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Preparation and evaluation of lubricity additives for low sulfur diesel fuel Li-ming Sun, Mengmeng Li, Changfeng Ma, Ping Li, and Jianzhong Li Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b00223 • Publication Date (Web): 09 Jun 2016 Downloaded from http://pubs.acs.org on June 14, 2016
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Preparation and evaluation of lubricity additives for low sulfur diesel fuel Liming Sun*,1 , Mengmeng Li1, Changfeng Ma2, Ping Li3, Jianzhong Li1 1
Petrochemical Research Institute, PetroChina Company Limited, Beijing 102206, People’s Republic of China 2
Advisory Center, China National Petroleum Corporation (CNPC), Beijing 100724, People’s Republic of China 3
School of Life Sciences and Technology, Tongji University, Shanghai 200092, China
Abstract This paper adopted the co-precipitation method to prepare Ni/Zr-loaded MgO/Al2O3 catalysts for the transesterification. And the catalysts were characterized by BET, FT-IR, TG-DSC and SEM. The catalyst had a platelet-like structure and an average size approximate 1-2μm. The surface area was affected by the calcinations temperature. And a sharp decrease in the surface area as the calcinations temperature was further increased from 820℃ to 920℃. Fatty acid methyl esters (FAMEs) were obtained by a process called the transesterification, which reacted waste vegetable oil with methanol under the action of the prepared catalyst. The effect of FAMEs on the lubricating performance of low sulfur diesel was determined by using the high frequency reciprocating rig (HFRR) test. FAMEs were efficient enough to serve as lubricity additive (LA) and the efficiency increased with increasing concentration of the additive. The low temperature flow performance of the additive was characterized by the cloud/pour test. Unsaturated FAMEs were effective in improving low temperature flow property of low sulfur diesel. Besides, a better low temperature performance was presented by adding kerosene to LSD/1%LA compare with adding to LSD in the test.
Introduction The human world is presently confronted with a twin crises of environmental deterioration and fossil fuel depletion.1-3 The researchers have contributed a lot to
*Correspondence: Liming Sun, Ph.D Petrochemical Research Institute, PetroChina Company Limited, Block A42, Science Base PetroChina, Xisha Village West, Shahe Town, Changping District Beijing 102206, People’s Republic of China Tel.: +86-10-80165453 E-mail:
[email protected] 1 / 12
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test the adaptability of long chain fatty acid methyl esters (FAMEs) and their derivatives may be used as diesel-fuel additives or even diesel fuel itself.4-10 Studies showed that biodiesel derived from renewable feed stocks, is a mixture of FAMEs that could solve environmental concerns and the limited resources of fossil fuels.11, 12 The majority of characteristics of biodiesel could compare with that of petroleum based diesel fuel, but economical efficiency is still the huge challenges ahead of us when employ biodiesel as a substitute to drive diesel-powered vehicles. In the 1990s, in order to protect the atmospheric environment developed countries continued to enact laws to make sure the sulfur and nitrogen content in fuel is reduced. Meanwhile, the malfunction of diesel-powered engines took place frequently, especially in California, USA and the Nordic region. It’s most likely to occur on vehicles with low sulfur diesel fuel. After investigation, we found that the malfunction is due to insufficient lubrication of low sulfur diesel.13 In china, with the promulgation of the New Environmental Protection Law the government focuses on hydro-refining technology. All these efforts are devoted to ensure that the sulfur content in fuel is strictly controlled. However, insufficient lubrication of low sulfur diesel as a widespread problem constantly comes out in recent years.13 The component which plays a lubricant role is removed, though the sulfur content can be reduced during the process of diesel hydro-refining. In simple terms, the lubricating property of diesel is greatly reduced. For this reason, serious mechanical wear of diesel engine happens all the time which bring us an inevitable economic loss and even serious casualty. Lubricating