Biodiesel Production

Methods of Biodiesel Production

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Preferred methods of production of biodiesel typically consist of reaction of oil sources with alcohols with aid of either acid or base catalysis.

2.1 General Biodiesel Production Procedures:

Fats and oils are composed of molecules called triglycerides. Each triglyceride is composed of three long-chain fatty acids of 8 to 22 carbons attached to a glycerol backbone. Biodiesel is composed of fatty acid chains that are chemically bonded to one methanol molecule. The glycerol molecules are almost completely removed from the final biodiesel product. Biodiesel is sometimes called fatty acid methyl esters or FAME. The glycerin byproduct has thousands of industrial chemical uses in common household products and foods. When the fatty acid chains break off the triglyceride, they are known as free fatty acids. Free fatty acids are desirable biodiesel feedstocks, but require different conversion processes compared to triglycerides. Biodiesel feedstock are classified based on their free fatty acid content as follows: - Refined oils, such as soy bean or refined canola oil (FFA <1.5%) - Low free fatty acid yellow greases and animal fats (FFA<4%) - High free fatty acid greases and animal fats (FFA 20%) Commercial biodiesel technologies can be grouped as follows: Base catalyzed transesterification with refined oils Base catalyzed transesterification with low free fatty acid greases and fats

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Acid esterification followed by transesterification of low or high free fatty acid greases and fats

Technologies can be run as batch or continuous processes. Given the limited size of the domestic market for biodiesel, most U.S. firms have used batch technology. Continuous processes used in Europe and in industrial processes in the U.S. (to produce methyl esters for uses other than as fuel) can use raw or may require refined oils. Batch processes provide excellent opportunities for quality control if variations in feedstock quality are common, such as with yellow grease and animal fats. The goal of all the technologies is to produce a fuel grade biodiesel whose properties meet ASTM PS 121. The key quality control issues involve the complete (or nearly complete) removal of alcohol, catalyst, water, soaps, glycerine, and unreacted or partially reacted triglycerides and free fatty acids. Failure to remove or minimize these contaminates causes the methyl ester product to fail one or more fuel standards.

The first basic steps for producing a batch of biodiesel is titration and determination of the presence of water in the feedstock. Titration is conducted to determine the amount of catalyst needed and for choosing the best route for transesterification, whether acid- or basecatalyzed or a combination of processes. Determination of water may be quickly accomplished by boiling a small sample of oil and checking for spattering, which will occur violently even in the presence of very small amounts of water due to rapid vaporization caused by the extreme difference in boiling points (over 300C for most oils). Most stored oils will contain some water that will settle out over time, but could be trapped in the oil with the presence of surfactants found in rancid oils such as soaps created by ambient saponification.

2.2 Titration:
Titration is necessary to first determine the best route for biodiesel production whether using the conventional alkali-catalyzed approach, acid-catalyzed approach, or acid pretreatment followed by the alkali approach. If the titration shows an excess of 15 percent or greater free fatty acid concentration as in the case of brown greases, typically an acid-catalyzed esterification and transesterification procedure is implemented. If the concentration of free fatty acids are between 5 and 15 percent as in the case with yellow greases, then an acid pretreatment followed by base-catalyzed procedure may be chosen. Typically for oils less than 5 percent free fatty acids, the alkalicatalyzed procedure will be implemented since the cost of an additional acid pretreatment could be cost-prohibitive. The titration determines the amount of excess catalyst needed in the chosen reaction mechanism. For alkali-catalyst procedure an excess amount of catalyst may be required to first neutralize the free fatty acids before transesterification of oil triglycerides to ethyl esters can occur. Typical concentrations of catalyst to achieve efficient transesterification range around 1 percent by weight and any excess catalyst is added beyond 1 percent based on the titration values. A simple titration procedure is outlined below.

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1. Measure 10 mL of ethanol in a test tube. 2. Measure 1 mL of oil and mix with ethanol. 3. Add about 0.5 mL of phenolphthalein solution (10 to 20 drops). 4. Titrate the oil/ethanol solution with 1 g/L KOH or NaOH solution in distilled or deionized water using a burette until the color begins to turn pink after adequate mixing (near pH 8.0). 5. Estimate amount of KOH or NaOH needed for transesterification from the following formula:
y=9+x where y is grams of KOH or NaOH catalyst (usually 9 to 15 g) to use in 1 L of oil (about 900 g) and x is the number of milliliters of KOH or NaOH solution used in titration. The 9 g of catalyst gives you a starting value of about 1 wt % in 1 L of oil and the additional catalyst designated by x is required to first neutralize any free fatty acids before rapid transesterification may take place.

