I NTERNATIONAL J OURNAL OF C HEMICAL R EACTOR E NGINEERING

Volume 5 2007 Article A37

Simulation, Case Studies and Optimization of a Biodiesel Process with a Solid Acid Catalyst
Alex H. West Dusko Posarac Naoko Ellis

University of British Columbia, awest@chml.ubc.ca University of British Columbia, posarac@chml.ubc.ca University of British Columbia, nellis@chml.ubc.ca ISSN 1542-6580 Copyright c 2007 The Berkeley Electronic Press. All rights reserved.

Simulation, Case Studies and Optimization of a Biodiesel Process with a Solid Acid Catalyst
Alex H. West, Dusko Posarac, and Naoko Ellis

Abstract
A commercial process simulator was used to develop a detailed simulation of a biodiesel production process, and carry out case studies and optimization. The simulated process produced biodiesel from a feedstock containing 5 wt.% free fatty acids in a xed-bed reactor with sulfated-zirconia as an acidic catalyst. Sized unit operation blocks, material and energy ows were used to conduct an economic assessment of the process. Total capital investment, total manufacturing cost, after tax rate-of-return and production cost ($/kg) were all determined for the process. The process was then optimized by maximizing the after tax rateof-return (ATROR). Based on our previous work, the most economical process for transesterication of waste vegetable oil at the scale of 8000 metric tones/yr of biodiesel production among the four processes examined was based on a solid acid catalyst reaction. Our results showed that the process is economically feasible, even without government subsidy, while at the same time, the produced biodiesel met the required ASTM standard for purity. KEYWORDS: biodiesel, sulfated-zirconia, process design, process simulation, economic assessment

The authors acknowledge the nancial support of the Natural Sciences and Engineering Research Council of Canada.

West et al.: Simulation, Case Studies and Optimization of a Biodiesel Process

INTRODUCTION

Biodiesel (mono-alkyl esters of long chain fatty acids) is a promising alternative or extender to conventional petroleum based diesel fuel. Biodiesel has a number of advantages it is derived from a renewable domestic resource (vegetable oil), reduces carbon dioxide emissions by 78% (Tyson, 2001) when compared to diesel fuel on a life cycle basis, and is non-toxic and biodegradable, making it a more environmentally benign fuel. Biodiesel is produced via a transesterification reaction between a vegetable oil or animal fat (which are composed of complex mixtures of triglycerides) and a low molecular weight alcohol, such as methanol. The reaction C57H104O6+3CH3OH = 3C19H36O2+C3H8O3 produces a complex mixture of fatty acid methyl esters and glycerol. The transesterification reaction can be catalyzed through a number of different methods: homogeneous alkali (Freedman et al., 1984); homogeneous acid (Canakci and Van Gerpen, 1999); supercritical alcohol with no catalyst (Saka and Kusdiana, 2001); and via heterogeneous catalysts. Currently, the high cost of biodiesel production is the major impediment to its large scale commercialization (Canakci and Van Gerpen, 2001), and is largely attributed to the cost of virgin vegetable oil as feedstock. Exploring methods to reduce the production cost of biodiesel has been the focus of much recent research, and has included feedstock substitution as well as alternate catalysts and reaction schemes. Another useful tool in optimizing biodiesel production is the use of process simulators to develop detailed models that can be adjusted to accommodate a variety of process conditions. Haas et al. (2006) developed a versatile ASPEN Plus process simulation model to estimate biodiesel production costs. The model was designed to allow the user to determine the effect of changing unit operations and material flows, as well as raw material costs on the process economics. However, the model was limited to a traditional alkali-catalyzed production method. Zhang et al. (2003a) developed a HYSYS based process simulation model to assess the technological feasibility of four biodiesel plant configurations a homogeneous alkali-catalyzed pure vegetable oil process; a two-step process to treat waste vegetable oil (WVO); a single step homogeneous acid-catalyzed process to treat WVO; and a homogeneous acidcatalyzed process using hexane extraction to help purify the biodiesel. An economic analysis of the four designs revealed that the one step acid-catalyzed process was the most economically attractive (Zhang et al., 2003b). West et al. (2006) developed a series of process simulation models in HYSYS using the traditional homogeneous processes as base cases, and comparing them with simulations of the heterogeneous acid-catalyzed process and the supercritical process. It was found that the heterogeneous acid process was the most economically advantageous, and the only one to yield a positive rate of return. The purpose of this work was to refine the heterogeneous acid catalyzed process simulation and perform a more detailed optimization, as well as conduct sensitivity analyses on key process parameters such as reaction conversion and plant capacity.

