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Life cycle assessment compares inorganic and biological catalysis for the production of biodiesel by transesterification. Inorganic route using catalysis by sodium hydroxide has been compared with a conceptual biological one using lipase produced by Candida antarctica.
Life cycle assessment compares inorganic and biological catalysis for the production of biodiesel by transesterification. Inorganic route using catalysis by sodium hydroxide has been compared with a conceptual biological one using lipase produced by Candida antarctica.
Life cycle assessment compares inorganic and biological catalysis for the production of biodiesel by transesterification. Inorganic route using catalysis by sodium hydroxide has been compared with a conceptual biological one using lipase produced by Candida antarctica.
A life-cycle comparison between inorganic and biological catalysis
for the production of biodiesel
K.G. Harding a, * , J.S. Dennis b , H. von Blottnitz a , S.T.L. Harrison a a Department of Chemical Engineering, University of Cape Town, South Africa b Department of Chemical Engineering, University of Cambridge, UK Received 8 February 2007; received in revised form 16 July 2007; accepted 30 July 2007 Available online 27 September 2007 Abstract Life cycle assessment (LCA) has been used to compare inorganic and biological catalysis for the production of biodiesel by transesterica- tion. The inorganic route, using catalysis by sodium hydroxide, has been compared with a conceptual biological one using enzymatic catalysis by the lipase produced by Candida antarctica. Although biological catalysis has not been used for industrial production of biodiesel to date, results from laboratory experiments suggest that it could have distinct advantages over the inorganic route, particularly with regard to a simplied owsheet for purication and concomitant energy savings. Five owsheet options have been included in the study to investigate the alkali and enzyme catalysed production routes from rapeseed oil, use of methanol or ethanol for transesterication and the effect of efciency of alcohol recovery. The LCA shows that the enzymatic production route is environmentally more favourable. Improvements are seen in all impact cate- gories. Global warming, acidication, and photochemical oxidation are reduced by 5%. Certain toxicity levels have more than halved. These results are mainly due to lower steam requirements for heating in the biological process. 2007 Elsevier Ltd. All rights reserved. Keywords: Biodiesel; Life cycle assessment (LCA); Biological catalysts; Candida antarctica lipase 1. Introduction Biodiesel is a generic term for alkyl esters of fatty acids, produced by esterication of vegetable oils with an alcohol (usually methanol, but also ethanol). It is blended with diesel fuel derived from crude oil to reduce the proportion of CO 2 at- tributed to the fossil-fuel when the mixture is burnt. Biodiesel can also decrease other emissions characteristic of normal die- sel fuel, such as particulates and SO x . The advantages of bio- diesel combustion over petroleum diesel are well documented [1e6]. Both virgin and waste vegetable oils can be converted to form the renewable fuel biodiesel. Industrially, methanol is used with a homogenous alkali catalyst. Acid catalysts can also be used to facilitate reaction [7e16]. However, recent studies, largely still at the laboratory stage, have explored the use of the enzyme lipase as a biological catalyst [17e34]. Other methods of preparation have also been pro- posed. These include using supercritical uids [35,36], or zeolites and metal catalysts [37e42]. The latter two process alternatives are not considered here. The purpose of this study is to compare the environmental impacts of various owsheets which could be proposed for the production of biodiesel at the industrial scale. These include the use of alkali or enzyme catalysts, the use of alcohols meth- anol and ethanol in reaction and varied recovery levels of ex- cess alcohol (Table 1). An LCA based methodology such as ISO 14040: 2006 is used [43]. It should be borne in mind that, currently, there are no industrial-scale processes for bio- diesel based on enzymatic esterication. An outcome of this study is to identify the scientic and technical barriers to over- come for a biological route to be competitive with established inorganic routes. * Corresponding author. Fax: 27 21 650 5501. E-mail address: kevin.harding@uct.ac.za (K.G. Harding). 