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Energy requirement estimates for single step ethanolysis of waste vegetable oils for biodiesel production

N. Ligeris, K. Jalama, E. Muzenda
Abstract —This study aimed at estimating the energy requirements for single-step biodiesel production process from waste vegetable oils (WVO) and ethanol in presence of an homogeneous acid catalyst. A process flowsheet consisting of feed preparation, esterification/transesterification of WVO, biodiesel refining, and ethanol and glycerol recovery was developed and simulated using ChemCad. The process energy requirements have been estimated as 6.65 MJ per kg of biodiesel produced with ethanol recovery accounting for the highest proportion of the energy required for the process.

reports on single-step WVO conversion into biodiesel using acid catalysts [6-8]. Most of these studies only report on the transestrification reaction kinetics and little is known on the process energy requirements as other steps such as alcohol recovery, biodiesel purification, etc. must also be considered in the process. This work aims at estimating the energy requirements for single-step biodiesel production process in presence of a homogeneous acid catalyst. This study will be done using ChemCad simulation package.
II. METHODOLOGY

Key words — Energy requirements, single step, ethanolysis, waste vegetable oil

I. INTRODUCTION IODIESEL is the name for a variety of ester-based oxygenated fuels from renewable biological sources. It can be made from processed organic oils and fats through the transesterification reaction of a vegetable oil (triglycerides) or animal fat with methanol or ethanol in the presence of an acid or alkali catalyst to yield methyl or ethyl esters (biodiesel) and glycerol. Free fatty acids (FFA) may also be directly esterified with an alcohol in the same catalytic environment as above to yield an alkyl ester and water [1]. The use of organic oils as feedstock for biodiesel production is seen as a direct threat to food production in some regions with limited land and water available to meet the requirements for growing crops. However, waste vegetable oils are cheap compared to virgin oils and their supply doesn’t compete with food production. The conversion of used vegetable oils will reduce/eliminate their disposal into waste drainage posing environmental problems. Around 379 million litres of waste cooking oil is produced per day in USA [2] and 1.9 – 2.6 million gallons/day in Europe [3]. The amount of waste cooking oil available in South Africa on a monthly basis is in excess of 30 million litres [4]. One major problem with WVO as feedstock for biodiesel production is the significant amount of FFA's and water that they contain. This is due to the thermal oxidation of the triglycerides and the food's inherent water during frying. For this reason, an alkali homogeneous catalyst must be avoided when WVO is used as feedstock for biodiesel production as an alkali catalyst has a high tendency to saponify the FFA and produce alkali soap. Soap generation not only consumes the alkali catalyst but also creates emulsions which lead to difficulties in downstream recovery and purification of biodiesel [5]. For this reason, the conversion of WVO is usually carried in two steps where the first consist of direct FFA esterification in presence of an acid catalyst followed by an alkali conversion of the oil in the second step. There are also

B

A single step homogeneous acid-catalyzed ethanolysis of WVO process simulation was developed using CHEMCAD 6.3.1. The processing plant capacity was specified at ca. 8000 metric tonnes of biodiesel per year which translates to WVO process feed of 1050 kg/h. Ethanol, glycerol, sulfuric acid, sodium hydroxide, water, calcium oxide, calcium sulphate, tri-sodium phosphate, triolein, oleic acid and ethyl oleate were the selected components used in the process simulation. The WVO was modeled by a mixture of triolein (94 wt.%) and oleic acid (6 wt.%). Biodiesel was represented by ethyl oleate and was referred to as fatty acid ethyl esters (FAEE). This component was not available in the CHEMCAD component library and was created using the Universal Functional Activity Coefficient (UNIFAC) group contribution method which requires input of a number of properties, such as normal boiling point, SG (60°F), molecular weight as well as the functional groups of the substance. The boiling point was taken as 210°C [9], molecular weight as 310.53g/mol and SG at 60°F as 0.8773 [10]. The non-random two liquid (NRTL) thermodynamic/activity model was selected as the global simulation model. Where applicable, local thermodynamics were set as modified UNIFAC with a vapour/liquid/liquid/solid phase option. All binary interaction parameters (BIP's) that were not available in the simulation databanks were regressed using the UNIFAC vapour–liquid equilibrium and UNIFAC liquid–liquid equilibrium models where appropriate. The simulated process flowsheet is presented in fig. 1 and includes esterification and transesterification reactor (R-1), distillation columns (C-1 to C-4), extraction columns (W1), heat exchangers (E-1 and E-2), pumps (P-1 to P-4) and a gravity separator (S-1). EtOH and H2SO4 were mixed together and pumped to another mixing tank where they were mixed with the WVO. The Ethanol to WVO ratio was 50:1 and the amount of H2SO4 used was 2.1% of the WVO. This mixture passed through a pre-heater (E-1) before being fed to the transesterification/esterification reactor (R1). The