PROCESS SIMULATION

ASPEN Plus version 2004.1 was used to conduct the simulation. Plant capacity, unit block operating conditions, and chemical components (except the catalyst) were selected based on the previous hetereogeneous acid catalyst (SnO) simulation (West et al., 2006). For the present simulation sulphated zirconia (SO4/ZrO2) was chosen as the catalyst, as it has been shown to effectively catalyze both the transesterification and esterification reactions by several authors (Furuta et al., 2004; Jitputti et al., 2006; Kiss et al., 2006; Lopez et al., 2005), whereas the use of SnO has only been demonstrated by one group (Abreu et al., 2005). Although the properties for triolein were available in the ASPEN data banks, different values for the boiling point and critical temperature were obtained from the literature (Tang et al., 2006) and used to re-estimate the Antoines vapour pressure coefficients since initial estimates and results were unsatisfactory. The NRTL model was selected as the thermodynamic model. Since no kinetic data were available for the SO4/ZrO2 reaction, the reactor was modelled as a stoichiometric reactor representing a packed bed reactor, eliminating the catalyst removal step. The conversion was set at 90.4% according to the work of Jitputti et al. (2006). It was assumed that no leaching of sulphate groups into either the organic or aqueous phase had occurred (Kiss et al., 2006). It was also assumed that no side reactions involving glycerol occurred, since there had been no reports of such reactions in the literature. Details of the reactor conditions are outlined in Table 1. Catalyst characteristics such as density and porosity have not been included in the reaction scheme since they have not been

Published by The Berkeley Electronic Press, 2007

International Journal of Chemical Reactor Engineering

Vol. 5 [2007], Article A37

reported in the literature and are likely to change with each method of synthesis. Additionally, since the reactor is modelled as a stoichiometric reactor, including such parameters would not have affected the results.

PROCESS DESIGN

In the process (shown in Figure 1) vegetable oil was transesterified in the reactor, followed by downstream purification, which consisted of: methanol recovery by distillation; glycerol separation; and methyl-ester purification by distillation. Table 1 gives details for the unit operations in the process. Table 2 presents the feed and product material flow details for the process. Multi-stage distillation was used to recover the excess methanol, as well as in the final purification of biodiesel. Distillation columns were specified to meet or exceed the ASTM standard for biodiesel purity, i.e., 99.65 wt.%. Reflux ratios for the columns were calculated by the unit operation blocks as a design variable. In order to achieve high methanol recovery, which increases the after tax rate of return of the process (West et al., 2006), vacuum operation in the methyl-ester purification column was necessary to keep the temperature of the bottom stream low enough, as glycerol is subject to degradation at temperatures above 150C (Goodrum, 2002; Newman, 1968). As in West et al. (2006), gravity separation was used to separate the biodiesel from the glycerol, and a satisfactory separation was achieved. While this particular separation has not been verified experimentally, Chiu et al. (2005) showed that methanol dissolves almost entirely in the glycerol phase of a methanol-glycerol-biodiesel mixture indicating that theoretically, a decanter is able to achieve high purity separation. The final purity of the methyl-ester product was quantified by reporting the product stream composition, which was determined by thermodynamic calculations in ASPEN. Mono- and di-glycerides were neglected as reaction intermediates (Zhang et al., 2003a).
Table 1. Summary of unit operating conditions for the process. Transesterification Catalyst Reactor Type Temperature (C) Pressure (kPa) Reactor volume A:O Ratio Residence time (hr) Conversion (%) Methanol Recovery Reflux Ratio Reflux Temp. Number of stages Feed stage position Condenser/Reboiler Pressure (kPa) %Recovery Distillate flowrate (kg/h) Distillate purity(%) 1.06 14 12 20/30 99.9 113.5 99.9 SO4/ZrO2 Packed bed 200 4050 1.45 m3 6:1 3 90.1 Glycerine Separation Biodiesel Purification Reflux ratio Number of stages Feed stage position Condenser/rebo iler Pressure (kPa) Distillate flowrate (kg/h) %Recovery Final purity Gravity separation 1.2 7 3 101.3/108.8 960.4 99.9 99.9

http://www.bepress.com/ijcre/vol5/A37

West et al.: Simulation, Case Studies and Optimization of a Biodiesel Process

EQUIPMENT SIZING

Process equipment was sized according to principles outlined in Turton et al. (2003) and Seider et al. (2003), and details regarding the calculations can be found in West et al. (2006). The principal dimensions of each unit are presented in Table 3. The equipment sizing calculations were conducted using FORTRAN blocks within the simulation. The reactor was sized for continuous operation by dividing the residence time (3 hours) requirement by the feed flowrate for the process. Distillation column diameters were calculated by the sub-modules available on the column worksheets. Results were verified by finding the flooding velocities using the Fair and Leva correlations (Seider et al., 2003) for a tray tower (diameter greater than 0.9 m) and packed column (diameter less than 0.9 m), respectively. Number of stages (and therefore tower height) were determined by optimizing the column according to the method of Luyben (2006) as described in Section 6.