0959-6526/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.jclepro.2007.07.003 Available online at www.sciencedirect.com Journal of Cleaner Production 16 (2007) 1368e1378 www.elsevier.com/locate/jclepro 2. Biodiesel production process 2.1. Introduction In order to determine the environmental impacts of biodie- sel production through life cycle assessment, process ow- sheets giving material and energy inputs and outputs are required. Simulation models for each process option have been developed using Aspen Plus
. Flowsheets were devel-
oped for each case, using NaOH for chemical catalysis and the enzyme lipase from Candida antarctica for biological catalysis. The process owsheets developed are continuous models converting rapeseed oil (assumed to be pure triacylglycerol e C 57 H 104 O 6 ), via a transesterication reaction, to biodiesel (Eq. (1)). The alkali catalysed process is based on the ap- proach of Zhang et al. [15], including supportive and alterna- tive conditions described by others (Table 2). 2.2. Alkali catalysed process As shown in Fig. 1, in the base case (case 1), methanol (stream 101) enters at a 6:1 molar ratio with respect to the oil (stream 105) (twice the stoichiometric requirement) allow- ing the equilibrium to be shifted towards biodiesel production (Fig. 1). The catalyst (NaOH) is present at a 0.01 mass fraction with respect to oil. An assumption is made that dehydrogen- ated vegetable oil with less than 0.5 wt.% free fatty acid, an- hydrous alkali catalyst and anhydrous alcohol are used as water and free fatty acids can lead to soap formation [44,45]. If waste cooking oils were used, a purication step is needed before the reactor to ensure a low free fatty acid and water content. The oil, catalyst and alcohol are fed (stream 102) into reac- tor R-101. The reactor is maintained at a temperature of 60
C and a pressure of 4 bar. After a 2 h residence time, a 95% con- version of oil to biodiesel and a glycerol co-product is assumed. The reactor products (stream 106) are fed to a methanol recov- ery unit (distillation column, T-201) where 94% of the metha- nol is separated by distillation and recycled back to R-101. Biodiesel from the transesterication reaction (stream 202) is separated from glycerol by counter current water washing (T-301). Zhang et al. [15] recommended 11 kg of wash water per 1050 kg fresh oil feed and the use of a second unspecied purication unit. The amount of water used was increased to 260 kg to achieve separation in a single step. The majority Table 1 Specications of the different biodiesel production process owsheets investigated Flowsheet 1 2 3 4 5 Catalyst Alkali Lipase Alkali Alkali Lipase Alcohol used Methanol Methanol Methanol Ethanol Ethanol Alcohol recovery (%) 94 e 50 94 e Table 2 Literature process conditions for transesterication of oils (alkali catalysts) Karaosmano glu et al. [12] Boocock et al. [11] Vicente et al. [10,16] Lang et al. [13] Antolin et al. [14] Zhang et al. [15] This study Oil used Rapeseed Soybean Sunower Rapeseed, linseed, sunower Sunower Waste cooking oil, triacylglycerol Triacylglycerol (rapeseed oil) Alcohol used Methanol Methanol, butanol Methanol Methanol, ethanol, 2-propanol, 1-butanol Methanol Methanol Methanol, ethanol Alcohol to oil ratio 6:1 6:1e30:1 6:1 6:1 9:1 6:1 6:1 Catalyst used NaOH NaOH or NaOCH 3 in THF NaOH KOH, sodium methoxide KOH NaOH NaOH Catalyst wt. fraction 0.016 0.002e0.01 0.013 0.01e0.02 0.0028e0.0055 0.01 0.01 Reactor temperature 65
C 20e60
C 20e65
C 25e110
C 60e70
C 60
C 60
