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International Journal of Green Energy

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Conversion of Degummed Soybean Oil to Biodiesel: Optimization of Degumming Methods and Evaluation of Fuel Properties
Xiaohu Fan , Rachel Burton & Greg Austic
a a a a

Piedmont Biofuels Industrial, Pittsboro, North Carolina, USA

Available online: 10 Dec 2010

To cite this article: Xiaohu Fan, Rachel Burton & Greg Austic (2010): Conversion of Degummed Soybean Oil to Biodiesel: Optimization of Degumming Methods and Evaluation of Fuel Properties, International Journal of Green Energy, 7:6, 593-599 To link to this article: http://dx.doi.org/10.1080/15435075.2010.529403

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International Journal of Green Energy, 7: 593599, 2010 Copyright Taylor & Francis Group, LLC ISSN: 1543-5075 print / 1543-5083 online DOI: 10.1080/15435075.2010.529403

CONVERSION OF DEGUMMED SOYBEAN OIL TO BIODIESEL: OPTIMIZATION OF DEGUMMING METHODS AND EVALUATION OF FUEL PROPERTIES Xiaohu Fan, Rachel Burton, and Greg Austic
Piedmont Biofuels Industrial, Pittsboro, North Carolina, USA
Biodiesel, known as fatty acid methyl ester, has become increasingly important due to the following advantages: it is renewable, biodegradable, non-toxic, and eco-friendly. At present, the main hurdle for its commercialization is high feedstock price. Crude soybean oil may be a cheap source for biodiesel production. However, it contains high amount of phosphorus, which can inhibit the action of the catalyst during transesterication. The degumming process can remove most of phosphorus in the crude soybean oil. In this paper, different degumming methods were investigated and an optimal method was determined based on phosphorus content, free fatty acid, and bound glycerin tests. Crude soybean oil degummed by the optimal method was further transesteried, and the fuel properties, including acid number, water and sediment, ash point, soap, moisture, methanol content, and free and total glycerin, etc., were further evaluated. It was found that the fuel properties were within ASTM D 6751 specications. Keywords: Biodiesel; Degumming; Transesterication

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INTRODUCTION Biodiesel, the most promising alternative diesel fuel, has received considerable attention in recent years due to its following merits: biodegradable, renewable, non-toxic, less emission of gaseous and particulate pollutants, and with higher cetane number than normal diesel (Antoln et al. 2002; Hu et al. 2004; Lang et al. 2001; Shieh, Liao, and Lee 2003; Vicente, Martnez, and Aracil 2004). In addition, it meets the currently increasing demands of world energy that, in a large degree, is dependent on petroleum-based fuel resources, which will be depleted in the foreseeable future if the present pattern of energy consumption continues. Biodiesel is derived from vegetable oils or animal fats through transesterication (Fukuda, Kondo, and Noda 2001). Transesterication is also called alcoholysis, which uses alcohols in the presence of a catalyst (e.g., base, acid, or enzyme depending on the free fatty acid (FFA) content of the raw material) that chemically breaks the molecules of triglycerides into alkyl esters as biodiesel fuels and glycerin as a by-product. The commonly used alcohols for the transesterication include methanol, ethanol, propanol, butanol, and amyl alcohol. Methanol and ethanol are adopted most frequently, particularly the former due to its low cost. The feedstocks used for biodiesel production currently are mainly high quality foodgrade vegetable oils, such as soybean oil in the United States, rapeseed oil in Europe, and
Address correspondence to Xiaohu Fan, Piedmont Biofuels Industrial, 220 Lorax Lane, Pittsboro, NC 27312, USA. E-mail: xfan@biofuels.coop