2.3 Alkali Transesterification:

The process design for the Alkali Transesterification process occurs in eight basic steps: 1. Storage and transfer: Oil is typically heated from the storage vessel to operating temperatures to reduce viscosity caused primarily by the presence of saturated fatty acids in the oil for easy transfer by pump to the reactor vessel. 2. Transesterification: Based on the kinetics of transesterification reactions typically yielding 90 to 98 percent oil conversion to alkyl esters, the reaction conducted at ambient pressure with temperatures ranging from room temperature to slightly below the boiling point of the alcohol was considered the best for economic conversion efficiencies. 3. Alcohol recovery: The excess alcohol from the transesterification reaction should be recovered to the greatest extent possible and recycled back to the transesterification step, requiring a complete distillation system and recycle system. Up to five theoretical stages with a reflux ratio of 2 should be employed to achieve efficient alcohol recovery. 4. Water washing: Multiple-stage water washing steps (up to four theoretical stages) are typically employed to purify the biodiesel from catalyst, free glycerol, and alcohols. 5. Biodiesel ester purification: To obtain ASTM-certified biodiesel at 99.6 percent purity, further purification of the esters must be employed with ester distillation with fourtheoretical stages where water and alcohols are removed as vent gases, esters removed as liquid distillate, and residual oils remain in the bottoms, which are recycled back to the transesterification step. 6. Alkali removal: The removal of alkali may be accomplished with the addition of phosphoric acid, resulting in a salting out of Na3PO4 or K3PO4. Potassium phosphate is much more desirable in that it may be further used as a fertilizer. 7. Glycerine purification: The glycerine should be purified into two grades to be sold commercially with the higher grade for food and pharmaceutical uses and lower grade for industrial or land application uses. With the use of UNIQUAC model in the simulations run by Zhang et al.,7

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glycerin of 92 percent high purity was obtained through four theoretical stages with a reflux ratio of 2 through the bottoms with water and alcohol removed in the vent gases. 8. Waste treatment: The compositions of waste streams, the alcohol recovery stages, ester purification, and glycerol purification consist primarily of water and alcohol and may be reused in the washing steps. Recovery of solid waste should be utilized as fertilizer to reduce waste treatment costs and water use. The transesterification reaction is shown where no more than 0.5 percent water can be present for the reaction to take place and to avoid significant saponification. This procedure is conducted in 50 mL centrifuge tubes for reduced transfer steps, but other volumes are typically used such as 15 mL centrifuge tubes or500 mL flasks. 1. Add 30 mL of oil to a 50 mL centrifuge tube (or 10 mL to a 15 Ml centrifuge tube or 300 mL to a 500 mL flask). 2. Add the appropriate weight of catalyst determined in the titration procedure to the alcohol and blend to completely dissolve in alcohol. For example, if the oil were primarily free of fatty acids as in the case with most refined oils, then you will need 9 g of catalyst per liter of oil. Therefore, the amount of catalyst for the 30 mL sample would be 9/1000 30 mL = 0.27 g of catalyst per sample. 3. Mix 9 mL catalyst and alcohol solution with the oil (or 3 mL to the 15 mL centrifuge tube or 90 mL to the 500 mL flask). This will produce approximately 6 to 1 molar ratio of ethanol to oil. 4. Heat at 55C and mix (or vortex) continuously or intermittently every 5 min for 1 h. Two layers should begin to form after 5 min with the darker glycerol layer sinking to bottom. If using ethanol and dark crude oil, the two layers will be initially difficult to distinguish due to solubilization of pigments into the upper layer by ethanol. 5. Centrifuge for 3 min at 3000 rpm (or let settle for several hours). Phase separation is an important step dependent on several factors, including the amount of excess alcohol and the amount and type of catalyst chosen. Korus et al.166 determined that the use of potassium hydroxide yielded better separation than potassium ethoxide. 6. Estimate the conversion produced by measuring the volume of glycerol and biodiesel layers.

2.4 Acid Esterification Pretreatment:

The Acid Esterification Pretreatment requires an additional three steps prior to the transesterification step.7 These steps include: 1. Esterification: The recommended approach for the esterification reaction requires a temperature of 70 C, resulting in a pressure of about 400 kPa when a 6:1 molar ratio methanol is used.171 A 1 wt % sulfuric acid to oil ratio is used to completely convert free fatty acids to biodiesel esters with formation of water. 2. Glycerin washing: Sulfuric acid and water must be completely removed before alkali transesterification may be accomplished. The addition of 10 wt % ratio of glycerin to oil with

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mixing will accomplish complete recovery of alcohol (about 60 percent of wash layer or stream), glycerol (33 percent of wash), sulfuric acid (3 percent sulfuric acid) and water (1 percent), and traces of esters and residual oil. 3. Alcohol recovery: The alcohol recovery is similar to that described previously with the exception that five theoretical stages were used with a reflux ratio of 5. 4. Acid neutralization: Sulfuric acid is recovered from the glycerol phase with calcium oxide to produce calcium sulfate, CaSO4, and water then separated by gravity settler.