C Reactor pressure 1 atm 1 atm 1 atm 1 atm 1 atm 4 bar 4 bar Residence time 38e50 min 10e15 min 8 h 40 mine3 h 2 h Oil conversion 97.4e99.7% (50 min) 70e95% 100% 98% (1 h) 96% 95% (2 h) 95% (2 h) Methanol recovery w100% 94% 94% 50% Wash water (kg/kg oil) Includes tannic acid or brine Includes H 3 PO 4 0.01 0.26 Neutralising acid H 3 PO 4 HCl THF e tetrahydrofuran. OOC R3 CH 2 OOC R2 CH CH 2 OOC R1 OH CH 2 OH CH CH 2 OH R1 COO R' R2 COO R' R3 COO R' 3 R'OH + + Catalyst Oil 3 (Biodiesel) Glycerol 3 (Alcohol) + + 1369 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378 of the glycerol and sodium hydroxide is taken out with the wa- ter stream (302), while the unreacted oil and biodiesel product remain in stream 301. Sodium hydroxide in stream 302 is neutralised in a second reactor (R-201). Zhang et al. [15] suggest phosphoric acid. As the thermodynamics of the resulting salt were unknown, hydrochloric acid (HCl) was chosen to replace it. Acid enters (acid stream) stoichiometrically so that all the alkali is treated. The products from the reactor (stream 304) were further puri- ed in distillation column T-501 to remove water (stream 501) which is split and recycled or discarded. The salt is removed by a crystalliser (X-302), leaving 105 kg of 85% purity glycerol (stream 305). The biodiesel and unconverted oil from the water washing unit (T-301) proceed to distillation column T-401 (stream 301) for separation. Oil is removed in the bottoms and recycled to reactor R-101 via stream 402B. A liquid/vapour mixture is ob- tained from the distillate of column containing 99.6 wt.% liq- uid biodiesel product (stream 401) and a vapour methanol (68%) stream (401A) which is split and recycled to reactor R-101 or discarded. 2.3. Biologically catalysed process Using the owsheet model for biodiesel production with an alkali catalyst outlined above, relevant changes were made to R-101 T-201 T-401 R-201 T-501 T-301 X-302 OIL (WASTE) WATER ALCOHOL CATALYST OIL ACID SALT BIODIESEL GLYCEROL METHANOL (WASTE) WATER (WASTE) 304 101 103 101A 102 106 201 202 301 401 401A 401B 401C 402 402A 402B 105 105A H2O ACID H2OA 302 501 501B 501C 502 306 305 Fig. 1. Biodiesel process owsheet to be used in LCA e alkali catalyst. R-101: transesterication reactor; T-201: distillation column (methanol recovery); T-301: counter current water washing; T-401: distillation column (biodiesel purication); R-201: alkali neutralisation; T-501: distillation column (water removal from glycerol/salt); X-302: crystalliser (salt removal from glycerol). R-101 T-401 T-501 T-301 OIL (WASTE) WATER ALCOHOL OIL BIODIESEL GLYCEROL METHANOL (WASTE) WATER (WASTE) 101 102 106 301 401 401A 401B 401C 402 402A 402B 105 105A H2O H2OA 302 501 501B 501C 502 Fig. 2. Biodiesel process owsheet to be used in LCA e biological catalyst. R-101: transesterication reactor; T-301: counter current water washing; T-401: dis- tillation column (biodiesel purication); T-501: distillation column (water removal from glycerol/salt). 1370 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378 accommodate an enzyme catalyst (case 2). Where possible, features were kept unchanged to facilitate comparison through life cycle analysis. Lipase from C. antarctica (immobilized on polyacrylate polymer beads as supplied by Novo Nordisk e Novozym 435
) was used as the enzyme catalyst.
As with the alkali catalysis scenario, enzyme catalysis con- sists of a continuous reactor feeding methanol (stream 101) and oil (stream 105) to reactor R-101 (Fig. 2). The enzyme loading is kept at 4 wt.% (biomass and support) as recommended by Shimada et al. [22]. Methanol is fed such that the concentration is kept low. A concentration higher than half the stoichiometric amount will denature the catalyst [21,22]. Reaction is main- tained at 25
C and 1 bar with a residence time of 20 h. Since 90% of the methanol reacts (no excess was added), there is little need for methanol recovery by distillation; hence unit T-201 is omitted. Also, since no alkali is present in the system, there is no need for neutralisation by acid and reactor R-201 and crystalliser X-302 are omitted. 2.4. Additional process owsheets Further process alternatives in this study include modica- tion of the original alkali catalysed process (case 1) to allow for a lower methanol recovery in T-201 (case 3). The alkali catalysed (case 1) and biologically catalysed (case 2) pro- cesses have also been modeled using ethanol instead of meth- anol (cases 4 and 5, respectively) (Table 3). The mass and energy balances obtained (Table 4) are then used for the life cycle assessment (LCA) study. 