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PRODUCTION OF BIODIESEL
Group 11
Elvina Ariani Widjaja (3191763) Johan Lukita (3215892) Michael Yuputra (3181878) Qian Xu (3193800)
RMIT University
2011
Executive Summary
Biodiesel is a clean and sustainable fuel that made from vegetable oils or animal oils. As the global competition in market increase, the needs of optimized process with higher productivity are required. This the driving force for us, Biomax pty ltd to did research on this biodiesel producing field for the purpose of creating maximize result by changing the design parameter of the process. It can be done after the technique of producing biodiesel is understood and applied later on in the lab. The method of producing biodiesel can be break down into 2 major steps which are mixing and washing. And to know the quality of the biodiesel produced, various characterizations need to be fulfilled. The results that been observed in the characterizations are the pH value, turbidity, mass density, kinematic viscosity, calorie, gas chromatography and cetane number. There were 5 experiments done in this report. The parameters of the production was varied a bit to see which configuration gave the best result. Basically the standard batch which is the 2nd batch made of 400 ml oil sunflower, 3.5 gram of KOH, 80ml methanol, and water washed with heating temperature of 60C. While the first batch has the heating temperature changed to 25C compared to the second batch. The third batch done by bubble wash technique instead of water wash method that been done by the standard batch. The batch 4 has it KOH value reduced to 1 gram compared to the original batch. While the last batch was made of canola and bubble washed. After the mixing and washing method completed, the biodiesel is taken to be characterized. The result came out that batch 1 have the highest turbidity value, mass density, kinematic viscosity and calorie. It has the lowest cetane number as well. While the standard batch has the lowest turbidity which indicate that this design resulted in the cleanest and low glycerol left. Batch 2 also has the highest cetane number that indicates it has smooth combustion process and the easiest to be combusted. As the value of kinematic viscosity and calorie increase, the better the quality of the biodiesel which can be seen in batch 2 compared to the other batch (excluding batch 1). All the statement above show that batch 2 is the best design for producing biodiesel and proven in the performance test seeing that it has the longest ignition time when it was tested.
Table of Contents
Executive Summary..........................................................................................................................................2 Table of Contents..............................................................................................................................................3 1.0 Introduction.................................................................................................................................................5 2.0 Background of Biodiesel.............................................................................................................................5 2.1 Transesterification Process......................................................................................................................5 2.2 Advantages and Disadvantages of Biodiesel..........................................................................................6 2.3 Ingredients of Biodiesel.........................................................................................................................7 2.3.1 Oil...................................................................................................................................................7 2.3.2 Alcohol...........................................................................................................................................9 2.3.3 Catalyst.........................................................................................................................................10 2.4 Industrial Process.................................................................................................................................10 3.0 Rationale for Conducting Laboratory Experiments..................................................................................12 4.0 Experimental Investigations Aim and Objectives....................................................................................12 5.0 Experimental investigations methodology...............................................................................................13 5.1 Washing.................................................................................................................................................13 5.1.1 Water Washing...............................................................................................................................13 5.1.2 Bubble Washing.............................................................................................................................14 5.2 Characterization....................................................................................................................................15 5.2.1 pH...................................................................................................................................................15 5.2.2 Turbidity.......................................................................................................................................16 5.2.3 Mass Density................................................................................................................................16 5.2.4 Viscosity.......................................................................................................................................17 5.2.5 Calorie..........................................................................................................................................17 5.2.6 Gas Chromatography...................................................................................................................18 5.2.7 Cetane Number or Aniline Point..................................................................................................20 6.0 Limitations................................................................................................................................................21 6.1 Experiment...........................................................................................................................................21 6.2 Gas Chromatography............................................................................................................................21 6.3 pH.........................................................................................................................................................23 6.4 Density ................................................................................................................................................23 6.5 Turbidity...............................................................................................................................................23 6.6 Viscosity..............................................................................................................................................23 6.7 Calorie...................................................................................................................................................23 6.8 Cetane Number....................................................................................................................................23 7.0 Experimental investigations procedure.....................................................................................................24 7.1 Mixing..................................................................................................................................................24 7.2 Washing................................................................................................................................................24 7.2.1 Water Washing............................................................................................................................24 7.2.2 Bubble Washing..........................................................................................................................25 7.3 Characterization...................................................................................................................................25 8.0 Biodiesel Standard....................................................................................................................................27 9.0 Experimental investigation results............................................................................................................28 9.1 pH.........................................................................................................................................................28 9.2 Turbidity...............................................................................................................................................28 9.3 Mass Density.........................................................................................................................................29 9.4 Viscosity................................................................................................................................................29 9.5 Calorie...................................................................................................................................................30 9.6 Gas Chromatography............................................................................................................................30 9.7 Cetane Number or Aniline Point...........................................................................................................33 9.8 Performance Tested...............................................................................................................................33 10.0 Experimental investigation analysis and interpretation of results..........................................................34 10.1 Reacting Temperature .......................................................................................................................34 10.2 Amount of KOH..................................................................................................................................36 10.3 Types of Oil Used...............................................................................................................................37 10.4 Washing Method ................................................................................................................................39
11.0 Critical Evaluation..................................................................................................................................41 12.0 Process Flow Chart.................................................................................................................................43 12.1 Initial Industrial Process Flow Chart.................................................................................................43 12.2 Initial Experimental Process Flow Chart...........................................................................................44 .....................................................................................................................................................................44 12.3 Modified Process Flow Chart.............................................................................................................45 13.0 Process Description based on PFD.........................................................................................................50 14.0 Mass Balance..........................................................................................................................................51 15.0 Conclusions.............................................................................................................................................53 16.0 Recommendations...................................................................................................................................54 17.0 References...............................................................................................................................................55 18.0 Appendices..............................................................................................................................................57
1.0 Introduction
Biodiesel is considered as a clean and sustainable fuel, which is functionally equivalent to petroleum and a diesel fuel which is used commonly in our daily lives. It faces a lot of problem to be use commercially. To begin with, it made from crops which mean that it will take away the food supply from society. Then it will also cause more land being used that in turn will cause global warming as well. Its property of releasing higher emission of NOx is also its contributing factor of causing global warming. However, there are many advantages of using biodiesel. First of all, the vegetable oil, which is the material used for making biodiesel, is a renewable energy source. For this reason, we can reduce the dependence on foreign oil sources. Secondly, biodiesel is significantly cleaner than traditional diesels. EPA testing confirms using biodiesel instead of petroleum based diesels can lower carbon monoxide emissions by up to 48%. It emits up to 100% less sulfur dioxide and 80100%less carbon dioxide than traditional diesel. The most important thing is that the pure biodiesel is biodegradable and breaks down as fast as sugar. Thirdly, it is more efficient than alterative renewable fuels. It breaks down four times faster than regular diesel. Last but not the least, biodiesel has higher flash point than traditional petroleum, and is non corrosive for human contact. Therefore, it is safer to transport and handle. Because of all the reason above, we decide to do research on biodiesel and try to produce the maximize performance biodiesel by changing the production configuration.
