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Vol. 8. Issue 5.
Pages 3681-3687 (September - October 2019)
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Vol. 8. Issue 5.
Pages 3681-3687 (September - October 2019)
Original Article
DOI: 10.1016/j.jmrt.2019.06.011
Open Access
Effect of biodiesel components on its lubrication performance
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Fashe Lia,b, Zuowen Liua,b,
Corresponding author
liuzuowen3@163.com

Corresponding author. Liu e-mail:liuzuowen3@163.com
, Zihao Nia,b, Hua Wanga,b
a Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650106, China
b State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kun-ming 650093, China
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Tables (6)
Table 1. Materials and reagents.
Table 2. Physicochemical properties of the biodiesel used in this study.
Table 3. Test equipment.
Table 4. The abrasive spot diameters of fourteen types of biodiesel and diesel.
Table 5. Main composition of 14 types of biodiesel.
Table 6. Statistical analysis of the model regression equation.
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Abstract

The composition of biodiesel significantly influences its lubrication performance. Gas chromatography, high frequency reciprocating friction, and wear test machines were used to determine the composition and abrasive spot diameter of biodiesels produced from fourteen different oil feedstocks. At the same time, the relationship between the grinding point diameter and chemical composition of biodiesel was quantified. The main components of the biodiesel are methyl stearate, methyl palmitate, methyl oleate, and methyl linoleate, with an average content of 92.18%. Among the various types of biodiesel, rubber seed methyl ester has a minimum grinding point diameter of 169.71 μm. Prickly ash methyl ester has the largest grinding point diameter of 187.35 μm. A linear correlation prediction model of wear point diameter was established (R = 0.91).

Keywords:
Biodiesel
Friction coefficient
Chemical composition
Abrasive spot diameter
Regression analysis
Oil feedstock
Full Text
1Introduction

The widespread use of fossil fuels in power plants, transport vehicles, generators, and mining equipment has resulted in higher energy consumption [1,2]. The devastating impacts of increasing consumption of fossil-oriented energy carriers have already gone well beyond the environmental sustainability. Climate change has, in fact, substantially endangered public health and these impacts are going to be far more comprehensive in the next decades [3–5].

The environmental pollution generated by fossil fuels is currently increasing [6]. Owing to the finite stock of fossil fuels and its negative impact on the environment, many countries across the world are now leaning toward renewable sources of energy such as solar energy, wind energy, biofuel, hydropower, geothermal, and ocean energy to ensure energy for the countries’ development security [7]. Biodiesel is a biodegradable, renewable, clean, and environmentally friendly liquid fuel. It is lipid-derived fuel produced by transesterification in the presence of a suitable catalyst [8]. Biodiesel has established itself as a partial substitute for diesel in existing diesel engines despite some differences in the properties of two fuels [9]. Compared to conventional diesel, good lubricity is an important feature of biodiesel. It reduces friction and wear for sliding parts and prolongs the life of the engine. Fazal et al. [10] observed the wear and friction characteristics of palm oil biodiesel (B10, B20, B50, and B100) under constant load at different rotational speeds (600, 900, 1200, and 1500 rpm). The results showed that when the ratio of biodiesel increased, wear and friction decreased, and the addition of biodiesel led to the effective reduction of the wear and friction of the sliding parts. Kumar et al. [11] observed the wear and friction characteristics of jatropha biodiesel blends (20, 40, and 100% JOME) in a four-ball tester. The results revealed that the fuel showed better lubricity with the increase in the biodiesel concentration, and the decrease in the load and temperature. Lubricating properties of biodiesel are usually evaluated using high frequency reciprocating friction and wear testing machine (HFRR) [12–14]. Sulek et al. [15] used HFRR to study the tribological properties of rapeseed biodiesel. They observed that the coefficient of friction of B5 (diesel mixed with 5% rapeseed biodiesel) and B100 was lower than that of diesel, respectively.

Xiao et al. reported that wear scar sizes of steel balls for steel–steel contact decreased with increasing concentration of biodiesel [16]. Sukjit et al. [17] observed that reduction of unsaturated molecules in unsaturated fatty acid methyl ester (H-FAME) decreased sensitivity to humidity. Chourasia et al. [18] indicated that the wear of B20A4 fueled engine was substantially lower than that of the diesel fueled engine. A regression model was also proposed to predict wear of the engine. The proposed regression model can be taken one step further to predict the overall wear of the engine. The total concentration of various metals debris collected in the lube oil sample (predicted using regression model) was found to be 640 mg kg−1 and 420 mg kg−1 for diesel and B20A4, respectively.

