Figure
1.
Schematic presentation of vacuum distillation experiment setup
| Citation: | Ping Yeong Siew, San Chan Yen, Chiat Law Ming, Kim Ung Ling Jordy. Improving cold flow properties of palm fatty acid distillate biodiesel through vacuum distillation[J]. Journal of Bioresources and Bioproducts, 2022, 7(1): 43-51. doi: 10.1016/j.jobab.2021.09.002
|
Palm fatty acid distillate (PFAD), a by-product of refining process of crude palm oil can be used as a potential feedstock for biodiesel production. However, the application of palm oil-based biodiesel is often hinder by its poor cold flow properties (CFP). Biodiesel fuel with poor CFP may crystallize and result in clogging of fuel lines, filters and injectors that cause engine operability problems. For that, a vacuum distillation method was designed and its feasibility and efficiency in improving the CFP was examined. A total of 13.60wt% of total saturated fatty acid methyl esters were successfully removed from the PFAD biodiesel, resulting in the improvement of the cloud point (CP), cold filter plugging point (CFPP) and pour point (PP) of PFAD biodiesel from 20 ℃, 19 ℃, and 15 ℃ to 13 ℃, 11 ℃, and 9 ℃, respectively. It is remarkable that the improved CFPP satisfied the requirements for grade C summer biodiesel for temperate climates in EN 14212 standard. Additionally, Sarin (UFAME) empirical correlation was evaluated and it was found to have a good prediction of CFP for PFAD biodiesel, with lower than 2 ℃ deviation.
Today, many researchers have introduced and recommended the use of biodiesel as alternative to conventional diesel fuels manufactured from petroleum sources as biodiesel reduces the greenhouse gas emissions, ensure sustainability and protect against higher oil prices (Rashed et al., 2016; Adepoju, 2020; Murta et al., 2021; Pourhoseini et al., 2021). Biodiesel is defined as a combination of saturated and unsaturated long chain fatty acid mono alkyl ester made from vegetable oils and animal fats, obtained by the process of transesterification of an oil and fat with an alcohol (Ali et al., 2016; Soly Peter et al., 2021).
Palm oil is one of the most common biodiesel feedstocks and it was reported that palm oil-based biodiesel is cheaper and has the highest oil yield as compared with other common biodiesel feed stocks. Ali et al. (2012) highlighted that the production of palm oil-based biodiesel is about 12 times higher than that of soybean. During the physical crude palm oil refining, a non-edible by-product known as palm fatty acid distillate (PFAD) is inevitably produced. The annual global production of PFAD is estimated at 2.5 × 106 t, where Malaysia (29%) and Indonesia (58%) are the main contributors (Xu et al., 2020). On a stand point to fully-utilize the PFAD, it has been widely used as raw material for soap and oleochemical products and also as feedstock for biofuel production (Akinfalabi et al., 2017; Baharudin et al., 2020). However, the usage of palm oil-based biodiesel is often hinder by its poor cold flow properties (CFP), which is generally determined by cloud point (CP), cloud filter plugging point (CFPP) and pour point (PP). The poor CFP of palm oil-based biodiesel are mainly due to the presence of high amount of saturated palmitic acid methyl ester (C16:0) or methyl palmitate (up to 48%). As a consequence, palm oil-based biodiesel is unsuitable to be used in geographical regions outside tropical latitudes because the biodiesel is prone to solidification at low temperature and results in the clogging of fuel lines, filter and injectors that can lead to engine start-up and operability problems (Abou-Arab and Abu-Salem, 2010; Yusup and Khan, 2010; Cukalovic et al., 2013; Lv et al., 2013; Sia et al., 2020).
Clearly, the CFP of the palm oil-based biodiesel need to be improved to prevent it from being solidified easily at low temperature. Several conventional techniques such as winterization, blending with petroleum diesel, transesterification with alcohol and the use of chemical additives have been employed to enhance the CFP of biodiesel or fatty acid methyl esters (FAME). However, these conventional techniques exhibit drawbacks that limit their application. For example, winterization could result in the loss of the total yield of biodiesel. On the other hand, blending of biodiesel utilize large proportion of blending agent (diesel) which is not sustainable and economically feasible (Edith et al., 2012; Sierra-Cantor and Guerrero-Fajardo, 2017; Sia et al., 2020). For that, searching for alternative approach to improve the CFP of palm oil-based biodiesel is necessary. Particularly, distillation process can be implemented to separate and obtain desired methyl esters (Dimian et al., 2007; Aqar et al., 2021). In that sense, distillation process can be used to remove those saturated methyl esters with unfavourable high melting points and low boiling points from biodiesel, which shall improve the CFP of biodiesel. Nonetheless, the conventional distillation process requires high cost and may induce thermal decomposition (cracking) that could affect the characteristic of biodiesel (Iakovlieva et al., 2017). An analogous method, but easier to implement, allows the esters to boiled at lower temperature and prevent cracking is to perform distillation under vacuum. Therefore, in this study, a simple vacuum distillation method was designed to modify the compositions of esters in PFAD biodiesel, aiming to improve its cold flow properties (CP, CFPP and PP). The composition of the PFAD biodiesel was analysed using gas chromatography that equipped with a flame ionisation detector (GC-FID). In addition, empirical correlations including Sarin (PFAME), Sarin (UFAME) and Su's methods were fitted to predict and validate the cold flow properties.