ECONOMIC ASSESSMENT

The economic analysis similar to the one performed in West et al. (2006) was used for this work. Plant capacity was set at 8000 tonnes/year biodiesel as in the previous work. Table 3 presents the breakdown of the unit operation costs and total capital investment for the process. Results for the total manufacturing cost are shown in Table 4. The direct manufacturing cost represents 80% of the total manufacturing cost in each process, of which the oil feedstock is the largest proportion, 53%. The final ATROR figure was 25.54%, which is still the only economically feasible process when compared to traditional homogeneous and supercritical processes (West et al., 2006).

Table 2. Feed and product stream information for the heterogeneous acid-catalyzed process. Feed Streams Temperature (C) Pressure (kPa) Molar flow (kmol/h) Mass flow (kg/h) Component mass fraction Methanol Triolein Oleic Acid MEOH-IN 25.0 101.3 3.24 103.9 1.000 0.000 0.000 WVO-IN 25.0 101.3 1.31 1050.00 0.000 0.9500 0.0500 D2 Temperature (C) 217.2 Pressure (kPa) 101.325 Molar flow (kmol/h) 3.26 Mass flow (kg/h) 960.4 Component mass fraction Methanol 0.0000 Glycerol 0.0001 Triolein 0.0000 M-oleate 0.9995 Oleic Acid 0.0000 Water 0.0003 Product Streams B2 544 108.8 0.111 96.7 0.0000 0.0000 0.9901 0.0099 0.0000 0.0000 GLYCEROL 25 101.325 1.19 96.7 0.0003 0.9679 0.0316 0.0000 0.0000 0.0000

Published by The Berkeley Electronic Press, 2007

International Journal of Chemical Reactor Engineering

Vol. 5 [2007], Article A37

Figure 1. Biodiesel process flowsheet with solid acid catalyst.

http://www.bepress.com/ijcre/vol5/A37

West et al.: Simulation, Case Studies and Optimization of a Biodiesel Process

Table 3. Equipment costs, fixed capital cost, total capital investment (units: $millions USD) and unit dimensions. Type Reactor Columns Other Description Transesterification Methanol Recovery Fame Purification Gravity Separators Heat Exchangers Pumps Others (vacuum system etc) Cost 0.075 0.031 0.100 0.039 0.169 0.050 0.082 0.529 0.095 0.624 0.159 0.783 0.117 0.900 Dimensions (DxH, m) 0.85 x 2.55 0.33 x 6.16 0.78 x 4.36 1.2 x 2.4

Total bare module cost, CBM Contingency fee, CCF = 0.18CBM Total module cost, CTM = CBM+CCF Auxiliary facility cost ,CAC = 0.3CBM Fixed Capital Cost, CFC = CTM+CAC Working capital CWC = 0.15CFC Total capital investment CTCI = CFC+CWC

Table 4. Total manufacturing cost and after tax rate-of-return. (Units: $millions USD). Value ($) Direct manufacturing cost Oil feedstock Methanol Catalyst Operating Labour Supervisory Labour LP steam HP steam Electricity Cooling Water Liquid waste disposal Solid waste disposal Maintenance and Repairs (M&R), 6% of CFC Operating Supplies, 15% of M&R Lab charges, 15% of operating labour Patents and royalties, 3% TMC Subtotal ADMC Indirect manufacturing cost Overhead, packaging and storage, 60% of sum of operating labour , supervision and maintenance Local Taxes, 1.5% of CFC Insurance, 0.5% of CFC Subtotal, AIMC 1.66 0.148 0.050 0.580 0.087 0.019 0.272 0.00 0.004 0.115 0.00 0.047 0.070 0.087 0.136 3.17 Depreciation 10% of CFC General expenses Administrative costs, 25% of overhead Distribution and selling, 10% of TMC Research &Development, 5% of TMC Subtotal Total production cost Glycerine Credit Total Manufacturing Cost, ATE Revenue from Biodiesel Net annual profit Income taxes, AIT 50% of ANP Net annual after tax profit, ANNP After tax rate of return, I = [ANNP-ABD]/CTC 0.078 0.107 0.452 0.226 0.785 4.52 0.575 3.95 4.56 0.616 0.308 0.308 25.54%