additive (LA) are organic or inorganic compounds that can significantly improve the anti-wear performance. Since the 1990s, when the low sulfur diesel were massively promoted and applied, the further research and development of LA of diesel has received more and more attention.14 At present, LA is mainly produced by the transesterification of renewable biological triglyceride sources (vegetable oils and animal fats) with alcohols using homogeneous catalysts.15-19 However, the homogeneous process has brought problems of pollution and corrosion . In this study, we recently synthesized layered double hydroxides as heterogeneous catalyst for the additive production. The process of synthesizing FAMEs by using the prepared catalyst was able to minimize environmental pollution, and prevent the device from corrosion. Meanwhile, studies found that unsaturated FAMEs as a multifunctional additive could remarkably improve lubricity and the low temperature flow property of fuel. Experimental section Materials Al(NO3)3 •9H2O, Mg(NO3)2 •6H2O, Ni(NO3)2 •6H2O, Zr(NO3)4 •5H2O, NaOH, Na2CO3, methanol, polyacrylamide, and glacial acetic acid were purchased from Sinopharm 2 / 12
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Group Chemical Reagent Co., Ltd (Shanghai, China). Sesbania powder was obtained from Hebei nortey Technology Development Co., Ltd. The low sulfur diesel fuel and kerosene were supplied by Daqing petrochemical company. The sulfur content of the low sulfur diesel and kerosene was 33ppm and 47ppm respectively. The oil was a waste product from Fenghai Agri-industries Co., Ltd. Waste vegetable oil was prepared in our lab using pre-treating process (Waste vegetable oil was treated with a small amount of activated carbon in 500mL vessel using a magnetic stirrer at room temperature at 200rpm for 6h. The pretreated waste vegetable oil was obtained by filtering.). GC/MS analysis The fatty acid methyl esters (FAMEs) were characterized by gas chromatography-mass spectrometry (GC-MS).20, 21 A mass spectrometer (Thermo Fisher) combined with a gas chromatograph (Agilent 7890A) was used for GC-MS analyses of samples. An INNOWAX column (30m × 250μm i.d. and 0.25μm film thickness) was employed in the test. The flow rate was 1.0mL/min and the split/column ratio was 100:1. The injector temperature stayed in 230℃. The voltage was 70 eV and the ionization source temperature was 220℃ in mass spectrometer. Preparation and characterization of extruded catalyst For the co-precipitation method, solution A and solution B were prepared first before co-precipitation. Solution A contained different metal nitrate (Mg(NO3)2 •6H2O, Al(NO3)3•9H2O, Ni(NO3)2•6H2O, Zr(NO3)4•5H2O) with the proper molar ratio, and solution B was usually a mixture solution of NaOH and Na2CO3. Then, solution A and solution B were simultaneously added dropwise to a vessel containing deionized water with vigorous stirring. During this process, the solution obtained was kept at a constant pH by controlling the dripping speed of the solution. After aging for a period of time, the precipitate obtained was separated from the mother solution, washed with deionized water, and dried at the set temperature to obtain mixture A. The extrusion process of catalysts starts on the preparation of the paste which is composed of five components. 1) activated aluminum oxide, 2) polyacrylamide, 3) sesbania powder, 4) glacial acetic acid, 5) mixture A. Procedure for the preparation of the paste is described as follows. Firstly, activated aluminum oxide was dried at 120℃ for 24h to remove water. Then a certain quantity of activated aluminum oxide, polyacrylamide, sesbania powder, glacial acetic acid and mixture A were mixed thoroughly. Added glacial acetic acid to the powder mixture obtained by the step 2 subsequently. After been mixed thoroughly, the paste was finally completed. The paste was put into an extruder, then the shaped-trifolium extrudates were come out from it. The extrudates were cut in 10 mm long pieces, dried at 120℃ overnight. By employing a heating ramp of 2℃/min, the extrudates were calcined at 820℃ for 3h. The water has been removed, the organic content has been burned off and the mechanical strength of catalysts has been strengthened in this process. Eventually, the extruded catalysts are being adopted in the transesterification. 3 / 12
