Scholarly article on topic 'Diesters Biolubricant Base Oil: Synthesis, Optimization, Characterization, and Physicochemical Characteristics'

Diesters Biolubricant Base Oil: Synthesis, Optimization, Characterization, and Physicochemical Characteristics Academic research paper on "Chemical engineering"

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Academic research paper on topic "Diesters Biolubricant Base Oil: Synthesis, Optimization, Characterization, and Physicochemical Characteristics"

Hindawi Publishing Corporation International Journal of Chemical Engineering Volume 2012, Article ID 896598, 10 pages doi:10.1155/2012/896598

Research Article

Diesters Biolubricant Base Oil: Synthesis, Optimization, Characterization, and Physicochemical Characteristics

Jumat Salimon, Nadia Salih, and Bashar Mudhaffar Abdullah

School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Selangor, 43600 Bangi, Malaysia

Correspondence should be addressed to Jumat Salimon, Received 10 September 2011; Accepted 11 October 2011 Academic Editor: Deepak Kunzru

Copyright © 2012 Jumat Salimon et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Diesters biolubricant base oil, oleyl 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoate (OLHYOOD) was synthesized based on the esterification reaction of 9,12-hydroxy-10,13-oleioxy-12-octadecanoic acid (HYOOA) with oleyl alcohol (OL) and catalyzed by sulfuric acid (SA). Optimum conditions of the experiment to obtain high yield % of OLHYOOD were predicted at ratio of OL/HYOOA of 2 : 1 mol/mol, ratio of SA/HYOOA of 0.7: 1 mol/mol, reaction temperature 110°C, and 7h of reaction time. At this condition, the yield of OLHYOOD was 88.7%. Disappearance of carboxylic acid (C=O) peak has been observed by FTIR with appearance of ester (C=O) peak at 1738 cm-1. 13C, and 1H NMR spectra analyses confirmed the result of OLHYOOD with the appearance of carbon-ester (C=O) chemical shift at 173.93ppm and at 4.05ppm for 13C and 1HNMR, respectively. The physicochemical characteristics of the OLHYOOD were also determined, which showed improved low temperature properties (PP) -62°C, viscosity index (VI) at 192 and also increased oxidative stability (OT) up to 215.24°C.

1. Introduction

Oleochemicals that are derived from natural fats and oils are referred to as natural oleochemicals [1]. Industrially, most fatty acids are obtained from animal or vegetable sources. It is possible to produce several industrial products from fatty acids (saturated and unsaturated). Fatty acid products have different utilization as resins, plastics, perfumes, coatings, flavors, cosmetics, solvents, soaps, medicinals, biofuels, and biolubricants [2].

Synthetic biolubricant based on renewable resources are important in developing environmentally acceptable lubricating oils [3]. Currently, lubricant-based petroleum worldwide end up in the environment via total loss applications, spills, or major accidents. A fact remains that about 3 million tones are lost in the European environment every year originating from loss and high-risk lubricants mostly based on mineral oil. Emissions of mineral oil may appear to be negligible importance compared to an accident involving an oil tanker spill [4]. And also, the emissions of mineral oil arising from lubricant applications in water make lubricants contribution to the pollution of water much more significant [5].

In the last decade, a lot of interest was developed to use environmental friendly biolubricant fluids [6]. The use of environmentally acceptable vegetable-oil-based product as biolubricants has many advantages. They are nontoxic, biodegradable, derived from renewable resource and have a reasonable cost when compared to other synthetic fluids [7]. Recently, modern approaches have been adopted to solve the problems associated with application of vegetable oils in biolubricants, and some of them used for chemical modification and additive treatment [8].

Esters are known as natural lubricating oils. Besides being used as biolubricants like other ester types (diesters, trimelli-ate esters, dimer acid esters, phthalate esters, and polyols), fatty acid esters can also be evaluated as synthetic bio-lubricants [7]. The monoesters of monoalcohols are fluid liquids or solid waxes. They are used as solvents in cosmetics or biolubricants in metal treatment, textile industry, and plastics industry. Esterification is usually catalyzed by an acid catalyst donor of protons such as sulfuric acid (SA) or by a metallic catalyst [9].