3. Production alternatives Even though conversion rates are generally slower in the enzyme catalysed route, interest in the process is justied by the resultant simplications and lower reaction temperatures. Advances in the technology have also resulted in a decrease in catalyst price which had been a previous concern [46]. The lipase catalyst does not impose restrictions on the water content or level of free fatty acids in the oil, and is able to yield similar conversions to the alkali catalysed option. There is a high ester yield and no saponication reaction occurs [4]. Chemical catalysts need to be neutralised before glycerol can be removed, forming a salt by-product that contaminates the glycerol product. In contrast, the immobilized lipase remains Table 3 Process conditions for biodiesel production used to compare alkali catalysed and biocatalysed biodiesel production Case 1 Case 2 Case 3 Case 4 Case 5 Oil used Triacylglycerol (rapeseed oil) Triacylglycerol (rapeseed oil) Triacylglycerol (rapeseed oil) Triacylglycerol (rapeseed oil) Triacylglycerol (rapeseed oil) Catalyst used NaOH Immobilized enzyme from Candida antarctica NaOH NaOH Immobilized enzyme from Candida antarctica Catalyst fraction 0.01 (molar) 0.04 (mass) 0.01 (molar) 0.01 (molar) 0.04 (mass) Alcohol used Methanol Methanol Methanol Ethanol Ethanol Alcohol to oil ratio 6:1 3:1 6:1 6:1 3:1 Alcohol recovery 94% (None required) 50% 94% (None required) Oil conversion 95% 90% 95% 95% 90% Reactor temperature 60
C 25
C 60
C 60
C 25
C Reactor pressure 4 bar 1 bar 4 bar 4 bar 1 bar Residence time 1.5 h 16 h 1.5 h 16 h Table 4 Mass and energy values obtained from owsheets for each case to be used in life cycle analysis Case 1 Case 2 Case 3 Case 4 Case 5 Products Biodiesel (kg) 1000 1000 1000 1000 1000 Glycerol (kg) 106 106 106 101 101 Feed Rapeseed oil (kg) 991 991 991 947 947 Methanol (kg) 112 111 146 e e Ethanol (kg) e e e 149.82 0.23 NaOH (kg) 10.4 e 10.4 10.0 e HCl (kg) 37.9 e 37.9 36.2 e Steam (kg) 1820 1540 2060 1820 1490 Electricity (kWh) 8.6 34.1 12.4 9.9 35.4 Water (process) (kg) 29.8 56.4 28.8 30.6 55.9 Water (cooling) (tons) 117 97.4 132 114 92.6 Waste Salt (kg) 15.2 e 15.2 14.5 e Methanol (kg) 2.9 2.4 36.1 e e Ethanol (kg) e e e 0 0.23 Water (kg) 57.5 50.9 57.8 57.4 51.0 Table 5 LCIA of biodiesel production (case 1) e CML 2 Baseline 2000 v2.1 Impact category Unit Characterisation Normalisation Abiotic depletion kg Sb eq 16.0 9.98E14 Global warming (GWP100) kg CO 2 eq 4150 8.97E14 Ozone layer depletion (ODP) kg CFC-11 eq 0.000827 7.24E16 Human toxicity kg 1,4-DB eq 145 2.41E15 Fresh water aquatic ecotoxicity kg 1,4-DB eq 14.1 6.82E15 Marine aquatic ecotoxicity kg 1,4-DB eq 277,000 3.66E13 Terrestrial ecotoxicity kg 1,4-DB eq 2.71 1.03E14 Photochemical oxidation kg C 2 H 2 1.45 1.35E14 Acidication kg SO 2 eq 30.2 9.65E14 Eutrophication kg PO 4 3 eq 37.6 2.85E13 Values are for 1000 kg of biodiesel product. 1371 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378 in the reactor and does not contaminate reaction products; hence glycerol recovery and purication may be simplied. Methanol is the most commonly used alcohol in the reac- tion because of its short chain length and low cost. Its use is a possible cause of environmental concern since it requires crude oil in production, both for energy and as a raw material. Ethanol is renewable and has suggested advantages due to be- ing environmentally based and carbon dioxide neutral [47], making it the most promising alternative. In this study, ethanol is produced from sugar and includes the uptake of CO 2 during sugarcane growth. In alkali catalysed biodiesel production, al- cohol is added in excess to favour the transesterication reac- tion. Alcohol recovery is required to minimise alcohol waste. A high recovery requires a higher energy input for distillation. The relative advantage of minimizing the energy requirement through lowering the recovery requires assessment (compari- son of cases 1 and case 3). In the enzyme catalysed route, al- cohol recovery is eliminated completely since a high alcohol concentration can inactivate the enzyme. Stepwise, stoichio- metric addition is required [21,22,26e28,48]. 