 N. Ligeris, K. Jalama and E. Muzenda are with the Department of Chemical Engineering in the School of Mining, Metallurgy and Chemical Engineering, University of Johannesburg, Johannesburg 2028, South Africa (Phone: +27-11-559-6157; fax: +27-11-559-6340; e-mail: kjalama@uj.ac.za).

Fig. 1: Simulated flowsheet for single step acid-catalyzed ethanolysis of WVO for biodiesel production

reactor was modelled as isothermal continuously stirred tank at equilibrium conditions assuming 95% conversion of WVO to FAEE. Downstream purification consisted of ethanol recovery by distillation (C-1), acid catalyst removal by neutralization with CaO (R-2) and gravity separation (S1), glycerol separation using a wash column (W-1) and distillation (C-3) and FAEE purification by distillation (C2). Reflux ratios were calculated using a shortcut-modelled distillation column to determine the minimum reflux ratio (Rmin), number of stages, feed stage location and reboiler duty. Thereafter these parameters were fed into a rigorous SCDS column model in ChemCad. For less than 50 ideal stages R was taken as 1.5xRmin and for up to 100xRmin for much larger columns. In the simulations, a top and bottom tray efficiency of 60 and 70% respectively were assumed with a linear efficiency profile. Because FAEE and glycerol are susceptible to thermal decomposition above 250 and 150°C respectively [11], vacuum operation for the FAEE and glycerine purification was necessary to keep the temperature at suitably low levels. ASTM standard purity for the produced biodiesel i.e. 99.65wt.% FAEE [11] was targeted in this study. Liquid–liquid extraction was used to separate FAEE from glycerol, ethanol and catalyst.
III. RESULTS AND DISCUSSION

Material and enthalpy balance data for the simulated process in fig.1 are presented in table 1 and the energy required for the process is presented in table 2. About 80% of ethanol from the transesterification reactor (stream 6, table 1) was recovered by distillation in column C-1 (fig. 1) and recycled. A second step for ethanol recovery was achieved by distillation in column C-4 (fig. 1) where ca. 97% of ethanol was recovered in stream 26 with a purity of ca. 94 wt.%. This purity was limited because of the waterethanol azeotrope. No azeotropic distillation was considered in this study. The overall material balance data (Table 1) show that ca. 2.8% of ethanol fed to the process was unrecovered and was lost in waste water stream (stream 27). Glycerol was recovered by distillation in column C-3. Also ca. 5% of the WVO fed to the process was recovered in stream 23 as unconverted oil which can possibly be recycled to the process. About 1.5% of the biodiesel produced in the reactor R-1 was lost through downstream biodiesel refining processes. The data in table 2 show that distillation columns require more energy than other equipment. As no heat integration opportunity was considered, only positive duties were considered as energy required. Therefore, the reboiler duty was taken as the energy required for a distillation column. 6.65 MJ are required to produce 1 Kg of biodiesel from WVO. The distribution of the process energy requirements is presented in fig. 2. Feed preparation and biodiesel production reaction only account for 2% of the energy required. Ethanol recovery (first and second step recovery) accounts for ca. 72% of the process energy requirements. This can be explained by a high ethanol-to-oil ratio required to achieve higher WVO oil conversion to biodiesel in presence of an acid catalyst. Biodiesel refining by distillation accounts for ca. 10% of the total process energy requirements. The process also includes glycerol recovery which accounts for 15% process energy requirements. This step is useful as it will produce concentrated glycerol that can be sold to improve the process economics.

