Energy Conversion and Management 49 (2008) 21602164

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Technoeconomic study of supercritical biodiesel production plant

J.M. Marchetti *, A.F. Errazu
Planta Piloto de Ingeniera Qumica (UNS-CONICET), Camino La Carrindanga Km. 7, 8000 Baha Blanca., Argentina

a r t i c l e

i n f o

a b s t r a c t
Over the last years, biodiesel has gained more market due to its benets and because it appears as the natural substitute for diesel. However, the highest cost of this process is associated with the raw material employed, making it a less competitive and more expensive fuel. Therefore, research is being done in order to use low price raw material, such as acid oils, frying oils or soapstocks. In this work, a biodiesel production plant was developed using supercritical methanol and acid oils as raw materials. This technology was compared with some other alternatives previously described with the aim of making a comparative study, not only on the technical aspects but also on the economic results. A process simulator was employed to produce the conceptual design and simulate each technology. Using these models, it was possible to analyze different scenarios and to evaluate productivity, raw material consumption, economic competitiveness and environmental impacts of each process. Although the supercritical alternative appears as a good technical possibility to produce biodiesel, today, it is not an economic alternative due to its high operating costs. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 27 October 2006 Received in revised form 20 June 2007 Accepted 20 February 2008 Available online 10 April 2008

Keywords: Biodiesel Supercritical production Economic analysis Technological improvement

1. Introduction The American Society for Testing and Materials (ASTM) denes biodiesel as the monoalkyl esters of long chain fatty acids derived from a renewable lipid feedstock, such as vegetable oils or animal fat. The biodiesel capacity in the world has increased considerably in the last 16 years as can be seen in Fig. 1 [1]. Fig. 1 show clearly that the biodiesel capacity in the world has increased due to several factors such as environmental benets. Other factors are involved in this increase, such as government policies about substituting a percentage of regular diesels with biodiesel. This is done in order to take advantage of this fuel property and use less non-renewable fuel such as petroleum or its derivatives. Conventional technology to produce biodiesel employs a homogeneous catalyst such as sodium or potassium hydroxide [29]. Although this technology achieves great conversion yields; it is only suitable when rened oils are employed. If a raw material with an amount of FFA over 0.10.5% is used, soap will be produced and the down stream separation and purication of the nal biodiesel will be more difcult. This will also cause a decrease in the global productivity. When an acid oil is used (3.540% FFA), other technologies should be employed [37,1017]. Some of them are summarized and technical as well as economic comparisons have been done [18]. These new technologies can not only treat a raw material
* Corresponding author. Tel.: +54 291 486 1700; fax: +54 291 486 1600. E-mail address: jmarchetti@plapiqui.edu.ar (J.M. Marchetti). 0196-8904/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.enconman.2008.02.002

with great amounts of FFA, but also, the heterogeneous alternatives provide some additional benets in the purity of the subproduct, glycerol. However, there are other options to be considered such as a supercritical process, in situ transesterication and many others. Besides the technical aspects, economic feasibility is becoming more and more important due to the possibility of future biodiesel production plants. Some economics analysis has been done about biodiesel plants; different technologies as well as different raw materials or alcohols have been treated. Also, different economic criteria have been employed. An economic study of a 100,000 ton/yr biodiesel production plant was performed by Nelson et al. [19]. The process was an alkali technology, and the economic criteria used in this work were the total capital cost. A similar work was performed by Noordam and Withers [20]; in their work, the raw material employed was Canola seed, and the productive plant could treat 7800 ton/yr. The economic criteria used by these authors were the total biodiesel cost. More detailed research on different possibilities to estimate the economics of a biodiesel production plant was performed by Bender [21]. This author has studied different feedstocks as well as different scale up plants. The plant proposed by this author is integrated with the oil processing plants. Different from the previous ones, Bender [21] has used capital equipment cost. A technical and economic study on an acid catalyst process was done by Zhang et al. [10,22]. The raw material employed was waste