The PFAD feedstocks were provided by Sarawak Oil Palm (SOP) Edible Oils Refinery Plant in Bintulu, Sarawak, Malaysia with free fatty acid (FFA) content of more than 80%. The feedstocks were converted into PFAD biodiesel via microwave-assisted esterification before the distillation experiment, as presented in our previous study (Yeong et al., 2019). The main fatty acid profile of the PFAD sample was found to be 47.51% palmitic acid, 38.69% oleic acid, 9.04% linoleate acid, and 4.76% of stearic acid, which gave an estimated molecular weight of 260.17 g/mol. The n-hexane (analytical grade), FAME-mix RM6 reference standard and methyl heptadecanoate for GC-FID analysis were purchased from Merck, Malaysia.
The vacuum distillation experiment was set-up in a laboratory scale. In this work, methyl palmitate with higher melting point was selected as the light key component (to be removed as distillate) while methyl oleate was selected as the heavy key component. A schematic presentation of the vacuum distillation setup is depicted in Fig. 1. The reflux divider (LSG 09089 model) shown in Fig. 1 was purchased from Normag, Germany. It consists of a jacketed water-cooled coiled condenser, a ground joint fitting for insertion of temperature measuring device, a distillate drains section (with two glass needle valves), a side-arm vacuum frame for venting or connection to the vacuum supply (with two spindle valves), and a stopcock valve above the receiving end joint. Fibre optic probes were inserted at two temperature measuring locations: 1) take-off section with ground joint fitting between the boiling flask and reflux divider; and 2) in the boiling flask, to record the instantaneous vapour and reboiler temperature respectively. The boiling flask (1 L) was half filled with the biodiesel sample to allow additional room for bubbling during boiling in experiment. This also helps in preventing splashing of the sample into the reflux divider. During the experiment runs, the flask was heated in an oil bath which is maintained at 210 ℃ under a vacuum pressure of 100 kPa. All the connecting joints of the glassware were lubricated with Dow-Corning high vacuum silicone grease. The flask was connected to a reflux divider which was a combination of a coil condenser and vacuum control valves that connect to a vacuum pump fitted with a cold trap. The collecting flask can be disconnected from the reflux divider from time to time by shutting off the needle valve and spindle valve which were closest to the collecting flask. The valves can be turned on to reintroduce vacuum into the collecting flask again. The distillates were collected in 10-min interval and characterized using GC-FID analysis. The experiment ended when the collected distillate significantly reduced when the distillation rate decreased below 0.3 g/min.
The biodiesel sample were poured into a test jar and pre-heated in a 40 ℃ water bath before test. Then, the sample is setup in a test jar according to ASTM standard D2500 (ASTM, 2011. D2500-11: Standard Test Method for Cloud Point of Petroleum Products. West Conshohocken, PA: ASTM International). A thermometer was inserted into the test jar. The temperature when a cloud of wax form at the bottom was recorded as the cloud point. The test was carried out in triplicates.
The CFPP of biodiesel gives a proper estimate of the lowest temperature at which the fuel could flow trouble-free in the fuel systems. The biodiesel sample was added into a CFPP apparatus as illustrated in ASTM standard D6371-05 (ASTM, 2010. D6371-05(2010): Standard Test Method for Cold Filter Plugging Point of Diesel and Heating Fuels. West Conshohocken, PA: ASTM International). The sample, which was cooled at 1 ℃ interval, was drawn into a pipette through a wire mesh filter under controlled vacuum. This process was repeated until the amount of wax crystals formed was sufficient to stop or slow down the flow such that the time taken to fill the pipette exceeded 60 s. The temperature indicated for the last successful filtration was recorded as the CFPP. The test was carried out in triplicates.