Biodiesel components have an important impact on their performance, including cetane number (CN), oxidative stability, heat of vaporization (HV), etc. [19]. Hosseinpour et al. [20] estimated the CN of biodiesel from its FAMES profile. Geller et al. and Hu et al. [21] showed that the FAME composition of biodiesel plays an important role in lubricity. A more intense research on biodiesel composition and its corrected abrasive spot diameter can help objectively evaluate the quality of biodiesel, extend its activity and commercial application, and provide intellectual support for the national energy-saving and emission reduction strategy involving renewable energy. In this study, gas chromatography, high frequency reciprocating friction, and wear testing were used to measure the FAME composition and calibrate the abrasive spot diameter of 14 types of biodiesel. The influence of FAME content of biodiesel on its corrected abrasive spot diameter was analyzed by multiple linear regression analysis. The relationship between the diameter of the corrected grinding spot and the chemical composition of the biodiesel was quantified, which provides some guidance and practical significance for the research on the lubricating properties of biodiesel.

2Materials and methods2.1Materials and reagents

Fourteen biodiesel samples (self-prepared), namely sunflower seed methyl ester (SSME), jatropha methyl ester (JME), camellia oleosa seed methyl ester (COSME), oryza sativa methyl ester (OSME), maize methyl ester (MME), canola methyl ester (CME), rapeseed methyl ester (RME), sesame methyl ester (SME), peanut methyl ester (PME), soya bean methyl ester (SBME), rubber seed methyl ester (RSME), prickly ash methyl ester (PAME), cooking oil biodiesel (OOB), and olive methyl ester (OME) were used in this study. The materials and reagents required for the test are listed in Table 1.

Table 1.

Materials and reagents.

Materials and reagents  Manufacturer 
Nitrogen (99.99%)  Messer Gas Company Limited 
Ultra-pure water  Ultrapure water generator (UK ELGA LabWater) 
Acetone  Wuhan Yuancheng Technology Development Co., Ltd. 
Petroleum ether  Borida Trade Co., Ltd. 
95% ethanol  Tianjin Komiou Co., Ltd. 
Methanol (HPLC grade)  Wuhan Yuancheng Technology Development Co., Ltd. 
Linolenic methyl ester (HPLC grade)  Aladdin Reagent. 
Oleic methyl ester (HPLC grade)  Aladdin Reagent 
Palmitic methyl ester (HPLC grade)  Aladdin Reagent 
Stearic methyl ester (HPLC grade)  Bailingwei Technology Co., Ltd. 
Arachidic methyl ester (HPLC grade)  Bailingwei Technology Co., Ltd. 
Behenic methyl ester (HPLC grade)  Bailingwei Technology Co., Ltd. 
Wood tar acid methyl ester (HPLC grade).  Bailingwei Technology Co., Ltd. 
2.2Biodiesel preparation

Biodiesel samples were produced through transesterification with methanol in the presence of potassium hydroxide (KOH) as a base catalyst at 75 °C for 3 h. Upon the completion of the reaction, glycerol was decanted and the crude biodiesel phase was washed five times with distilled water at 60 °C. Subsequently, the purified biodiesel was dried in an oven at 100 °C for 2 h. The basic physicochemical properties of the produced biodiesel are listed in Table 2.

Table 2.

Physicochemical properties of the biodiesel used in this study.

Number  Sample  Kinematic viscosity at 40℃ (mm2/s)  Cetane number(min)  Flash point(℃)  Density(kg/m3Water content(%)  Carbon residue(%)  Sulfur content(%) 
SSME  4.22  46.7  162  868.2  0.092  0.048 
JME  4.06  51  164  862.0  0.081  0.046  0.041 
COSME  4.54  52.3  150  874.5  0.086  0.38  0.046 
MME  4.30  47.4  170  867.4  0.083  0.038  0.033 
OSME  3.24  55.7  152  876.4  0.084  0.047  0.034 
CME  4.53  54.3  178  875.2  0.088  0.003  0.039 
RME  4.63  48.00  163  884.8  0.096  0.023  0.046 
SME  4.20  50.48  170  867.2  0.086  0.023  0.042 
PME  5.06  58.41  174  877.1  0.087  0.036  0.043 
10  PAME  4.35  52.34  165  882.2  0.035  0.032  0.052 
11  SBME  4.12  51.80  159  884.6  0.091  0.02  0.027 
12  RSME  4.79  50.40  158  862.3  0.069  0.046  0.042 
13  OME  5.05  58.70  171  876.2  0.079  0.029  0.045 
14  OOB  5.83  51.48  176  880.6  0.031  0.051  0.065 
2.3Test equipment