J.M. Marchetti, A.F. Errazu / Energy Conversion and Management 49 (2008) 21602164

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Nomenclature Abbreviation Complete name TG triglycerides DG diglyceride MG monoglyceride FAME M G FFA fatty acid methyl ester methanol glycerol free fatty acid

cooking oil. The process description as well as the economic analysis has taken into account a lot of other cost and variables involved in each process. The economic criteria proposed by these authors were the xed capital cost and total manufacturing cost. A very complete economic study of a production plant using an alkaline catalyst was done by Haas et al. [23]. They reported a complete biodiesel plant using commercial software and gave a good technical description of the process they studied. Dorado et al. [24] have recently done research on biodiesel economics using Ethiopian mustard oil seed. Although this study shows a good rst approach to the economics involved, there is not a full description of the process and the cost associated with it. In this work, the production of biodiesel using a supercritical process from oils with high content of free fatty acids has been studied. The results obtained have been compared with previous results from other technologies involved in biodiesel production alternatives. 2. Reaction models The reactions taking place in any transesterication reactor are the following ones. As can be seen in Scheme 1, the main reaction is a series of reactions that take place one after the other; going from TG to DG, which is transformed into MG, and nally, this is converted into glycerin. In all these steps, biodiesel is produced. Simultaneously with this main reaction, the direct esterication reaction might occur if the amount of FFA is considerably high. This

plant will be designed to treat 36,036 ton/yr of acid oils with 5% FFA. Therefore, the direct esterication reaction will take place. The plant that was conceptually designed and analyzed was a modication of the one used by Vera et al. [25], while the kinetics as well as the other parameters of the process were obtained from Refs. [2529]. 3. Study case A supercritical production plant was conceptually designed and compared with the technological alternatives previously studied [18], where three different processes were studied: (1) homogeneous alkaline catalyst with acid pre-esterication, (2) homogeneous acid catalyst and (3) heterogeneous solid catalyst The main purpose is to make a comparison of the supercritical technology with those above described to determine if this process is suitable, from a technical as well as from an economic point of view. All the technologies were proposed as a continuous process in order to achieve an economic scale of oil processing; however, batch plants are still used industrially. The raw material for biodiesel production is acid oils, a general term that can be associated with wasted or recycled frying oils, residues from rening (soapstocks, distillates) and so on. For example, in soapstocks, the amount of FFA can be as high as 30% of the feed stream [9]. 3.1. Case The process involved in this work can be seen on a process ow diagram of Fig. 2. The oil and the alcohol stream are fed into the supercritical reactor at 1 bar and 25 C. Before entering the reactor itself, both streams are heated and pressurized in order to achieve desirable operational conditions, T = 200 C and P = 70 bar used on the rst reactor. Supercritical reactor 1 represents this equipment in the previous gure. After this equipment, a distillation column is required to separate the methanol, which will be recycled from the rest. This is done to have a better global separation in the following decanter (decanter 1 in Fig. 2). In the last equipment, the glycerin is separated from the oil phase; this last one is fed to Super critical reactor 2. To have a better nal conversion of the oil into biodiesel, another stream of alcohol should be added to the second reactor in order to maintain the molar ratio of alcohol/oil close to 42:1. In this reactor, the reaction occurs at 350. Just as in the previous reaction step, a distillation column is used, followed by a decanter that allows separation of the biodiesel from the glycerin. Kusdiana and Saka [26] have obtained kinetics parameters for transesterication with supercritical methanol and different operational conditions, and those kinetics parameters have been employed in this work. 4. Results and discussion

Biodiesel capacity (millon liters)

3750 3000 2250 1500 750 0 1991

1993

1995

1997

1999

2001

2003

2005

Year
Fig. 1. Changes in biodiesel capacity from 1991 to 2005.

TG + M FAME + DG DG + M FAME + MG MG + M FAME + G FFA + M FAME + H 2O

Scheme 1. Reactions involved.