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The surface areas of the catalysts were determined using the adsorption/desorption method by the standard BET method using TriStar II 3020M equipment. The FT-IR spectra were obtained using KBr pellet technique with a PE GX-2000 FT-IR spectrometer in the range of 4000-400 cm-1. Thermal gravimetric analysis and differential scanning calorimetrer (TG-DSC) were carried out in an airflow on a NETZSCH STA409PC thermal analysis system at heating rate of 10℃/min. The morphology of catalysts was examined by using scanning electron microscopy (SEM, JEOL JSM-6510). Synthesis of lubricity additive The transesterification process was carried out using the prepared catalyst. Transesterification experiments were performed using a setup consisting of material supply units, a fixed-bed reactor (13mm i.d. and 400mm in length), a heated upstream pressure regulator for maintaining a constant pressure in the reactor, and a separator for collecting the liquid products of the reaction. The volume of the catalyst charged into the reactor was 5mL, and the catalyst particle size was 0.6-0.8 mm. The reaction conditions were 230℃, 0.1 MPa of pressure, in N2 atmosphere, and 2 h-1 of liquid hourly space velocity (LHSV). The methanol-to-oil molar rate was 15:1. Under the above conditions, methanol was in the gaseous state and the oil, esters, and glycerol were in the liquid state. After 20h, the mixture was transferred into a separatory funnel and kept still for 6h. The layering phenomenon is showing up gradually. The top layer was methyl ester and the bottom layer was glycerol. The glycerol layer was removed from the mother solution, washed the top layer with deionized water for 1-3 times until neutralization, settled for another 2h, then discarded the bottom water. Finally, anhydrous sodium sulfate was being used to dry the ester layer. Lubrication properties To evaluate the impact of additives on the lubrication performance of low sulfur diesel fuel, High Frequency Reciprocating Test Rig (HFRR) was used for measurement, on the basis of the ASTM D6079 method.22 A vibrator with a load of 200g drives a steel ball to perform a back and forth movement on a steel disk which is fasten to the oil groove. A 2ml sample was positioned in the oil groove at 60℃. Make sure the ball and the disk are both immersed in the tested sample. The vibration frequency of the steel ball is 50Hz with a 1mm stroke length. 75 minutes later, take down the ball from the vibrator. The wear scar appears in the ball's surface can be measured by the diameter of wear scar. The value of WSD is calculated using the following equation. WSD=(X+Y)/2, X is the length of wear scar in x direction, Y is the length of wear scar in y direction. The WSD of a fuel is less than or equal to 450um at 60℃ that will be regarded as acceptable. And the size of the wear scar was directly related to the lubrication property of the tested sample. ASTM D2500 cloud point analysis 4 / 12
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The cloud point (CPT) is the temperature value at which a cloud is observed in the tested specimen during the process of cooling according a standard test method. The prepared samples were evaluated through the cloud point test according the ASTM D2500 method.23 The samples were cooled at a designated rate and should be tested in 1℃ increments. ASTM D97 pour point analysis The pour point (PPT) is the critical point of temperature tested at which the sample demonstrates no movement when the test tube is tilted slightly during the process of cooling. The prepared samples were evaluated through the pour point test according the ASTM D97 method.23 The tested sample was heated in advance and cooled at a designated rate. Then flow characteristics of the sample was tested in 3 ℃ increments. Results and discussion Characterization of waste vegetable oil GC-MS was used for determination FAME groups present at the produced additive. Table 1 showed there were four main characteristic peaks of FAMEs appearing by the retention time and the data of GC-MS analysis. These four peaks identified FAMEs as hexadecanoic acid methyl ester (C16:0), octadecanoic acid methyl ester (C18:0), oleic acid methyl ester (C18:1), linoleic acid methyl ester (C18:2). The identified FAMEs were verified by the retention