Two-stage reaction processes incorporating an acid esterification pretreatment step followed by an alkali transesterification step have been proposed to increase yields of biodiesel from free fatty acid (FFA) containing oils. When oils exceed FFA values of 5 percent, the following procedure should be considered. 1. Add 30 mL of oil to a 50 mL centrifuge tube (or 10 mL to a 15 mL centrifuge tube or 300 mL to a 500 mL flask). 2. Make a 1 wt % acid catalyst solution in dry alcohol by using sulfuric acid. 3. Mix 9 mL catalyst solution to the oil (or 3 mL to the 15 mL centrifuge tube or 90 mL to the 500 mL flask). 4. Heat at 50 to 60C and mix (or vortex) continuously or intermittently every 15 min for 2 h. A water layer will begin to develop, depending on the amount of FFA initially present. Some glycerol will also be liberated by acid-catalyzed transesterification. 5. Centrifuge for 3 min at 3000 rpm (or let settle for several hours) and remove water layer. 6. Add 5 mL of glycerol to wash the mixture by inverting slowly. 7. Titrate the biodiesel mixture to test for residual free fatty acids or acid catalyst. 8. Centrifuge for 3 min at 3000 rpm to remove wash layer and measure pH. 9. Titrate the sample and repeat the pretreatment procedure if necessary until less than 5 wt % of free fatty acids remain. 10. Proceed to the Alkali Transesterification procedure to convert the remaining oil to biodiesel.

2.5 Acid Esterification and Transesterification:

Acid esterification and transesterification using sulfuric or hydrochloric acids are another convenient way to produce biodiesel, but often takes 1 to 2 days to complete the reaction compared to only 1 hour for the alkali-catalyzed techniques. When the FFA have exceeded 15 wt % creating brown grease, the pretreatment step outlined about earlier may be applied followed by alkali transesterification. To achieve adequate conversion of FFA to alkyl esters, allowing the reactions to proceed to completion with acid catalyst is recommended to avoid excessive and time-consuming wash steps.

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1. Add 30 mL of oil to a 50 mL centrifuge tube (or 10 mL to a 15 mL centrifuge tube or 300 mL to a 500 mL flask). 2. Make a 1 wt % acid catalyst solution in dry alcohol with sulfuric acid. 3. Mix 9 mL catalyst solution to the oil (or 3 mL to the 15 mL centrifuge tube or 90 mL to the 500 mL flask). 4. Heat at 50 to 60C and allow reacting overnight in a heated shaker bath. The free fatty acids present will react to create alkyl esters and a water layer. Some glycerol will also be liberated by acidcatalyzed transesterification. (Note: As water is liberated during esterification of FFA, this will further slow the transesterification step.) Intermittent centrifugation to remove water may be necessary to complete the conversion process. 5. Centrifuge for 3 min at 3000 rpm (or let settle for several hours) and remove water layer.

6. Estimate the conversion produced by measuring the volume of glycerol and biodiesel layers.

2.6 Biodiesel Water Wash:

Washing the biodiesel is necessary to remove excess catalyst, glycerol, and glycerides not fully reacted that would be detrimental to an engine. If an excessive amount of MAG, DAG, or TAGs as well as FFAs exist, then further esterification or transesterification may be necessary to achieve ASTM biodiesel standards for free and total glycerin.
Laboratory Scale

1. Pour the top layer (biodiesel) into a second centrifuge tube. 2. Add about 20 mL of water and invert tube gently several times. 3. Allow to settle in 50 C bath for 5 min. 4. Centrifuge 3 min at 3000 rpm (if separation does not occur, add several drops of acetic acid to help break emulsion). 5. Pour top layer into third centrifuge tube. 6. Measure pH of bottom wash layer; initially the wash water will be cloudy due to catalyst, glycerol, and soap formation. 7. Repeat washing process until pH drops to 7.0 and specific gravity is between 0.85 and 0.9. 8. Repeat the washing process as needed to obtain the desired pH. The wash water removed should become clear as another indicator of adequate washing.

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General biodiesel production process fl ow diagram for varied oil sources, including waste cooking oils.