Disadvantages
Low Energy Output - Require greater quantities to produce same energy level Higher NOx Emissions Cold Weather Properties - Gels on cold weather but depends on the oil properties, it could be solved by adding a fuel heater in the tank Using food resources Undesired Smell Grows Mold - solved by adding 1% of petroleum
According to Make Biodiesel (2010), Disadvantages of Biodiesel (2011), (Leray, 2011) Table 1. Advantages and Disadvantages of Biodiesel
2.3
Ingredients of Biodiesel
2.3.1 Oil
Source of oil can be from vegetable oil, animal fats, and used cooking oils. Making biodiesel with used cooking oil will lead to difficulty in determining exactly what kind of oil is being used since the oil could be from many different restaurants and mixed together causing difficulty in determining the cloud point. (Addison, 2011) Even it will make a cheaper cost in producing biodiesel, but it is too risky to be used remembering it affects the properties of biodiesel. Animal fats can not be renewable while it is one of the main points of biodiesel; vegetable oil is a good choice for producing renewable biodiesel. (Bioenergy, 2010) According to Make Biodiesel (2010), Saturated fats which are fatty acids without double bonds are holding an important role. The lower the saturated fat contents in the material, the lower the gel point of its biodiesel. Looking at figure2 and figure3, canola oil and sunflower oil have the least saturated fats which means lower cold filter plugging point, this will be good for four season country like Australia. Canola oil is the best oil for making biodiesel since it ages slowly, remains liquid to low temperatures, and has a high energy content. Canola oil is also being supported by Australia production, figure4 and table2 showed that production of canola oil in Australia has been increasing from year to year with holding the largest amount in canola seed production in year 2000 onwards. (Nelson, 2011)
2.3.2
Alcohol
Most primary alcohol used in biodiesel production are ethanol and methanol. Price of methanol is much cheaper than ethanol. Furthermore, since the unused alcohol must be recovered and recycled back into the process to minimize operating costs and environmental impacts, methanol will be a good choice since it is easier to be recovered than ethanol since it does not form aezotrope. (Addison, 2011)
2.3.3
Catalyst
2.3.3.1 Base catalyst: Most of the biodiesel produced today is done with the base catalyzed reaction for a number of reasons: It is low temperature and pressure. It yields high conversion (98%) with minimal side reactions and reaction time. It is direct conversion to biodiesel with no intermediate compounds. No exotic materials of construction are needed. 2.3.3.2 Acid catalyst It is too slow for industrial processing 2.3.3.3 Enzyme Catalyst Although enzyme catalysts such as lipases can be used in the production of the biodiesel, the commercial use of enzymes is limited. The rate of reaction is slower than other catalysts when using the enzymatic catalysts for the production of alkyl fatty acid esters, and yield to methyl esters are typically less than 99.7% required for fuel grade biodiesel. Furthermore, the costs of the enzymes catalysts are too high. Sodium hydroxide (NaOH) and Potassium hydroxide (KOH) are two common catalysts being used in biodiesel production. Compare to acid catalyst, base catalyst like NaOH and KOH is being used since it yields high conversion with minimal side reactions and reaction time, no intermediate compounds, and no exotic materials of construction needed. Even though NaOH is cheaper but since KOH is easier to use and does a better role, KOH is a better catalyst. (Addison, 2011)
2.4
Industrial Process
Figure 5. Continuous Process Flow The industrial scale of biodiesel production is achieved by using continuous stirred tank reactors (CSTR). In the first stage of this process, the based catalyst (KOH) along with Methanol will mixed first in the mixer to ensure the essentially constant composition throughout the reactor. This will increase the dispersion of the glycerol product in the ester phase. The mixture then goes through heat exchanger at 60C before they enter reactor. The transesterification reaction occurred in the reactor, where the pre-heated canola oil, the mixture of KOH and methanol is added. During this stage, the canola oil is reacted with methanol in exist of catalyst (KOH). In this process, the pressure should keep at 1atm condition and the reactor needs to be heated in order to keep the constant temperature of 60C. The products (biodiesel and glycerin), together with excess methanol, oil and KOH from the reactor will enter the settler. The main product, biodiesel, can be separated from the glycerin in the settler and then entered decanter at 65C for water washing. For purifying of the biodiesel, biodiesel with traces of water from the decanter then entered the flash evaporator where all of the water will be flashed off. Then pure biodiesel which exit the system at 45.8C can be collected as the final product. The neutralizing acid (H3PO4) is needed for the treatment of potassium hydroxide, methanol and glycerin from the settler. In this stage, the acid will react with KOH and formed KH2PO4. After filtration, glycerin and methanol can be separated from KH2PO4.the preheated glycerin and methanol at 100C will enter the flash evaporator at 56C for separating of methanol and glycerin. Methanol and water then enter the condenser before it goes to distillation column where water can be separated from methanol. In distillation column, water remains in the column as it has higher boiling point than methanol and can be recycled after it enters reboiler. The methanol from distillation column can be recovered and entered to the mixer in the first stage. (Gerpen & Clements, 2004)
5.2 Characterization
5.2.1 pH
pH is a measure of amount of acid in the solution. By measuring the pH in each biodiesel sample using pH meter, the acidity in each biodiesel sample can be compared. It is to know whether the biodiesel is corrosive or not. It is also can be used as an indicator whether further washing need to be done or not, if the pH of the biodiesel is more than 7, it means that the biodiesel is still not clean enough since there are still alcohols in it. But apparently, pH is not that significantly useful in this project to indicate the biodiesel product quality.