TABLE I MATERIAL AND ENTHALPHY BALANCE FOR THE SIMULATED FLOWSHEET FOR WVO ETHANOLYSIS
Stream No. Temperature [ oC] Presure [kPa] Enthalpy [MJ/h] Flow rates [kg/h] Ethyl Oleate Ethanol triolein Glycerol Oleic Acid Water Sulfuric Acid Calcium Oxide CaSO4 Total flowrate [kg/h] Stream No. Temperature [ oC] Presure [kPa] Enthalpy [MJ/h] Flow rates [kg/h] Ethyl Oleate Ethanol triolein Glycerol Oleic Acid Water Sulfuric Acid Calcium Oxide CaSO4 Total flowrate [kg/h] Stream No. Temperature [ oC] Presure [kPa] Enthalpy [MJ/h] Flow rates [kg/h] Ethyl Oleate Ethanol triolein Glycerol Oleic Acid Water Sulfuric Acid Calcium Oxide CaSO4 Total flowrate [kg/h] Stream No. Temperature [ oC] Presure [kPa] Enthalpy [MJ/h] Flow rates [kg/h] Ethyl Oleate Ethanol triolein Glycerol Oleic Acid Water Sulfuric Acid Calcium Oxide CaSO4 Total flowrate [kg/h] 1 25.0 100.0 -4475.0 0.000 743.016 0.000 0.000 0.000 0.000 0.000 0.000 0.000 743.016 8 55.0 200.0 -20994.0 9.778 3082.471 987.000 0.000 63.000 13.065 22.050 0.000 0.000 4177.363 1 5 25.0 200.0 290.3 0.000 0.000 0.000 0.000 0.000 0.000 0.000 12.607 0.000 12.607 2 2 65.4 20.0 -2691.6 1046.462 0.014 0.667 0.000 0.000 3.178 0.000 0.000 0.000 1050.321 2 25.0 100.0 -176.5 0.000 0.000 0.000 0.000 0.000 0.000 22.050 0.000 0.000 22.050 9 55.0 200.0 -21357.0 1062.038 2926.351 49.350 97.526 3.150 16.882 22.050 0.000 0.000 4177.348 1 6 59.9 200.0 -6906.0 1052.260 586.877 49.350 97.526 3.150 3.825 22.050 12.607 0.000 1827.645 2 3 253.8 30.0 -114.3 2.332 0.000 48.683 0.000 3.080 0.000 0.000 0.000 0.000 54.095 3 25.0 100.0 -4651.6 0.000 743.016 0.000 0.000 0.000 0.000 22.050 0.000 0.000 765.066 1 0 42.1 20.0 -14221.0 9.778 2339.474 0.000 0.000 0.000 13.057 0.000 0.000 0.000 2362.310 1 7 60.0 200.0 -7419.7 1052.260 586.877 49.350 97.526 3.150 7.875 0.000 0.000 30.607 1827.645 2 4 60.0 120.0 -7405.0 3.467 586.863 0.000 97.526 0.070 204.697 0.000 0.000 0.000 892.623 4 25.1 200.0 -4651.4 0.000 743.016 0.000 0.000 0.000 0.000 22.050 0.000 0.000 765.066 1 1 42.2 200.0 -14220.0 9.778 2339.474 0.000 0.000 0.000 13.057 0.000 0.000 0.000 2362.310 1 8 60.0 200.0 -335.3 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 30.607 30.607 2 5 43.3 20.0 -6740.3 3.467 586.863 0.000 0.000 0.001 204.446 0.000 0.000 0.000 794.776 5 20.0 100.0 -2266.1 0.000 0.000 987.000 0.000 63.000 0.000 0.000 0.000 0.000 1050.000 1 2 53.0 30.0 -7226.2 1052.260 586.877 49.350 97.526 3.150 3.825 22.050 0.000 0.000 1815.038 1 9 60.0 200.0 -7084.4 1052.260 586.877 49.350 97.526 3.150 7.875 0.000 0.000 0.000 1797.038 2 6 42.0 20.0 -3958.4 0.018 566.385 0.000 0.000 0.000 36.194 0.000 0.000 0.000 602.597 6 26.2 200.0 -2265.3 0.000 0.000 987.000 0.000 63.000 0.000 0.000 0.000 0.000 1050.000 1 3 53.1 200.0 -7225.7 1052.260 586.877 49.350 97.526 3.150 3.825 22.050 0.000 0.000 1815.038 2 0 25.0 200.0 -3171.7 0.000 0.000 0.000 0.000 0.000 200.000 0.000 0.000 0.000 200.000 2 7 61.2 30.0 -2760.1 3.449 20.478 0.000 0.000 0.001 168.252 0.000 0.000 0.000 192.180 7 37.9 200.0 -21137.0 9.778 3082.471 987.000 0.000 63.000 13.065 22.050 0.000 0.000 4177.363 1 4 60.0 200.0 -7196.2 1052.260 586.877 49.350 97.526 3.150 3.825 22.050 0.000 0.000 1815.038 2 1 47.7 110.0 -2851.2 1048.793 0.014 49.350 0.000 3.080 3.178 0.000 0.000 0.000 1104.415 2 8 173.0 30.0 -670.8 0.000 0.000 0.000 97.526 0.070 0.251 0.000 0.000 0.000 97.847