The pour point test of the biodiesel sample was conducted according to ASTM standard D97 (ASTM, 2015. D97-15: Standard Test Method for Pour Point of Petroleum Products. West Conshohocken, PA: ASTM International). Biodiesel sample was poured into a test jar. Then, a thermometer was inserted into the jar such that the bulb was 1 inch from the bottom surface of the test jar. The test jar was placed in the cloud and pour point bath (0 ℃). The condition of the biodiesel sample was inspected every 3 ℃ drop in the temperature. The temperature when the biodiesel sample did not flow at all after tilted horizontally for 5 s was recorded. The pour point of the tested sample was identified by adding 3 ℃ to the recorded temperature. The test was repeated in triplicates.
The GC-FID was employed for quantitative analysis of the FAMEs in the PFAD biodiesel samples. The analysis was carried out using the Agilent 6890N Network GC system with an FID detector with operating conditions as reported by Yeong et al. (2019). The GC system was installed with an Agilent HP-5 column (30 m × 320 μm × 0.25 μm) (Li et al., 2013). For quantitative FAME conversion, a sample was prepared in a 2 mL vial by diluting 50 mg of biodiesel sample and 10 mg of methyl heptadecanoate in 1 mL n-hexane. Methyl heptadecanoate with known concentration was used as an internal standard to determine the precise concentration percentage for the peaks shown by the biodiesel compound in the chromatogram. The identification of the composition of the major fatty acids in the biodiesel sample was carried out by comparing the components with FAME-mix RM6, which was used as the reference standard (Ho et al., 2015). The FAME conversion was calculated by using Equation (1) as expressed in the EN 14103 standard (British Standards Institution, 2011. BS EN 14103: 2011 Fat and oil derivatives-Fatty acid methyl esters (FAME)-determination of ester and linolenic acid methyl ester contents):
| $$ \text { Ester content }=\frac{\sum \mathrm{A}--\mathrm{A}_{\mathrm{IS}}}{\mathrm{A}_{\mathrm{IS}}} \times \frac{\mathrm{m}_{\mathrm{IS}}}{\mathrm{m}} \times 100 \% $$ | (1) |
where ΣA is the sum of all FAME peak areas, AIS is the internal standard (methyl heptadecanoate) peak area, mIS is the mass of the internal standard, and m is the mass of the sample.
The cold flow properties of biodiesel were estimated using several sets of empirical correlations as follows:
(1) Sarin method which is based on the content of methyl palmitate (PFAME, wt%) (Sarin et al., 2009; Sarin et al., 2010):
| $$ \mathrm{CP}=0.526 \mathrm{P}_{\mathrm{FAME}}-4.992\left(0 <\mathrm{P}_{\mathrm{FAME}} \leq 45\right), \mathrm{R} 2=0.963 $$ | (2) |
| $$ \mathrm{PP}=0.571 \mathrm{P}_{\mathrm{FAME}}-12.24\left(0 <\mathrm{P}_{\mathrm{FAME}} \leq 45\right), \mathrm{R} 2=0.863 $$ | (3) |
| $$ \text { CFPP }=0.511 \mathrm{P}_{\text {FAME }}-7.823\left(0 <\mathrm{P}_{\text {FAME }} \leq 45\right), \mathrm{R} 2=0.863 $$ | (4) |
(2) Sarin method which is based on the content of total unsaturated FAMEs (UFAME, wt%) (Sarin et al., 2009; Sarin et al., 2010):
| $$ \mathrm{CP}=-0.576 \mathrm{U}_{\mathrm{FAME}}+48.255\left(0 <\mathrm{U}_{\mathrm{FAME}} \leq 84\right), \mathrm{R} 2=0.973 $$ | (5) |
| $$ \mathrm{PP}=-0.626 \mathrm{U}_{\mathrm{FAME}}+45.594\left(0 <\mathrm{U}_{\mathrm{FAME}} \leq 84\right), \mathrm{R} 2=0.874 $$ | (6) |
| $$ \mathrm{CFPP}=-0.561 \mathrm{U}_{\mathrm{FAME}}+43.967\left(0 <\mathrm{U}_{\mathrm{FAME}} \leq 84\right), \mathrm{R} 2=0.872 $$ | (7) |
(3) Su's method which is based on the weighted average number of carbon atoms in FAME (Nc) and the composition of total unsatu-rated FAMEs (UFAME) (Su et al., 2011):
| $$ \mathrm{CP}=18.134 \mathrm{~N}_{\mathrm{c}}-0.790 \mathrm{U}_{\mathrm{FAME}} $$ | (8) |
| $$ \mathrm{PP}=18.880 \mathrm{~N}_{\mathrm{c}}-1.000 \mathrm{U}_{\mathrm{FAME}} $$ | (9) |
| $$ \mathrm{CFPP}=18.019 \mathrm{~N}_{\mathrm{c}}-0.804 \mathrm{U}_{\mathrm{FAME}} $$ | (10) |
These correlations help to validate the cold flow tests of PFAD biodiesel before and after distillation.