Figure 9. pH meter
5.2.2
Turbidity
Turbidity is a measure of the degree to which the solution loses its transparency due to the presence of suspended particulates. Higher turbidity means that there are more foreign particles mixed or suspended in the solution. Turbidity is being measured by measuring the amount light that passes through the solution. In this project, the turbidity of the biodiesel sample in batch 1,2,3,4, and 5 are measured to know the amount of concentration of free and total glycerol. Turbidity is measured using turbidity meter by ASTM.
Figure 10 . Turbidity Meter Measuring the turbidity of the biodiesel sample is important since there will be free and total glycerol left in the washed biodiesel, and this could affect the fuel quality in several ways. Biodiesel with excessive free glycerol usually causes problems with glycerol settling in storage tanks, creating a viscous mixture which can plug fuel filters and create combustion problems in engines. Residual glycerides in the biodiesel indicate incompleteness of the transesterification reaction into mono alkyl esters. High levels of mono-,di- and triglycerides in the biodiesel will cause injector deposits and adversely affect cold weather operation.
5.2.3
Mass Density
Mass Density is a measure of mass per unit volume. Denser oil contains more energy. It is an important design parameter for diesel fuel injection systems and is an area biodiesel are different from diesel. Biodiesel is denser than diesel fuel with sample values ranging between 877 kg/m3 (tallow methyl ester) to 884 kg/m3 (soy methyl ester)
compared with diesel at 835 kg/m3. Thus, it tells us that the density of the final product of biodiesel in each sample depends mostly on the feedstock used in each sample. It is important for this experiment to measure the mass density in each biodiesel sample, since comparison of different oil feedstock is conducted. Since the transesterification process has been found in some cases to reduce the biodiesel fuel density, density could also be used to know the completeness of the transesterification process. From the density measurement, the amount of lower density contaminants in the biodiesel such as methanol or ethanol also could be known, since it will decrease overall density of the fuel. Density dictates the energy content of fuel where high densities indicate more thermal energy for the same amount of fuel and therefore better fuel economy.
5.2.4
Viscosity
Viscosity is a measure of thickness of the biodiesel. It is determined by measuring the amount of time taken for given measure of biodiesel to pass through an orifice. Viscosity affects injector lubrication and fuel atomization. Biodiesel with low viscosity may not provide sufficient lubrication for the precision fit of biodiesel injection pumps which result in leakage or increased wear. On the other hand, biodiesel with high viscosity will cause poor combustion, increased exhaust smoke and emissions since it tends to form larger droplets on injection.
5.2.5
Calorie
The calorific value or heat of combustion of fatty compounds in the biodiesel determines the amount of energy generated by the combustion of a unit value of the biodiesel. Combustion is the reaction of the fuel with oxygen in the air which result in the release of heat. The force of the explosion caused by the reaction is what drives the pistons down in the cylinder, turning the crankshaft and eventually resulting in the wheels moving. The higher the calorific value,
the higher the amount of energy generated in the biodiesel. It is important to measure the amount of calorie in this experiment to compare which of the biodiesel sample gives a better heat of combustion. This parameter varies with different feedstocks, with similar compounds (containing similar long-chain, unbranched alkanes) having similar heats of combustion.
5.2.6
Gas Chromatography
Gas chromatography involves each of the biodiesel samples to be injected onto the head of the chromatographic column. The sample is transported through the column by the the flow of inert, gaseous mobile phase. The column itself contains a liquid stationary phase which is adsorbed onto the surface of an inert solid. Gas chromatography is used to measure free and total glycerol levels according to ASTM Standard D6751. It is used to measure the completeness of the reaction. Gas chromatography has to date been the most widely used method for the analysis of biodiesel due to its generally higher accuracy in quantifying minor components.
1. An injection port at one end of a metal column packed with substrate material and a detector at the other end of the column. 2. A carrier gas propels the sample down the column. Since the gas need to be not reacted with the sample or column to get reliable result, mostly the carrier gases used are hydrogen, nitrogen or helium. The carrier gas system also contains a molecular sieve to remove water and other impurities. 3. Flow meters and pressure gauges to maintain a constant gas flow.
