (2) ) compared to the first one (Eq. (1)).

Table 4 Analysis of biodiesel produced at Fox Petroli and European specification for FAME used in diesel engines.

Parameter

Unit

Value

Specification EN 14214

Method

 

Min

Max

Acid value Ash sulphated Carbon residue Cetane number Cold filter plugging point Cloud point Methanol content Monoglyceride content Diglyceride content Triglyceride content Free glycerol Total glycerol Copper strip corrosion (3 h at 50 C) Density at 15 C Ester content Flash point Iodine number Linolenic acid methyl ester Alkali content

mgKOH/g

0.27

0.5

EN 14104

% m/m

<0.01

0.02

ISO3987

% m/m

0.10

0.30

EN ISO 10370 EN ISO 5165

53

51.0

C C % m/m % m/m % m/m % m/m % m/m % m/m Rating kg/m 3 % m/m C gI 2 /100g % m/m mg/kg

6

EN116

0

-20

EN 23015 EN 14110 EN 14105 EN 14105 EN 14105 EN 14105 EN 14105 EN ISO 2160 EN ISO 3675 EN 14103 EN ISO 3679 EN 14111 EN 14103 EN 14108 (Na) EN 14109 (K) EN 14107 EN 14112 EN ISO 20846 EN 12662 EN ISO 3104 EN ISO 12937

<0.05

0.2

0.69

0.8

0.08

0.2

0.1

0.2

0.006

0.02

0.20

0.25

Class 1

Class 1

883.5

860

900

97.3

96.5

183

120

119

120

7.3

<2

5

Phosphorus content Oxidation stability, 110 C Sulphur content Total contamination Viscosity at 40 C Water content

mg/kg hours mg/kg mg/kg m m 2 /s mg/kg

1.4

10

7.2

6

<2

10

9

24

4.46

3.5

5

236

500

40

F. Ferella et al. / Fuel 89 (2010) 36–42

Furthermore temperature alone (factor B) has a slight positive effect on the final DC, nevertheless, this factor does not have the re- quired significance if compared to the variance of the experimental error. As regards monoglycerides (see Fig. 2 ), there are four main fac- tors and interactions that influence their concentration at the end of the reaction. As usual, factor A has a significant negative effect, even though not so important as for triglycerides and diglycerides. Temperature, factor B, seems to have a positive effect on the fi- nal MC, but this means that it plays a negative role in the conver- sion of monoglycerides to methyl esters in the range from 50 to 60 C. Reaction time (factor C) has a negative effect, so it will be useful to extend the time to achieve a greater yield of FAME. The interaction AC has a very small positive effect: increasing simultaneously both concentration of KOH and reaction time the total conversion of monoglycerides to methyl esters lightly decreases.

3.2. Regression analysis

Experimental results were fitted by empirical models according to RSM [30,31], in order to predict TC, DC and MC by weight under different operating conditions. The complete models suitable to fit the experimental data are second-order models, having the follow- ing general structure:

Y ¼ a 0 þ a 1 X 1 þ a 2 X 2 þ a 3 X 3 þ aÞ 12 X 1 X 2 þ a 13 X 1 X 3 þ a 23 X 2 X 3

þ a 11 X 2 þ a 22 X 2 2 þ a 33 X

1

2

3

ð

7Þ

where all the independent variables are in the coded form and all coefficients a 0 , a 1 , a 2 , a 3 , a 12 , a 13 , a 23 , a 11 , a 22 , a 33 were estimated by linear regression procedures. Coded variables can be obtained from the real ones by the following expressions:

X 1 ¼

X 2 ¼

X 3 ¼ ðC 60Þ =30

ðA 0: 4Þ= 0: 2

ðB 55 Þ =5

8Þ

9Þ

ð 10Þ

ð

ð

A first regression analysis was carried out in order to obtain an useful tool, able to calculate the final TC, DC, MC of the first transe- sterification reaction, even for different KOH concentration, tem- perature and time. Three statistical models were developed as a consequence of the first regression analysis. However, these models did not show a good agreement with the experimental results of the whole fac- torial design, because correlation coefficients of the regression

design, because correlation coefficients of the regression Fig. 3. Mono, di and triglyceride trends as a

Fig. 3. Mono, di and triglyceride trends as a function of extent of reaction.

were not satisfactory and the significance of all the model param- eters was rather low. The regression analysis was repeated, removing the results ob- tained from tests 14 and 16. The poor agreement between experi-

mental results and factorial design is particularly strong in case of mono and diglyceride data fitting: this behaviour is probably due to their trend as a function of the extent of reaction, as shown in Fig. 3 .