With the aim to improve CP, PP and CFPP of PFAD biodiesel, a simple vacuum distillation process described under Section 2.2 was set-up to remove the selected FAME. The ester composition in the PFAD biodiesel with their respective melting and boiling points is shown in Table 1 and compared with other studies (Cermak et al., 2012; Lokman et al., 2014). As shown in Table 1, methyl stearate has the highest melting point (37.7 ℃), followed by the methyl palmitate (28.5 ℃). In spite of having higher melting points, methyl stearate was not selected as the key component to be separated from the PFAD biodiesel because its amounts were relatively lower as compared with methyl palmitate, which was only 4.76%. On the other hand, the composition of methyl palmitate was found to be 47.51%, which was the highest among the four esters presented in the PFAD biodiesel. This is in agreement with the composition reported by Lokman et al. (2014). For that, methyl palmitate was chosen as the key component to be separated.
| Ester | Melting point (℃)a | Boiling point (℃/1.33 kPa)a | Composition (wt%)b | Composition (wt%)c |
| Methyl myristate | 18.1 | 161 | Negligible | 1.93 |
| Methyl palmitate | 28.5 | 184 | 47.51 | 45.68 |
| Methyl stearate | 37.7 | 205 | 4.76 | 4.25 |
| Methyl oleate | -20.2 | 201 | 38.69 | 40.19 |
| Methyl linoleate | -43.1 | 200 | 9.04 | 7.90 |
| Total saturated FAMEs | - | - | 52.27 | 51.86 |
| Total unsaturated FAMEs | - | - | 47.73 | 48.09 |
| Notes: a, Cermak et al., 2012; b, in this work; c, Lokman et al., 2014. | ||||
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The experiment was carried out under vacuum as Bonhorst et al. (1948) reported that the decomposition of saturated acid esters would occur progressively at temperature above 205 ℃ under atmospheric pressure. As shown in Table 1, the boiling point of methyl palmitate was 184 ℃ at an absolute pressure of 1.33 kPa. Thus, in order to avoid the thermal degradation of esters during the distillation process, the experiment was carried out at the boiling temperature of methyl palmitate under 100 kPa vacuum pressure. During the vacuum distillation experiment, the esters were successfully separated from the heated PFAD biodiesel sample, where about 430 g of PFAD methyl esters were obtained in the boiling flask during the distillation run.
The temperature profiles of the liquid (in boiling flask) and vapour (before condensed into distillate) were recorded and presented as Fig. 2. As shown in Fig. 2, the vapour temperatures were consistent, with 10 ℃ lower than the reboiler temperature throughout the distillation experiment. It was observed that the PFAD biodiesel in liquid phase reached its boiling point about 35-40 min before the distillation began. The highest biodiesel temperature recorded was 194.8 ℃ at the 35th minute before the first distillate sample collection took place. At this stage, the molecules in the biodiesel sample possessed enough kinetic energy to escape from the liquid phase to vapour phase. This was shown by the immediate increase in vapour temperature, where the vapour temperature rose from the room temperature to over 180 ℃, indicating that more vapour was actually produced to achieve stable total reflux condition in the distillation system. Another interesting observation is that it was noticed that it is nearly impossible to distillate the esters with lower boiling point than methyl palmitate (e.g., boiling point of methyl myristate: 161 ℃) that present in small portion in the PFAD biodiesel. In other words, only one distillate fraction was obtained as the vapour temperatures remained steady at the range of 183-184 ℃ during the experiment. This was acceptable as taking subsequent fractions at higher temperature would inevitably remove a higher amount of methyl oleate and methyl linoleate from the biodiesel which would beat the purpose of conducting distillation on PFAD biodiesel.
The light key component, methyl palmitate, was removed from the system and collected in the form of distillate every 10 min at a reflux ratio of 1:1. The amount of distillate collected at each interval during the distillation experiment is plotted in Fig. 3. It was observed that the distillate removal rate increased during the first 60 min but decreased at a faster rate after that. By the 60th minute, the amount of distillate obtained was 29.99wt% of the initial feed. After 100 min, the amount of distillate that was enriched with methyl palmitate increased to 39.76 wt% whereas the bottom product left in the boiling flask was enriched in the higher boiling component (methyl oleate). By the end of the experiment, the remained bottom product (distilled biodiesel) in the boiling flask was collected.
