18th European Symposium on Computer Aided Process Engineering – ESCAPE 18 Bertrand Braunschweig and Xavier Joulia (Editors) © 2008 Elsevier B.V./Ltd. All rights reserved. Biodiesel production by heat-integrated reactive distillation Anton A. Kissa, Alexandre C. Dimianb, Gadi Rothenbergb a Akzo Nobel Chemicals, Research and Technology Center, Arnhem, The Netherlands van’t Hoff Institute for Molecular Sciences, University of Amsterdam, The Netherlands tony.kiss@akzonobel-chemicals.com, alexd@science.uva.nl, gadi@science.uva.nl b Abstract This paper outlines the properties of biodiesel as renewable fuel, as well as the problems associated with its conventional production processes. The pros and cons of manufacturing biodiesel via fatty acid esterification using metal oxides as solid acid catalysts are investigated. A novel sustainable process based on catalytic reactive distillation is proposed as base case and a heat-integrated design as alternative. Significant energy savings of ~45% are possible compared to conventional RD designs. Keywords: reactive distillation, heat integration, green catalysts, sustainable fuels. 1. Introduction The depletion of petroleum reserves, increased energy demands, as well as concerns of rising greenhouse gas emissions, make the implementation of alternative and renewable sources of energy a crucial issue worldwide. Biodiesel has become increasingly attractive because it is sustainable and combines high performance with environmental benefits. Unlike petroleum diesel, biodiesel consists of a mixture of alkyl esters of long chain fatty acids. It can be produced from vegetable oils, animal fat or even recycled grease. Biodiesel has several advantages over petroleum diesel: it is safe, renewable, non-toxic and biodegradable; it contains no sulfur and is a better lubricant.1 Despite the chemical differences these two fuels have similar properties. The presence of oxygen in biodiesel (~10%) improves combustion and reduces CO, soot and hydrocarbon emissions, while slightly increasing the NOx emissions. Table 1 illustrates the biodiesel vs. petroleum diesel emissions. Biodiesel brings also additional benefits to the society: rural revitalization, less global warming, energy supply security. Its production is increasing rapidly as biodiesel can be distributed using today's infrastructure. The current biodiesel manufacturing processes have several disadvantages: shifting the equilibrium to fatty esters by using an excess of alcohol that must be separated and recycled, making use of a homogeneous catalysts that require neutralization hence causing salt waste streams, expensive separation of fatty esters products from the reaction mixture, high production costs due to relatively complex processes involving one or two reactors and several separation units. This paper presents the findings of the experimental work, and the results of the rigorous simulations of the reactive distillation process using AspenTech AspenPlus™. The heat integrated design proposed in this work overcomes these shortcomings of conventional processes, by combining reaction and separation into one unit. Compared to classic reactive distillation, the energy requirements in this heat integrated design are further decreased with –43% and –47% for heating and cooling, respectively. 2 A. A. Kiss et al. Table 1. Average biodiesel emissions compared to conventional petroleum diesel. Emission type Total unburned hydrocarbons Carbon monoxide (CO) Carbon dioxide (CO2) – life cycle production Particulate matter Nitrogen oxides (NOx) Sulfur oxides (SOx) Polycyclic Aromatic Hydrocarbons (PAH) Nitrated PAH's (nPAH) B20 –20% –12% –16% –12% +2% –20% –13% –50% B100 –67% –48% –79% –47% +10% –100% –80% –90% 2. Problem Statement Fatty acid methyl esters (FAME) – the main components of biodiesel – are currently manufactured by trans-esterification using liquid Na/KOH catalyst, or esterification of free fatty acids (FFA) using H2SO4 as catalyst. Note that due to the EU restrictions on sulfur content in diesel fuels (< 15 ppm), the catalyst removal is a crucial issue. The problem is that these liquid catalysts require neutralization and an expensive multistep separation that generates salt waste streams, thus making biodiesel an attractive but still costly alternative fuel. To solve these problems, we replaced the homogeneous catalyst with solid acids2 and developed a sustainable esterification process based on catalytic reactive distillation. Previously, we have screened a large number of zeolites, heteropoly-compounds, metal oxides, ion-exchange resins, and carbon-based solid acids.3 In this work, we focus on the application of metal oxides catalysts (based on niobia, zirconia, titania and tin oxide) in a heat-integrated reactive-separation design that is able to shift the chemical equilibrium to completion and preserve the catalyst activity by continuously removing the products. The heat-integrated design is based on the experimental findings and rigorous simulations in AspenTech Aspen Plus™. 