{Peanut Biodiesel + Glycerol + Ethanol} at Atmospheric Pressure

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Liquid−Liquid Equilibrium of the System {Peanut Biodiesel + Glycerol + Ethanol} at Atmospheric Pressure Iza Estevam Pedrosa Toledo,† Leandro Ferreira-Pinto,*,‡ Fernando Augusto Pedersen Voll,§ Lucio Cardozo-Filho,∥ Lucas Meili,† Dayana de Gusmão Coel̂ ho,† Sandra Helena Vieira de Carvalho,† and João Inać io Soletti†

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†

Laboratory of Separation Systems and Process Optimization (LASSOP)-Center of Technology, Federal University of Alagoas, Maceió-AL, 57072-900, Brazil ‡ Departament of Energy Engineering, Sao Paulo State University (UNESP), Rosana-SP, Brazil § Department of Chemical Engineering, Federal University of Parana, Curitiba-PR, Brazil ∥ Department of Chemical Engineering, State University of Maringá, Maringá-PR, Brazil

ABSTRACT: This study reports experimental data for the liquid−liquid equilibrium (LLE) for a {peanut biodiesel (1) + glycerol (2) + ethanol (3)} system at 303.15 K and 323.15 K at atmospheric pressure. Solubility (binodal) curves were obtained by a cloud-point method. The reliability of the experimental data was confirmed using the Hand and Othmer−Tobias correlations. The regression coefficients were above 0.97 for all data sets. The universal quasichemical model was successfully used to correlate LLE data, which showed root-mean-square deviations of 0.99%, indicating accuracy close to experimental uncertainties.

1. INTRODUCTION

a higher rate of reaction and yield because methanol is more reactive than ethanol. Due to its physical−chemical characteristics and low cost, methanol is the most commonly used alcohol; however, in this study, ethanol was used because it is readily available in Brazil compared with methanol.8−10 Another considerable advantage of the use of ethanol is that it is carbon neutral as it has a closed carbon cycle because it is obtained from plants.5,11−15 Brazil has a well-established production process for ethanol from sugar cane, and it is available at a low cost, is sustainable, and is renewable; these characteristics have led to a considerable interest in its utilization for biodiesel production. Brazil has considerable potential to produce biodiesel from vegetable oils because of its huge variety of climate and soil, which allows this country to cultivate and produce different

In recent decades, there has been an increase in interest and studies related to renewable energy to replace or complement the use of petroleum-based fuels because of the high price of fossil fuels and the decrease in petroleum reserves as well as the fact that most accessible petroleum is located in countries that have political problems.1−4 In addition, fossil fuels are responsible for the emission of air pollutants, including gases that cause global warming, which contribute to the increase in the temperature of the Earth. Worldwide, 80.3% of the primary power consumed comes from fossil fuels, 57.7% of this is used by the transport sector.5 Because the environmental impacts caused by the combustion of fossil fuels have been growing, the search for alternative fuels and biodiesel is a great option. Biodiesel is defined as a mixture of esters derived from animal or vegetable oils; it is obtained mainly from the transesterification or esterification of fatty acids.6,7 Alcohol in excess is used to shift the reaction toward the formation of products, and the reaction requires an alkaline catalyst to increase the reaction yield. In general, biodiesel produced with methanol has © XXXX American Chemical Society

Special Issue: Latin America Received: December 10, 2018 Accepted: April 19, 2019

A

DOI: 10.1021/acs.jced.8b01185 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