In order to study the efficiency of the vacuum distillation, the composition of the biodiesel samples before and after distillation were subjected to GC-FID analysis for fatty acid composition studies. The ester compositions in the PFAD biodiesel before and after the distillation were identified from chromatograms (Fig. 4) and shown in Table 2. As shown in Table 2, the PFAD biodiesel before distillation was composed of 47.36% methyl palmitate, 38.46% methyl oleate and 14.19% other esters. However, it was found that the methyl palmitate content in the distilled PFAD biodiesel decreased by 15.44% after the distillation, from 47.36% to 31.91%. Meanwhile, the amounts of other esters increased, where the methyl oleate, methyl linoleate and methyl stearate were increased by 11.32%, 2.28% and 1.85%, respectively. That said, the dominant ester in PFAD biodiesel after distillation have changed from the saturated ester methyl palmitate to the unsaturated ester methyl oleate. The amount of total unsaturated FAMEs in the PFAD biodiesel was increased by 13.60% after the distillation.
| Ester | Carbon chain | Retention time (min) | Molar mass (g/mol) | Normalized composition (%) | Change | |
| Pre-distillation | Post-distillation | |||||
| Methyl palmitate | (C16:0) | 9.19 | 270.5 | 47.36 | 31.91 | -15.44 |
| Methyl stearate | (C18:0) | 12.78 | 294.5 | 5.01 | 6.86 | 1.85 |
| Methyl oleate | (C18:1) | 12.37 | 296.5 | 38.46 | 49.78 | 11.32 |
| Methyl linoleate | (C18:2) | 12.21 | 298.5 | 9.17 | 11.45 | 2.28 |
| Total saturated FAMEs | - | - | - | 52.37 | 38.77 | -13.60 |
| Total unsaturated FAMEs | - | - | - | 47.63 | 61.23 | 13.60 |
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The ester compositions of the ten distillate samples collected during the experiment at 10-minute interval were also identified using GC-FID analysis (Fig. S1). By referring to Fig. 4, the changes in the FAME compositions of distillate over time was monitored. It was observed that the ester compositions of the ten distillate samples were at the range of: about 60%-69% methyl palmitate, 19%-29% of methyl oleate, 5%-7% of methyl linoleate, and 2%-3% of methyl stearate (Table S1). The first distillate sample contained the highest fraction of methyl palmitate (68.60%) and the lowest fraction of methyl oleate (19.17%). Its content of methyl stearate and linoleate were the lowest as well. However, in the subsequent samples, the fraction of methyl palmitate in distillate dropped gradually while the composition of the other three esters in the distillate samples increased. Noticeably, the first four distillate samples had relatively higher amounts of methyl palmitate, ranging from 66.21% to 68.60%. This dropped to 60.80% at the sixth sample when the amount of distillate collected were the highest at (32.38±4.95) g (Fig. 3a). In this study, after the distillation, the total yield of distillate obtained was 39.76% while the yield of bottom product (distilled biodiesel) was 59.62%. Align with this finding, the mass balance of the vacuum distillation experiment is shown in Table S2.
Clearly, the yield of biodiesel after distillation is comparatively lower, but it is possible due to the small difference in boiling point. At an absolute pressure of 1.33 kPa, which is close to the experimental operating pressure in this study, the difference between the boiling points of methyl palmitate (light key) and oleate (heavy key) was 17 ℃ (Table 1) and this may greatly affect the distillation performance. However, it is worth mentioning that a winterization process of removing 12.5wt% total saturated methyl esters from soybean oil-based biodiesel took about one week time and only produced 25% total product yields, as reported by Dunn et al. (1996). In contrast, in our study, 13.60wt% of total saturated methyl esters were removed in 170 min (including time taken to boil the biodiesel) and the total product yield was found to be 59.62%, highlighting the potential of vacuum distillation in modifying the compositions of esters, at the same time ensuring higher yield of biodiesel.