Figure 14. The Splitless Injector To ensure proper separation, the sample must enter the column in a discreet, compact packet. The sample is injected into the injection port with a hypodermic needle and syringe capable of measuring the specimen amount. The needle is stuck into a replaceable neoprene or silicone rubber septum that covers the injection port. The injection port is maintained at a temperature at which the sample vaporizes immediately. The column is a metal tube, packed with a sand-like material to promote maximum separation. As the sample moves through the column, the different molecular characteristics determine how each substance in the sample interacts with the column surface and packing. The column allows the various substances to partition themselves. On the other hand, the substance which does not stick to the column or packing move through the column rapidly, they will be eventually elute from the column. Ideally, the various components in the sample separate before eluting from the column end. A detector is used to measure the different compounds as they emerge from the column. There are various types of detector which can be choose according the use, such as the argon ionization detector, flame ionization detector, flame
emission detector, cross section detector, thermal conductivity detector, and the electron capture detector.
5.2.7
Cetane number is measures of the readiness of a fuel to auto ignite when injected into the engine. It is generally dependent on the composition of the fuel and can impact the engines startability, noise level, and exhaust emissions. Cetane number also indicated the smoothness of the combustion process. Higher cetane number gives more easily and evenly combusted fuel, the higher the cetane number, the shorter the delay interval and the greater its combustibility. Fuels with low cetane numbers will result in difficult starting, noise and exhaust smoke. The cetane number of biodiesel depends on the distribution of fatty acids in the original oil or fat from which it was produced. The longer the fatty acid carbon chains and the more saturated the molecules, the higher the cetane number. It is important to measure the cetane number in this experiment to compare the combustibility and the readiness to auto ignites in each biodiesel sample.
6.0 Limitations
6.1 Experiment
There are some limitations in conducting this experiment. Firstly, when we measured the amount of KOH and methanol, the measurements can affect the results in the end. We have to make sure that the value is correct although it's not possible to get the exact value that we need. The temperature also needs to be checked every time. If the temperature reading was done wrong (less temperature required in heating), it will result an incomplete reaction. The ratio of methanol and KOH also need to be pressed on. If, less KOH and methanol used to make sodium methoxide solution, when it mixes with cooking oil, the reaction is incomplete and low quality biodiesel will be produced. In addition, constant speed , temperature and time are needed to achieve complete reaction and acquire high quality biodiesel after the heating and mixing. The washing processes are important in this experiment. Firstly, the speed of bubble washing has to be set in low speed in order to avoid emulsification and lot of soap. The speed of bubble washing also needs to be in constant speed. Secondly, the speed of water washing has to be rotated gently because we don't want to get lot of soap and less biodiesel resulted. After the washing, a new clean bottle required to do more washing repeated. If the bottle is dirty, there will be small amount of soap left in the bottle which will make the biodiesel not 100% pure (not very clear biodiesel and need to re-do the washing couple times). After we got really clear biodiesel and assuming no contaminates left in the biodiesel, the biodiesel have to be heated to make sure there is no water left in it and then the characterisation of the biodiesel can be conducted.
Worn Septum
Leaking septum will affect the GC instrument's sensitivity. If a portion of the specimen leaks back out of the septum, the amount of the specimen is not recorded. This event makes any eventual quantitative result erroneous. Furthermore, if air leaks into the injection port through a worn septum, the oxygen and water contained in air may skew the results. Any oxygen may react with the specimen components. If this happens, the GC instrument will provide results indicating the presence of this unintended reaction product, instead of the original compounds present in the specimen vial. Any water in the column adversely affects the GC instrument's ability to separate components.
Residual Impurities
Since ideally, all components of an elute completely from the GC column. If any substance remains inside the column, the substance may elute during subsequent analyses with other specimens. This may result in an unexpected peak in the output. The peak produced should be broad.
Carrier Gas
An unstable carrier gas flow rate may produce a drifting baseline and false broad peaks. Regular changing of the gas filter should prevent significant impurities. When the carrier gas thermal conductivity is in the range of the thermal conductivity of any compound in the specimen, a false peak may occur, so extra care is needed.
Crucial Factors
Records of GC instrument's make, model, serial number, injection temperature, column temperature, carrier gas flow rates and pressure, identify the type of detector used, and observe any manipulation of the data by use of a computer should be made. Ensure that the technician properly starts measuring the time at injection and records the time of elution. Any discrepancy in the time will produce an erroneous retention time.
6.3
pH
Wash the pH probe with distilled water before using it to measure the biodiesel to prevent false reading.
6.4
Density
Before using the density flask, make sure the density flask is clean, clean the density flask with ethanol and rinse it with water. Make sure it is completely dry by drying it with air. Since it will effect on the mass of the flask when it is being weighed on the balance, and this will produce false reading of density of the biodiesel.
6.5
Turbidity
Before using the turbidity meter, make sure the glass tube is really clean since it will effect on the way of the light to pass through the biodiesel. This event could cause false reading in the turbidity value.
6.6
Viscosity
When the temperature of biodiesel is below 5C, its viscosity will increase dramatically. The time recorded reading can affect the results.
6.7 Calorie
Make sure the string is touching the biodiesel sample otherwise, the result will be zero, since the calorie meter can not read the sample.
7.2
Washing
7.2.1 Water Washing
1. Put the biodiesel into a 1 L bottle. 2. Add water with ratio 1:1 compared to the biodiesel to the bottle. 3. Gently mix the solution by rotating it slowly and gently for 1 minute. 4. Let it settle for 10 15 minutes. 5. Separate the water and soap from the biodiesel. 6. Mix the biodiesel and water with ratio of 3:1 in the 500 mL separating funnel. 7. Repeat step 3-6 for 3 or 4 time until the water is clear and the pH close to 7. 8. Let it settle for 1 day. Once the mixture has settled, the biodiesel will be floating on top of the water. 9. Separate the clear water from the biodiesel.