time data and mass fragmentation pattern from previous studies. Furthermore, GC-MS analysis of the produced additive at the processing condition confirms completeness of the transesterification process of triglycerides in the waste vegetable oil into FAMEs. Characterization of catalyst The surface areas of catalysts were measured by the BET method. The surface area of Ni/Zr-loaded MgO/Al2O3 catalyst was found to be 205.1 m2/g. The surface area of prepared catalyst was found to reduce marginally (from 205.1 to 197.4 m2/g) when the calcinations temperature was increased from 520℃ to 820℃. Therefore, an increase in the calcinations temperature up to 820℃ had not any remarkable impact on the porosity of the catalyst. However, a sharp decrease in the surface area (from 197.4 to 135.6 m2/g) of catalyst was recorded when the calcinations temperature was further increased from 820℃ to 920℃. The decrease in the surface area at the calcinations temperature 920℃ could be due to the partial collapse of the porous structure at this calcinations temperature. The FT-IR spectrum of the catalyst was displayed in Figure 1. Three main absorption bands were clearly observed. The first one is strong and board, centered at 3470cm-1. The second one is strong and sharp, centered at 1385cm-1. The third one is also sharp but weaker than the second, centered at 1643cm-1. The cause in forming of these 5 / 12
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three absorption bands is stretching vibrations of hydroxyl groups, vibration of CO32and bending mode of water molecules. While the cause in forming of the absorption band in low-frequency region of the spectrum is lattice vibration modes, for instance the M-O-H vibration centered at 586cm-1 and the O-M-O vibration centered at 413cm-1. As an essential physical-chemical property, the thermal stability of catalysts has been discussed. In Figure 2, three major weight loss events can be observed in the TGA curve. The first weight loss 4.39% was caused by the loss of interlayer water, temperature is in the range of 20℃ to 220℃. The second weight loss 12.07% was caused by the decomposition of hydroxyl ions in the layer, temperature is in the range of 220℃ to 500℃. And the last weight loss 28.96% was caused by the removal of carbonate ions in the layer, temperature is in the range of 500℃ to 920℃. There are two noticeable endothermic peaks at 311℃ and 863℃ and a small broad endothermic peak at 145℃ in the DSC curve. Morphological information characterized by scanning electron microscopy (SEM) was shown in Figure 3. Results showed almost darkness micrograph with sheets with predominantly smooth texture. The crystal morphology of the catalyst displayed platelet-like structure. The disk diameter of sample was mostly around 1-2μm. Quality of the FAMEs FAMEs were obtained by a process called the transesterification, which reacted waste vegetable oil with methanol under the action of the prepared catalyst at 230℃ in N2 atmosphere. The fatty acid concentration profile of the FAME product has been presented, as shown in Table 4. The total methyl ester content is 97.81%. The concentration of linoleic acid methyl ester of FAMEs product compare with that of waste vegetable oil in Table 1 fell by 2.48%. And the concentration of eicosenoic acid methyl ester of FAMEs product compare with that of waste vegetable oil in Table 1 increase by 0.59%. We have learnt that the value change is around 0.1% after comparison of the rest chemical components in Table 1 and Table 4. The acid value of waste vegetable oil is 0.17 mg KOH/g. And the acid value of FAMEs product is 0.10 mg KOH/g. Our findings indicated that waste vegetable oil exists primarily in the form of fatty acid glycerides and contains a small amount of free fatty acids. Efficiency as lubricity additive Lubricity contributions of the additives were measured with respect to wear scar diameter (WSD). Effect of additive concentration on the lubricating performance was also studied. Experiments were conducted at first with low sulfur diesel followed by low sulfur diesel blended the additive. It was obvious that the additive improved the fuel lubricity in Table 2. It should be noted that the WSD of LSD fuel can be decreased obviously by adding 0.2% additive to it. Meanwhile, 1%~10% of the additive was the favorable concentration for LSD fuel to maintain a stable WSD about 260 μm. As 6 / 12