(1a) Or

Oleyl alcohol + H2SO4

Figure 1: Esterification reaction of HYOOA to produce OLHYOOD. Notes: 9-hydroxy-10-oleioxy-12-octadecanoic acid (1a); 12-hydroxy-13-oleioxy-9-octadecanoic acid (2a); oleyl 9-hydroxy-10-oleioxy-12-octadecanoate (1b); oleyl 12-hydroxy-13-oleioxy-9-octadecanoate (2b); oleic acid (R) and oleyl alcohol (R').

In this study, we presents a novel synthetic approach for esterification reaction of 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoic acid (HYOOA) with oleyl alcohol (OL) catalyzed by SA (Figure 1). It is investigated to produce diesters oleyl 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoate (OLHYOOD) as a lubricating oil candidate to improve the physical properties of biolubricants product such as low temperature (pour point), flash point,

viscosity, and oxidative stability. In this study, the esterification of HYOOA with (OL) was presented as lubricating oil for the first time. The objective of this study was to optimize process variables of esterification reaction. The process variables studied using D-optimal design were ratio of OL/HYOOA (mol/mol), ratio of SA/HYOOA (mol/mol), reaction temperature (°C), and reaction time (h). D-optimal design was applied to relate these four

Table 1: Independent variables and their levels for D-optimal design of the esterification reaction.

Independent variables Variable Levels _-1_0_+1

(1) OL/HYOOA (mol/mol) Xi 2 3 4

(2) SA/HYOOA (mol/mol) X2 0.7 1 1.3

(3) Temperature (C) X3 90 100 110

(4) Time (h) X4 5 6 7

process variables with the response (diesters biolubricant yield %).

2. Methodology

2.1. Experimental Procedure. The esterification reaction was carried out using oleyl alcohol (OL) and sulfuric acid (SA) as a catalyst to prepare 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoate (OLHYOOD) [9]. Table 1 shows the different OL/HYOOA ratio, different SA/HYOOA ratio, different reaction temperature, and different reaction time using D-Optimal design. Factors (variables) such as ratio OL/HYOOA (mol/mol, Xi), SA/HYOOA (mol/mol, X2), reaction temperature (°C, X3), and reaction time (h, X4) were performed under the same experimental conditions. The reactions were performed in a 250 mL three-neck flask equipped with a reflux condenser and a contact thermometer. The reaction mixture was heated on a magnetic heater and stirrer until it reached the experiment temperature; catalyst SA and desiccant of silica gel (SG) were added to the mixture at that moment. The reaction temperatures were held constant within a range of ±1°C. A mixture of HYOOA (5 g; 0.01 mol), OL (2 : 1-4: 1 mol/mol) in a 250-mL three-neck flask equipped with a cooler, dropping funnel and thermometer was heated for 1 h at 90°C, during the 1h reaction SG was put in the oven at 180°C for drying. After 1 h SG drying the SG (50% of the HYOOA) and SA (0.7: 1-1.3 : 1 mol/mol) were added to the mixture. The reaction mixture was subsequently heated to different temperatures 90-110°C and refluxed at different times 57 h at this temperature range. After reaction termination, the heating was stopped and the mixture was left to stand overnight at ambient temperature. After the reaction under conditions was selected as optimal, the flask was allowed to cool to room temperature. The mixture was filtered using acetic acid (AA) as a solvent to remove the SG from the product. The mixture was washed repeatedly with distilled water until all the catalysts were removed. The mixture was washed with the water and the organic layer was dried over magnesium sulphate; the solvent was removed using a vacuum evaporator. Excess OL in the mixture was removed using the distillation method. The yield % of the ester product was determined. The FTIR and 13C, 1H NMR were analysed and the physicochemical properties of the product were also studied.