The equipment used in this study are listed in Table 3.

Table 3.

Test equipment.

Test equipment  Manufacturer  Country 
Gas chromatograph  Agilent Technologies 7890A  United States 
High frequency reciprocating friction and wear testing machine  Meryer  Shanghai, China 
Purelab Classic  Elga Lab Water  Britain 
XS205DU electronic balance  Mettler Toledo  Switzerland 
R-215 rotary evaporator  Buchi  Switzerland 
SK5200HP Ultrasonic Cleaner  Kudos  Shanghai, China 
Constant temperature drying oven.  Chongming Experimental Instrument Factory  Shanghai, China 
2.3.1Working principle of high frequency reciprocating friction and wear tester

The working principle of the high frequency reciprocating friction and wear tester is shown in Fig. 1. The test oil sample (2 mL) is placed in an oil bath at a given temperature. The steel ball fixed in the fixture vertically loads the horizontally installed steel sheet. The ball reciprocates at a frequency of 50 Hz and a stroke of 1000 μm, the test load is 200 g, the test temperature is 60 °C, and the contact interface between the test ball and the test piece is completely immersed in the oil. According to the test environment (temperature and humidity), the wear scar diameter of the steel ball was corrected to the value under the standard condition. The lubricity of the test sample was expressed by the corrected wear scar diameter. The wear scar diameter mentioned in this study was corrected wear spot diameter.

Fig. 1.

Schematic illustration of high frequency reciprocating friction and wear tester.

(0.19MB).
2.3.2Calculation of test data

The measured wear spot diameter needs to be corrected according to the water vapor pressure of 1.4 kPa. The corrected wear spot diameter is expressed by using WS1.4. The calculation method is as follows [22]:

  • (1)

    Unadjusted average wear spot diameter is expressed in MWSD (μm) and is calculated as follows:

    where X is the vertical wear scar diameter in the direction of vibration (μm); and Y is the horizontal wear scar diameter in the direction of vibration (μm).

  • (2)

    Absolute vapor pressures (AVP1 and AVP2) at the beginning and end of the test. The mean absolute vapor pressure (AVP) during the experiment is calculated as follows:

    where RH1 is the relative humidity of the incubator at the beginning of the test and RH2 is the relative humidity of the incubator at the end of the test expressed in percentage. The calculation formulas for v1 and v2 are as follows:
    where t1 is the temperature of the incubator at the beginning of the test and t2 is the temperature of the incubator at the end of the test.

  • (3)

    WS1.4 is calculated as follows:

    Note: For unknown oil samples, the HCF value is 60.

3Results and discussion3.1Lubrication performance of biodiesel

A high-frequency reciprocating friction and wear tester was used to measure the abrasive spot diameters of biodiesel and 0# diesel according to the ISO 12156-1 standard. The results are presented in Table 4.

Table 4.

The abrasive spot diameters of fourteen types of biodiesel and diesel.

Number  Sample  Abrasive spot diameter (μm) 
SSME  180.99 
JME  177.44 
COSME  176.89 
OSME  185.16 
MME  181.27 
CME  184.62 
RME  186.47 
SME  182.14 
PME  169.97 
10  SBME  179.15 
11  RSME  169.71 
12  OME  171.84 
13  OOB  175.58 
14  PAME  187.35 
15  0#diesel  365.35 

