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again. The advantage to this process is that it is closed cycle contributing no net increase of green house gasses, unlike the open cycle system utilized today.
THEORY: In this lab, we center our attention on processing raw fuel, triglyceride into
a more refined product, fatty-acid- methyl-esters, which are better suited to the currently available energy conversion technologies available today.
The reaction pictured above in Figure 1 is carried out by mixing KOH with Methanol to form the strong organic base Methoxide. Methoxide solution is added to Triglyceride with heating and stirring to complete the reaction. The reaction proceeds via the following nucleophillic substitution mechanism.
Reaction Mechanism
O C C H2 O H2 C
O C O H3C O-
Methoxide
O C C H2 H3C OO
O C C H2 O CH3
HO HO HO
CH2 CH CH2
Methyl Ester
Glycerol
Unfortunately, life is not that simple. All chemical reactions are theoretically reversible and this one lends a significant reality to that theory. The reverse reaction is possible via a similar nucleophillic mechanism.
Methyl Ester
O C C H2 HO HO HO O CH2 CH CH2 CH3
C H2 O C O HO CH2 CH CH2 HO CH3
Methanol
Glycerol
HO
Mono-Glyceride
Thus, there are three linked equilibrium relationships being modeled. This leads to six Arrhenius dependent kinetic parameters as one would expect from the Reaction Kinetics classes. Using experimental data to determine the kinetic parameters the following reaction model can be derived.
kf 1
This model will give an idealized optimal reaction time given perfect mixing, the first assumption on which modeling assumption are based upon. The trans-esterification reaction is mildly exothermic; an isothermal approach to the kinetics is a valid assumption.
PRELIMINARY PREPARATIONS:
Using a basis of 500 ml oil, the first assignment to be completed before pre-lab is, given the following physical properties, determine the amount of Methanol and KOH that need to be mixed for a stoichiometric conversion. The density of Methanol and vegetable oil are 0.79 g/ml and 0.9 g/ml respectively. Use 885 g/mole as an average molecular weight for the vegetable oil. From your stoichiometric calculations, we are going to double the amount of Methanol, and be prepared to explain why were going to do this. Second, were going to double the amount of base as well due to the fact that some of the triglyceride breaks down naturally leaving free fatty acids in the oil. This free acid will use up your Methoxide and not leave enough for adequate conversion of the Triglyceride into Methyl-Ester. High fatty acid content in used oil leads to other problems as well. Base catalysis cannot convert free fatty acids into Methyl-Esters. To convert free fatty acids, an immobilized Sulfuric acid catalyst system can be used.
SAFETY PRECAUTIONS:
The mixing of Methanol and KOH is highly exothermic and must be carried out in the hood without heating. The KOH will dissolve with stirring. Those little bubbles you see if you mix too much too fast are methanol vapor that is just as hazardous as the liquid.
Appropriate eye protection and chemical resistant gloves are required at all times. Look up safety sheets for all chemicals that will be used.
EQUIPMENT:
See Diagram
PROCEDURE:
To introduce the experiment a small batch reaction is first carried out. Under the hood in the lab a 500 ml sample of vegetable oil is heated to 50 C in a water bath. While the oil is heating up, KOH is dissolved in Methanol. In large scale operation, it is advisable to pretest the oils acid content prior to reaction to ensure enough catalyst is utilized. The mixing of Methanol and KOH is highly exothermic and must be carried out in the hood without heating!! The KOH will dissolve with stirring. Those little bubbles you see if you mix too much too fast are methanol vapor that is just as hazardous as is the liquid. Appropriate eye protection and chemical resistant gloves are required at all times when handling Methanol and KOH. The Methoxide, once mixed, can be poured into the flask containing the oil. Upon pouring the Methoxide into
the oil you will see two distinct phases. A polar phase will be seen on top of a lipid phase. With stirring, a homogeneous phase will be observed, but in reality if one was to look on a sufficiently small scale one would see a dispersed phase in which small spheres (why spheres?) of the minority component in a sea of the main constituent. The size and quantity of the spheres are inversely related and will follow a rectangular hyperbola in shape as the Reynolds number is increased. Since the reaction can only occur at the interface of the two phases it makes sense and has been shown experimentally that the kinetic rate constants follow the same rectangular hyperbola as does the total surface area. The reaction is run for an hour at 50 C with the magnetic bar spinning at least 300 rpm. At the end of the reaction the heating and stirring are stopped, and within 5-10 minutes two phases will be seen to develop. What reaction components will be found in each phase? Where is your product? For the next lab period the large reactor (water heater) will be utilized. The basis for your calculations will be 50 gallons of used vegetable oil from various UCONN food establishments. We will maintain the same methanol ratio as the small batch reaction. Since there is variability in the acid content of used oil you will first titrate a small representative sample to determine its acid content. First, dissolve 1.4025 gm of KOH in 1 liter of distilled water (0.1% w/v KOH solution, weight-to-volume). In a smaller beaker, dissolve 1 ml of the oil in 10 ml of pure isopropyl alcohol. Warm the beaker gently by standing it in some hot water, stir until all the oil dissolves in the alcohol and turns clear. Add 2 drops of phenolphthalein solution. Using a graduated syringe or a pipette, add 0.1% KOH solution drop by drop to the oil-alcohol-phenolphthalein mixture, stirring all the time. It might turn a bit cloudy, keep stirring. Keep on carefully adding the KOH solution until the mixture starts to turn pink (magenta) and stays that way for 15 seconds. Take the number of milliliters of 0.1% KOH solution you used and add 4.908 (the basic amount of KOH needed for virgin oil). This is the number of grams of KOH you'll need per liter of the oil you titrated. Scale the quantity of KOH needed up to 50 gallons of oil. The quantity of Methoxide that needs to be mixed cannot be made at once due to the exothermic nature of the reaction. Methanol is obtained from the 55 gallon drum in the flammable liquid