The CFP of biodiesel are generally accessed by the determination of CP, CFPP and PP (Sia et al., 2020). The CFP of the PFAD biodiesel sample before and after the distillation were shown in Table 3. As shown in Table 3, prior to the distillation, the CP, CFPP and PP of the PFAD biodiesel was 20 ℃, 19 ℃ and 15 ℃, respectively; whereas, after the distillation, the CP, CFPP and PP of the PFAD biodiesel were found to reduce to 13 ℃, 11 ℃ and 9 ℃, respectively. The reduction was expected as a total of 15.44% reduction of methyl palmitate (saturated ester) and a net increase of 11.32% of methyl oleate (unsaturated ester) was observed in the distilled PFAD biodiesel sample (Table 2). With the removal of saturated ester and increment of degree of unsaturation in the distilled PFAD biodiesel, the CFP would inevitably reduce, and this result is in good accordance to the results published by Elias et al. (2016). Notably, the effectiveness of vacuum distillation designed in this study is found to be promising and comparable with other techniques, considering the magnitude of CFP improvements are about the same. For example, it was reported that the CP and CFPP of palm oil biodiesel was reduced from 18 ℃ and 16 ℃ to 11.33 ℃ and 8.67 ℃, respectively after blending the palm oil methyl ester-biodiesel with 30% of technical-grade of methyl oleate (Altaie et al., 2015). It can be noticed that the improvement of CP and CFPP value of their study (∆CP = ~7 ℃, ∆CFPP = ~8 ℃) is about the same to our finding (∆CP = 7 ℃, ∆CFPP = 8 ℃), suggesting that the vacuum distillation technique used in this study can be used as an alternative approach to improve CFP. On the other hand, Verma et al. (2016) blend palm biodiesel with 20% of diesel and found that the CP and PP of palm biodiesel are improved from 21 ℃ and 19.7 ℃ to 8.9 ℃ and 6.2 ℃, respectively. However, it is noteworthy that despite significant improvements, blending requires large proportion of blending agent which is not environmentally friendly and economically feasible for the development of alternative fuel.
| Cold flow property | In this work (℃) | Sarin (PFAME, ℃)a | ∆T (℃) | Sarin (UFAME, ℃)a | ∆T (℃) | Su's method (℃)b | ∆T (℃) |
| Pre-distillation PFAD biodiesel | |||||||
| CP | 20 | 19.92 | 0.08 | 20.82 | 0.82 | 15.76 | 4.24 |
| CFPP | 19 | 16.38 | 2.62 | 17.24 | 1.76 | 13.02 | 5.98 |
| PP | 15 | 14.80 | 0.20 | 15.77 | 0.77 | 19.19 | 4.19 |
| Post-distillation PFAD biodiesel | |||||||
| CP | 13 | 11.79 | 1.21 | 12.99 | 0.01 | 10.72 | 2.28 |
| CFPP | 11 | 8.48 | 2.52 | 9.62 | 1.38 | 7.76 | 3.24 |
| PP | 9 | 5.98 | 3.02 | 7.26 | 1.74 | 11.53 | 2.53 |
| Notes: a, Sarin et al., 2009; Sarin et al., 2010; b, Su et al., 2011. | |||||||
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Another interesting finding is that the CFPP values improved the most among the three properties (∆CFPP = 8 ℃). This could be due to the increment of unsaturated esters, where it was reported that CFPP values are highly correlated to the contents of total unsaturated esters (Park et al., 2008; Sarin et al., 2010). It is also remarkable that the improved CFPP satisfied the requirements for grade C summer biodiesel for temperate climates in European Standard for Biodiesel (EN 14212 standard) (British Standards Institution, 2014. BS EN 14214:2012+A1:2014 Liquid petroleum products—Fatty acid methyl esters (FAME) for use in diesel engines and heating applications—Requirements and test methods: BSI Standards Limited 2014).
By using the designed vacuum distillation process reported in this study, improvement in cold flow properties of PFAD biodiesel was observed, even though the difference in the boiling points of the light key and heavy key was less than 20 ℃. With only 13.60% removal of the total saturated FAMEs in the distilled PFAD biodiesel, the CFP of the PFAD biodiesel were improved by 6-8℃ after 170 min of simple vacuum distillation (including boiling time for biodiesel). To further validate the obtained results, three empirical correlation methods provided under Section 2.5, namely Sarin (PFAME) method, Sarin (PFAME) method and Su's method were used (Sarin et al., 2009; Sarin et al., 2010; Su et al., 2011).