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expected, the samples showed better lubricating performance compared to pure low sulfur diesel. WSD decreased with increasing additive concentration. That is, the additive was acting more efficiently at higher concentration level. Cloud point and pour point test Different concentrations ranging from 0 wt% to 5 wt% of kerosene in LSD and LSD/LA blend were tested as pour point depressant and the experimental data were grouped in Table 3. A cloud point of 5℃ and pour point of 0℃ was observed for low sulfur diesel. The cloud point of LSD has dropped from 5℃ to -1℃ when mixed with 5 wt% of kerosene. In the meantime, the pour point of LSD has dropped from 0℃ to -9℃ when mixed with 5 wt% of kerosene. The data indicated that kerosene was efficient as pour point depressant and the efficiency increased by increasing the concentration of kerosene. A cloud point of 4℃ and pour point of -3℃ was observed for LSD/1%LA blend. Adding 5% kerosene in LSD/1%LA blend produced a significant reduction, a cloud point of -1℃ and pour point of -12℃. Again more depression in the pour point is observed in the case of LSD/1%LA blend with 10% kerosene. The extended conformation of kerosene added LSD/1%LA blend may be responsible for showing its better efficiency in comparison to kerosene added LSD. In addition, unsaturated fatty acid methyl esters were effective in improving low temperature flow performance of low sulfur diesel. Because the long-chains contained in saturated FAMEs are more regular and easy to crystallize. In comparison, the carbon chains contained in unsaturated FAMEs have more bending and present a curved shape. So the aggregation is tough to implement. With an increase in unsaturated degree, the capacity of the long-chains for aggregation and crystallization is decreased. And the more the unsaturated fatty acid content is, the better the low temperature property of the obtained additive is. Conclusions In this paper, a series of Ni/Zr-loaded MgO/Al2O3 catalysts were prepared by the co-precipitation method and characterized by BET, FT-IR, TG-DSC and SEM. These analyses revealed surface area, particle size and shape of the catalyst. The surface area was found to be affected by the calcinations temperature. The surface area reduced marginally from 205.1 to 197.4 m2/g when the calcinations temperature was increased from 520 to 820℃. However, a sharp decrease in the surface area from 197.4 to 135.6 m2/g was recorded when the calcinations temperature was further increased from 820 to 920℃. The decrease in the surface area could be due to the partial collapse of the porous structure at the calcinations temperature 920℃. FAMEs were produced by the transesterification with Ni/Zr-loaded MgO/Al2O3 catalyst. The effect of FAMEs on the lubricating performance of low sulfur diesel was determined by HFRR method, and results showed that 1%~10% of the additive was the favorable concentration for LSD fuel to maintaining a stable WSD about 260 μm. FAMEs were efficient enough to serve as LA and the efficiency increased with 7 / 12
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increasing concentration of the additive. In addition, the low temperature flow performance of the additive was characterized by the cloud/pour test. Unsaturated fatty acid methyl esters were effective in improving low temperature flow performance of low sulfur diesel. And the more the unsaturated fatty acid content is, the better the low temperature property of the obtained additive is. Moreover, adding kerosene to LSD/1%LA was found to be superior to adding kerosene to LSD in improving low temperature flow performance. Author information Corresponding author Telephone: 86-10-80165453, E-mail:
[email protected] Notes The authors declare no competing financial interest. Acknowledgment This work was supported by Petrochemical Research Institute, PetroChina Company Limited. References 1.
Kombe, G. G., Re-esterification of high free fatty acid oils for biodiesel production. Biofuels 2015,
6, 31-36. 2.
S.P. Singh, D. S., Biodiesel production through the use of different sources and characterization of
oils and their esters as the substitute of diesel: A review. Renewable and Sustainable Energy Reviews 2010, 14, (1), 200-216. 3.
