Stream name Pressure (kPa) Temperature (C) Molar flow (gmol/hr) Mass flow (kg/hr) Volumetric flow (m3/hr)

Component mass fraction Methanol TGA triolein Methyl oleate Glycerol NaOH H3PO4 H2O Na3PO4

101 101.3 25.00 17644 565.3 0.7192 1.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000

105-FVO 101.3 25.00 5929 5250 5.770 0.000 1.000 0.000 0.000 0.000 0.000 0.000 0.000

103 400.0 26.69 36880 1192 1.510 0.956 0.000 0.000 0.000 0.044 0.000 0.000 0.000

106 400.0 60.00 42810 6442 7.007 0.093 0.041 0.778 0.080 0.008 0.000 0.000 0.000

201 20.00 28.20 17390 574.4 0.7340 1.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000

202 30.00 142.8 24880 5868 48.70 0.004 0.045 0.854 0.088 0.009 0.000 0.000 0.000

301 110.0 59.39 17640 5284 6.205 0.001 0.050 0.948 0.000 0.000 0.000 0.001 0.000

401 10.00 70.97 17150 4999 5.968 0.001 0.002 0.996 0.000 0.000 0.000 0.000 0.000

305 101.3 163.1 6534 533.7 4.943 0.004 0.000 0.000 0.967 0.000 0.000 0.029 0.000

502 30.00 180.0 5743 518.6 0.5214 0.000 0.000 0.000 0.995 0.000 0.000 0.005 0.000

Figure 2.3. Flow diagram and properties of main streams of Alkali-FVO process

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Transesterification of fresh canola oil The conditions for transesterification reaction were set at 400 kPa and 60C. A conversion reactor, CRV-100, was used with the specified triolein conversion of 95%. 5250 kg/hr (5929 mol/hr) of fresh canola oil, 105-FVO, was pumped to 400 kPa by P-102 and heated to 60C by E-101 before entering the reactor. Sodium hydroxide (NaOH), stream 102, was chosen as the alkali-catalyst. The amount of NaOH was 1 wt% of the canola oil and it was mixed with methanol before the reaction. The necessary amount of methanol was considered to be 6:1 molar ratio of methanol to oil and the reaction time was 1 hr (Meher et al., 2006). Since approximately 50% of the required amount of methanol was provided from the recycled stream from T-101, only 565.3 kg/hr (17640 mol/hr) of fresh methanol (stream 101) was fed to the process.

Methanol recovery Due to the excess amount of methanol provided for the transesterification reaction, the product stream from CRV-100 contains a large amount of methanol that did not participate in the reaction. This methanol is recovered by a multi-stage distillation column and recycled back to the reactor. In the process simulation, 96% of methanol in stream 106 was recovered by using 6 theoretical stages in the distillation column. The pressures in the condenser and reboiler were set at 20.0 and 30.0 kPa, respectively, to keep the operating temperature below 200C to avoid decompositions of methyl oleate and glycerol. As a result, the temperatures in the condenser and reboiler were 28.20 and 142.8C, respectively.

Water washing In the liquid-liquid extraction column, T-102, the bottom product stream from T-101 was washed with water at 110 kPa to get rid of glycerol and NaOH. The number of stages required for this separation was 4. The simulation results showed that glycerol was almost completely separated from methyl oleate using 50.0 kg/hr of water. Stream 203 also contained unreacted triolein from transesterification reaction, and 99.7% of the triolein was separated into stream 301. Since the triolein mass faction in stream 301 was 0.0495, a distillation column, T-103, was used for the final biodiesel purification.

Neutralization and settler Stream 302 from the liquid-liquid extraction column contains glycerol along with NaOH, which needs to be neutralized before glycerol purification. Stoichiometric amount of phosphoric acid

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(H3PO4) was used to neutralize 52.5 kg/hr of NaOH. Water and trisodium phosphate (Na 3PO4) were generated as reaction products. Na3PO4 was then separated as a precipitate in a decanter (X-100). Biodiesel purification Column T-103 was designed for separating biodiesel from unreacted triolein, methanol and water. The simulated column had 6 theoretical stages in total, and the reflux ratio was 1.10. The pressures at the condenser and reboiler were 10.0 and 15.0 kPa, respectively. As a result, 96.4% of triolein was separated out in the bottom product stream. Stream 401 contained 99.6 wt% methyl oleate, 0.19 wt% triolein, 0.13 wt% methanol and 0.05 wt% water, which satisfied both European (EN14214) and American (ASTM D6751) biodiesel standards.

Glycerol purification Glycerol was purified in the column T-102 to eliminate water and methanol contained in the feed stream. The required number of theoretical stages was 5, and the reflux ratio was 2.0. The pressures in the condenser and reboiler were set at 20.0 and 30.0 kPa, respectively, to maintain moderate operating temperature in the column to avoid decomposition of glycerol. The corresponding temperatures were 50.96 and 180.0C in the condenser and reboiler, respectively. As a result, glycerol with high purity (99.5 wt%) was obtained as the bottom product of the distillation column.

2.3.2. Alkali-WVO process Alkali-WVO process has additional pre-treatment steps before transesterification of waste vegetable oil with methanol. The pre-treatment process aims to decrease high FFA contents in WVO by esterification reaction in the presence of an acid catalyst. With the reduced amount of FFAs, undesirable soap formation by the reaction between FFAs and alkali catalysts is minimized. A flow diagram of the pre-treatment step is shown in Figure 2.4a.

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