in the presence of tricaprylin as an internal standard. The biodiesel produced was based on specialized literature20,22 and is briefly described in this text. The pilot unit used included a glass reactor with a capacity of 2 L, and it was jacketed and connected to a thermostated bath (TECNAL, TE184) and coupled with a mechanical stirrer (TECNAL, TE2003). The equipment was submitted to a constant agitation of 600 rpm, and the temperature was set to 303.15 K. After obtaining the predetermined experimental conditions, a mixture containing sodium hydroxide and ethanol was added to the reactor. The reaction comprised 2 wt % of the catalyst and oil and ethanol in 1:6 molar ratio, and the total reaction time was 30 min. After the reaction, the sample was collected and centrifuged to separate the biodiesel and glycerolrich phases. The obtained biodiesel was repeatedly washed with distilled water until pH 7.0 was reached with progressive reduction of the washing water. Initially, the water/biodiesel proportion used was 1:10 at 343.15 K to remove the catalyst, ethanol, and mono- and diacylglycerols. Next, the purified biodiesel was dried, filtered, and analyzed by gas chromatography to determine the reaction yield.20 The fatty acid ethyl esters (FAEEs) produced from peanut oil were determined by gaseous chromatography (VARIAN, CP3800) with an FID detector. A 3-m capillary column was used with an injector temperature of 513 K, and the temperature of the detector was 523 K. The oven’s temperature was programmed from 423 to 533 K at a heating rate of 10 K/min, and the carrier gas used was high-purity hydrogen (99.95%). To determine the yield of biodiesel obtained by transesterification, a ∼0.15 g sample of the dried reaction product was accurately weighed into a vial, and 1.0 mL of a solution of the internal standard, tricaprylin in chloroform (0.100 g/100 mL), was added. Aliquots of the mixture were analyzed by gaseous chromatography. The biodiesel yield was calculated from eq 1:

types of oleaginous plants, such as soybeans, palm trees, and peanuts, to produce biodiesel.11 Peanut was chosen for this study because it is an excellent oleaginous plant to use for biodiesel production. Some varieties have up to 50% oil in addition to presenting better oxidation resistance than other oils, because of its higher content of oleic acid.16,17 According to reports in the literature, oleic acid corresponds to 80−90% of the total fatty acids in peanut oil.16,17 The knowledge of phase diagrams for a multicomponent mixture is key to the design, simulation, and process optimization. Thus, the availability of phase diagrams for these components is a fundamental step for the biodiesel industry.18,19 By determining the miscibility and immiscibility regions of the ternary system {biodiesel (1) + glycerol (2) + ethanol (3)} and the tie lines, it is possible to determine the composition of each component on each side of the binodal curve, allowing optimization for the biodiesel industry by decreasing the operating costs and increasing the quality of biodiesel.18,19 The thermodynamics of {peanut biodiesel (1) + glycerol (2) + ethanol (3)} system were studied, and we obtained the binodal curves at 303.15 K and 323.15 K at atmospheric pressure (∼101 kPa, Maceió City, State of Alagoas, Brazil) and the respective tie lines. The biodiesel used was obtained from the transesterification of peanut oil. We used sodium hydroxide as the catalyst. The universal quasichemical (UNIQUAC) model has been widely used to correlate experimental data of the activity coefficients, and was also used in this study. Hand and Othmer− Tobias correlations were used to determine the quality of the data obtained because they were also used for determining the tie lines.

2. EXPERIMENTAL SECTION 2.1. Materials. The peanut seeds were dried in an oven for 12 h. Then, the oil was extracted in a hydraulic press (TECNALTE098) under a pressure of 12 tonnes. The extraction yield was evaluated based on the extraction time (maximum of 200 min). The materials were weighed on a precision balance (Mars, model AM220, Brazil) that had an uncertainty of ±0.001 g. The oil was subjected to vacuum filtration and dried on magnesium sulfate20 (>97 wt %, purchased from Nuclear) at 333.15 K. Anhydrous ethanol (>99 wt %), glycerol (>99 wt %), and sodium hydroxide (>97 wt %) were obtained from Nuclear and used without any prior purification. 2.2. Biodiesel Production from Peanut Oil. The chemical composition of the major fatty acids was determined by the gas chromatography (GC) analysis using the AOCS official methods21 Ce 1-62 and Ce 2-26 (see Table 1). It was considered that the percentage composition of each fatty acid was integrally converted into each of their respective esters. The produced peanut biodiesel comprised 99.1% fatty acid ethyl esters (FAEEs). The biodiesel yield, described as the amount of FAEEs formed in the transesterification reaction, was quantified