Table 4 summarizes that RSME has the smallest abrasive spot diameter of 169.71 μm. Compared to 0# diesel, biodiesel has a lower abrasive spot diameter, which is attributed to the fact that the composition of biodiesel is mainly composed of FAMEs. Table 5 presents that the main components of 14 types of biodiesel are methyl stearate, methyl palmitate, methyl oleate, methyl linoleate, and the average content of four components reached 92.18%, of which the content of methyl oleate and methyl linoleate was the largest, with the average of 79.37%, and others were relatively small. The selection of biodiesel is aimed at representing the entire saturated–unsaturated and monounsaturated–polyunsaturated FAME ranges as illustrated in the ternary plot in Fig. 2. Biodiesel contains a polar functional ester group, and polar molecules are more easily adsorbed on the metal surface to form a physical adsorption membrane [23]. At the same time, residual glycerol monoester and diglyceride during biodiesel production affect the lubricating properties of biodiesel. Importantly, some studies have shown that changes in the concentration of monoglycerides have a significant positive effect on the biodiesel lubricity [24,25]; therefore, lubricity of biodiesel is better than that of 0# diesel.

Table 5.

Main composition of 14 types of biodiesel.

FAME  C16:0  C16:1  C18:0  C18:1  C18:2  C18:3  C20:1  C20:0  C22:0  C22:1  Cothers 
SSME  6.76  0.00  3.48  28.13  59.36  0.25  0.29  0.00  0.02  0.71  1.00 
JME  14.29  0.00  7.02  41.70  36.99  0.00  0.00  0.00  0.00  0.00  0.00 
COSME  8.58  0.00  2.22  78.80  9.44  0.00  0.00  0.68  0.00  0.00  0.28 
OSME  16.91  0.24  1.55  40.27  36.94  0.90  0.66  0.83  0.00  0.00  1.70 
MME  12.61  0.00  1.74  30.16  53.97  0.67  0.44  0.41  0.00  0.00  0.00 
CME  4.27  0.24  2.49  57.33  23.55  6.57  0.69  1.58  0.62  0.90  1.74 
RME  1.60  0.27  1.85  59.38  19.82  6.35  0.76  1.65  0.80  1.63  2.89 
SME  8.74  0.00  5.65  38.87  45.67  0.41  0.65  0.00  0.00  0.00  0.00 
PME  11.46  0.00  4.08  42.14  36.05  0.00  1.80  1.04  3.42  0.00  0.00 
SBME  11.08  0.00  3.90  24.21  53.14  5.35  0.50  0.00  0.94  0.00  0.69 
RSME  9.50  0.44  7.58  27.22  35.82  19.04  0.41  0.00  0.00  0.00  0.00 
OME  10.82  3.05  79.30  5.00  0.57  0.86  0.41  0.00  0.00  0.00  0.00 
OOB  18.93  7.35  31.37  30.00  4.13  1.50  0.67  1.08  1.09  0.08  3.79 
PAME  4.13  0.31  1.90  48.61  16.22  6.61  0.97  4.39  0.99  13.37  2.48 

Note: Cm:n denotes FAME; where m indicates the number of carbons of the fatty acid; n represents the number of CC bonds, and Cother indicates the rest untested components.

Fig. 2.

Ternary plot describing the FAME composition of the tested biodiesels.

(0.14MB).
3.2The abrasive spot diameter of the four main components of biodiesel

Fig. 3 presents the values of abrasive spot diameter of RSME, methyl palmitate (C16:0), methyl oleate (C18:1), methyl linoleate (C18:2), and methyl stearate (C18:0). Fig. 3 exhibits that the abrasive spot diameters of C18:1 and C18:2 containing carbon–carbon double bonds are significantly smaller than that of C18:0, which indicates that the carbon–carbon double bond has positive impact on the lubricating performance of biodiesel. The main factor influencing the lubricating performance is the strength of the adsorption membrane. The stronger the intermolecular binding in the adsorption membrane, the stronger the stability and the compactness of the adsorption membrane. The intermolecular interaction in the adsorption membrane is mainly electrostatic. The greater the number of double bonds, the greater the electrostatic force [26]. The double bonds make it easier for fatty acid esters to form a dense adsorption film on the metal surface, which increases the strength of the lubricating film. This is also consistent with previous research results [27].

Fig. 3.

Abrasive spot diameter of biodiesel and its four main components.

(0.21MB).

The above mentioned results only explain the reasons for the change in the lubricating properties of the main components of biodiesel. Fig. 2 demonstrates that there is no significant relationship between the number of double bonds in the structure of biodiesel and the lubricating performance. Therefore, analysis of the quality of biodiesel lubrication presented in Table 2 will be pursued in further study.