In the following sections, the results of the simulation process of this technology, as well as those obtained for the previous work

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J.M. Marchetti, A.F. Errazu / Energy Conversion and Management 49 (2008) 21602164

Methanol2 Methanol Methanol Oil

Methanol 2 FAME
Glycerin 2

Supercritical reactor 1

Glycerin 1

Supercritical reactor 2

Fig. 2. Case process ow diagram: supercritical alternative.

[18], are revised, and a comparative analysis between them is performed. 4.1. Main process results This work was done for a plant that could treat 36,036 ton/yr; the process simulation software, SuperPro Designer [30], was employed. This software allows a good representation of a chemical process and has the capabilities of performing an economic study of any chemical plant. In Table 1, some results for each technology can be seen. All of them are suitable alternatives to produce biodiesel. The nal conversion achieved by all the technologies is over 98%. For the supercritical alternative (Case IV in the following tables), the total free glycerin involved in the biodiesel stream satised the ASTM standard, making it a fuel suitable for engines. Also, per kg of oil, 1.005 kg of biodiesel is produced. As in Case III, no washing water needed to be added to Case IV, making the down stream separation of glycerin and methanol much easier. As in all the other technologies, there is no soap formation in this process. 4.2. Economic assumptions and results The costs of raw material, equipment, utilities etc. and the price of biodiesel were estimated based on international prices and specic references [18]. A preliminary analysis can be accomplished for the conventional process (alkaline homogeneous). It requires raw material with an amount of FFA less than 0.1%. Today, the price of this degummed oil is around 500 US$/ton. With this raw material cost

and without considering taxation incentives, it can be concluded from the following gure that the process will not become protable (see Fig. 3). This is the reason why low cost oils with high FFA content were employed as raw material in the present analysis. The cost for the waste oils is very variable, from 110 US$/ton [22] to 220 US$/ton [23]. In our case, the price assumed was estimated as 400 US$/ ton according to the internal market of oil in Argentina. 4.2.1. Fixed capital cost Table 2 presents the prices for each equipment for each alternative. Other costs associated with each equipment have also been taken into account following the percentages described in Table 3 (see Table 4). 4.2.2. Operating cost A break down of the operating cost involved in each process can be seen in Table 5. The other costs associated with the operation of each technology have also been added to this table. As raw material, only the acid oil was quantied. However, for global economic analysis, the costs associated with other compounds involved, such as alcohol, catalyst etc, have been taken into account
40

NPV (MM U$S)

20

-20

Table 1 Main technical aspects of each case Case I [18] Operation temperature of reactorsa [C] Feed streams [kg/h] Oil % Of free fatty acids Alcohol (methanol)b Catalyst [kg/h]* [Ton]+ Washing water Out coming streams [kg/h] Biodiesel (>98%) Total glycerin in biodiesel Performance (ton biodiesel/ton MP) Glycerin (solution/pharmaceutical grade)
a

Case II [18] 60

Case III [18] 150

Case IV 200/350

-40 250

300

350

400

450

500

550

Oil Cost (u$s/ton)

Fig. 3. Variation of the net present value due to changes in the oil cost.

60

4550 5 750 84* 420 4497 0.20% 0.9884 625/

4550 5 1500 42* 420 4496 0.53% 0.9881 540/

4550 5 760 12.13+ 4568 0.17% 1.0040 /434

4550 5 7000/ 2200 4573 0.001% 1.005 /428

Table 2 Economical indicators Equipment Pre-mixer of the catalyst Pre-esterication reactor 1st transesterication reactor 2nd transesterication rector Neutralizer reactor Decanter(all of them together) Distillation column to purier biodiesel* Distillation column to separate the methanol for recycle Distillation column to separate the glycerin Case I [18] $150,000 $349,000 $350,000 $350,000 $13,500 $116,000 $60,000 $40,000 $77,500 Case II [18] 150,000 N/A $480,000 $480,000 $35,000 $97,500 $62,000 $47,500 $82,000 Case III [18] N/A N/A $410,000 $390,000 N/A $50,000 $56,000 $78,500 $30,000 Case IV N/A N/A $655,000 $407,000 N/A $50,000 N/A $268,000 N/A

The values on each side of the dash represent the temperature for each supercritical reactor. b The values on each side of the dash represent the amount of alcohol for each reactor involved in the process.