% yield =

Cx:ya

molar mass (g·g mol−1)

mass percentage (wt %)

palmitic oleic linoleic arachidic

16:0 18:1 18:2 20:0

256.43 282.47 280.45 312.54

6.8 89.7 2.4 1.1

A tricaprylin ms

100 (1)

where mtricaprylin, f tricaprylin, and Atricaprylin represent the mass, response factor, and peak area of the internal standard, respectively, AB is the sum of the peak areas of biodiesel, and ms is the mass of the sample. 2.3. Binodal Curves and Tie Lines. To determine the binodal and tie line curves, reported methodologies were used.7,8,23,24 The phase boundaries were determined by turbidimetric analysis using a titration method under isothermal conditions. A jacketed equilibrium cell was used that had a capacity of 50 mL (see Figure 1) and that was connected to a thermostatic bath (TECNAL, TE18, with an uncertainty of ±0.5 K) at temperatures of 303.15 K and 323.15 K. The mixture was agitated using a magnetic stirrer (PHOX, MS-HS2). The procedure included adding known masses of two components in the equilibrium cell and titrating that mixture with a third component. For the biodiesel-rich phase, biodiesel and ethanol were mixed, and this mixture was titrated with glycerol. Hence, for the glycerol-rich phase, glycerol and ethanol were mixed, and this mixture was titrated with biodiesel. This is known as the cloud-point method.25 After the immiscibility region of the binodal curves was delimited, the tie lines were determined at different chosen component proportions. For the determination of the tie line, the compositions in the two phases were selected, keeping the molar ratio between

Table 1. Major Fatty Acid Components of Peanut Oil Used in This Work fatty acid

mtricaprylinABftricaprylin

a

Cx:y, x = carbon number and y = number of double bonds. B



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3. THERMODYNAMIC MODELING The experimental results of this study were used to estimate parameters for the UNIQUAC activity coefficient model.32 The correlation showed an excellent agreement with the experimental data. It considered the percentage composition of each fatty acid was integrally converted of their respective esters. The values for ri and qi from the UNIQUAC model were calculated by applying eqs 4 and 5 for glycerol and ethanol, respectively, while eqs 6 and 7 were used for the peanut oil biodiesel, which was considered to be a single pseudocomponent. G

∑ vk ,iR k

ri =

(4)

k G

qi =

∑ vk ,iQ k

(5)

k C

Figure 1. Experimental apparatus of equilibrium cell: (1) cell equilibrium; (2) magnetic stirrer bar; (3) thermostatic bath.

G

∑ xm,i ∑ vk ,mR k

ri =

m C

qi =

glycerol and biodiesel constant and changing the proportion of ethanol. Glycerol and biodiesel were added to the equilibrium cell in known masses. Then, ethanol was added to the mixture to obtain different compositions of the overall phase and measurement of the tie lines. The predetermined mixtures for the study were agitated with a mechanical stirrer and allowed to stand for 12 h. After the process, the formation of two phases with well-defined interfaces was verified. Samples of each phase were collected for subsequent quantification. To determine the composition of ethanol in the ternary system, its mass fraction was quantified in the extract and in the raffinate by evaporation in a drying oven. The tie lines were established by interpolation of the results from the viscosity values observed on and below the binodal curve. The mixture composition was determined from binodal curves that were previously measured by identifying the point that represents the composition of the specified component. For each sample and for each phase, at least three individual measurements were performed, with an average uncertainty to 1 wt %. On the basis of the total system mass and of the phase and overall compositions, the mass balances were also checked. 2.4. Quality of the Experimental Data. The Hand26 (eq 2) and Othmer−Tobias25 (eq 3) correlations were used because a consistency test cannot be used to evaluate tie-line data. ij w I yz ij w II yz lnjjjj 3I zzzz = A + B lnjjjj 3II zzzz k w1 { k w2 {