3.3Quantitative relationship between the biodiesel composition and its corrected abrasive spot diameter

 C18:0, C18:1, C18:3, C16:1, C20:1, C20:0, C22:0, C16:0, C22:1, and Cother were used as independent variables, and the biodiesel calibration spot diameter was used as the dependent variable. The multiple linear regression analysis method was used to build up the corrected abrasive spot diameter prediction model based on the biodiesel composition as follows:

where C18:0, C18:1, C18:3, C16:1, C20:1, C20:0, C22:0, C16:0, C22:1, and Cother correspond to stearic methyl ester, oleic methyl ester, linolenic methyl ester, palmitic methyl ester, palmitoleic methyl ester, eicosenoic methyl ester, arachidic methyl ester, behenic methyl ester, palmitic methyl ester, and erucic methyl ester, respectively; and Cother represents the sum of the contents of wood acesuic acid methyl ester and other unknown components. D is the corrected abrasive spot diameter of biodiesel. The main statistical analysis results of the regression analysis equation are listed in Table 6.

Table 6.

Statistical analysis of the model regression equation.

Sample size  Correlation coefficient R  F test  Significance test 
60  0.91  29.32  ≪0.01 

Table 6 summarizes that the correlation coefficient (R = 0.91) was significantly higher than the statistically significant zero-order value (Rmin = 0.281). Therefore, the corrected spot diameter (d) of biodiesel has a significant correlation with the ten established variables, thereby indicating that the model is feasible. The results of the model are as follows: F = 29.32, significance ≪0.01, thereby revealing a significant effect of the model in describing the linear relationship between the corrected abrasive spot diameter of biodiesel and the independent variables. The ten-step linear regression analysis method was thus found to be reliable. The linear regression coefficient indicates that the first order of the influencing factors of the correction abrasive spot diameter of biodiesel was  C16:1>C22:0>C20:1>C18:0>C18:3>C16:0>C18:1. The correlation coefficients of C16:0 and C18:3 were low; therefore, the corrected abrasive spot diameter of biodiesel was not reduced and Cother>C20:0>C22:1. The FAME percentage composition of the biodiesel predicted its corrected abrasive spot diameter. The deviation between the predicted and the experimental values is shown in Fig. 4.

Fig. 4.

Calculated versus measured values based on the regression model.

(0.09MB).

Fig. 4 exhibits that 60 data points are evenly distributed on both sides of the diagonal, and most of the experimental–predicted value gaps are less than 1.5 μm (within the test error range). The significance level of the correlation coefficient is 0.01, and it is clear that the experimental values are highly correlated with the predicted values. The regression model can predict the corrected abrasive spot diameter of biodiesel based on its FAME composition.

4Conclusions and future prospects

  • (1)

    The main components of the 14 types of biodiesel are methyl stearate, methyl oleate, methyl linoleate, and methyl palmitate. The average content of the four components is 92.18%. Among 14 biodiesel oil samples, rubber seed oil biodiesel exhibits the smallest wear scar diameter, which is 169.71 μm. Zanthoxylum oil has the largest wear scar diameter of 187.35 μm.

  • (2)

    The carbon–carbon double bonds make it easier for fatty acid esters to form a dense adsorption film on the metal surface, which increases the strength of the adsorption film and improves the lubricating properties of biodiesel.

  • (3)

    A highly linear correlation prediction model for the biodiesel induction period was established. Based on the chemical composition of the feedstock oil or the biodiesel sample, the corrected abrasive spot diameter of biodiesel can be directly predicted. This method is highly convenient for the application and research of biodiesel. Moreover, this methodology provides the basis for the promotion and application of biodiesel in different environments.

5Future prospects

The composition of biodiesel is very complex and exploration of the lubrication mechanism of biodiesel is difficult. In future study, scanning electron microscopy or optical microscopy will be employed to obtain the images of the wear tracks in order to explain the related mechanism in detail.

Conflicts of interest

The authors declare no conflicts of interest.

Acknowledgements

The authors greatly acknowledge the support provided by the National Natural Science Foundation of China (51766007), NSFC-Yunnan Joint Fund Project (U1602272), and Research Fund from State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization (CNMRCUTS1704).

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Copyright © 2019. The Authors
Journal of Materials Research and Technology

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