Chapter 5: Conclusions and Future work
5.2 Future work
Future biodiesel synthesis studies can be pursued in the following three directions:
1. The effect of biodiesel decomposition under different non-catalytic conditions There is evidence that decomposition products will improve some biodiesel physical properties, for example cold flow property and viscosity. But there is not a systematic study which provides enough data to show exactly how biodiesel decomposition effects the quality of biodiesel fuel. It would be valuable to pursue studies in this direction.
2. How the component of gas product change with reaction conditions
Under non-catalytic condition, there will be gas biodiesel decomposition products produced with liquid products. There is little study which describes how the gas product components change with reaction conditions. It is necessary to understand the
decomposition products formed in order to optimize reaction conditions at which there will be a maximum yield and less decomposition.
3. The effect of water in methanol/ ethanol
One big problem biodiesel industrial production faces now is the high cost of feedstocks which are of good quality triglycerides and the use of dry alcohol. Microalgae shows great potential to provide cheap and good quality oil. To further lower the cost, it is necessary to avoid using expensive dry alcohol. Considering that biodiesel synthesis under supercritical conditions is tolerant to water content, it would be valuable to study how different water content effects biodiesel product quality and the synthesis process under supercritical conditions.
Appendix A: Flow rates of methanol and triolein in Chapter 3
The flow rates of methanol and triolein were calculated according to the molar volume of reactants mixture, the volume the reactor, and residence time. The molar volume was calculated using Peng-Robinson equation of state.
( ) ( ) Where ω is the acentric factor, R is the universal gas constant. For a mixture of two pure components i and j, the mixing rule applied here is (Prausnitz, Lichtenthaler, & de Azevedo, 1999):
Using the equation above, we can calculate the value of V, the molar volume of the mixture under 150bar, 385℃. The value is:
3
0.432 m V kmol
Because the volume of the reactor is 9.65 ml, according to each residence value, the mole flow rate and volume flow rate of methanol and triolein were calculated and listed in the following table. Table A1 describes the flow rates of methanol and triolein at each specific reaction condition.
Table A1 Flow rates of methanol and triolein at different residence time.
Run
Appendix B: Calibration functions in Chapter 3
ASTM D-6584 was applied to determine the concentration of glycerol, monoolein, diolein, and triolein in samples. First, it is necessary to construct calibration curves for each component. The standards solution component concentrations and corresponding peak areas from gas chromatography are shown in Table B1. For each reference substance, response ratio (rspi) and amount ratio (amti) are calculated using Eq.B1 and Eq.B2:
( / )
The calibration curves for each component were prepared by plotting the response ratio (rspi), as the y-axis, versus the amount ratios (amti), as the x-axis. The linear equations are in the form:
/ ( / )
i is x i is x
W W a A A b (B3) Where ax and bx are slope and intercept of the calibration function, respectively.
Fig. B1 shows calibration curves of each component according to data in Table B1.
Table B1 Peak report of standard solutions.
Component Glycerol Monoolein Diolein Tiolein I.S. 1 I.S.2
mass
Fig. B1. Calibration curves of glycerol, monoolein, diolein, and triolein.
Table B2 shows peak areas of each component in samples made from run 1 to run 4. The data of run 1, run 2, run 3, and run 4 in Table 3-1 in Chapter 3 was calculated by the calibration equations shown in Fig. B1 according to the data provided by Table B2.The peak report of Mr.
Tao Cong’s (Cong & Tavlarides, 2010) work is not shown here.
Table B2 Peak reports of biodiesel samples.
Run
Appendix C: Calculation of mass balance over the reactor in Chapter 3 The example provided below is based on the first set of data in Table 3-1.
According to residence time and the molar ratio of 9:1, feed flow rate of triolein and methanol was determined. Assume the feed flow rate of methanol and triolein is m t g/min and
3.073m t g/min, respectively. In t min, there will be m g methanol and 3.073m g triolein flowing into the reactor. Say these amounts of feedstock generate n g ester phase product. Take the residence time of 0.5 min as an example (weight percentage data from Table 3-1).
Fig. C1. Mass balance diagram. The example provided is based on the first set of data in Table 3-1.
In the diagram above , each molecule of triolein will either be unreacted or reacted with methanol to produce either one molecule of diolein and an ester molecule, one molecule of monoolein and two ester molecules, or one molecule of glycerol and three ester molecules. So the mass balance of triolein is:
Initial triolein = unreacted triolein + triolein to produce monoolein + triolein to produce diolein + triolein to produce three ester or one glycerol, which is further described as:
0.0112 0.1615 0.509
3.073 0.3155 885.4
356.54 621 3 296.49
n n n
m n (C1)
Also one molecule generated methyl oleate means one molecule methanol was consumed. So the mass of consumed methanol is : (0.509n 296.49) 32 g. So the mass of unreacted methanol is: m(0.509n 296.49) 32 g.
From Eqn. C1, m n0.3515.