0.428 0.012 0.004 0.444

Published by The Berkeley Electronic Press, 2007

International Journal of Chemical Reactor Engineering

Vol. 5 [2007], Article A37

SENSITIVITY ANALYSES AND OPTIMIZATION

Sensitivity analyses were conducted to determine the effect of reactor conversion and plant capacity on the process economics. Since the conversion data for the heterogeneous acid-catalyzed processes were taken from bench-scale research, the economics of scale may not be accurately reflected. Thus the effect of reduced conversion on the ATROR was examined. As shown in Figure 2, the ATROR drops nearly linearly as the reaction conversion decreases, and becomes negative around 83% conversion. This implies that if high conversion cannot be maintained when the process is scaled up, then it may no longer be economically viable. It was also desired to determine the effect of plant capacity on the ATROR, as both Zhang et al. (2003b) and Haas et al. (2005) indicated that capacity had a significant effect on ATROR. Figure 3 demonstrates that as plant capacity is increased, the ATROR of the process increases. This implies that the increase in revenues gained from greater biodiesel production offsets the increase in TCI that results from increasing the scale of the plant. For every hundred kg/h increase in oil feed, the ATROR increased by approximately 12 percentage points, indicating there are significant gains to be made by scaling up the proposed process.

30 After tax rate of return (%) 20 10 0 -10 -20 -30 -40 75 80 85 90 95 Reaction conversion (%)

0.8
After tax rate of return (%)

70 60 50 40 30 20 10 0 -10 -20 700 800

0.7 0.6 Cost/kg ($/kg) 0.5 0.4 0.3 0.2 0.1 0 900 1000 1100 1200 1300 1400 Plant capacity (kg/hr oil)

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 Cost/kg ($/kg)

Figure 2. Effect of reaction conversion on ATROR.

Figure 3. Effect of plant capacity on ATROR.

The methanol recovery and methyl-ester distillation columns were optimized by selecting the number of stages and feed stage position to minimize column diameter, reboiler heat input and reflux ratio. Figure 4 presents the results for the methanol recovery column. The maximum for each curve occurs at the feed stage position second from the bottom of the column (i.e., on the 9 stage curve the top stage is 4 and the bottom is 8, therefore the maximum for ATROR is at feed stage 7). The maximum ATROR becomes slightly larger as the number of stages of the column is increased. Although this increases the cost of the unit, it results in an energy savings due to decreased reboiler heat, which is greater than the increased column cost, thereby slightly increasing the ATROR. This method was used to size both methanol recovery and methyl ester purification columns. Lastly, the effects on the ATROR due to changes in raw material costs were investigated both for methanol and waste vegetable oil, as well as for the selling prices of glycerol and biodiesel. In all cases, the response to a change in price was linear. For an increase of 2 c/kg in the cost of methanol, the cost of biodiesel changed by 0.26 c/kg; a 1 c/kg increase in waste oil increased the cost of biodiesel by 1.3 c/kg. With respect to glycerol, as the selling price goes up 2.5 c/kg, the cost of biodiesel decreases by 0.24 c/kg. The selling price of biodiesel has no effect on its manufacturing cost. However, it does affect the ATROR for the process: increasing the selling price of biodiesel by 2c/kg boosts the ATROR by 8.77 percentage points.

http://www.bepress.com/ijcre/vol5/A37

West et al.: Simulation, Case Studies and Optimization of a Biodiesel Process

27 26 25 24 ATROR (%) 23 22 21 20 19 18 17 16 15 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Feed stage

9 stages 10 stages 11 stages 12 stages 13 stages 14 stages 15 stages

Figure 4. Effect of feed stage position and number of stages on ATROR for methanol recovery column (DC-1).

CONCLUSION

A continuous process to produce biodiesel at a rate of 8000 tonnes/year based on the heterogeneous acid-catalyzed process in West et al. (2006) was simulated in ASPEN Plus. The process was designed to employ a packed bed reactor, eliminating the need for the hydrocyclone. The economic assessment of the current process revealed that it had a higher total capital investment, owing to the high-pressure reaction scheme which necessitated higher strength unit operations. Raw material and utilities consumption remained nearly constant, however the conversion of the reaction is lower than that reported with tin(II) oxide, decreasing the revenue from biodiesel and therefore the ATROR. The final value for the ATROR was 25.54%. An analysis of the effect of reaction conversion on ATROR revealed that the ATROR for the process becomes negative below approximately 83% conversion. It was found that plant capacity had a linear effect on the ATROR. Increasing the oil feedstock flowrate by 100 kg/h caused an increase of 12 percentage points on the ATROR, implying that there are significant advantages to be gained by designing a plant as large as possible. Although the ATROR was less than that of the SnO catalyzed process, the SO4/ZrO2 acid-catalyzed process still yielded a positive economic outcome without any government subsidy. Further research to develop and scale up the process is warranted.