In the case of pre-distillate PFAD biodiesel sample, it was found that Sarin (PFAME) method was able to estimate the CP and PP of the biodiesel sample with negligible temperature difference (∆T = 0.08-0.20 ℃), but the CFPP value showed a ∆T of 2.62 ℃. It is important to point out that the amount of methyl palmitate of the sample was 47.36% (Table 2), which was slightly higher than the upper boundary value (0 < PFAME ≤ 45wt%) given in Eqs. (2)-(4). Thus, the decision of implementing Sarin (PFAME) method solely based on the calculation on this sample remain doubtful. On the other hand, it was noticed that the Sarin (UFAME) method was able to predict CFP of the PFAD sample with less than 2 ℃ deviation. Whereas, the predicted values using Su's method was found to exhibit high temperature difference (∆T = 4.19-5.98 ℃) which is the highest among the three methods.
For the post-distillation PFAD biodiesel sample, requirements for using both Sarin's (PFAME) (0 < PFAME ≤ 45wt%) and (UFAME) (0 < UFAME ≤ 84wt%) correlation were satisfied. As shown in Table 3, it was found that the Sarin (UFAME) method gave the lowest temperature difference among the three methods. Noticeably, the CP value was estimated accurately with ∆T of 0.01 ℃, but the difference for CFPP and PP prediction was found to be slightly higher with ∆T of 1.38 ℃ and 1.74 ℃, respectively. It is remarkable that the predicted CFP of PFAD biodiesel sample were only deviated at less than 2 ℃ as compared to the experimental results. It is important to point out that the temperature differences were comparatively lower than the errors predicted using Sarin (PFAME) method. In short, it was found that the Sarin (UFAME) correlation method allowed the best prediction of the CFP of PFAD biodiesel samples in this work.
A simple vacuum distillation process was used to improve the cold flow properties of PFAD biodiesel. A total of 13.60wt% of total saturated fatty acid methyl esters were separated from the biodiesel. As a result, the CP, CFPP and PP were reduced from 20 ℃, 19 ℃, and 15 ℃ to 13 ℃, 11 ℃, and 9 ℃, respectively. Remarkably, the improved CFPP satisfied the requirements for grade C summer biodiesel for temperate climates in EN 14212 standard. Among the three empirical correlations employed for the prediction of biodiesel cold flow properties, Sarin (UFAME) method was found to best predict the cold flow characteristics of PFAD biodiesel in this work, with less than 2 ℃ deviation. Clear improvements were noticed by employing vacuum distillation as shown in this work and can be considered as an alternative approach in industrial application. Nonetheless, simulation work shall be performed in the future to validate the experimental results. Also, continuous mode of the vacuum distillation process should also be considered in future studies as in general, the continuous flow mode of process could be more time-effective and productive. Additionally, due to the complexity of sources to produce biodiesel, future studies are still needed to compare the effectiveness of vacuum distillation with other conventional approaches like winterization and blending with diesel to improve the CFP of PFAD biodiesel and potentially the combination of these technologies may offer novel prospect for the improvement of CFP in an efficient, economical and environment-friendly manner.
The authors declare that there is no conflict of interest.
Supplementary data associated with this article can be found, in the online version, at doi: 10.1016/j.jobab.2021.09.002.
Acknowledgements: The study was supported by the Malaysian Ministry of Higher Education (No. FRGS/2/2014/TK06/CURTIN/02/1).|
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Figures(4) / Tables(3)
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Supported by: Beijing Renhe Information Technology Co. Ltd support: info@rhhz.net