So the weight fraction of each compound is calculated from the following equations:
Triolein:
Glycerol and others:1 (0.2204 0.1128 0.0078 0.2555 0.2072) 0.0963 Weight profiles of other runs were calculated by the same procedure shown above.
Appendix D: Diffusion behavior from methanol to triolein
Methanol and triolein were mixed at a T-shaped joint before entering the microtube reactor. The following calculation estimates how long it takes to change from a slug flow to a homogeneous flow. Because it is only an estimation without experimental data, and there is not a published study about mixing issues in non-catalytic biodiesel synthesis being published, several assumptions were made:
1. The length of slugs are 1.6 mm. This is based on the slugs length in a previous study (Guan, G. et al., 2009).
2. Since there is no equation to accurately calculate the diffusion coefficient for this case, the Wilke-Chang correlation was chosen to estimate the diffusion coefficient roughly.
0.5 molecular weight of solvent B; T is the temperature in K; μ is the viscosity in centipoises; VA is the molar volume of solute A at its normal boiling temperature. So in this study, A is methanol as solute, B is triolein as solvent. T is 658.15 K. μ is 1.67 cp (Rowley etal., 2004). MB is 885 g/mol. VA= 40.5 cm3/mol. φ =1.So DAB= 9.4 10 5cm2/s.
At 385 oC and 150 bar, the density of methanol is 0.1 g/cm3. So the concentration of pure methanol slugs before mixing is 3.125 mol/l. From Appendix A, the molar volume of methanol-triolein mixture is 0.432 m3/kmol which means the concentration of the mixture is 2.3 mol/l.
Because the molar ratio of methanol to triolein is 9:1, it is assumed that when methanol is totally
mixed with triolein, the concentration of methanol is 2.08 mol/l, and the initial concentration of triolein is 0.23 mol/l. Fig. D1 also describes this problem.
Fig. D1. Methanol diffusion into triolein slug.
The diffusion was assumed to match the following differential equation:
2 The boundary conditions are: C(0,t)=3.125 mol/l, and when x=L which is the middle
point of diffusion distance,
The initial condition is: when t=0, C(0,0)=0.
The solution is (D3)
The result when t=5, 10, and 20s were plotted as shown in Figure D2 from which we can see it would take about 15 seconds for methanol to diffuse into triolein to reach a final average methanol concentration as 2.08 mol/L ( when methanol to triolein molar ratio of 9:1). The above calculation does not consider chemical reaction which occurs with diffusion, which actually contributing establishing a homogeneous phase quickly.
2 2
Figure D2. Methanol Concentration vs. diffusion distance. Triolein slug lengths are assumed to be equal to the reactor diameter.
Appendix E: Calibration functions in Chapter 4
The method to construct calibration curves is exactly the same as the one in Appendix B.
In Chapter 4, Table 4-3 describes the concentration of glycerol, monoglyceride, diglyceride, and triglyceride in each sample according to ASTM D-6584 where monoolein, diolein, and triolein are used as reference standard for monoglyceride, diglyceride, and triglyceride.
Table E1 shows the standard solution peak report of the work done in Chapter 4.
Because of slightly different gas flow rate and deviation of preparing solution, peak area of each component is different from the relative ones in Table B1.
Table E1 Peak report of standard solutions.
Component Glycerol Monoolein Diolein Tiolein I.S. 1 I.S.2
mass (ug)
Area mass
(ug)
Area mass
(ug)
Area mass
(ug)
Area mass
(ug)
Area mass
(ug)
Area
Std 1 0.00054 24170.21 0.0108 249496.4 0.0054 104956 0.00538 68546 0.011 357212.6 0.086 1340868
Std 2 0.0016 63979.47 0.0269 651057.9 0.0108 217738 0.0108 139462 364030.6 1298139
Std 3 0.00269 111407.19 0.0538 1287900 0.0215 437748 0.0215 290388 377574.2 1307563
Std 4 0.00376 154045.56 0.0806 1923978 0.0376 764020 0.0376 526752 379707 1343968
Std 5 0.00538 217574.99 0.108 2553647 0.0538 1083968 0.0538 753446 362107.3 1326713
According to the data shown above in Table E1, calibration curves of glycerol, monoglyceride, diglyceride, and triglyceride were constructed as shown in Fig.E1.
Fig.E1 Calibration curves of glycerol, monoglyceride, dioglyceride, and triglyceride using glycerol, monoolein, diolein, and triolein as reference standards, respectively.
Table E2 reports the peak area of glycerol, monoglyceride, diglyceride, triglyceride, internal standard 1, and internal standard 2, which was used to generate Table 4-3 in Chapter 4.
Table E2 Peak area from chromatograms of biodiesel samples in Chapter 4.
11103606 127695534 4817757 388905 1355035 2 385 9:1 4 3578953 8058423 3577599 356756 383075 1358591
a- Glycerol. b- monoolein. c- diolein. d- triolein. e- internal standard 1. f- internal standard 2.