2.2. Experimental Design and Statistical Analysis. To explore the effect of the operation variables on the response in

the region of investigation, a D-optimal design was performed [10]. Ratio of OL/HYOOA (mol/mol, X1), ratio of SA/HYOOA (mol/mol, X2), reaction temperature (°C, X3), and reaction time (h, X4) were selected as independent variables. The range of values and coded levels of the variables are given in Table 1. A polynomial equation was used to predict the response as a function of independent variables and their interactions. In this work, the number of independent variables was three and therefore the response for the quadratic polynomials becomes

Y = fc + X P>x> + X Ai*2 + X X PjXXj, (1)

where fio, fin, and fiij are constant, linear, square and interaction regression coefficient terms, respectively, and xi and Xj are independent variables. The Minitab software version 14 (Minitab Inc., USA) was used for multiple regression analysis, analysis of variance (ANOVA), and analysis of ridge maximum of data in the response surface regression (RSREG) procedure. The goodness of fit of the model was evaluated by the coefficient of determination R2 and its statistical significance that was checked by the F-test.

2.3. Physicochemical Characteristics

2.3.1. FTIR and 1H, 13C NMR. FTIR of the products was recorded on a Perkin Elmer Spectrum GX spectrophotometer in the range 650-4000 cm-1. A very thin film of the sample was applied to NaCl cells (25 mm i.d X 4 mm thickness) for analysis. 1H and 13C NMR spectra were recorded using a JEOL JNM-ECP 400 spectrometer operating at a frequency of 400.13 and 100.77 MHz, respectively, using a 5 mm broadband inverse Z-gradient probe in DMSO-d6 (Cambridge Isotope Laboratories, Andover, MA) as solvent. Each spectrum was Fourier-transformed, phase-corrected, and integrated using MestRe-C 2.3a (Magnetic Resonance Companion, Santiago de Compostela, Spain) software [9].

2.3.2. Low Temperature Operability. Pour point (PP) values were measured according to the American National Standard Method using U-tube tester (ASTM D5949 method) [9].

2.3.3. Flash Point Values. Flash point (FP) determination was run according to the American National Standard Method using a Tag Closed Tester (ASTM D 56-79) [9].

2.3.4. Viscosity Index Measurements. Viscosity Index Monitor HV M472 obtained from Walter Herzog (Germany)

Table 2: D-optimal design arrangement and yield % response of OLHYOOD.

RUn no Coded independent variable levels Response

OLa/HYOOAb (mol/mol, Xi) SAc/HYOOA (mol/mol, X2) Temperature (°C, X3) Time (h, X4) Yieldd (%, Y)

1 2 0.70 90 5 38.7

2 2 1.30 110 7 66.7

3 2 1.30 110 7 78.3

4 4 1.00 100 6 45.7

5 3 1.15 100 6 41.5

6 2 1.00 90 7 75.9

7 4 1.00 90 5 47.5

8 4 1.00 110 7 84.4

9 4 0.70 110 5 45.9

10 4 0.70 110 5 50.1

11 2 1.30 90 5 43.1

12 2 1.30 90 5 46.4

13 2 0.70 110 7 88.7

14 4 1.30 110 6 60.2

15 3 1.30 110 5 44.5

16 2 0.70 110 7 51.5

17 3 0.70 100 6 58.1

18 2 1.00 110 5 68.2

19 4 1.30 90 7 78.3

20 4 0.70 90 7 55.7

21 3 1.00 110 6 76.7

22 2 1.00 100 6 65.9

23 3 1.00 90 6 69.5

24 4 1.30 100 5 50.8

25 4 1.30 90 7 72.3

Notes: oleyl alcohol (a); 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoic acid (HYOOA) (b); sulfuric acid (c); yield % of oleyl 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoate (OLHYOOD) (d).

was used to measure viscosity. Measurements were run in a Temp-Trol (Precision Scientific, Chicago, IL, USA) viscometer bath set at 40.0 and 100.0°C. The viscosity and viscosity index were calculated using ASTM method ASTM D 2270-93 [9], respectively.