A non satisfying data fitting was obtained for triglycerides as

well, although they showed a different trend as a function of extent of reaction. Fig. 3 allows to define as critical tests 14 and 16, because their experimental data are located in the rise side of the curve. This area is particularly difficult to fit for the second-order model, which, of

course, is defined by a parabolic trend. This problem is guessable from a chemical point of view: if the catalyst to triglycerides molar ratio is at least equal to the stoichi- ometric one, triglycerides react quickly facilitating monoglycerides formation, but this is going to decrease in case of lower catalyst concentrations. This is the case of test 14, where monoglyceride concentration is very low, because triglyceride species are poorly converted. Thus, test 14 shows experimental results which are not fitted with success by the second-order model.

A similar situation happens when the reaction time is too low:

in this case triglyceride species is poorly converted with conse- quently scarce mono and diglyceride concentration, as they have not had enough time to form (case of test 16). Results of the second

regression analysis for TC are given in Table 5 . According to this analysis, the following equation was then used in order to predict TC, as a function of catalyst concentration, tem- perature and reaction time:

TCð %w= wÞ ¼ 4:49 8: 13 X 1 0: 85 X 3 þ 3: 58X 2

1

ðR 2 ¼ 0: 97Þ

ð

11Þ

Eq. (11) was utilized for the optimization of the first transeste- rification reaction as concerns FAME production. The adequacy of the mathematical model obtained by the regression analysis was confirmed by a scatter diagram ( Fig. 4 ), where experimental data for TC were reported as a function of the calculated ones. As it is possible to note, all points are disposed close to the straight line, confirming a good agreement between the experi- mental results and those ones calculated by the model. Eq. (11) was also employed to represent the best-fitting re- sponse surface as a function of KOH concentration and reaction time. Dependence on temperature misses, because of low signifi- cance of the coefficients a 2, a 12, a 23, a 22 . As shown in Fig. 5 , conversion of triglycerides is rather low when KOH concentration is below 0.45%. In case of higher values, KOH enhances the chemical reactions, reaching more satisfactory conversion values. At the same time, keeping constant KOH con-

Table 5 Estimated values for parameters in Eq. (5).

Coefficient (%)

s.d

Significance

a 0

4.49

0.65

100

a 1

8.13

0.49

100

a 2

n.s.

a 3

0.85

0.46

90

a 12

n.s.

a 13

n.s.

a 23

n.s.

a 11

3.58

0.61

100

a 22

n.s.

a 33

n.s.

R 2 = 0.96

F. Ferella et al. / Fuel 89 (2010) 36–42

41

20 Tri Di Mono 15 10 5 0 0 5 10 15 20 Calculated (%
20
Tri
Di
Mono
15
10
5
0
0
5
10
15
20
Calculated (% w/w)

Experimental (% w/w)

Fig. 4. Scatter diagram of the experimental TC, DC and MC vs those concentrations calculated by Eqs. (11)–(13) .

vs those concentrations calculated by Eqs. (11)–(13) . Fig. 5. Response surface of TC vs. catalyst

Fig. 5. Response surface of TC vs. catalyst concentration and reaction time, obtained by Eq. (11) .

centration on high values, reaction time shows a positive effect on triglyceride conversion. A statistical model was also developed for

DC by a different regression analysis, according to the following

equation:

DCð %Þ ¼ 2: 64 5: 91X 1 2: 98X 2

1

ð R 2 ¼ 0: 96 Þ

ð12 Þ

In this equation there are only three significant coefficients, a 0 , a 1 , a 11 , as result of a strong dependence on catalyst concentration, which mainly drives the reaction between diglycerides and meth- anol. The scatter diagram of the experimental DC versus those val-

ues obtained by Eq. (12) is reported in Fig. 4 : a good agreement

between the two set of data can be observed, confirming that the model interprets the experimental range studied adequately. As a

interprets the experimental range studied adequately. As a Fig. 7. Response surface of MC vs. catalyst