7.2.2
1. 2. 3. 4. 5. 6. 7. 8. 9.
Bubble Washing
Put the biodiesel and water with ratio of 3:1 to the 500 mL separating funnel. Bubble it for 5 minutes. Let it settle for 5 minutes. Separate the water and soap from the biodiesel. Repeat step 1 4 for 6 times. Mix the biodiesel and water with 3:1 ratio in the separating funnel Bubble it for 5 minutes. Let it settle for 1 day. Separate the clear water from the biodiesel.
7.3
Characterization
pH 1. Place the biodiesel sample into a 100 mL beaker. 2. Washed the calibrated pH probe with distilled water and gently dry it with paper tissue. 3. Place the calibrated pH probe into the beaker. 4. Allow several minutes for the pH probe to settle and gain an accurate reading. 5. Once the value on the pH reader had become almost constant, the value is then recorded and analysed. Density 1. Wash the density flask with ethanol, and dry it. Make sure the density flask is clean. 2. Record the volume written in the flask and the mass of the density flask by weighing it. 3. Fill the density flask with the biodiesel until the volume of the flask had been occupied and the lid replaced. 4. Wipe any excess of biodiesel in the flask. 5. Record the mass of the flask and the biodiesel by weighing it. 6. Mass of biodiesel can be calculated by subtracting the mass of the flask and biodiesel from the mass of the density flask. 7. Density of the biodiesel can be calculated by dividing the mass of biodiesel by the volume of the flask. Turbidity 1. Place the biodiesel sample into a small tube (40 mL), sealed with a plastic lid.
2. Place the tube inside the turbidity meter. 3. Allow 4-5 minutes for the sample reading to become almost constant to get an accurate reading. Calorie 1. Place approximately 0.5 g of biodiesel sample into the circle metal plate. Record the mass of the biodiesel sample since it could be not exactly 0.5g. 2. Place it into the bomb calorimeter. 3. Allow 15 minutes for the sample reading. Gas chromatography 1. Dissolve the biodiesel sample in low concentrations in an organic solvent. 2. Add it to be injected to the syringe. 3. Inject it into the injector port. 4. Wait for a several minutes until the GS record several peaks. 5. After seen all of the peaks which suspected to be in the mixture, or when the recorder has shown a flat baseline for a few minutes, stop it. Viscosity 1. Biodiesel sample is poured into the viscometer. 2. Measure the time require for a volume of the biodiesel sample to flow under gravity through a calibrated glass capillary tube. Cetane Number 1. The test method covers the Calculated Cetane Index formula, which represents a means for directly estimating the ASTM cetane number of distillate fuels from API gravity and mid-boiling point. The index value, as computed from the formula, is termed the Calculated Cetane Index. 2. The Calculated Cetane Index is not an optional method for expressing ASTM cetane number. It is a supplementary tool to estimate cetane number when used with due regard for its limitations. 3. Then, record the cetane number from the test.
ASTM D2709 EN 14103 EN 14107 ASTM D664 EN 12662 ASTM D6584 ASTM D6584 EN14112 prEN 15751 5mg/kg Group I (Na, K) EN 14538 5mg/kg Group II (Ca, Mg) (Group I) EN 14538 (Group II) 0.20%(m/m) EN 14110 if the biodiesel contains no EN ISO 2160 more than ASTM D130 10 mg/kg of sulfur - Class 1 (max) ASTM D130 if the biodiesel contains more than 10 mg/kg of sulfur - No. 3 (max) 51.0 (min)
Cetane number or Derived cetane number Table 3. Australian Biodiesel Standard according to Australian Government, 2009.
18 Sep 2005
Batch 1 is being heated only up to 25 C, while the others batch are being heated at 60 C.
9.1
pH
Batch 1 2 3 4 5 Table 4. pH value PH 4.6 4.54 4.77 5.08 4.31
9.2
Turbidity
Batch 1 2 3 4 5 Table 5. Turbidity value Turbidity (NTU) 2.2 1.45 1.65 1.95 1.75
Batch 1 2 3 4 5
Table 6. Mass of Biodiesel Batch Mass Density (g/cm3) 1 0.885966 2 0.882029 3 0.882029 4 0.878199 5 0.878091 Table 7. Mass Density value
9.4 Viscosity
Kinematic Viscosity = Viscosity/Density Mass Density (g/cm3) 1 0.885966 2 0.882029 3 0.882029 4 0.878199 5 0.878091 Table 8. Kinematic Viscosity value Viscosi Kinematic ty Viscosity (Pa.s) (mm2/s) 0.0141 12.492121 0.0057 5.0275653 0.0052 4.5865508 0.0034 2.9858766 0.0059 5.1807369
Batch
http://www.bdpedia.com/biodiesel/char/char.html
9.5 Calorie
Batch Calorie (MJ/Kg) 1 39.6 2 39.32 3 38.727 4 38.67 5 39.18 Table 9. Calorific Value
9.6
Gas Chromatography
Cetane Number 65 96
Figure 16. Gas Chromatography of Batch 2 The comparison of reacting temperature is done in this experiment by differing the reacting temperature at 25 C and 60 C. This comparison is used to determine which of the reacting temperature is best to produce a better biodiesel product. Looking at the results of Gas chromatography and turbidity in batch 1 and batch 2, it can be seen that there are more contaminants (free and total glycerol) in batch 1. Since the turbidity in batch 1 is higher than batch 2, the GC graph in batch 1 is also having lots of peaks. The kinematic viscosity in batch 1 is also much higher than viscosity in batch 2 where the viscosity of batch 2 is in the range of the Australian biodiesel standard. High viscosity which is already mentioned before, if the viscosity is too high, it will cause poor combustion, increased exhaust smoke and emissions since it tends to form larger droplets on injection. Though, the density value and the calorie or the heat energy in batch 1 is slightly higher than batch 2, which means there are more thermal energy for the same amount of fuel in batch 1 compare to batch 2 and therefore batch 1 is better fuel economy. Furthermore, after testing the biodiesel sample in an engine, the performance of batch 2 is better than batch 1. From here, it can be concluded that batch 2 is better than batch 1, which means the reacting temperature used is better at 60 C than 25 C. Even though, there are slightly more thermal energy in batch 1, but since there are lot of contaminants in the biodiesel, and high viscosity which could affect the environment, we can say the performance of batch 1 is not as good as batch 2. It was also proven from the trial of performance in a device and the cetane number, where batch 2 had the shorter ignition time than batch 1.