2.3.5. Oxidative Stability. Pressurized DSC (PDSC) experiments were accomplished using a DSC 2910 thermal analyzer from TA Instruments (Newcastle, DE) [9]. Typically, a 2-lL sample, resulting in a film thickness of <1 mm, was placed in an aluminum pan hermetically sealed with a pinhole lid and oxidized in the presence of dry air (Gateway Airgas, St. Louis, MO), which was pressurized in the module at a constant pressure of 1378.95 kPa (200 psi). A 10°C min^1 heating rate from 50 to 350°C was used during each experiment. The oxidation onset (OT, °C) was calculated from a plot of heat flow (W/g) versus temperature for each experiment.

3. Results and Discussion

3.1. Effect of Process Parameters and Statistical Analysis. Diesters biolubricant oleyl 9(12)-Hydroxy-10(13)-oleioxy-12(9)-octadecanoate (OLHYOOD) was synthesized from direct esterification of HYOOA, where the corresponding HYOOA react with OL in the presence of a suitable catalyst such as sulfuric acid (SA). The acid catalysts are the most common catalysts used in biolubricant industry because the process provides faster reaction conditions and moderate compared to the alkali catalyst [9].

In the present study, biolubricant production using homogeneous acid-catalyzed esterification process SA was proposed. The influence of the ratio of OL/HYOOA (2 : 1-4: 1 mol/mol; X1), ratio of SA/HYOOA (0.7:11.3 : 1 mol/mol; X2), reaction temperature (90-110°C; X3), and reaction time (5-7 h; X4) to the esterification reaction was studied Table 2. The process variables were optimized

Table 3: Regression coefficients of the predicted quadratic polynomial model for response variables of the yield % of OLHYOOD.

Variables Coefficients (ß), yield % of OLHYOOD (Y ) T P Notability


X1 -1.67 0.12 0.7286

X2 2.50 0.40 0.5334

X3 3.99 1.35 0.2594

X4 10.83 19.83 0.0002 ***


X11 -0.59 4.580E-003 0.9474

X22 -9.66 2.41 0.1512

X33 7.96 0.85 0.3775

X44 0.90 8.067E-003 0.9302


X12 2.49 0.46 0.5149

X13 -0.36 9.453E-003 0.9245

X14 0.92 0.063 0.8069

X23 -2.85 0.60 0.4574

X24 1.69 0.20 0.6624

X34 -1.40 0.14 0.7116

R2 0.69

Notes: X1 =OL/HYOOA; X2 = SA/HYOOA; X3 **P< 0.05; ***P< 0.01. T: F test value.

reaction temperature; X4 = reaction time.

See Table 2 for a description of the abbreviations.

Table 4: Analysis of variance (ANOVA) for Y response of OLHYOOD.


Sum of squares

Mean square

F value

Prob > F

Model Residual Lack-of-fit Pure error

4 20 15

2828.18 2523.33 1731.87 791.47

707.05 126.17 115.46 158.49



Significant Not significant

using the D-optimal design in obtaining the maximum yield % of biolubricant Y. This method was also applied to determine the significance and interaction of the variables affecting the diesters biolubricant production. Results obtained from the observed experiments are summarized in Table 2. The results developed a second-order polynomial equation that could relate diesters biolubricant yield to the parameters study. The following quadratic model was explained in (2) [10]

Y = +59.19 - 1.67Х1+2.50Х2 + 3.99ХЗ + Ю.8ЗХ4

- 0.59Х2 - 9.66Х| + 7.96Х2 + 0.90Х42 + 2.49Х1Х2

- 0.З6Х1ХЗ + 0.92Х1Х4 - 2.85Х2ХЗ + 1.69Х2Х4

- 1.40ХЗХ4.