Fig. 7. Response surface of MC vs. catalyst concentration and reaction time.

result, the mathematical model which is able to predict the DC in

the range of the investigated factors (0.2% < A < 0.6%; 50 C < B <

60 C; 30 min < C < 90 min) is a simple second-order curve, as shown in Fig. 6 .

The trend reported in Fig. 6 suggests that the minimum catalyst

concentration required to be sure that all diglycerides react with

methanol is 0.53–0.55% w/w. The second-order mathematical model resulting from the regression analysis is as follows:

MC ð%Þ ¼ 1:26 3: 07X 1 0: 38X 3 þ 1:82 X 2 þ 0 :30X

1

2 3 ð R 2 ¼ 0 :97 Þ

ð 13Þ

MC calculated by Eq. (13) was reported in Fig. 4 together with

MC

obtained by the experimental tests. A very good R 2 value justi-

fies

the choice of the model above, so it can be used in a proficient

way to understand the behaviour of MC for different experimental conditions which were not directly tested. Eq. (13) can be represented as dimensional surface and contour plot: this surface shows the predicted MC for the experimental range both of reaction time and initial catalyst concentration of ra- peseed oil. The tri-dimensional surface reported in Fig. 7 is the most useful approach in terms of visualization of the reaction sys-

tem, because it gives the simultaneous dependence from the two

most significant parameters (KOH concentration and time) which affect the production of FAME. As Fig. 7 highlights, behaviour of monoglycerides is similar to that of triglycerides: it is rather low when KOH concentration is below 0.40–0.45% whilst, in case of higher values, KOH catalyst improves the chemical reaction en- abling more satisfactory reaction rates. At the same time, keeping constant KOH concentration on high values, reaction time shows a positive effect on monoglyceride conversion: in particular, after 60 min the conversion to esters is complete.

12 10 8 6 4 2 0 0 0.2 0.4 0.6 0.8 DC (% w/w)
12
10
8
6
4
2
0
0
0.2
0.4
0.6
0.8
DC (% w/w)

KOH (% w/w)

Fig. 6. Response surface of the DC using Eq. (12) .

4. Conclusions

In this paper a study of the optimization of the rapeseed oil transesterification reaction parameters was carried out by means of Response Surface Methodology (RSM). In particular KOH catalyst effect, temperature and reaction time were investigated consider-

ing the influence on triglyceride, diglyceride and monoglyceride

concentration. The analysis of variance (ANOVA) showed that to obtain satisfactory triglyceride conversion, the higher catalyst con- centration studied was needed, together with a reaction time of about 90 min. Moreover, increasing both temperature and KOH concentration higher conversion rate could be achieved. Similar re-

42

F. Ferella et al. / Fuel 89 (2010) 36–42

sults were obtained for diglyceride species; time does not seem so significant as in previous case: this is probably due to the greater reaction rate of diglyceride compared to the triglyceride one. As re- gards monoglycerides, their behaviour is very close to that of tri- glycerides; however, the increase of both catalyst concentration and time leads to lower ester conversions. The same negative effect is reached in case of higher temperature values. The statistical models developed for predicting TC, DC and MC showed a good agreement between experimental and calculated yields ( R 2 P 0.96), demonstrating the usefulness of regression analysis as a tool for optimization purposes. In conclusion, results evidenced the essential role of the catalyst, taking into account the methanol to catalyst ratio that remained constant; a very good conversion of triglycerides, diglycerides and monoglycerides into FAME was ob- tained by 0.6% w/w KOH, 60 methanol to KOH ratio by weight at 50 C after 90 min of reaction. The final concentrations were 0.05% triglicerides, 0.09% diglycerides and 0.36% monoglycerides. This suggests further work which will be aimed at the optimization of the second transesterification reaction, achieving a full optimi- zation of the Fox Petroli’s process.

Acknowledgements

Authors are very grateful to Ing. Francesca Forgione for her pre- cious collaboration during the experimental work at Fox Petroli’s laboratories.

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