4. Life cycle assessment (LCA) Comparison of the different routes of biodiesel production was done with the LCA software package SimaPro v6 (PRe Fig. 3. Process contributions of biodiesel production (case 1) e single score EPS 2000 v2.1. Fig. 4. LCA results e chemical vs. biological catalysts (biodiesel production by alkali catalysis assuming 94% methanol recovery (case 1) is compared to pro- duction using lipase as a biocatalyst (case 2)). 1372 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378 Consultants B.V.), using the CML 2 Baseline 2000 v2.1 as- sessment method. The system was dened as cradle-to-gate production of 1000 kg of biodiesel, equivalent to a fuel with a caloric value of 27.1 GJ, or 33.3 MJ/l [49]. The LCA in- cluded all raw materials, agricultural inputs and biodiesel pro- cessing required for the nal biodiesel product. The impacts of process plant and equipment construction were not included in the LCA results. The production includes the useful by- product glycerol which, due to process design and stoichiom- etry, is of equal purity and in equal proportion to biodiesel in each process. Because of varying costs of glycerol as a func- tion of purity and its stoichiometric yield, burden allocation has been based on mass ratios of useful end product. The results do not include impacts of the biological catalyst since the immobilized enzyme is re-used resulting in a very low re- quirement of environmentally benign protein, hence expecta- tions are that such an impact would be low. 5. Results 5.1. Alkali catalyst and methanol (case 1) Using the CML 2 Baseline 2000 v2.1 method, for 1000 kg of biodiesel produced by alkali catalysis in the presence of methanol (case 1), 4150 kg carbon dioxide equivalent is re- leased into the atmosphere, while 30.2 kg SO 2 eq. and 37.6 kg PO 4 3 eq. are emitted. Using the world data set from the CML method, normalized results show large impacts in marine aquatic toxicity and, due to rapeseed farming impacts, eutrophication. Abiotic depletion, global warming and acidi- cation also show signicant impacts (Table 5). The major contributing process in the biodiesel production is the farming process, including fertilizer production. Further contributors include the energy requirements from natural gas, diesel and heat oil, as well as the impacts associated with steam production. Impacts from methanol production are also highly rated in the single score of the EPS 2000 impact assessment method (Fig. 3). Because of the high energy contribution, milder process conditions are expected to improve LCA results as investi- gated in case 2. Reducing methanol recovery should also re- duce the energy needs (case 3). To further improve LCA results, changing the alcohol used to ethanol allows compari- son with methanol from both the original alkali and enzyme processes (cases 1 and 2 for methanol and cases 4 and 5 for ethanol). 5.2. Chemical vs. biological catalysts When comparing biodiesel production (CML 2 Baseline 2000 v2.1 method) using inorganic and biological catalysts with methanol as the transesterication alcohol (cases 1 and Fig. 5. LCA results e reduced methanol recovery (biodiesel production by alkali catalysis assuming 94% methanol recovery (case 1) is compared to production assuming 50% methanol recovery (case 3)). 1373 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378 2), all LCA impacts were lower for the enzyme catalysed pro- cess. Fresh water aquatic toxicity was reduced by approxi- mately 12%, while marine aquatic toxicity and human toxicity were also reduced by almost 10%. Terrestrial ecotox- icity was reduced by over 40% (mainly due to the removal of hydrochloric acid from the biologically catalysed process). Ozone layer depletion was reduced by 6%, abiotic depletion and acidication by 4%. Reductions in other categories are be- low 5%, but favour biological catalysts in every case (Fig. 4). 5.3. Reduced methanol recovery When methanol recovery in the alkali catalysed process was lowered from 94 to 50% (case 1 vs. 3), impacts increased in all categories. In order to maintain an equal amount of bio- diesel product, ow rates in the product recovery section in- crease when methanol recovery decreases. This results in greater pumping requirements and higher loads in distillation columns. Reducing recovery also increases waste methanol re- leased and the methanol feed. Reducing methanol recovery to 50% increased all recorded toxicity levels by at least 20%. Abiotic depletion increased by 12%, ozone layer depletion by 8% and global warming, pho- tochemical oxidation and acidication by 5%. The increase in eutrophication is not signicant since it is attributed to the farming component (Fig. 5). 