Table 2 illustrates the yield % effect related with alcohol, catalyst, reaction temperature, and reaction time. As expected, at high temperature (110°C) and long time (7h) showed high yield at about 88.7% compared with temperatures of 90 and 100°C. As described in the mechanism, most of the carboxylic acid groups were consequently converted into and ester bonds in the molecule. The decrease of biolubricant yield % at a higher reaction temperature and

longer time was probably as a result of losing OL due to the fact that it did not condense effectively at a higher temperature as the boiling point of OL is 107°C [11].

The quadratic regression coefficient obtained by employing a least squares method technique to predict quadratic polynomial models for the yield % (Y) of OLHYOOD are given in Table 3. The yield % of OLHYOOD (Y), the linear term of reaction time (X4) was high significant (P < 0.01).

The lack of fit F-value for the Y response showed that the lack of fit is not significant (P > 0.05) relative to the pure error. This indicates that all the models predicted for the Y response were adequate. Regression models for data on response Y was significant (P < 0.05) with satisfactory R2. However, the predicted values match the observed values reasonably well, with R2 of 0.69, and the model was significant. Table 4 summarizes the analysis of variance (ANOVA) for the response of this study.

Figures 2(a) and 2(b) are the Design-Expert plots for all the responses. In the diesters biolubricant reaction of OLHYOOD, performing the technique using high-reaction temperature and long time would give the desired yield % of OLHYOOD as shown in Figure 2. The biolubricant yield % increased as the reaction time increased to its high level


Yield %

100 ve. 100

100 105


Figure 2: Response surface (a) and contour plots (b) for the effect of reaction temperature (X3, °C) and reaction time (X4, h) on the yield (Y, %) of OLHYOOD.

Table 5: The main wavelengths in FTIR functional groups of HYOOA and OLHYOOD.

Wavelength of HYOOAa Wavelength of OLHYOODb Functional groups

3413 3445 OH stretching (alcohol)

3003 3003 C=C bending vibration (aliphatic)

2925, 2855 2925, 2554 C-H stretching vibration (aliphatic)

1737 1738 C=O stretching vibration (ester)

1711 — C=O stretching vibration (carboxylic acid)

1461 1461 C-H scissoring and bending for methylene group

1176, 1117 1173,1117 C-O stretching vibration (ester)

1279 — C-O stretching assymmetric (carboxylic acid)

967 967 C-H bending vibration (alkene)

723 723 C-H group vibration (aliphatic)

Notes: 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoic acid (a); oleyl 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoate (b).

(7h). The biolubricant yield % also increased with reaction temperature to its high level (110°C), and the stronger influence of reaction time occurred when reaction time was at its high level. The relationships between the parameters and yield % of OLHYOOD were linear or almost linear (Figure 2).

Optimum conditions of the experiment to obtain high yield % of OLHYOOD were predicted at ratio of OL/HYOOA of 2 : 1 mol/mol, ratio of SA/HYOOA of 0.7: 1 mol/mol, reaction temperature 110°C, and reaction time 7h. At this condition, the yield % of OLHYOOD was 88.7%. The observed value was reasonably close to the predicted value as shown in Figure 3. Experimental variables should be carefully controlled in order to obtain reasonable yield.

3.2. FTIR Analysis of OLHYOOD. The spectrum from the FTIR analysis displays several absorption peaks as shown in Figure 4. The main peaks and their assignment to functional groups are given in Table 5. FTIR peaks of OLHYOOD indicated disappearance of absorption band at 1711 cm-1 which belongs to the C=O carboxylic acid, while it appears in HYOOA. For the ester carbonyl functional groups C=O at 1737 cm-1 of OLHYOOD which showed the same absorption band in HYOOA at 1738 cm-1.

FTIR Peaks at 2925 to 2855 cm-1 indicated the CH2 and CH3 scissoring of HYOOA and OLHYOOD. The FTIR spectroscopy analysis of HYOOA and OLHYOOD indicated the presence of peak at 3003 cm-1 which belongs to the double bond C=C (stretching aliphatic), while at 3445 and

Table 6: The main signals present in 13C NMR functional groups of HYOOA and OLHYOOD.