TABLE II ENERGY REQUIREMENTS FOR MAJOR PROCESS EQUIPMENT IN THE SIMULATED PROCESS FLOWSHEET (FIG. 1)
Equipment ID P-2 P-1 E-1 R-1 C-1 Description Pump (EtOH/H2SO4 feed) Pump (WVO oil feed) Heat exchanger (feed pre-heater) Reactor (Esterification + Transesterification) Distillation column (Ethanol recovery, 31 stages, reflux ratio: 0.025) Condenser Reboiler P-3 P-4 E-2 R-2 S-1 17 C-2 Pump (Ethanol recycle) Pump (neutralization reactor feed) Heat exchanger (neutralization reactor feed pre-heater) Reactor (Neutraliser) Gravity separator Washing column Distillation column (FAEE refining, 23 stages, reflux ratio: 0.020) Condenser Reboiler C-3 Distillation column (Glycerol refining, 16 stages, reflux ratio: 0.010) Condenser Reboiler C-4 Distillation column (Ethanol refining, 31 stages, reflux ratio: 3.93) Condenser Reboiler Total Biodiesel production [kg/h] Energy requirement in MJ/kg biodiesel -2937.7893 2946.7402 6958.05* 1046.5 6.65 -1032.9681 1024.21 -667.4139 712.7953 -2189.968 2100 0.73512 0.49464 29.637 -513.7299 Energy required [MJ/h] 0.1278 0.15444 143.1569 -363.1761

* equal to the sum of positive heat duties

(6) 42%

(1) 2%

(2) 30%

(3) 1% (4) 10%

flowsheet simulation in ChemCad. With no attempt on process energy integration, the energy required to produce 1 kg of biodiesel was estimated as 6.65 MJ. Methanol recovery accounts for the highest portion of the process energy requirements followed by glycerol recovery which accounts for ca. 15% of the energy required for the process. The feed preparation and reaction accounted for 2% and the biodiesel refining by distillation for 10% of the total energy required by the process. ACKNOWLEDGMENT We would like to thank the University of Johannesburg for financial support.

(5) 15%

Fig. 2: Energy requirement distribution by process step: (1): Feed preparation and esterification + transesterification; (2): First step ethanol recovery and recycle; (3): Neutralization; (4): FAEE refining; (5): Glycerol recovery; (6): Second step ethanol recovery
IV. CONCLUSION

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The energy required by the process of producing biodiesel from WVO and ethanol in a single step using an acid catalyst has been estimated by performing a process

[4] [5]

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