II y ij 1 − w1I yz i zz = A′ + B′ lnjjj 1 − w2 zzz lnjjj z j j wI z j w II zz 1 2 k { { k

(6)

k G

∑ xm,i ∑ vk ,mQ k m

(7)

k

where vk,i is the number of groups, k, in component i, G is the number of groups, xm,i is the molar fraction of component m in pseudocomponent i, and vk,m is the number of groups k in component m. C is the number of components in pseudocomponent i. The components used were ethyl esters related to the fatty acids presented in Table 2. The mole fractions of the ethyl esters in the biodiesel were considered to be equal to the molar fractions of the respective free fatty acids. Parameters Rk and Qk were obtained from UNIFAC group contribution model (Magnussen et al.).33 The UNIQUAC binary interaction parameters were estimated by minimization of the sum of the square differences between the experimental and calculated data; see eq 8: NP NT NC

OF =

calc 2 ∑ ∑ ∑ (wiexp , n , p − wi , n , p) p

n

wexp i,n,p

(8)

i

wcalc i,n,p

where and are the experimental and calculated mass fractions of the i component at the n tie line in the p phase, respectively. The values of wcalc i,n,p were calculated by Gibbs free energy minimization using eq 9, which does not consider chemical reaction predictions.34 The overall compositions used for obtaining wcalc i,n,p were the middle points of each experimental tie line. NC NP

(2)

G* =

NC NP

∑ ∑ ni ,p(ln(ni ,p) − ln(ntp)) + ∑ ∑ ni ,p ln(γi ,p) i=1 p=1

i=1 p=1

(9)

where ni,p is the number of moles of each component i in phase p, ntp is the total number of moles of phase p, and γi,p is the activity coefficient of i in phase p (calculated by the UNIQUAC model). During the G* minimization, auxiliary variables, which are used to obtain ni,p values so that the system mass balance is always correct, were considered as decision variables. The minimizations of eqs 8 and 9 were performed by a sequential use of the Particle Swarm Optimization (PSO)35 and deterministic (Nelder−Mead, from the “f minsearch” function of the open source software Scilab 6.0.1) algorithms. Since wcalc i,n,p is obtained

(3)

where wI1 is the biodiesel mass fraction in the biodiesel-rich phase, wI3 is the alcohol mass fraction in the biodiesel-rich phase, wII3 corresponds to the alcohol mass fraction in the glycerol-rich phase, and wII2 corresponds to the glycerol mass fraction in the glycerol-rich phase. Parameters A and B are from the Hand correlation, and A′ and B′ are parameters from the Othmer− Tobias correlation. The correlation factors, R2, indicate the reliability of the related experimental data.27−31 C



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for the UNIQUAC parameter estimation procedure, but also for model predictions of phase separations for systems with known overall compositions. The molar mass used for the peanut biodiesel (308.832 g·mol−1) was calculated according to the mole fractions of the fatty acids presented in Table 1.

Table 2. Binodal Curve Data of the Ternary System {Peanut Oil Biodiesel (1) + Glycerol (2) + Ethanol (3)} at 303.15 and 323.15 K at Normal Atmospheric Pressure, Where w is the Weight Fractiona T = 303.15 K

T = 323.15 K

w1b

w2b

w3b

w1b

w2b

w3b

0.0065 0.0300 0.0341 0.0703 0.0892 0.1313 0.1759 0.2259 0.2908 0.3299 0.3788 0.4013 0.4548 0.5231 0.5759 0.5759 0.6109 0.6688 0.7120 0.7727 0.8028 0.8204 0.8725 0.9015 0.9833

0.5620 0.4263 0.3941 0.3358 0.3075 0.2632 0.2193 0.1838 0.1615 0.1468 0.1334 0.1209 0.1016 0.0821 0.0605 0.0605 0.0546 0.0435 0.0343 0.0254 0.0199 0.0140 0.0180 0.0281 0.0167

0.4315 0.5437 0.5718 0.5939 0.6034 0.6056 0.6047 0.5903 0.5477 0.5233 0.4878 0.4778 0.4436 0.3947 0.3636 0.3636 0.3345 0.2877 0.2537 0.2019 0.1773 0.1656 0.1096 0.0703 0.0000