5 (ppm) of HYOOAa 5 (ppm) of OLHYOODb Assignment

25.76-34.38 25.75-34.37 Aliphatic Carbons

64.41 64.37 -OH Alcohol

127.90-130.57 129.61-130.46 -CH=CH- Olefinic carbons

174.01 173.93 C=O Ester

178.11 — C=O Carboxylic acid

Notes: 9,12-hydroxy-10,13-oleioxy-12,9-octadecanoic acid (a); 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoate (b).

91.13 -

77.92 -

I 64.7 -£

51.49 -

38.27 -

38.27 51.49 64.7 77.92 91.13 Actual

Figure 3: Predicated versus actual plot of Y (OLHYOOD).

80 Vv /\

60 \ y \ J

40 C=C

120 100 80 - 60 - 40 20 0

0 0 0 4

Figure 4: FTIR spectrum of the HYOOA (a) and OLHYOOD (b).

3413 cm-1 it belongs to -OH stretching of OLHYOOD and HYOOA, respectively.

The peaks at 1176, 1173, and 1117 cm-1 of HYOOA and OLHYOOD are referred to as C-O stretching ester. FTIR spectrum also showed absorption bands at 723 cm-1 of C-H

Carboxylic acid

Ester Olefinic carbons


200 180 160 140 120 100 80 60 40 20 0 (PPm) (a)

Olefinic carbons


—■—i—■—i—■—i—■—i—■—i—■—i—■—i—■—i—■—i—■—i—■—i—■— 200 180 160 140 120 100 80 60 40 20 0

(PPm) (b)

Figure 5:13C NMR spectrum of HYOOA (a) and OLHYOOD (b).

group vibration. A similar observation has been reported for the FTIR spectrum of other studies [9].

3.3. 13 C and 1HNMR Analysis of OLHYOOD

3.3.1. 13 C NMR Analysis. Figures 5(a) and 5(b) indicates the 13C NMR spectrum of HYOOA and OLHYOOD, respectively. The 13 C spectroscopy shows the main signals assignment of HYOOA and OLHYOOD as shown in Table 6. Figure 5(b) showed disappearance of carbon atom of the carbonyl group (carboxylic acid) of OLHYOOD which has appeared for HYOOA at 178.11 ppm, while at 173.93174.01 ppm it has appeared in OLHYOOD and HYOOA which refer to ester group. The signals at 127.90 to

Table 7: The main signals present in *H NMR functional groups of HYOOA and OLHYOOD.

£ (ppm) of HYOOAa £ (ppm) of OLHYOODb Assignment

0.82-0.84 0.86-0.88 -CH3

1.23-2.06 1.25-2.01 -CH2

2.26-2.33 2.26-2.29 -CH

3.62 3.62 -CHOH

4.06 4.05 -CHOCOR

5.31-5.40 5.33-5.37 -CH=CH-

Notes: 9,12-hydroxy-10,13-oleioxy-12,9-octadecanoic acid (a); 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoate (b).

130.74 ppm refer to the unsaturated carbon atoms (olefinic carbons) for both HYOOA and OLHYOOD.

Figures 5(a) and 5(b) can confirm the appearance of OH alcohol of OLHYOOD and HYOOA at about 64.37 and 64.41 ppm, respectively. The other distinctive signals were aliphatic carbons for OLHYOOD and HYOOA at about 25.76-34.38 ppm which are common for these types of compounds belonging to the methylene carbon atoms of HYOOA and OLHYOOD [9].

3.3.2. 1H NMR Analysis. The !H NMR spectroscopy shows the main signals assignments in HYOOA and OLHYOOD as shown in Table 7. The results show the distinguishable peaks that appeared in OLHYOOD and HYOOA for -CH-OH at 3.62 ppm while -CHOCOR at 4.06 and 4.05 ppm as shown in Figures 6(a) and 6(b), respectively. The signals at 0.82-0.88ppm referred to the methylene group (-CH3) of OLHYOOD which also appear in HYOOA next to the terminal methyl (-CH2) at 1.23-2.06 ppm of OLHYOOD and HYOOA. The other distinctive signals were those of methine at about 2.26-2.33 ppm, which are common for these types of compounds [12]. However, the methane proton signals (-CH=CH-) were shifted upfield at about 5.33-5.37 ppm of OLHYOOD [9].