Batch 2 4
In order to get a comparison between the amounts of KOH should be used, in this project; the biodiesel sample was differed from using 2.5 g and 3.5 g of KOH. This comparison was used to know how much of KOH is better to be used to get a better biodiesel product. From the results of Gas chromatography and turbidity in batch 2 and batch 4, it can be seen that there are more contaminants (free and total glycerol) in batch 4. The kinematic viscosity in batch 2 is higher than the kinematic viscosity in batch 4, though the kinematic viscosity at both sample are in the range of the Australian Biodiesel Standard which is from 3-5 mm2/s. Furthermore, the density value and the calorie or the heat energy in batch 2 is higher than batch 2, which means there are more thermal energy for the same amount of fuel in batch 2 compare to batch 5 and therefore batch 2 is better fuel economy. From here, it can be concluded that batch 2 is better than batch 4, which means the better amount of KOH as catalyst used is 3.5 g compare to 2.5 g.
Batch 3 5
Figure 19. Gas Chromatography of Batch 5 In order to compare the difference of the biodiesel performance for using different oil used, canola oil and sunflower oil, we conduct 2 experiments for production of biodiesel. In Batch 3, 400ml of sunflower oil is reacted with 3.5g KOH, and 80ml of Methanol. In batch 5, 400ml of canola is reacted with same amount of KOH and methanol under the same condition. By comparing the results of gas chromatography and turbidity in batch 3 and batch 5, it can be seen that biodiesel produced from Canola oil has more contaminate than the one in batch 3. The calorie of the batch 5 is slightly higher than the one in batch 3, which results a higher thermal energy for the same amount of fuel in batch 5 compare to batch 3. On the other hand, the viscosity of biodiesel in batch 5 is higher than the one in batch 3, shows that the biodiesel produced from batch 5 has a poor combustion, increased exhaust smoke and emissions as it tends to form larger droplets on injection. Furthermore, the mass density of biodiesel in batch 3 is higher than the one in batch 5. This means that biodiesel produced from sunflower oil has a better performance than using canola oil since it has a higher thermal energy for the same amount of the fuel. In conclusion, the biodiesel performance produced from sunflower is better than produced from canola oil.
Batch 2 3
Turbidity Mass Density Viscosity Calorie pH (NTU) (g/cm3) (mm2/s) (MJ/Kg) 4.54 1.45 0.882029 5.0275653 39.32 4.77 1.65 0.882029 4.5865508 38.727 Table 15. Properties of Batch 2 and Batch 3
Kinematic
Cetane Number 96 75
Figure 17 . Gas Chromatography of Batch 3 It is important to wash the crude biodiesel for removing the impurities such as methanol and KOH. In this project, we invest two washing method including water washing and bubble washing. By looking at the results of gas chromatography in batch 2 and 3, it can be seen that the free and total glycerol levels in batch 2 is slightly higher than the one in batch 3, which means biodiesel using the bubble washing method gives a purer results although both of them are pure compare to batch 1, 4, and 5. As shown in the results, the value of calorie for the biodiesel obtained using water washing (39.32 MJ/Kg) is greater than the one using bubble wash. This show that the amount of energy generated from biodiesel in batch 2 is higher than the one in batch 3. As discussed above, the higher the density value, the more thermal energy for the same amount of fuel. The density of biodiesel in batch 2 is also larger than the one in batch 3. Therefore, we can conclude that the performance of biodiesel purified using water washing is better than using bubble washing.