J.M. Marchetti, A.F. Errazu / Energy Conversion and Management 49 (2008) 21602164 Table 3 Other costs associated with each equipment involved Other costs Piping Instrumentation Insulation Electrical facilities Building Yard improvement Auxiliary facilities Unlisted equipment installation % Of the purchase cost 35 40 3 10 45 15 40 50 Plant capacity [ton/yr] Biodiesel revenues (US$/yr) Credits for Glycerin (US$/yr) Total incomes (US$/yr) Equipment cost (US$) Total investment (US$) Raw material cost (US$/yr) % of the total operating cost Total operating costs (US$/yr) Biodiesel unitary cost (US$/kg) Gross margin Return Over investment (roi) Net present value (7%) Internal return rate (IRR) Table 6 Economical indicators Case I [18] 36,036 $16,029,000 $2,660,000 $18,689,000 $1,503,000 $7,415,000 $14,414,000 79.60 $18,109,000 $0.5084 5.50% 19.68% $1,797,000 11.17% Case II [18] 36,036 $16,023,000 $2,548,000 $18,571,000 $1,477,000 $7,327,000 $ 14,414,000 78.51 $ 18,359,000 $0.5156 4.16% 16.69% $(1,275,000) 6.95% Case III [18] 36,036 $16,281,000 $3,573,000 $19,854,000 $1,010,000 $5,151,000 $14,414,000 76.28 $18,896,000 $0.5223 7.74% 33.23% $ 7,789,243 31.95% Case IV 36,036

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$16,309,000 $2,432,000 $18,741,000 $1,377,000 $8,438,000 $14,414,000 40.58 $35,514,000 $0.98 1.41% 11.00% $(2,575,271) 1.80%

Table 4 Summary of the xed costs involved for each process Case I [18] Total capital investment Equipment purchase cost Direct xed capital (DFC) Working capital Start up and validation cost $7,415,000 $1,506,000 $5,598,000 $1,536,000 $280,000 Case II [18] $7,327,000 $1,434,000 $5,323,000 $1,677,000 $266,000 Case III [18] $5,151,000 $1,014,500 $3,333,000 $1,655,000 $163,000 Case IV $8,438,000 $1,377,000 $5,054,000 $3,132,000 $252,000

Table 5 Operating cost Case I [18] Total operating cost Raw materials Equipment dependant Labor dependant Utilities Laboratory Insurance Factory expenses Fringe benets Supervision Operating supplies Administration $18,109,000 $16,044,000 $1,130,000 $547,000 $305,000 $83,000 $55.984 $279.920 $95.040 $47.520 $23.760 $142.560 Case II [18] $18,359,000 $16,564,000 $1,005,000 $365,000 $357,000 $68,000 $53.237 $266.184 $79.200 $39.600 $19.800 $118.800 Case III [18] $18,896,000 $15,919,000 $684,000 $365,000 $1,874,000 $54,000 $33.340 $166.700 $63.360 $31.680 $15.840 $95.040 Case IV $35,514,000 $32,630,000 $1,022,000 $273,000 $1,547,000 $41,000 $50.581 $252.903 $47.520 $23.760 $11.880 $71.280