H.A. Farag, A. E.-M., Nahla A. Taha, Optimization of factors affecting esterification of mixed oil
with high percentage of free fatty acid. Fuel Processing Technology 2011, 92, (3), 507-510. 4.
Vivian Vicentini Kuss, A. V. K., Rosana Gomes da Rosa, Donato A.G. Aranda, Yordanka Reyes Cruz,
Potential of biodiesel production from palm oil at Brazilian Amazon. Renewable and Sustainable Energy Reviews 2015, 50, 1013-1020. 5.
M.R. Avhad, J. M. M., A review on recent advancement in catalystic materials for biodiesel
production. Renewable and Sustainable Energy Reviews 2015, 50, 696-718. 6.
Marchetti, J. M., A summary of the available technologies for biodiesel production based on a
comparison of different feedstock's properties. Process Safety and Environmental Protection 2012, 90, (3), 157-163. 7.
Arun Balasubramanian Kuthalingam, G. A., Vivar Marta, Igor Skrybin, Srithar Karuppiah,
Perfomance and emission characteristics of double biodiesel blends with diesel. Thermal Science 2013, 17, (1), 255-262. 8.
N.L. Panwar, S. C. K., Surendra Kothari, Role of renewable energy sources in environmental
protection: a review. Renewable and Sustainable Energy Reviews 2011, 15, (3), 1513-1524. 8 / 12
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9.
J.M. Marchetti, V. U. M., A.F. Errazu, Possible methods for biodiesel production. Renewable and
Sustainable Energy Reviews 2007, 11, (6), 1300-1311. 10. M. Berrios, J. S., M.A. Martin, A. Martin, A kinetic study of the esterification of free fatty acids (FFA) in sunflower oil. Fuel 2007, 86, (15), 2383-2388. 11. Nassereldeen Ahmed Kabbashi, N. I. M., Md Zahangir Alam, Mohamed Elwathig Saeed Mirghani, Hydrolysis of Jatropha curcas oil for biodiesel synthesis using immobilized Candida cylindracea lipase. Journal of Molecular Catalysis B: Enzymatic 2015, 116, 95-100. 12. May Ying Koh, T. I. M. G., A review of biodiesel production from Jatropha curcas L. oil. Renewable and Sustainable Energy Reviews 2011, 15, (5), 2240-2251. 13. David M. Stamper, R. E. M., Michael T. Montgomery, Depletion of lubricity improvers from hydrotreated renewable and ultralow-sulfur petroleum diesels by marine microbiota. energy & fuels 2012, 26, 6854-6862. 14. Sarah M. Lundgren, K. P., Gregor Mueller, Bengt Kronberg, Jim Clarke, Mohammed Chtaib, Per M. Claesson, Unsaturated fatty acids in alkane solution: adsorption to steel surfaces. Langmur 2007, 23, 10598-10602. 15. A. Murugesan, D. S. A. A., An empirical and statistical analysis of biodiesel production by transesterification process. Biofuels 2015, 6, 79-86. 16. Joana M. Dias, M. C. M. A.-F., Manuel F. Almeida, Comparison of the performance of different homogeneous alkali catalysts during transesterification of waste and virgin oils and evaluation of biodiesel quality. Fuel 2008, 87, (17-18), 3572-3578. 17. Jeane Q.A. Brito, C. S. S., Jorge S. Almeida, Maria G.A. Korn, Mauro Korn, Leonardo S.G. Teixeidra, Ultrasound-assisted synthesis of ethyl esters from soybean oil via homogeneous catalysis. Fuel Processing Technology 2012, 95, 33-36. 18. Xiaoling Miao, R. L., Hongyan Yao, Effective acid-catalyzed transesterification for biodiesel production. Energy Conversion and Management 2009, 50, (10), 2680-2684. 19. Nestor U. Soriano Jr., R. V., Dimitris S. Argyropoulos, Biodiesel synthesis via homogeneous Lewis acid-catalyzed transesterification. Fuel 2009, 88, (3), 560-565. 20. Syed Ghulam Musharraf, M. A. A., Noureen Zehra, Quantification of FAMEs in biodiesel blends of various sources by gas chromatography tandem mass spectrometry. Analytical Methods 2015, 7, 3372-3378. 21. Mahsa Jabbar, H. G., Use of GC-MS combined with resolution methods to characterize and to compare the essential oil components of green and bleached cardamom. International Journal of Research in Chemistry and Environment 2015, 5, 76-85. 22. Kapila Wadumesthrige, M. A., Steven O. Salley, K. Y. Simon Ng, Investigation of lubricity characteristics of biodiesel in petroleum and synthetic fuel. Energy & Fuels 2009, 23, 2229-2234. 23. Chuang-Wei Chiu, L. G. S., Galen J. Suppes, Impact of cold flow improvers on soybean biodiesel blend. Biomass and Bioenergy 2004, 27, 485-491.