Appendix F: GC-FID chromatography of the screening experiments (Table 4-2) in Chapter 4
Runs 1-6, 7-13, and 14-17 are performed at 350, 385, and 400 oC, and different residence times, pressure, and molar ratio. Figure F1 through F9 are the chromatograms of the biodiesel samples from the screening experiments.
Fig. F1. Chromatography of biodiesel samples made at 350 oC, 150 bar, molar ratio of 6:1 and 9:1, residence time of 6 and 8 minutes.
0
Fig. F2. Chromatography of biodiesel samples made at 350 oC, 200 and 150 bar, molar ratio of 9:1, residence time of 8 and 10 minutes.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
350℃ 200 bar 9:1 8 min
350℃ 150 bar 9:1 10 min
Fig. F3. Chromatography of biodiesel samples made at 350 oC, 200 and 300 bar, molar ratio of 9:1 and 12:1, residence time of 12 and 10 minutes.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
350℃ 200 bar 9:1 12 min
350℃ 300 bar 12:1 10 min
Fig. F4. Chromatography of biodiesel samples made at 385 oC, 150 bar, molar ratio of 6:1 and 9:1, residence time of 6 minutes.
385℃ 150 bar 6:1 6 min
385℃ 150 bar 9:1 6 min
Fig. F5. Chromatography of biodiesel samples made at 385 oC, 150 and 200 bar, molar ratio of 9:1, residence time of 8 minutes.
385℃ 200 bar 9:1 8 min 385℃ 150 bar 9:1 8 min
Fig. F6. Chromatography of biodiesel samples made at 385 oC, 150 bar, molar ratio of 9:1, residence time of 10 and 12 minutes.
385℃ 150 bar 9:1 10 min
385℃ 150 bar 9:1 12 min
Fig. F7. Chromatography of biodiesel samples made at 385 and 400 oC, 200 bar, molar ratio of 12:1 and 6:1, residence time of 10 and 6 minutes.
385℃ 200 bar 12:1 10 min
400℃ 200 bar 6:1 6 min
Fig. F8. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 9:1, residence time of 6 and 10 minutes.
400℃ 200 bar 9:1 6 min
400℃ 200 bar 9:1 10 min
Fig. F9. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 12:1, residence time of 6.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 12:1 6 min
Appendix G: GC-FID chromatography for runs listed in Table 4-3 in Chapter 4.
Figure G1 through G13 are chromatograms of runs listed in Table 4-3 at different reaction conditions (385 and 400 oC, 200 bar, methanol to oil molar ratio of 9 and 12, and residence times from 3 to 12 min).
Fig. G1. Chromatography of biodiesel samples made at 385 oC, 200 bar, molar ratio of 9:1, residence time of 3 and 4 minutes.
0
Fig. G2. Chromatography of biodiesel samples made at 385 oC, 200 bar, molar ratio of 9:1, residence time of 5 and 6 minutes.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
385℃ 200 bar 9:1 5 min
385℃ 200 bar 9:1 6 min
Fig. G3. Chromatography of biodiesel samples made at 385 oC, 200 bar, molar ratio of 9:1, residence time of 7 and 8 minutes.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
385℃ 200 bar 9:1 7 min
385℃ 200 bar 9:1 8 min
Fig. G4. Chromatography of biodiesel samples made at 385 oC, 200 bar, molar ratio of 9:1, residence time of 9 and 10 minutes.
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
385℃ 200 bar 9:1 9 min
385℃ 200 bar 9:1 10 min
Fig. G5. Chromatography of biodiesel samples made at 385 and 400 oC, 200 bar, molar ratio of 9:1, residence time of 12 and 3 minutes.
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
385℃ 200 bar 9:1 12 min
400℃ 200 bar 9:1 3 min
Fig. G6. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 9:1, residence time of 4 and 5 minutes.
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 9:1 4 min
400℃ 200 bar 9:1 5 min
Fig. G7. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 9:1, residence time of 6 and 7 minutes.
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 9:1 6 min
400℃ 200 bar 9:1 7 min
Fig. G8. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 9:1, residence time of 8 and 9 minutes.
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 9:1 8 min
400℃ 200 bar 9:1 9 min
Fig.G9. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 9:1, residence time of 10 and 12 minutes.
200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 9:1 10 min
400℃ 200 bar 9:1 12 min
Fig. G10. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 12:1, residence time of 3 and 4 minutes.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 12:1 3 min
400℃ 200 bar 12:1 4 min
Fig. G11. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 12:1, residence time of 5 and 6 minutes.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 12:1 5 min
400℃ 200 bar 12:1 6 min
Fig. G12. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 12:1, residence time of 7 and 9 minutes.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 12:1 7 min
400℃ 200 bar 12:1 9 min
Fig. G13. Chromatography of biodiesel samples made at 400 oC, 200 bar, molar ratio of 12:1, residence time of 10 and 12 minutes.
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
0 200 400 600 800 1000
0 5 10 15 20 25 30 35 40 45
400℃ 200 bar 12:1 10 min
400℃ 200 bar 12:1 12 min
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