5.4. Alternative alcohol (methanol vs. ethanol) When methanol is replaced with ethanol (produced biolog- ically from sugarcane) (case 1 vs. 4 (Fig. 6), case 2 vs. 5 (Fig. 7)), LCA results are mixed. Human and fresh water aquatic toxicity and acidication were higher with ethanol than when using methanol. The changes from methanol use to ethanol use are quantitatively similar in the alkali catalysed and enzymatic routes (Fig. 7). There is a large reduction in abiotic depletion (12.5%) and ozone layer depletion (27.3%), while improvements in photochemical oxidation (2%) and eutrophication (1.3%) are not signicant. Despite what was expected, the reduction in greenhouse gases (1.4%) is not large when replacing methanol with ethanol, even with the biologically derived ethanol taking up CO 2 dur- ing agricultural processes. There is a mixed result for toxicity with an improvement in marine aquatic and terrestrial ecotox- icity only. Terrestrial ecotoxicity improves to such an extent in case 5 (biological catalyst and ethanol) that it shows a positive impact. Negative effects of ethanol use are seen in human tox- icity and fresh water aquatic toxicity. This is partly due to the sugar based-ethanol LCA module used in this study [50] which has an unusually high coal demand compared to other models. If directly discharged into water, stillage from sugar (which is not taken into account here) will further increase the fresh water aquatic toxicity levels. Fig. 6. LCA results e alternative alcohol (methanol vs. ethanol) using alkali catalysis (biodiesel production by alkali catalysis assuming 94% methanol recovery (case 1) is compared to production using ethanol at 94% recovery (case 4)). 1374 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378 Fig. 8. LCA results for all owsheeting options (CML 2 Baseline 2000 v2.1 method). Fig. 7. LCA results e alternative alcohol (methanol vs. ethanol) using lipase biocatalysis (biodiesel production by lipase biocatalysis using methanol (case 2) is compared to production by lipase biocatalysis and ethanol (case 5)). 6. Conclusions Enzyme catalysed biodiesel production has environmental advantages due to avoided use of chemical catalyst and neu- tralising acid. The lower pressures and temperatures obtained help to give more favourable LCA results and all environmen- tal impacts considered are reduced (Fig. 8). The major contributing processes to LCA impacts are sim- ilar in all ve processes. Agricultural processes, steam produc- tion, natural gas and diesel are all rated highly on the EPS Table 6 LCIA of biodiesel production e CML 2 Baseline 2000 v2.1 Impact category Unit Case 1 Case 2 Case 3 Case 4 Case 5 Abiotic depletion kg Sb eq 16.0 15.4 18.0 14.0 13.4 Global warming (GWP100) kg CO 2 eq 4150 4050 4370 4090 3990 Ozone layer depletion (ODP) kg CFC-11 eq 0.000827 0.000777 0.000895 0.000601 0.000555 Human Toxicity kg 1,4-DB eq 145 134 184 162 153 Fresh water aquatic ecotoxicity kg 1,4-DB eq 14.1 12.4 17.3 42.1 40.6 Marine aquatic ecotoxicity kg 1,4-DB eq 277,000 252,000 352,000 169,000 147,000 Terrestrial ecotoxicity kg 1,4-DB eq 2.71 1.72 3.58 0.669 0.302 Photochemical oxidation kg C 2 H 2 1.45 1.43 1.52 1.42 1.40 Acidication kg SO 2 eq 30.2 29.3 31.7 31.4 30.5 Eutrophication kg PO 4 3 eq 37.6 37.5 37.7 37.1 37.1 Fig. 9. Process contributions for all owsheeting options e single score EPS 2000 v2.1. 