Cetane Number 65 96 75 72 78
As we can see, batch 2 which consist of 400 ml sunflower oil, 3.5 gram of KOH, and 80 mL of methanol is the best biodiesel achieved from our experiment. The number of pH is not really important but the value is not really correct. This is because the pH testing only works in solutions that contain water. pH testing dry oil or dry biodiesel does not work. Therefore, the erratic readings acquired are totally meaningless. pH testing the wash water or wet biodiesel or wet oil will work. The turbidity of the biodiesel sample also shown that batch number 2 is the best biodiesel. Only small amount of turbidity (1.45) compared to the others. That means batch 2 will be quite free and low glycerol left. Biodiesel with excessive free glycerol will cause problems in storage tanks and create combustion problems in engines. Although the reaction was complete, there are still some residual glycerides left in the biodiesel which means the reaction of transesterification was slightly incomplete. It will also affect the machine operated in cold weather. The mass density shown that all of 5 batches are contained varied in biodiesel standards. The biodiesel high quality standards are between 860 890 kg/m3. This means that different oil feedstocks, different mass density resulted. It is also important to know the completeness of the transesterification process. From density measurement, the amount of lower density contaminants in biodiesel could be known since it will decrease overall density of the fuel. Density will affect the energy content of the fuel where in our case, batch 2 will have more energy therefore it has better fuel economy. Kinematic Viscosity could be calculated by dividing viscosity with the density of the samples. As we can see, batch 2 is the best in kinematic viscosity value. The standards range for kinematic viscosity is 3.5 5 mm2/s. Although batch 3 and 4 are also in the standards range, batch 2 is still is the best because low viscosity shown that it may not provide sufficient lubrication for biodiesel injection pumps which result in leakage or increased wear whereas higher viscosity will cause poor combustion, some exhaust and emissions increased since it tends to form larger droplets on injection. So, batch 2 is still very good since it's acceptable between 3.5-5 mm2/s standards and higher than batch 3 and 4. The calorie of batch 2 is the 2nd highest compare to others. But still, it can be said as
high quality biodiesel. 39.32 MJ/kg determines the amount of energy generated by the combustion of biodiesel. The high amount of calorie means the higher energy generated. Although batch 1 is the best in this calorie case, but the other factors such as turbidity and kinematic viscosity are not in high quality standards for biodiesel. The minimum value of cetane number is biodiesel high quality standards is 51. Basically, 5 of our batches shown that they are ready to ignite when biodiesel are injected into the engine. But, batch 2 has the highest cetane number which means that it has very smooth combustion process and more easily combusted. Furthermore, it has shorter delay interval which means very good to the car performance. Fuels with low cetane number will result in difficult starting, noise and exhaust smoke. The water washing is the best by comparing the results using bubble and water washing at gas chromatography. It can be seen that the free and total glycerol levels in batch 3 is slightly higher than the one in batch 2, which means biodiesel using the water washing method gives a purer results although both of them are pure compare to batch 1, 4, and 5. When we lower the amount of KOH, the results are not really good biodiesel quality. It means that the reaction is incomplete. It needs more catalyst to react completely. So, the ratio of KOH methanol and oil must be calculated to get an excellent biodiesel quality. The sunflower oil is better compared to canola oil from the result in this experiment. But, from the literature review, canola oil is the best to produce biodiesel. This is because the supply of canola oil is much more compared to sunflower seed oil. So, the cost of sunflower seed oil is more expensive than canola oil although the performance of sunflower seed oil is better than canola oil. When we test couple drops of B80 biodiesel with small car, batch 2 have the best ignition time. The engine started for 12 seconds compared to other batches which only started for 4-7 seconds. But, the engine won't ignite for B90 and B100. The cause of this can be because the quality of the biodiesel is not really good. There is some contaminates left in biodiesel (not 100% pure) and therefore the engine will not ignite. The other reason is that the heat combustion was a bit poor since the exhaust and emission increased; therefore it tends to form larger droplets on injection.
Equipment List
Displayed Text
E-10 E-11 E-12 E-13 E-14 E-15 E-16 E-17 E-18 E-19 E-3 E-8 E-9
Description
Biodiesel- Water Separator 1 Mixer Oil Pre-Heater Washer-2 Biodiesel- Water Separator 2 Washer-3 Biodiesel- Water Separator 3 Washer-4 Biodiesel- Water Separator 4 Biodiesel Heater Reaction Vessel Washer-1 Biodiesel -Glycerol Separator
Manufacture r
Materia l
Model
Mass Balance in Reactor S_01 Oil Biodiesel glycerol methanol water KOH 371.2 0.00 0 0 0 0 371.20 S_02 0 0 0 63.28 0 3.5 66.78 Total 371.20 0.00 0.00 63.28 0.00 3.50 437.98
Conversion 100% mol MWt in Stoich. 885.50 296.50 92.00 32.00 18.00 56.11 0.419 0.000 0.000 1.978 0.000 0.062 -1.0 3.0 1.0 -3.0
Oil + 3 methanol --> 3Biodiesel + glycerol Limiting -4.19E01 Change -0.419 1.258 0.419 -1.258 0.000 0.000 mol out 0.000 1.258 0.419 0.720 0.000 0.062 S_04 0.00 372.88 38.57 23.04 0.00 3.50 437.98
-6.59E01
4.192E01
SEP-1 Oil Biodiesel glycerol methanol water KOH S_04 0 372.8768 38.56623 23.03697 0 3.5 437.98 Total in 0 372.8768 38.56623 23.03697 0 3.5 437.98 Splits 0.99 0.00 0.99 0.00 0.00 0.00 S_06 0.000 0.000 38.181 0.023 0.000 0.004 38.207 wt% 0.0% 0.0% 99.9% 0.1% 0.0% 0.0% 100% S_05 0.00 372.88 0.39 23.01 0.00 3.50 399.77 wt% 0.0% 93.3% 0.1% 5.8% 0.0% 0.9% 100%
15.0 Conclusions
Overall, Biodiesel has many advantages due to environment and the economy in the world. It reduces engine friction and heat and the most important part it is biodegradable. Engines fueled with biodiesel blends will emit lower CO, CO2, particulate and hydrocarbons. It can be produced from many vegetable oil or animal fat feedstocks. Conventional processing involves transesterification where triglyceride which can be found in vegetable oils or animals fats are being converted into chemicals called long-chain mono alkyl esters or biodiesel. The triglyceride is reacted with alcohol in the presence of a catalyst. The process produces two products which are methyl esters the biodiesel and glycerin, a sugar which is the byproduct that can be used in other products. The purpose of this report is to produce high quality of biodiesel by using different variables such as different feedstocks, different catalyst, different alcohol used, different washing techniques, etc. In conclusion, Biomax pty ltd recommend using sunflower seed oil as the feedstocks with 400 mL oil, 80 mL methanol, and 3.5 gram potassium hydroxide to create an excellent biodiesel quality. The biodiesel production will be conducted by mixing the KOH and methanol to create the methoxide solution and heating the oil and mix it with the methoxide solution for 60C for constant speed. Let it settle for 1 week and drain the glycerol and start the next step which is washing step. Water washing is the best to wash the impure biodiesel to remove the particulates and soaps. Wash it for 3-4 times until the biodiesel is very clear. The last step is to characterize the biodiesel and compare it with the high quality biodiesel standards. The tests were consisted of pH, turbidity, mass density, kinematic viscosity, calorie and cetane number tests. The tests shows that 400 mL sunflower seed oil, 80 mL methanol, and 3.5 gram potassium hydroxide were the best to produce high quality biodiesel. However, it only works for B80 biodiesel (80% biodiesel and 20% diesel).