3.4. Physicochemical Characteristics. The physicochemical characteristics of OLHYOOD compound are summarized in Table 8, in an effective way to introduce branching on the fatty acid (FA) chain. The branched product has significantly improved the pour point (PP), flash point (FP), viscosity index (VI), and higher oxidative stability (OT) comparing HYOOA with other diesters compounds such as IBHYBOD [9].

Esterification reaction improved the PP at -62° C significantly of OLHYOOD (Table 8) compared with last step HYOOA at 51°C and with IBHYBOD at -60°C. Attachment of OL to produce OLHYOOD was the most effective decreasing the PP to -62. It can be assumed that the presence of a large branching point on the fatty acid ester creates a steric barrier around the individual molecules and inhibits crystallization, resulting in lower PP [13]. Table 8 has shown the improvement in FP of OLHYOOD which increased to 264° C compared with 251° C of HYOOA, which means that the result agrees with the various international standards that the biolubricants FP are combustible with higher than 43°C.

From the VI data of compounds HYOOA 153 and OLHYOOD 192 (Table 8), the result showed that VI increases


ch=ch sichoh ch

10 9876543210 (PPm)


10 9876543210 (PPm)

Figure 6: *H NMR spectrum of HYOOA (a) and OLHYOOD (b).

with increasing chain length (number of carbons), which the result of OLHYOOD higher than other compound such as IBHYBOD 123. A high VI indicates small viscosity changes with temperature. Therefore, it is expected that biolubricant oil that has a high VI can cause a very little change in viscosity with temperature extremes and is considered to have a stable viscosity temperature relation [14].

In this study, using OL for esterification of HYOOA which significantly improves the oxidation stability (OT) for OLHYOOD at 215.24°C (Figure 7) more than oxirane ring opening compound HYOOA at 180.94° C and both these

Table 8: Physicochemical characteristics of OLHYOOD.


Pourpoint (° C) -51 -62 -60

Flash point (°C) 251 264 297

Viscosity at 40° C (cSt) 324.5 136.5 —

Viscosity at 100° C (cSt) 33.05 22.3 —

Viscosity Index (° C) 153 192 123

Oxidative stability OT (° C) 180.24 215.24 64

Notes: 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoic acid (a); oleyl 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanate (b); isobutyl 9-hydroxy-10-behenoxyoctadecanate [7] (c).

Onest 215.24° C

40 60 80 100 120 140 160 180 200 220 240 260 280

(° C)

Figure 7: Differential scanning calorimetry oxidation stability curve of OLHYOOD.

compound OLHYOOD and HYOOA are higher in oxidation stability than in (see other studies such as IBHYBOD at 64° C which is prepared [9] Table 8). These results are in agreement with other studies on synthetic esters; the oxidative stability increased with increasing chain length of the esterified FA [15]. At high OT would suggest a high oxidation stability of OLHYOOD.

4. Conclusion

The results show that the optimum conditions of the experiment to obtain high yield % of OLHYOOD were predicted at ratio of OL/HYOOA of 2 : 1 mol/mol, ratio of SA/HYOOA of 0.7:1 mol/mol, reaction temperature 110°C, and 7h of reaction time. At this condition, the yield of OLHYOOD was 88.7%. Based on the results obtained, an increase in the molecular weight of the OLHYOOD had a positive influence on the low temperature properties PP -62° C of the biolubricant product. The results have shown the improvement in FP, which increased to 264° C. The VI increased up to 192 and also the OT increased to 215.24°C due to high molar weight, and especially the altered structure of their molecules.


The authors thank UKM and the Ministry of Science and Technology for research Grants UKM-GUP-NBT-08-27-113 and UKM-OUP-NBT-29-150/2011.


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