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palm oil in Malaysia (Azam, Waris, and Nahar 2005). Most soybean oils used for biodiesel production are degummed to remove phosphorus-containing compounds that are known as phosphatides or phospholipids. As the rst rening step, degumming involves the removal of phospholipids, the molecules either present in a hydratable or a non-hydratable form, using the degumming process. The non-hydratable form occurs when the phospholipids are combined with calcium, magnesium, or iron cations. This form must be treated with acid in order to convert them to hydrated gums. The hydratable form is treated by water degumming and directly converted into hydrated gums. These gums are then removed by centrifugation. Commonly used degumming methods include water degumming, acid degumming, dry degumming (phosphatide removal and bleaching are combined in a single process), enzymatic degumming, soft degumming [the non-hydratable phosphatides are decomposed by the action of ethylenediaminetetraacetic acid (EDTA)], and miscellaneous degumming (Williams and Merrilees 1970). At present, the primary obstacle for biodiesel commercialization is the high feedstock cost, which is reported over 85% of total biodiesel production cost (Haas et al. 2006; Yuste and Dorado 2006; Zhang et al. 2003). Biodiesel produced from unprocessed crude soybean oil will lower the production cost. However, unprocessed crude soybean oil may contain high amount of phosphorus, which showed the following disadvantages to biodiesel production: (1) It can inhibit the action of the catalyst during the biodiesel production reaction (Freedman, Pryde, and Mounts 1984); (2) Excess phosphorous in the fuel can cause damage to catalytic converters since it can coat the inside of the converters; (3) It may show emulsifying effect and inhibit the separation of biodiesel from glycerin and water; (4) ASTM D 6751-09 requires the maximum amount of 10 ppm phosphorus content in the nal biodiesel fuel. Therefore, it is necessary to evaluate the effect of phosphorus level on the biodiesel properties before considering using unprocessed crude soybean oil as raw material to produce biodiesel. In this paper, different degumming methods were investigated to evaluate their effects on phosphorus reduction. Moreover, the properties of biodiesel produced from crude soybean oil degummed by using optimized degumming method were characterized. MATERIALS AND METHODS Materials Methanol and potassium hydroxide were purchased from Fisher Scientic (Pittsburgh, PA, USA). Crude soybean oil was obtained from AgroFuel LLC. (Statesville, NC, USA). Degumming Methods Ten different degumming methods were investigated to examine their effects on the reduction of phosphorus level. Measure 97 ml of oil into a small ask, and shake oil to ensure it is homogenized before measuring. Using the water bath, heat the ask of oil to 75 C. Also place 100 ml centrifuge tube in the hot water bath or isotemp oven to help maintain heat while being centrifuged. Add H3 PO4 (75 wt% concentration) solution, cap the ask with a stopper, and shake vigorously for 1 min. If the sample has no water wash step, place the ask on a hot plate and add a stir bar. Set the hotplate to maintain 75 C, and stir at 150 rpm for the determined amount of time. Keep the stopper on the ask, occasionally checking temperature of the mixture. If the sample has a water wash step,

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add the appropriate amount of water and set the sample on the hotplate as described above for the determined amount of time. All the degumming procedures (method 1 through 10) include the same centrifuge conditions: centrifuge time: 10 min; centrifuge temperature: 85 C. Ten different degumming methods are listed as below. (1) Add 2 vol% water at 70 C, shake, separate immediately. (2) Add 2 vol% water at 70 C, shake, separate in 20 min. (3) Add dilute acid (0.18 vol% H3 PO4 and 0.6 wt% water), react (stir bar/hot plate), and separate immediately. (4) Add dilute acid (0.18 vol% H3 PO4 and 0.6 wt% water), react (stir bar/hot plate), and separate at 20 min. (5) Add dilute acid (0.18 vol% H3 PO4 and 2.0 wt% water), react (stir bar/hot plate), and separate immediately. (6) Add dilute acid (0.18 vol% H3 PO4 and 2.0 wt% water), react (stir bar/hot plate), and separate at 20 min. (7) Add concentrated acid (0.18 vol% H3 PO4 ), react, add water (stir bar/hot plate), and separate immediately. (8) Add concentrated acid (0.18 vol% H3 PO4 ), react, add water (stir bar/hot plate), and separate at 20 min. (9) Add dilute acid (0.18 vol% H3 PO4 and 0.6 wt% water), react, add water (stir bar/hot plate), and separate immediately. (10) Add dilute acid (0.18 vol% H3 PO4 and 0.6 wt% water), react, add water (stir bar/hot plate), and separate at 20 min. Transesterication of the Soybean Oil Degummed by the Optimized Method The soybean oil degummed was transferred to the reaction ask and preheated to the desired reaction temperature. Calculated amount of potassium hydroxide was dissolved in the methanol required. The solution of KOH and methanol was preheated to the reaction temperature. Finally, the methanolic solution was added to the degummed soy oil. The transesterifcation was carried out on the hot plate and constant stirring speed was maintained. After reaction, the reaction mixture was poured into separatory funnel and allowed to settle overnight. After settlement, the top layer, methyl esters, was rst washed with water and magnesol and then dried with anhydrous sodium sulfate. Analytical Methods Phosphorus content was analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES) according to ASTM D4951. ASTM D664 was used for FFA determination of crude soybean oil. The AOCS (American Oil Chemists Society) method Cc 1795 was routinely used for soap determination in methyl esters derived from crude soybean oil. KarlFisher method (ASTM D6304) was preferred to measure the moisture of crude soybean oil and its methyl ester. An automatic cool on column injection gas chromatograph (GC, 5890 Series II; Agilent Technologies, Santa Clara, CA, USA) was used for the determination of free and total glycerin in accordance with ASTM D6584. A capillary GC column [Restek, Bellefonte, PA, USA; Rtx-biodiesel column (15 m 0.32 mm id 0.10 m lm)] was used in the apparatus. The temperature of ame ionization detector (FID) was 380 C. The initial GC oven temperature was kept at 50 C for 1 min, heated at 15 C/min to 180 C, and then heated at 7 C/min to 230 C, nally heated at the ramp of 30 C/min to 380 C, at which it was kept for 10 min. About 100 mg of biodiesel sample was weighed into a 10 ml septa vial. Exactly 100 ml of each internal standard and N-Methyltrimethylsilytriuoroacltamide (MSTFA) silylating agent were added to the vial. The vial was shaken and allowed to sit for 15 min at room temperature. Then, 8