which was assumed according to the Argentinean market because these plants were designed to satisfy Argentinean requirements. 4.3. Comparison of technologies Supercritical technology is more than suitable to produce biodiesel; it has been studied for several years, and the results achieved in this work agree with those from the literature. From Table 1, it can be seen that the supercritical alternative satises all the requirements to produce biodiesel suitable to be used on normal engines. In addition, it produces more than a kilo of fuel per kilo of oils used. From Table 6, it can be determined that all the processes have 78% (on average), except for the supercritical technology, of the production cost associated with the price of the raw material, and they have almost the same price per kg of biodiesel produced. However, Case IV has the highest investment, which is expected due to the investment required to achieve the high pressure and temperature needed for each reactor, as well as the need for thick equipment to contain the desired reaction. The economic analysis of the supercritical process shows that this alternative is suitable to be used but not nancially protable. The return over investment rate is the lowest; the pay back time is too high, around 9 years to recovery the investment; and the net present value is not good if a 7% interest rate is taken into account. However, Van Kasteren and Nisworo [31] have proved that a supercritical biodiesel production plant that used propane as a co-solvent is economically suitable. The authors have also used one reaction step, which decreases the operating cost considerably. On the other hand, as discussed in Ref. [18], the heterogeneous processes showed the best economic indicators based on internal return rate and net present value with similar amounts of investment to those of the other technologies. 5. Conclusions The supercritical alternative is a suitable alternative for biodiesel production from a technical point of view. However, from an economic

4.2.3. Economical indicators In Table 6, the most relevant economic indicators, as well as a summary of the previous costs already shown, have been summarized. From Table 6, it can be seen that almost all the processes have similar revenue due to the biodiesel that is sold, however, the heterogeneous alternatives have a much better selling price of the glycerin due to its purity, making a better income in this product. On the equipment cost showed in Table 6, only the purchase cost is considered, while in the total investment required for each technology, other costs have been taken into account. They are in agreement with the purchase cost of all the equipment involved in the process, taken into account in Table 3. From the total investment row, the heterogeneous process has the lowest investment required due to less amount of equipment involved in the process, The total operating cost is quite similar for all these technologies, around 18.5 million US$, except for the supercritical alternative, which is around 35 million due to the high temperature and pressure required. The per cent associated with the raw material employed (acid oil, catalyst and alcohol) is around 78% for all the technologies, but around 40% for the supercritical alternative. From the economic indicators, it can be determined that the heterogeneous alternatives appear as the ones that are more profitable and have the better NPV and IRR values. However, the selling price in the USA is around 2.7 US$per gallon, and Europe is buying biodiesel at around 0.8 /l. For Argentina, the selling price used in this work for the biodiesel was 0.45 US$/l,