1376 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378 2000 v2.1 single score method. The methanol production im- pact is higher than the ethanol production impact and plays a large role in the overall LCA results in these scenarios (cases 1, 2 and 3 and cases 4 and 5, respectively) (Fig. 9). In the alkali catalysed process, lower alcohol recovery re- quires greater ows to give similar product yield and purity. This increases energy needs as well as pollutants and causes a less favourable production route when analysed using life cycle assessment. Using ethanol instead of methanol in biodiesel production gives mixed LCA results (Table 6). In both alkali and enzyme catalysed routes, similar changes are observed when ethanol is used. Advantages or disadvantages are caused by the alcohol itself and do not interfere with other variables in the owsheet e which remain the same. References [1] Sheehan J, Camobreco V, Dufeld J, Graboski M, Shapouri H. Life cycle inventory of biodiesel and petroleum diesel for use in an urban bus. Colorado: United States Department of Agriculture and United States Department of Energy (USDA AND U.S. DOE); 1998. [2] Ma F, Hanna MA. Biodiesel production: a review. Bioresour Technol 1999;70:1e15. [3] Srivastava A, Prasad R. Triglyceride based diesel fuels. Renew Sust En- ergy Rev 2000;4:111e33. [4] Fukuda H, Kondo A, Noda H. Review: biodiesel fuel production by transesterication of oils. J Biosci Bioeng 2001;92(5):405e16. [5] Dorado MP, Ballesteros E, Arnal JM, Gomez J, Lopez FJ. Exhaust emis- sions from a diesel engine fueled with transesteried waste olive oil. Fuel 2003;82:1311e5. [6] Knothe G, Matheaus AC, Ryan III TW. Cetane numbers of branched and straight-chain fatty esters determined in an ignition quality tester. Fuel 2003;82:971e5. [7] Junek H, Mittelbach M, Andreae F. German patent 3,727,981; 1998. [8] Enchelmaier H, Rasenhorn HJ. German patent, 4,328,195; 1994. [9] Germani MM. German patent, 4,324,875; 1994. [10] Vicente G, Coteron A, Martinez M, Aracil J. Application of the factorial design of experiments and response surface methodology to optimize bi- odiesel production. Ind Crops Prod 1998;8:29e35. [11] Boocock DGB, Konar SK, Mao V, Sidi H. Fast one-phase oil-rich process for the preparation of vegetable oil methyl esters. Biomass Bioenerg 1996;11(1):43e50. [12] Karaosmano glu F, Ci gizo glu KB, Tuter M, Ertekin S. Investigation of the rening step of biodiesel production. Energy Fuel 1996;10:890e5. [13] Lang X, Dalai AK, Bakhshi NN, Reaney MJ, Hertz PB. Preparation and characterization of bio-diesels from various bio-oils. Bioresour Technol 2001;80:53e62. [14] Antol n G, Tinaut FV, Brice~no Y, Casta~no V, Perez C, Ram rez AI. Op- timisation of biodiesel production by sunower oil transesterication. Bioresour Technol 2002;83:111e4. [15] Zhang Y, Dube MA, McLean DD, Kates M. Review paper: biodiesel pro- duction from waste cooking oil: 1. Process design and technological as- sessment. Bioresour Technol 2003;89:1e16. [16] Vicente G, Mart nez M, Aracil J. Integrated biodiesel production: a com- parison of different homogenous catalyst systems. Bioresour Technol 2004;92:297e305. [17] Mittelbach M. Lipase catalyzed alcoholysis of sunower oil. J Am Oil Chem Soc 1999;67:168e70. [18] Shaw J-F, Wang D-L, Wang YJ. Lipase-catalysed ethanolysis and isopro- panolysis of triglycerides with long-chain fatty acids. Enzym Microb Technol 1991;13:544e6. [19] Nelson LA, Foglia TA, Marmer WN. Lipase-catalyzed production of bio- diesel. J Am Oil Chem Soc 1996;73:1191e5. [20] Kaieda M, Samukawa T, Matsumoto T, Ban K, Kondo A, Shimade Y, et al. Biodiesel fuel production from plant oil catalyzed by Rhizopus or- yzae lipase in a water-containing system without an organic solvent. J Biosci Bioeng 1999;88:627e31. [21] Shimada Y, Watanabe Y, Samukawa T, Sugihara A, Noda H, Fukuda H, et al. Conversion of vegetable oil to biodiesel using immobilized Can- dida antarctica lipase. J Am Oil Chem Soc 1999;76:789e93. [22] Shimada Y, Watanabe Y, Sugihara A, Tominaga Y. Review: enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing. J Mol Catal B: Enzym 2002;17:133e42. [23] Uosukainen E, Lamsa M, Linko Y-Y, Linko P, Leisola M. Optimization of en- zymatictransestericationof rapeseedoil ester usingresponse surfaceandprin- cipal component methodology. Enzyme Microb Technol 1999;25:236e43. [24] Abigor RD, Uaudia PO, Foglia TA, Hass MJ, Jones KC, Okoefa E, et al. Lipase-catalysed production of biodiesel fuel from some Nigerian lauric oils. Biochem Soc Trans 2000;28:979e81. [25] Samukawa T, Kaieda M, Matsumoto T, Ban K, Kondo A, Shimada Y, et al. Pretreatment of immobilized Candida antarctica lipase for biodie- sel production from plant oil. J Biosci