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ml of n-heptane was added to the vial, which was then briey shaken. A 1 l splitless injection volume was used. A calibration curve was generated from four standards [i.e., triolein (TG), diolein (DG), monoolein (MG), and glycerine] and two internal standards [i.e., 1,2,4-butanetriol for glycerine and 1,2,3-tricaproylglycerin (tricaprin) for glycerides]. Methanol content was determined by headspace-GC in compliance with modied EN 14110. The analytical column, Rtx.-1, was from Restek (30 m 0.32 mm id, 3 m lm). The temperature for injector and FID was 160 C and 250 C, respectively. The oven program was 50 C (1 min) to 130 C at 10 C/min, nal hold 0.5 min. The sample and syringe were incubated at 50 C for at least 15 min before analysis. The injected amount of the sample was 1 ml. The soy methyl esters (B100) produced in this study were characterized in relation to the technical limits established by ASTM D6751, using the following methods: ASTM D4951 for phosphorus content, ASTM D2709 for water and sediments, ASTM D93 for ash point, ASTM D664 for acid number, and ASTM D6584 for free and total glycerin.

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RESULTS AND DISCUSSION Effect of Degumming Methods on Phosphorus Content Most soybean oils used for biodiesel production are degummed to remove phosphorus-containing compounds known as phosphatides or phospholipids. Phosphatides are similar to triglycerides but differ in that one fatty acid has been replaced by a phosphate group that may be linked to an alcohol by one of its remaining acid functions. Absence of such an alcohol leads to the free acid referred to as phosphatidic acid (PA). If the alcohol is choline, the resulting phosphatide is called phosphatidylcholine (PC); ethanolamine leads to phosphatidylethanolamine (PE), and inositol leads to phosphatidylinositol (PI). The phosphatides are either present in a hydratable or a non-hydratable form. If PA forms a salt with a divalent metal such as calcium or magnesium, this salt is non-hydratable; PE cannot be removed by hydration unless other enough hydratable phosphatides are present. Water degumming cannot remove non-hydratable gums (Table 1, methods 1 and 2). The non-hydratable form must be treated with acid in order to convert them to hydrated gums. However, acid degumming alone cannot remove non-dissociated PA from the oil so that residual phosphorus levels in the oil are still high (Table 1, methods 3, 4, 5, and 6). The combination of water degumming with acid degumming showed efcient reduction of phosphorus (Table 1, methods 9 and 10), except methods 7 and 8. Both methods 7 and 8 use relatively high concentration acid, which will decrease the pH, thus worsening the complete partial dissociation of PA. The crude soybean oil exhibited a high amount of phosphorus content, 1148 ppm. After degumming, the highest phosphorus content was 344 ppm, 70% reduction of phosphorus content in the crude soybean oil (Table 1), while the lowest phosphorus content was only 3 ppm, taking out almost 99.7% of the phosphorus content of crude soybean oil. This low amount of phosphorus contents was obtained by using degumming method 10. Moisture and Free Fatty Acid It could also be seen from Table 1 that after treated with different degumming methods, all the moisture levels were below 3000 ppm, and all the FFAs were lower than 0.5 wt%, indicating that direct alkaline-catalyzed transesterication process was applicable.