REFERENCES
Abreu, F.R., Alves, M.B., Macedo, C.C.S., Zara, L.F., Suarez, P.A.Z., 2005. New multi-phase catalytic systems based on tin compounds active for vegetable oil transesterification reaction. J. Mol. Catal. A-Chem., 227, 263-267. Canakci, M., Van Gerpen, J., 1999. Biodiesel production via acid catalysis. Trans. ASAE, 42, 1203-1210. Canakci, M., Van Gerpen, J., 2001. Biodiesel production from oils and fats with high free fatty acids. Trans. ASAE, 44, 1429-1436.

Published by The Berkeley Electronic Press, 2007

International Journal of Chemical Reactor Engineering

Vol. 5 [2007], Article A37

Chiu, C.W., Goff, M.J., Suppes, G.J., 2005. Distribution of methanol and catalysts between biodiesel and glycerin phases. AIChE J., 51, 1274-1278. Freedman, B., Pryde, E.H., Mounts, T.L., 1984. Variables affecting the yields of fatty esters from transesterified vegetable-oils. J. Am. Oil Chem. Soc., 61, 1638-1643. Furuta, S., Matsuhashi, H., Arata, K., 2004. Biodiesel fuel production with solid superacid catalysis in fixed bed reactor under atmospheric pressure. Catalysis Communications, 5, 721-723. Goodrum, J.W., 2002. Volatility and boiling points of biodiesel from vegetable oils and tallow. Biomass Bioenerg., 22, 205-211. Haas, M.J., McAloon, A.J., Yee, W.C., Foglia, T.A., 2006. A process model to estimate biodiesel production costs. Bioresour. Technol., 97, 671-678. Jitputti, J., Kitiyanan, B., Rangsunvigit, P., Bunyakiat, K., Attanatho, L., Jenvanitpanjakul, P., 2006. Transesterification of crude palm kernel oil and crude coconut oil by different solid catalysts. Chemical Engineering Journal, 116, 61-66. Kiss, A.A., Dimian, A.C., Rothenberg, G., 2006. Solid acid catalysts for biodiesel production - towards sustainable energy. Advanced Synthesis & Catalysis, 348, 75-81. Lopez, D.E., Goodwin, J.G., Bruce, D.A., Lotero, E., 2005. Transesterification of triacetin with methanol on solid acid and base catalysts. Applied Catalysis, A: General, 295, 97-105. Luyben, W.L., 2006. Distillation Design and Control Using Aspen Simulation. Wiley-Interscience, Hoboken, New Jersey. Newman, A.A., 1968. Glycerol. CRC Press, Cleveland. Saka, S., Kusdiana, D., 2001. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol. Fuel, 80, 225 231. Seider, W.D., Seader, D., Lewin, D.R., 2003. Process Design Principles: Synthesis, Analysis and Evaluation. 2nd ed. John Wiley & Sons, Chichester, UK. Tang, Z., Do, Z.X., Min, E.Z., Gao, L., Jiang, T., Han, B.X., 2006. Phase equilibria of methanol-triolein system at elevated temperature and pressure. Fluid Phase Equilibria, 239, 8-11. Turton, R., Bailie, R.C., Whiting, W.B., Shaeiwitz, J.A., 2003. Analysis, Synthesis, and Design of Chemical Processes. 2nd ed. Prentice Hall, Upper Saddle River, New Jersey. Tyson, K.S., 2001. Biodiesel: Handling and Use Guidelines. National Renewable Energy Laboratory, Golden CO. West, A.H., Posarac, D., Ellis, N., 2006. Assessment of four biodiesel production processes using HYSYS.Plant. Bioresour. Technol., (Submitted for publication February 2006). Zhang, Y., Dube, M.A., McLean, D.D., Kates, M., 2003a. Biodiesel production from waste cooking oil: 1. Process design and technological assessment. Bioresour. Technol., 89, 1-16. Zhang, Y., Dube, M.A., McLean, D.D., Kates, M., 2003b. Biodiesel production from waste cooking oil: 2. Economic assessment and sensitivity analysis. Bioresour. Technol., 90, 229-240.

http://www.bepress.com/ijcre/vol5/A37