0.0000 0.0150 0.0365 0.0380 0.0467 0.0593 0.0941 0.1145 0.1490 0.2097 0.2424 0.3040 0.3378 0.4261 0.4619 0.5226 0.5356 0.6561 0.6871 0.7204 0.7318 0.7642 0.8399 0.8509 0.8634 0.9138 0.9847

0.7148 0.5268 0.4368 0.4377 0.4019 0.3748 0.3289 0.3072 0.2791 0.2368 0.2079 0.1759 0.1695 0.1313 0.1159 0.0930 0.0903 0.0546 0.0477 0.0319 0.0308 0.0311 0.0309 0.0273 0.0242 0.0184 0.0153

0.2852 0.4581 0.5267 0.5243 0.5514 0.5659 0.5771 0.5783 0.5719 0.5535 0.5497 0.5201 0.4927 0.4426 0.4222 0.3844 0.3741 0.2893 0.2652 0.2477 0.2374 0.2047 0.1292 0.1218 0.1124 0.0678 0.0000

4. RESULTS 4.1. Correlation Model. The experimental ternary LLE data obtained for the peanut biodiesel (1) + glycerol (2) + ethanol (3) system at 303.15 K and 323.15 K at atmospheric pressure (95 kPa) are presented in Tables 2 (binodal curves) and 3 (tielines) and shown in Figures 2 and 3. The accuracy and precision

Standard uncertainties u are u(T) = 0.5 K, u(w) ≤ 1.0 wt %. w1: mass biodiesel; w2: mass fraction glycerol; w3: mass fraction ethanol. Estimated standard error of 1%.

Figure 2. (Liquid + liquid) equilibrium data for the system {peanut oil biodiesel (1) + glycerol (2) + ethanol (3)} at 303.15 K: ●, global composition; ○, experimental solubilities; ---, calculated (UNIQUAC) solubility line; -□-, experimental tie-lines; ···△···, calculated (UNIQUAC) tie lines.

from minimizing eq 9, which is inherently nonconvex, it is necessary to guarantee that the global minimum of G* is obtained for each interaction used for the minimization of eq 8. In that sense, a stochastic method (PSO) is always used for initial guess in the parameters estimation procedure, followed by a refining in the solution by the deterministic method Simplex. It is worth saying that the minimization of eq 9 was not only used

of the experimental data were evaluated through Type A uncertainty, calculated by the standard deviations of the analytical measurements.36 The uncertainties of the equilibria compositions ranged from (0.1 to 0.68)% by mass for biodiesel, (0.09 to 0.45)% for ethanol, and (0.09 to 0.77)% for glycerol. As shown in Figures 2 and 3, the UNIQUAC model correlated accurately experimental data, as indicated by the root-mean-

a

b

Table 3. (Liquid + Liquid) Equilibrium Data for the System {Peanut Oil Biodiesel (1) + Glycerol (2) + Ethanol (3)} at 303.15 and 323.15 K at Normal Atmospheric Pressure, Where w is the Weight Fractiona experimental (tie-lines) overall composition

biodiesel rich-phase

glycerol rich-phase

T (K)

w1b

w2b

w3b

w1b

w2b

w3b

w1b

w2b

w3b

303.15

0.4506 0.3962 0.3433 0.3292 0.4512 0.4081 0.3567 0.3084

0.4786 0.4398 0.3884 0.3112 0.4692 0.4065 0.3527 0.3041

0.0708 0.164 0.2683 0.3596 0.0888 0.1853 0.2906 0.3875

0.9412 0.9073 0.8762 0.8270 0.9457 0.8972 0.8491 0.8118

0.0221 0.0178 0.0161 0.0160 0.0182 0.0191 0.0158 0.0171

0.0367 0.0749 0.1077 0.1570 0.0361 0.0837 0.1351 0.1711

0.0053 0.0133 0.0151 0.0123 0.0112 0.0153 0.0203 0.0301

0.8916 0.7441 0.6173 0.4886 0.8572 0.7321 0.5743 0.4597

0.1031 0.2426 0.3676 0.4991 0.1316 0.2526 0.4054 0.5102

323.15

a Standard uncertainties u are u(T) = 0.5 K, u(w) ≤ 0.6%. bw1, mass biodiesel; w2, mass fraction glycerol; w3, mass fraction ethanol. Estimated standard error of 1%.