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J.M. Marchetti, A.F. Errazu / Energy Conversion and Management 49 (2008) 21602164 [9] Canakci M, Van Gerpen J. Biodiesel production from oils and fats with high free fatty acids. Trans ASAE 2001;44(6):142936. [10] Zhang Y, Dub MA, McLean DD, Kates M. Biodiesel production from waste cooking oil: 1. Process design and technological assessment. Bioresource Technol 2003;89:116. [11] Zheng S, Kates M, Dub MA, McLean DD. Acid-catalyzed production of biodiesel from waste frying oil. Biomass Bioenerg 2006;30(3):26772. [12] Marchetti JM, Miguel VU, Errazu AF. Heterogeneous esterication of high free fatty acid contents oil. In: XIV Congreso Argentino de Catlisis; 2005. [13] Peterson GR, Scarrah WP. Rapeseed oil transesterication by heterogeneous catalysis. J Am Oils Chem Soc 1984;61(10):15937. [14] Kaieda M, Samukawa T, Matsumoto T, Ban K, Kondo A, Shimada Y, et al. Biodiesel fuel production from plant oil catalyzed by Rhizopus oryzae lipase in a water-containing system without an organic solvent. J Bio-sci Bioeng 1999:62731. [15] Nelson LA, Foglia TA, Marmer WN. Lipase-catalyzed production of biodiesel. JAOCS 1996;73(8):11915. [16] Watanabe Y, Shimada Y, Sugihara A, Noda H, Fukuda H, Tominaga Y. Continuous production of biodiesel fuel from vegetable oil using immobilized Candida Antarctica lipase. J Am Oils Chem Soc 2000;77(4):35560. [17] Haas MJ, Scott KM, Marmer WN, Foglia TA. In situ alkaline transesterication: an effective method for the production of fatty acid ester from vegetable oils. JAOCS 2004;81(1):839. [18] Marchetti JM, Miguel VU, Errazu AF. Techno economical assessment of biodiesel alternatives. In: Engineering conferences international. Bioenergy I: from concept to commercial processes; 2006. [19] Nelson RG, Howell SA, Weber JA. Potential feedstock supply and costs for biodiesel production. In: Bioenergy94 proceedings of the sixth national bioenergy conference; 1994. [20] Noordam M, Withers R. Producing biodiesel from Canola in the inland northwest: an economic feasibility study Idaho agricultural experiment station bulletin N 785; 1996. [21] Bender M. Economic feasibility review for community-scale farmer cooperatives for biodiesel. Bioresource Technol 1999;70:817. [22] Zhang Y, Dub MA, McLean DD, Kates M. Biodiesel production from waste cooking oil: 2. Economic assessment and sensitivity analysis. Bioresource Technol 2003;90:22940. [23] Haas MJ, McAloon AJ, Yee WC, Foglia TA. A process model to estimate biodiesel production costs. Bioresource Technol 2006;97(4):6718. [24] Dorado MP, Cruz F, Palomar JM, Lpez FJ. An approach to the economics of two vegetable oil-based biofuels in Spain. Renew Energ 2006;31:12317. [25] Vera CR, DIppolito SA, Pieck CL, Parera JM. Production of biodiesel by a twostep supercritical reaction process with adsorption rening. In: 2nd Mercosur congress on chemical engineering, 4th Mercosur congress on process systems engineering; 2005. [26] Kusdiana D, Saka S. Kinetics of transesterication in Rapeseed oil to biodiesel fuel as treated in supercritical methanol. Fuel 2001;80:693. [27] Demirbas A. Biodiesel fuels from vegetable oils via catalytic and non catalytic supercritical alcohol transesterication and other methods: a survey. Energ Convers Manage 2003;44:2093. [28] Saka S, Kusdiana D. Biodiesel fuel from Rapeseed oil as prepared in supercritical methanol. Fuel 2001;80:25. [29] Warabi Y, Kusdiana D, Saka S. Reactivity of triglycerides and fatty acids of Rapeseed oil in supercritical alcohols. Bioresource Technol 2004;91: 2837. [30] SuperPro Designer v. 4.55 software Intelligen Inc.; 2007. [31] Van Kasteren JMN, Nisworo AP. A process model to estimate the cost of industrial scale biodiesel production from waste cooking oil by supercritical transesterication. Resour Conserv Recy 2007;50(4):44258.

analysis, this technology, under the operation conditions studied on this work, does not appear to be a good alternative because of the high cost associated with the energetic requirements of the process. The investment is the highest of all the technologies studied and also has the highest unit cost per kilo of biodiesel. This technology has around 40% of the total operation cost associated with the raw material that is used, different from the 78% for all the other technologies mentioned in this work. The other high cost is the operating cost; if this were diminished to 40% or less, plants using this technology could be economically sustainable. Another alternative is to develop a new technology where the remaining pressure after the rst ash separation could be used to pre- pressurize the second rector. In spite of the economic disadvantages, this technology is environmental good, since it has less efuents, and the secondary product, glycerin, will have a really good high quality. Disclaimer The authors and Plapiqui do not accept responsibility for any decision taken based on these model results. The model used in this work is for research purpose only. For specic applications, please contact the authors for recommendations regarding the limitations and scope of the model. Acknowledgements Jorge Mario Marchetti would like to thank the National Committee of Science and Technique of Argentina (CONICET) for its nancial support. References
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