Table 1. The chemical components of waste vegetable oil Peak#
Retention（min）
Compound
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GC-MS yield (ω%)
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1
29.077
Myristic acid (C14:0)
0.09
2
32.894
Hexadecanoic acid (C16:0)
5.68
3
36.410
Octadecanoic acid(C18:0)
2.41
4
36.795
Oleic acid (C18:1)
11.56
5
37.678
Linoleic acid (C18:2)
78.72
6
38.676
Linolenic acid (C18:3)
0.14
7
39.669
Arachidic acid (C20:0)
0.41
8
40.071
Eicosenoic acid (C20:1)
0.25
9
43.950
Docosanoic acid (C22:1)
0.34
Total
99.60
Table 2. HFRR lubricity characteristics of low sulfur diesel (LSD) in the presence of additives (LA) No. blend/additive
Blend ratio (wt% additive)
WSD (µm)
1
LSD/LA
0
545
2
LSD/LA
0.1
489
3
LSD/LA
0.2
432
4
LSD/LA
0.5
368
5
LSD/LA
1
296
6
LSD/LA
2
273
7
LSD/LA
5
238
8
LSD/LA
10
221
Table 3. Low temperature properties of low sulfur diesel (LSD), lubricity additive (LA) and LSD/1%LA blends treated with kerosene Sample
LSD
LAa
a
LSD+1%LA
Blend ratio (wt% Kerosene)
CPT (℃)
PPT（℃）
0 5 10 0 5 10 0 5
5 -1 -3 -1 -2 -3 4 -1
0 -9 -12 -6 -12 -15 -3 -12
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10 a
-3
-18
Lubricity additive (LA) is defined as an improver used in fuels to reduce friction and or wear, refers to fatty acid
methyl ester (FAME) in this article.
Table 4. The chemical components of FAMEs product Peak#
Retention （min）
Compound
GC-MS yield (ω%)
1 2 3 4 5 6 7 8 9
29.149 32.970 36.482 36.869 37.762 38.734 39.737 40.125 44.066
Myristic acid methyl ester(C14:0) Hexadecanoic acid methyl ester(C16:0) Octadecanoic acid(C18:0) Oleic acid methyl ester(C18:1) Linoleic acid methyl ester(C18:2) Linolenic acid methyl ester(C18:3) Arachidic acid methyl ester(C20:0) Eicosenoic acid methyl ester(C20:1) Docosanoic acid methyl ester(C22:1)
0.10 5.74 2.29 11.46 76.24 0.30 0.56 0.84 0.28
Total
97.81
4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm-1)
0
Figure 1. The FT-IR spectra of the catalyst (sample was grinded into fine powder and pressed into a sheet)
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100 Weight loss (%)
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Energy & Fuels
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6.0
B
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Temperature (℃ ℃)
Figure 2. TG-DSC curves of the catalyst (at heating rate of 10℃/min). (A) TGA/Weight loss curve; (B) Differential Scanning Calorimeter (DSC) curve
Figure 3. The SEM imagine (5000×) of the catalyst.
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