Bioeng 2000;90(2):180e3. [26] Watanabe Y, Shimada Y, Sugihara A, Noda H, Fukuda H, Tominaga Y. Continuous production of biodiesel fuel from vegetable oil using immobi- lized Candida antarctica lipase. J Am Oil Chem Soc 2000;77(4):355e60. [27] Watanabe Y, Shimada Y, Sugihara A, Tominaga Y. Enzymatic conversion of waste edible oil to biodiesel fuel in a xed-bed bioreactor. J Am Oil Chem Soc 2001;78(7):703e7. [28] Watanabe Y, Shimada Y, Sugihara A, Tominaga Y. Conversion of de- gummed soybean oil to biodiesel fuel with immobilized Candida antarc- tica lipase. J Mol Catal B: Enzym 2002;17:151e5. [29] Iso M, Chen B, Eguchi M, Kudo T, Shrestha S. Production of biodiesel fuel from triglycerides and alcohol using immobilized lipase. J Mol Catal B Enzym 2001;16:53e8. [30] Bela-Bako K, Kovacs F, Gubicza L, Hancsok J. Enzymatic biodiesel production from sunower oil by Candida antarctica lipase in a solvent-free system. Biocatal Biotransfor 2002;20:437e9. [31] Kose O, Tuter M, Aksoy HA. Immobilized Candida antarctica lipase- catalyzed alcoholysis of cotton seed oil in a solvent free medium. Biore- sour Technol 2002;83:125e9. [32] Al-Zuhair S. Production of biodiesel by lipase-catalyzed transesterication of vegetable oils: a kinetics study. Biotechnol Prog 2005;21:1442e8. [33] Nouredini H, Gao X, Philkana RS. Immobilized Pseudomonas cepacia lipase for biodiesel fuel production from soybean oil. Bioresour Technol 2005;96:769e77. [34] Salis A, Pinna M, Monduzzi M, Solinas V. Biodiesel production from triolein and short chain alcohols through biocatalysis. J Biotechnol 2005;119:291e9. [35] Kusdiana D, Saka S. Kinetics of transesterication in rapeseed oil to bio- diesel fuel as treated in supercritical methanol. Fuel 2001;80:693e8. [36] Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in su- percritical methanol. Fuel 2001;80:225e31. [37] Peterson GR, Scarrah WP. Rapeseed oil transesterication by heteroge- neous catalysis. J Am Oil Chem Soc 1984;61(10):1593e7. [38] Bayenes CR, Hinnekens H, Martens J. Esterication process, United States Patent 5,508,457; 1996. [39] Corma A, Iborra S, Miquel S, Primo J. Catalysts for the production of ne chemicals: production of food emulsiers, monoglycerides, by glyc- erolysis of fats with solid base catalysts. J Catal 1998;173:315e21. [40] Leclercq E, Finiels A, Moreau C. Transesterication of rapeseed oil in the presence of basic zeolites and related solid catalysts. J Am Oil Chem Soc 2001;78(11):1161e5. [41] Suppes GJ, Bockwinkel K, Lucas S, Botts JB, Mason MH, Heppert JA. Calcium carbonate catalyzed alcoholysis of fats and oils. J Am Oil Chem Soc 2001;78(2):139e45. [42] Suppes GJ, Dasari MA, Doskocil EJ, Mankidy PJ, Goff MJ. Transester- ication of soybean oil with zeolite and metal catalysts. Appl Catal A Gen 2004;257:213e23. [43] ISO 14040. Environmental management elife cycle assessment eprinci- ples and framework. International Organization for Standardization; 2006. [44] Basu HN, Norris ME. Process for production of esters for use as a diesel fuel substitute using a non-alkaline catalyst, US Patent 5525126; 1996. 1377 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378 [45] Liu KS. Preparation of fatty acid methyl esters for gas chromatographic analysis of lipids in biological materials. J Am Oil Chem Soc 1994;71(11):1179e87. [46] Tan T, Nie K, Wang F. Production of biodiesel by enzymatic conversion. Proceedings of renewable resources and bioreneries, Ghent, Belgium, 19e21 September 2005. [47] Demibras x A. Biodiesel fuels from vegetable oils via catalytic and non- catalytic supercritical alcohol transesterications and other methods: a survey. Energy Convers Manage 2003;44(13):2093e109. [48] Soumanou MM, Bornscheuer UT. Improvement in lipase catalyzed syn- thesis of fatty acid methyl esters from sunower oil. Enzym Microb Technol 2003;33:97e103. [49] Beer T, Grant T, Williams D, Watson H. Fuel-cell greenhouse gas emis- sions from alternative fuels in Australian heavy vehicles. Atmos Environ 2002;36:753e63. [50] Theka E. A life-cycle assessment of ethanol produced from sugarcane molasses, MSc dissertation, Department of Chemical Engineering, Uni- versity of Cape Town; 2002. 1378 K.G. Harding et al. / Journal of Cleaner Production 16 (2007) 1368e1378