16.0 Recommendations
Equipment recommendations: In order to optimization of the process, a simple heat exchanger system replacing a heater and cooler is recommended and extremely beneficial. Furthermore, for producing high grade purity of biodiesel product, using a DES system of choline chloride and urea is suggested for purification of biodiesel instead of just using water washing step. As a result of using methanol as one of reactants for biodiesel production, further methanol recovery equipment is suggested. Process recommendations: Potassium hydroxide is a better choice as a catalyst for biodiesel production. Sunflower oil is chosen as a solution through this project. However, an alternative oil source can be used depends on the location of the plants in the regions. The recommended reaction time is between 1 to 8 hours in order to process the reaction completely. Poor results obtained from bubble washing technique. It is easy to do bubble washing for removing contaminates of the products. However, it takes a lot of times for completing the washing steps. Water washing technique is recommended compare to bubble washing. Furthermore, if the reaction is not process far enough, the unconverted triglycerides remains in the unwashed biodiesel will convert to diglycerides and monoglycerides while washing, which will cause emulsion when washing the biodiesel so that it wont separate from the wash water. The wash test and the methanol test is recommended prior of the washing step to check whether the process went far enough or not. Economic Recommendations: In order to minimizing the equipment, operating, and maintenance costs throughout the whole biodiesel production process, the number of equipment is always recommended in a process as long same or better results are obtained. An alternative oil selection is recommended upon on the plants location in the regions.
17.0 References
Australia Government, 2009, Summary of the Current Biodiesel Fuel Quality Standard, viewed 17 March 2011, <http://www.environment.gov.au/atmosphere/fuelquality/standards/biodiesel/summary.html> Addison, K, 2011, Make Your Own Biodiesel, Journey to forever, viewed 10 March, 2011, <http://journeytoforever.org/biodiesel_make.html#biodnew> Animal fat, 2010, Bioenergy WIKI, viewed 10 March 2011, <http://www.bioenergywiki.net/index.php/Animal_fat Biodiesel Basics, 2011, National Biodiesel Boards, viewed 11 March 2011, <http://www.biodiesel.org/resources/biodiesel_basics/> Biodieselkits, 2011, Quality BioDiesel Specifications, viewed 20 March 2011, <http://www.biodieselkits.co.uk/quality-biodiesel-specifications/> Disadvantages of Biodiesel, 2011, Energy Revolution, viewed, 11 March 2011, <http://www.energyrevolution.co.za/index.php> Douglas, F, 2009, GC/MS Analysis, viewed 20 March 2011, <http://www.scientific.org/tutorials/articles/gcms.html> Gerpen, J & Clements, D, 2004, Biodiesel Production Technology, National Renewable Energy Laboratory, viewed 14 March 2011, <http://www.scribd.com/doc/20244579/Modified-Biodiesel-Production-Manual> Green Trust, 2010, Wash Biodiesel, viewed 20 March 2011, <http://www.green-trust.org/washing_biodiesel.htm>
Jon Van Gerpen, 2011, Cetane Number Testing of Biodiesel ,viewed 15 March 2011, <http://www.biodiesel.org/resources/reportsdatabase/reports/gen/19960901_gen-187.pdf>
JhaKrittikaSwamee, M K & Sharma T, 2010, Study of Biodiesel Viscosity variation with temperature, viewed 17 March 2011, <http://www.scribd.com/doc/52319423/Biodiesel-Basics-Viscosity> Leray, C, 2011, Biodiesel, Cyberlipid, viewed 12 March 2011, <http://www.cyberlipid.org/glycer/biodiesel.htm> Makes Biodiesel, 2010, viewed 12 March 2011, <http://make-biodiesel.org/> Nelson, R& Barrett, 2011, Future of Canola Production in Australia, viewed 12 March 2011, <http://adl.brs.gov.au/data/warehouse/pe_abarebrs99000657/PC11874.pdf> Rickdatech, 2011,Make Biodiesel, viewed 13 march 2011, <http://www.make-biodiesel.org/Quality-Testing/homebrew-tests-listed.html#N2>
Sheffield Hallam University, 2009, Gas chromatography, viewed 25 March 2011, <http://teaching.shu.ac.uk/hwb/chemistry/tutorials/chrom/gaschrm.htm> Yanowitz, J & Nelson, R, 2009, Biodiesel Handling and Use Guide, fourth edition, viewed 15 March 2011, <http://www.nrel.gov/vehiclesandfuels/npbf/pdfs/43672.pdf>
http://www.bdpedia.com/biodiesel/char/char.html
18.0 Appendices
Figure 24. Separation of Biodiesel at the top and glycerol at the bottom
Figure 25. Biodiesel After Washing at the top and waste water at the bottom