CONVERSION OF DEGUMMED SOYBEAN OIL TO BIODIESEL Table 1 Phosphorus, moisture, and FFA content of degummed soybean oil. Degummed soybean oil Degumming method 1 2 3 4 5 6 7 8 9 10 Moisture (ppm) 1661 2036 1865 2511 1484 1959 1908 2129 1693 2108 FFA (%) 0.33 0.34 0.33 0.58 0.34 0.37 0.55 0.35 0.34 0.26 Phosphorus (ppm) 19 17 199 340 13 14 344 24 9 3

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Note: Phosphorus content of crude soybean oil is 1148 ppm.

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0.3
Bound glycerol (%)

0.25

0.2

0.15

4 5 6 7 Degumming method

10

Figure 1 Bound glycerin content of soybean oil degummed by different methods.

Bound Glycerin Test Figure 1 showed the bound glycerin results of the biodiesel produced from soybean oil degummed with different methods. The values ranged from 0.17 wt% to 0.24 wt%. All the values were within the limit, 0.22 wt%, except the one using degumming method 6. The best result was the one using degumming method 10. Based on the above test results, degumming method 10 was considered to be the optimal one. Crude soybean oil was rst degummed using degumming method 10. Then the degummed soybean oil was transesteried. Fuel properties were further evaluated.

Fuel Properties of Biodiesel from Soybean Oil Degummed by Optimal Method The physical and chemical properties of methyl esters of degummed soybean oil are shown in Table 2. The moisture and soap for this fuel were 344 ppm and 14 ppm, respectively. Other ASTM test results were as below.

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Table 2 Properties of biodiesel derived from degummed soybean oil. Property Phosphorus Water and sediment Acid number Methanol content Flash point (closed cup) Free glycerin Total glycerin Test method D4951 D2709 D664 Modied EN14110 D93 D6584 D6584 Limits 0.001 max 0.05 max. 0.50 max. 0.2 max. 93 min. 0.020 max. 0.240 max. Units % mass % vol. mgKOH/g % vol. C % mass % mass Results 0 0 0.20 0.0385 >110 0 0.16

Water and Sediment Biodiesel contaminated with water can cause engine corrosion or reaction with glycerides to produce soaps and glycerin. Water can also serve as media for bacteriological growth, leading to lter blockage. Due to these negative effects, ASTM D6751-09 set the maximum allowable content of 0.05 vol% for water in biodiesel. Water and sediment test showed no water in biodiesel produced from degummed soybean oil.

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Acid Number The acid number, expressed as milligrams of potassium hydroxide per gram of sample, is a measure of acidic substance in the oil. It is used as a guide in the quality control as well as monitoring oil degradation during storage. Acid number of biodiesel is less than 0.50 mgKOH/g specied as the maximum value according to ASTM D675109. As for biodiesel produced from degummed soybean oil, the very low acid number, 0.20 mgKOH/g, was obtained. Methanol Content Monitoring residual methanol in biodiesel is a safety issue since even small amounts of this material can reduce the ash point of the biodiesel. Moreover, residual methanol can affect fuel pumps, seals, and elastomers, resulting in poor combustion properties. EN 14110 (2003) standard specications require the methanol content to be less than 0.2 wt%. GC analysis of biodiesel obtained from degummed soybean oil indicated very low methanol content, 0.0385 wt%, which was further conrmed by the high ash point results, greater than 110 C.

Free and Total Glycerin Fuel with excessive free glycerin can increase aldehydes and acrolein emissions and will usually have a problem with glycerin settling out in storage tanks, creating a very viscous mixture that can plug fuel lters and cause combustion problems in the engine. Bound glycerin (mono-, di-, and triglycerides) is the indicator of the completeness of biodiesel production process. Lower bound glycerin indicates more complete transesterication process. GC results showed that free and total glycerin contents were within the standard requirement, 0 and 0.16 wt%, respectively.

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CONCLUSION Among 10 different degumming methods investigated, the Degumming Method 10, acid degumming combined with water degumming process, was found to be the optimal method based on phosphorus content, FFA, and bound glycerin tests. The reduction percentage of phosphorus content in the crude soybean oil can be as high as 99.7%. Using this optimal degumming method, crude soybean oil was degummed and further transesteried. The biodiesel obtained showed satisfactory fuel properties, including phosphorus content, acid number, ash point, water and sediment, methanol content, and free and total glycerin. All the test results were within ASTM D6751-09 requirements. ACKNOWLEDGMENT
The authors are grateful to the Piedmont Biofuels Industrial for the nancial support.

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