locker; it is transported to the hood in a 20 liter poly-propylene carboy. Methoxide is mixed in a six liter Erlenmeyer flask in the hood. 5.5 liters of Methanol is added to the flask which is then placed on the stirrer. About 600 grams of KOH will be added to the flask at a maximum of 100 g at a time to allow the heat of dissolution to dissipate. About 15-20 minutes per flask will be the quickest you will be able to complete this procedure. Once mixed, remove the stirrer and carry the flask over to the Methoxide tank and pour it in. replace the cap on the tank to prevent Methanol vapors from escaping into the room. Repeat this procedure for as many times as needed then dilute to the desired amount with pure Methanol. The reactor is an 80 gallon hot water heater with the upper heating element disconnected (why?). Oil is pumped into the reactor via the fitting in the circulating loop. There is a vent line that must be opened at all times when the reactor is being filled or emptied (why?). The heating element is never turned on without the tank at least half full and the circulating pump on. Mixing in the reactor is accomplished only via the circulating pump, and the valves must be configured accordingly to allow this. Once the
oil is at 120 F, Methoxide is added to the reactor when the circulating pump is on by closing the valve from the reactor to the pump and simultaneously opening the valve from the Methoxide tank to the pump. While Methoxide is being pumped into the reactor, the line from the vent is placed into the Methoxide tank so that if you did not calculate volumes correctly, your spill will be contained. Once all of the Methoxide is in the reactor close the reactor vent (why?). Your group needs to come up with an estimate as to how long to run the reaction. At the end of the reaction turn the heating element off. Open the vent and pump the contents of the reactor over to the cone tank by opening and closing the appropriate valves. Phase separation will occur over the next half hour. Your waste phase can be transferred to one of the 30 gallon drums in the plastic oval tank. Your product is now partially converted due to the equilibrium nature of the reaction, probably 75 85 % converted based on your recipe utilized. To attain fuel of ASTM quality it must be reacted again with stoichiometric KOH and Methanol via the same procedure. At the end of the second reaction, there will probably be only one phase as you will most likely not generate enough Glycerol to allow the formation of two phases. We will use water as a stripping agent in the cone tank to remove any water soluble components (what are they?) from the Methyl-Ester product. Using the sprinkler and water from the sink add an equivalent volume of water to the product. It will look like white rain falling through the Ester layer. Once enough water is added it is pumped off into the sink taking care not to pump product out of the cone tank. This process is repeated at least 3-4 times, until the water in the tube is clean enough to see through. At this point the fuel is clean, but wet. We now use compressed air to bubble air through the Ester to dry the fuel. This takes 1-2 days to complete. The more bulk water you remove prior to initiating the air, the sooner your fuel will be dry enough for use. As your fuel dries, a few possible outcomes are possible. Good starting material will yield good clean fuel. Fuel with high fatty acid content will precipitate fatty acids as the emulsion is broken by drying the fuel. This precipitate must be removed prior to use as it will clog the fuel filter. The second possible complication is that if the oil was thermally abused in the cooking process it may be fully saturated rather that partially unsaturated. This raises the cloud point of the fuel such that it may actually solidify in the tank. Both phenomena have been observed here with university oil.
ANALYSIS:
What type of reactor is the large reactor? What type of unit operation is the washing step? Why does air dry the fuel? Would the fuel dry without compressed air? Describe the mass transfer that is occurring in the reaction, the washing, and the drying operations? How does mass transfer affect the overall kinetics of the reaction? Is the final equilibrium conversion a function of mass transfer? Explain in terms of Gibbs energy why we see two phases?
What is the catalyst being used in the experiment? How does the presence of a catalyst affect the conversion? How does the presence of a catalyst affect the kinetics? What part of Methoxide, Methanol or KOH, determines the equilibrium conversion? What part of Methoxide, Methanol or KOH, is responsible for its catalytic effect? To make this process commercially viable you would need to recover excess Methanol from the product and discarded phases, how can you do this? To make this process commercially viable you would need to make this a continuous process. How could this be done? Sulfuric acid immobilized catalyst kinetics are slower and the equilibrium conversion is less than that of base catalysis. Its advantage is that it can catalyze free fatty acids. Choose the appropriate unit operation and describe the ratios of feed stock to Methanol relative to the base conditions utilized in this lab. Can reaction and separation occur in the same unit operation? Could this be advantageous? This reaction can be run with ethanol but it must be 99% anhydrous. Ethanol has an azeotrope with water at 95%. What is an azeotrope? How can we obtain 99% pure Ethanol? In the analytical section of the Senior Lab Biodiesel experience, you will be introduced to gas chromatography as an analytical tool. You will be taught how to use gas chromatography to derive concentration vs. time plots like the following.
Using the species concentration vs. time data utilized to develop graphs like this and the differential equations seen in the Polymath model, how can the kinetic parameters be determined?
REPORT:
Describe the design of your experiment and your results (including a discussion of their precision and accuracy). Provide thoughtful and quantitative discussion of results, explain trends using physical principles and relate your experimental results to accepted empirical values from literature or predicted from theory. Express any discrepancies between observed and expected results in terms of quantified experimental uncertainties or limitations in published values or theory. You may find it useful to answer the questions in the analysis section above to help complete your report.
REFERENCES:
1. G. Knothe et. al. The Biodiesel Handbook. 2005.