Ping Yeong Siew, San Chan Yen, Chiat Law Ming, Kim Ung Ling Jordy. Improving cold flow properties of palm fatty acid distillate biodiesel through vacuum distillation[J]. Journal of Bioresources and Bioproducts, 2022, 7(1): 43-51. doi: 10.1016/j.jobab.2021.09.002
| Ester | Melting point (℃)a | Boiling point (℃/1.33 kPa)a | Composition (wt%)b | Composition (wt%)c |
| Methyl myristate | 18.1 | 161 | Negligible | 1.93 |
| Methyl palmitate | 28.5 | 184 | 47.51 | 45.68 |
| Methyl stearate | 37.7 | 205 | 4.76 | 4.25 |
| Methyl oleate | -20.2 | 201 | 38.69 | 40.19 |
| Methyl linoleate | -43.1 | 200 | 9.04 | 7.90 |
| Total saturated FAMEs | - | - | 52.27 | 51.86 |
| Total unsaturated FAMEs | - | - | 47.73 | 48.09 |
| Notes: a, Cermak et al., 2012; b, in this work; c, Lokman et al., 2014. | ||||
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CSV
| Ester | Carbon chain | Retention time (min) | Molar mass (g/mol) | Normalized composition (%) | Change | |
| Pre-distillation | Post-distillation | |||||
| Methyl palmitate | (C16:0) | 9.19 | 270.5 | 47.36 | 31.91 | -15.44 |
| Methyl stearate | (C18:0) | 12.78 | 294.5 | 5.01 | 6.86 | 1.85 |
| Methyl oleate | (C18:1) | 12.37 | 296.5 | 38.46 | 49.78 | 11.32 |
| Methyl linoleate | (C18:2) | 12.21 | 298.5 | 9.17 | 11.45 | 2.28 |
| Total saturated FAMEs | - | - | - | 52.37 | 38.77 | -13.60 |
| Total unsaturated FAMEs | - | - | - | 47.63 | 61.23 | 13.60 |
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CSV
| Cold flow property | In this work (℃) | Sarin (PFAME, ℃)a | ∆T (℃) | Sarin (UFAME, ℃)a | ∆T (℃) | Su's method (℃)b | ∆T (℃) |
| Pre-distillation PFAD biodiesel | |||||||
| CP | 20 | 19.92 | 0.08 | 20.82 | 0.82 | 15.76 | 4.24 |
| CFPP | 19 | 16.38 | 2.62 | 17.24 | 1.76 | 13.02 | 5.98 |
| PP | 15 | 14.80 | 0.20 | 15.77 | 0.77 | 19.19 | 4.19 |
| Post-distillation PFAD biodiesel | |||||||
| CP | 13 | 11.79 | 1.21 | 12.99 | 0.01 | 10.72 | 2.28 |
| CFPP | 11 | 8.48 | 2.52 | 9.62 | 1.38 | 7.76 | 3.24 |
| PP | 9 | 5.98 | 3.02 | 7.26 | 1.74 | 11.53 | 2.53 |
| Notes: a, Sarin et al., 2009; Sarin et al., 2010; b, Su et al., 2011. | |||||||
DownLoad:
CSV
| Ester | Melting point (℃)a | Boiling point (℃/1.33 kPa)a | Composition (wt%)b | Composition (wt%)c |
| Methyl myristate | 18.1 | 161 | Negligible | 1.93 |
| Methyl palmitate | 28.5 | 184 | 47.51 | 45.68 |
| Methyl stearate | 37.7 | 205 | 4.76 | 4.25 |
| Methyl oleate | -20.2 | 201 | 38.69 | 40.19 |
| Methyl linoleate | -43.1 | 200 | 9.04 | 7.90 |
| Total saturated FAMEs | - | - | 52.27 | 51.86 |
| Total unsaturated FAMEs | - | - | 47.73 | 48.09 |
| Notes: a, Cermak et al., 2012; b, in this work; c, Lokman et al., 2014. | ||||
| Ester | Carbon chain | Retention time (min) | Molar mass (g/mol) | Normalized composition (%) | Change | |
| Pre-distillation | Post-distillation | |||||
| Methyl palmitate | (C16:0) | 9.19 | 270.5 | 47.36 | 31.91 | -15.44 |
| Methyl stearate | (C18:0) | 12.78 | 294.5 | 5.01 | 6.86 | 1.85 |
| Methyl oleate | (C18:1) | 12.37 | 296.5 | 38.46 | 49.78 | 11.32 |
| Methyl linoleate | (C18:2) | 12.21 | 298.5 | 9.17 | 11.45 | 2.28 |
| Total saturated FAMEs | - | - | - | 52.37 | 38.77 | -13.60 |
| Total unsaturated FAMEs | - | - | - | 47.63 | 61.23 | 13.60 |
| Cold flow property | In this work (℃) | Sarin (PFAME, ℃)a | ∆T (℃) | Sarin (UFAME, ℃)a | ∆T (℃) | Su's method (℃)b | ∆T (℃) |
| Pre-distillation PFAD biodiesel | |||||||
| CP | 20 | 19.92 | 0.08 | 20.82 | 0.82 | 15.76 | 4.24 |
| CFPP | 19 | 16.38 | 2.62 | 17.24 | 1.76 | 13.02 | 5.98 |
| PP | 15 | 14.80 | 0.20 | 15.77 | 0.77 | 19.19 | 4.19 |
| Post-distillation PFAD biodiesel | |||||||
| CP | 13 | 11.79 | 1.21 | 12.99 | 0.01 | 10.72 | 2.28 |
| CFPP | 11 | 8.48 | 2.52 | 9.62 | 1.38 | 7.76 | 3.24 |
| PP | 9 | 5.98 | 3.02 | 7.26 | 1.74 | 11.53 | 2.53 |
| Notes: a, Sarin et al., 2009; Sarin et al., 2010; b, Su et al., 2011. | |||||||
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