3. Experimental work The reaction pathways and the possible products are shown in Figure 1 (left). The solid catalyst for esterification should have high activity and selectivity to avoid the formation of by-products; it should be water-tolerant to avoid catalyst deactivation and stable at relatively high temperatures to achieve high reaction rates. Additionally, it must be an inexpensive material that is readily available at industrial scale. Figure 1 (right) shows the chemical and phase equilibrium (CPE) diagram of the chemicals involved. Obviously, the region with two liquid phases should be avoided. REACTANTS Fatty Acid Acid, 298ºC Ester, 267ºC 1 Alcohol VLE esterification dehydration etherification X2 (acid+ester) 0.8 Equilibrium reaction 0.6 LLE 0.4 0.2 Fatty Ester Main product Ether Water Alkene Secondary products 0 Alcohol, 65ºC 0 0.2 0.4 0.6 X1 (water+acid) 0.8 1 Water, 100ºC Figure 1. Reaction pathways and possible products. Generalised CPE diagram. Biodiesel production by heat-integrated reactive distillation 6 6 Alcohol:Acid = 2:1 T=130C, 2 %wt cat. Amb-15 4 10% 5% 3% 1.5% 5 SZ / MMO Nb2O5 3 2 X / (1-X) / [-] X / (1-X) / [-] 5 3 Uncatalyzed 4 Amberlyst-15 Sulfated Zirconia 3 Cs2.5 Nb2O5 Alcohol:Acid = 1:1 T=150C, SZ catalyst 0.5%w 2 Cs2.5 1 Non-catalyzed 1 Non-catalyzed 0 0 0 30 60 90 120 0 Time / [min] 30 60 90 120 Time / [min] Figure 2. Esterification of dodecanoic acid: (left) at 130C using solid acid catalysts (2 wt%), (right) non-catalyzed and catalyzed (0.5-10 wt% SZ catalyst) In a previous study we investigated metal oxides with strong Brønsted acid sites and high thermal stability.4 Based on the literature reviews and our previous experimental screening we focus here on application of metal oxide catalysts based on Zr, Ti, and Sn. Sulfated zirconia (SZ) outperformed other solid acids, and by increasing the amount of catalyst the reaction rate can be further increased (Figure 2). SZ also showed good thermal stability, high activity and selectivity for the esterification of fatty acids with a variety of alcohols ranging from C1 to C8. In our experiments using metal oxides as catalysts, no by-products were observed by GC analysis, under the reaction conditions. Remarkably, sulfated titania and tin oxide catalysts performed slightly better than SZ, showing increased conversion of the fatty acid. Nevertheless, SZ is less expensive and it is readily available at industrial scale. Note that the catalytic activity of SZ can be further enhanced by preparing it from using a chlorosulfonic acid precursor dissolved in an organic solvent, instead of the conventional H2SO4 impregnation. Other metals, such as iron, can also be added to enhance the activity. Higher sulfur content corresponds to higher acidity of the catalyst and consequently higher catalytic activity. The pore size plays an important role as the reactants and the products must be able to fit inside the catalyst to take full advantage of the total surface area available. The pore size of metal oxides are sufficiently large (>2 nm) to facilitate the mass transfer into and from the catalyst pores. This compensate for their lower acidity compared to other solid acids. Table 2 gives an overview of the tested catalysts, showing their pro/cons with respect to the fatty acid esterification reaction. Table 2. Advantages and disadvantages of the acid catalysts tested for fatty acids esterification. Catalyst H2SO4 Ion-exchange resins H3PW12O40 Cs2.5H0.5PW12O40 Zeolites (H-ZSM-5, Y and Beta) Sulfated metal oxides (zirconia, titania, tin oxide) Advatanges Highest activity Very high activity Very high activity Super acid Controlable acidity and hydrophobicity High activity Thermally stable Disadvantages Liquid catalyst Low thermal stability Soluble in water Low activity per weight Small pore size Low activity Deactivates in water, but not in organic phase 4 A. A. Kiss et al. 4. Results and discussion The design of the process is based on a reactive distillation column (RDC) that integrates reaction and separation into a single operating unit. An additional flash and a decanter or a distillation column, are used to guarantee the high purity of the products. RDC consists of a core reactive zone completed by rectifying and stripping separation sections, whose extent depends on the separation behavior of the reaction mixture. Since methanol and water are much more volatile than the fatty ester and acid, these will separate easily in the top. The conceptual flowsheet of the process is shown in Figure 3. MeOH recycle Reflux drum Fatty acids Methanol recovery sep1 RDC MeOH Water reaction sep2 MeOH Flash separator FAME Figure 3. Flowsheet of biodiesel production by catalytic reactive distillation. F-ESTER RDC is operated in the temperature range of 70–210 °C, at ambient pressure. Out of the 15 stages of the reactive distillation column, the reactive zone is located in the middle of the column (stages 3-10). The fatty acid stream is fed on top of the reactive zone while the alcohol is fed as saturated liquid, below the reactive zone. The reflux ratio in RDC is relatively low (0.1 kg/kg) since a higher reflux ratio is