D



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Figure 4. Correlations for the {peanut oil biodiesel (1) + glycerol (2) + ethanol (3)} ternary system: (A) Hand (■, 303.15 K; □, 323.15 K); (B) Othmer-Tobias (●, 303.15 K; ○, 323.15 K). Figure 3. (Liquid + liquid) equilibrium data for the system {peanut oil biodiesel (1) + glycerol (2) + ethanol (3)} at 323.15 K: ●, global composition; ○, experimental solubilities line; ---, calculated (UNIQUAC) solubility line; -□-, experimental tie-lines; ···△···, calculated (UNIQUAC) tie lines.

Table 6. Hand and Othmer−Tobias Correlations Results, see eqs 2 and 3 Hand

square deviation of 0.99%. The ri and qi parameters for the studied system are shown in Table 4, while the binary interaction parameters are shown in Table 5. Table 4. Parameters ri and qi for Peanut Biodiesel (1), Glycerol (2), and Ethanol (3)a i

ri

qi

1 2 3

13.9638 4.7957 2.5755

11.4861 4.9080 2.5880

The peanut biodiesel structural parameters were determined from the composition of the equivalent fatty acids analyzed and estimated from UNIFAC structural parameters via eqs 6 and 7.

■

Table 5. Estimated UNIQUAC Interaction Parameters between Peanut Oil Biodiesel (1), Glycerol (2) and Ethanol (3) for 303.15 K and 323.15 K ΔUij/K

ΔUji/K

1−2 1−3 2−3

−13.388 401.17 264.52

561.15 −126.32 −46.157

T (K)

R

303.15 323.15

0.9986 0.9763

T (K)

R2

A′

B′

303.15 323.15

0.9829 0.9850

−1.6465 −1.5317

0.5484 0.7152

A −1.6953 −1.5722 Othmer-Tobias

B 0.7160 −0.8691

data are coherent and accurate. Additionally, the UNIQUAC activity model was used to correlate the experimental data with the corresponding binary interaction parameters. The UNIQUAC model satisfactorily correlated LLE experimental data with a root-mean-square deviation of 0.99%.

a

pair i−j

2

AUTHOR INFORMATION

Corresponding Author

*Tel. +55 18 3284 9683. E-mail: [email protected]. ORCID

Leandro Ferreira-Pinto: 0000-0002-0656-9471 Funding

We thank the following Brazilian agencies for financial support: CAPES (Ministry of Education) and CNPq (National Council for Scientific and Technological Development). L.F.P. thanks the Fundaçaõ de Amparo à Pesquisa do Estado de São Paulo, FAPESP (Brazil), for financial support through Grant 2018/ 23063-1.

4.2. Reliability of the LLE Data. Quality tests of the experimental values were performed using the Othmer− Tobias25 and Hand26 correlations. The correlation tests at 303.15 and 323.15 K are shown in Figure 4. The fitting parameters and regression coefficients (R2) for each temperature are presented in Table 6. As shown, regression coefficients above 0.97 were obtained for all data sets. This clearly indicates the reliability of the experimental LLE data obtained in this study.

Notes

The authors declare no competing financial interest.

■

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5. CONCLUSIONS LLE experimental data were obtained for the peanut biodiesel (1) + glycerol (2) + ethanol (3) system at 303.15 and 323.15 K, and at atmospheric pressure. Hand and Othmer−Tobias correlations indicated that the observed experimental tie-line E



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{Peanut Biodiesel + Glycerol + Ethanol} at Atmospheric Pressure

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