detrimental as it brings back water by-product into the column, thus decreasing the fatty acids conversion by shifting the equilibrium back to reactants. High purity products are possible, but due to the thermo-stability and high boiling points of the fatty esters (i.e. high temperature in the reboiler) this should be avoided. By allowing ~0.2% of alcohol in the bottom stream, the reboiler temperature in RDC can be limited to ~200 °C. The base-case design (Figure 4) is amenable to heat integration, as the feed stream could be pre-heated using the fatty ester product stream. Obviously, a feed-effluent heat exchangers (FEHE) should replace each of the two heat exchangers HEX1 and HEX2. TOP HEX1 ACID F-ACID REC-ACID DEC RDC HEX2 ALCO WATER F-ALCO REC-ALCO FAME BTM FLASH COOLER Figure 4. AspenPlus flowsheet of biodiesel production by catalytic reactive distillation. WATER Biodiesel production by heat-integrated reactive distillation 5 F-ESTER2 TOP FEHE1 ACID F-ACID REC-ACID DEC RDC FEHE2 F-ALCO F-ESTER ALCO REC-ALCO F-ESTER3 FLASH FAME BTM COOLER Figure 5. Flowsheet of biodiesel production by heat-integrated reactive distillation. The conceptual process design is further improved in this work by adding heatintegration around the reactive distillation column (Figure 5). The hot bottom product of the column, a mixture of fatty esters, is used to pre-heat both reactants: the fatty acid and alcohol feed streams. Figure 6 shows the composition, temperature and reaction rate profiles in the reactive distillation column. The mass balance of these designs is given in Table 2, while Table 3 shows a comparison between the base case and the heatintegrated alternative, in terms of energy requirements. Compared to the conventional reactive distillation design, the energy requirements in the heat-integrated case are further decreased with –43% and –47% for heating and cooling, respectively. Note that both design alternatives are suitable for a large range of fatty acids and alcohol feedstocks. These processes based on RD have no additional separation steps and produce no waste salt streams as water is the only by-product. By combining reaction and separation, one can shift the reaction equilibrium towards products by continuous removal of reaction products, instead of using an excess of reactant. Temperature / °C Molar fraction 0 0.2 0.4 0.6 0.8 60 1 100 140 180 220 0 0 3 3 Water Acid 6 6 Stage Reaction rate 9 9 12 12 Ester Methanol Temperature 15 15 0 0.2 0.4 0.6 Molar fraction 0.8 1 0 0.5 1 1.5 2 2.5 Reaction rate / kmol/hr Figure 6. Profiles in RDC: liquid composition (left), temperature and reaction rate (right). 6 A. A. Kiss et al. Table 2. Mass balance of the biodiesel production process based on reactive-distillation. F-ACID Temperature K Mass Flow kg/hr METHANOL ACID WATER ESTER-M Mass Frac METHANOL ACID WATER ESTER-M F-ALCO BTM REC-ALCO FAME TOP WATER 418.1 338.6 480.4 480.4 303.1 372.8 323.1 0 1167.607 0 0 188.631 0 0 0 1.883 0.144 0.005 1249.195 0.391 0 0.001 0.834 1.492 0.144 0.003 1248.361 0.011 0.11 104.988 0.01 0.011 0.015 104.986 0 0 1 0 0 1 0 0 0 0.002 0 0 0.998 0.319 0 0.001 0.68 0.001 0 0 0.999 0 0.001 0.999 0 0 0 1 0 Table 3. Comparison of energy consumption: base case vs heat-integrated design. Operating unit Heating requirements 1. RDC reboiler 2. HEX1 / FEHE1 3. HEX2 / FEHE2 Cooling requirements 1. RDC condenser 2. Decanter 3. Cooler Base case KW 136 95 8 KW –72 –6 –141 Heat integration KW 136 0 0 KW –72 –6 –38 Difference –43 % –47 % 5. Conclusions The integrated design proposed in this work is based on catalytic reactive distillation, powered by metal oxides as solid acid catalysts for fatty acids esterification. By adding heat integration to the conventional reactive distillation setup, significant energy savings of ~45% are possible. This heat integrated alternative improves the HSE benefits and economics of traditional biodiesel processes, and reduces dramatically the number of downstream processing steps. The major benefits of this approach are: 1. Very high conversions, as the chemical equilibrium is shifted towards completion. 2. Increased unit productivity, up to 5-10 times higher than conventional processes. 3. No excess of alcohol required, as both reactants are fed in stoichiometric ratio. 4. No catalyst neutralization step hence no salt waste streams nor soap by-products. 5. Sulfur-free fuel, since solid acid catalysts do not leach into the biodiesel product. 6. Multifunctional plant suitable for a large range of alcohols and fatty acids mixtures. 7. Reduced investment costs, due to less operating units required vs typical designs. 8. Minimum energy consumption, due to heat integrated reactive distillation design. Acknowledgement. We thank Marjo C. Mittelmejer-Hazeleger and Jurriaan Beckers from HIMS (University of Amsterdam) for the technical support. References B. Buczek, L. Czepirski, 2004, Inform, 15, 186. T. Okuhara, 2002, Chemical Reviews, 102, 3641. A. A. Kiss, A. C. Dimian, G. Rothenberg, 2006, Adv. Synth. Cat., 348, 75. A. A. Kiss, G. Rothenberg, A. C. Dimian, F. Omota, 2006, Top. Catal., 40, 141.