KET050 Biodiesel Production from Microalgae Dept of Chemical Engineering, Lund University, Faculty of Engineering

Final Report on

Biodiesel Production from Microalgae

- A Feasibility Study
Presented to StatoilHydro ASA Oslo, Norway May 16, 2008

Principal investigators:
Merit Lassing Peter Mrtensson Erik Olsson Marcus Svensson

Tutors: I
Christian Hulteberg, Lund University Hans T. Karlsson, Lund University Brre T. Brresen, StatoilHydro ASA Hans Eklund, StatoilHydro ASA

Disclaimer
This report was prepared as a project in the course Feasibility Studies on Industrial Plants, (KET050), Department of Chemical Engineering, Faculty of Engineering, LTH, Lund University Sweden in cooperation with the Norwegian company StatoilHydro. Neither Lund University nor the authors of this report or StatoilHydro may be held responsible for the effects following from using the information in this report. Nor the authors, Lund university or StatoilHydro makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy or completeness of this information. No reproduction is authorized without the written permission from the authors, or StatoilHydro or Lund University.

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Abstract
This is a student assignment for the Norwegian oil and gas company StatoilHydro, The aim of this study is to investigate the potential of large scale production of biodiesel from microalgae. Since the technology is new and no large facilities exist to date, this report focuses on suitable technologies for future biodiesel production. There exist many different algae strains with high oil content e.g. Phaeodactylum tricornutum, Nannochloropsis salina and Botryococcus braunii. The alga Botryococcus braunii was first selected for large scale biodiesel production, but after encountering many problems when looking into the process, the string of Nannochloropsis salina was chosen instead. The high hydrocarbon content of B. braunii was one of the key factors when this alga initially was chosen, together with the algaes ability to produce hydrocarbons during growth without the use of methods such as nitrogen starvation. Difficulties encountered when using this alga strain were separation problems since B. braunii has its hydrocarbons on the outside connecting the colonies, hence it is quite slimy. At the same time the colonies could be an advantage since the larger size means an easier separation. The fact that B. braunii is a fresh water algae is a big disadvantage in large scale production of biodiesel, if not having fresh water readily available, since this require a large desalination facility. Nannochloropsis salina on the other hand is a halotolerant string that prefers saline water similar to common seawater and has characteristics of producing high oil content within its cells. Nannochloropsis salina is therefore the alga strain used in this feasibility study for large scale biodiesel production. It is concluded that the most promising reactor type is the closed photobioreactor, since the other main alternative, the open pond, suffers from contamination risks, high evaporative losses of water and diffusion losses of CO2. Among the different types of closed photobioreactors; tubular, flat and polyethylene bags, the tubular seems to be the best choice since it has a higher photoefficiency than the flat reactor. The polyethylene bag reactor still needs developing and is not yet a viable alternative. After the algae have been harvested it is suggested that an increased dry weight is accomplished by a flocculation and sedimentation stage. The chosen method for the disruption of the cells is the utilization of a hydrodynamic cavitation process, followed by a stirring settling tank, where the oil floats and the cell debris sediment. Since hydrodynamic cavitation is a relatively unknown method, an alternative process using a wet bead mill for the cell breakage is presented as an alternative. However calculations are only performed on the former process alternative. In order to minimize losses in further refining and fulfill the EN 14214 standard for biodiesel production, the algal oil will in most cases need some kind of pretreatment. The most important purification steps will be degumming, which removes phosphorous content, as well as reaction of free fatty acids into methyl esters in order to avoid soap formation in the transesterification process. Suitable plant locations for StatoilHydro to put up a large scale biodiesel production facility are Qatar, South Africa and Australia. All cost estimates are made for a plant location in South Africa where the most suitable conditions can be found.

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The following factors showed to be most accountable in the cost estimates of this production facility:
The productivity of algae Lifespan of the photobioreactor Interest rate on capital for investment Harvesting concentration

Different scenarios were estimated and the production cost ranges from 0.38 /L to 1.95 /L between the best and worst case scenario with 0.87 /L as the base case. An approximation that has been made is that nutrient/flocculant cost and algae meal revenue will balance each other. If the algae meal turns out to be worthless this will increase the algae oil price by 0.26 /L and hence could be fatal to the biodiesel production from microalgae. The price of comparable bio-based crude oil is today 122 $ barrel (palm oil) (1), which is approximately 0.49 per liter. This shows that even though profitability is still not achieved, it is concluded that profitability is not far away.

IV

Contents
1 Introduction .............................................................................................................................................. 1 1.1 Why Algae for Production of Biodiesel?............................................................................................ 1 1.2 Technology State-of-the-Art ............................................................................................................... 2 1.3 Brief Description of Production System ............................................................................................. 2 2 Technology Suitable for Large-Scale Production ................................................................................. 4 2.1 Problems in Photobioreactors ............................................................................................................. 4 2.1.1 Oxygen Oversaturation ............................................................................................................... 5 2.1.2 pH-value ...................................................................................................................................... 5 2.1.3 Temperature ................................................................................................................................ 5 2.2 Open Pond System.............................................................................................................................. 5 2.2.1 Advantages .................................................................................................................................. 6 2.2.2 Disadvantages ............................................................................................................................. 6 2.3 Closed Photobioreactors ..................................................................................................................... 6 2.3.1 Advantages .................................................................................................................................. 6 2.3.2 Disadvantages ............................................................................................................................. 6 2.3.3 Comparison of Different Systems of Closed Photobioreactors ................................................... 6 2.4 Conclusions - Type of Reactor ........................................................................................................... 7 2.5 Choosing the Right Algae................................................................................................................... 7 2.5.1 General Aspects to Consider ....................................................................................................... 7 2.5.2 Algae Strains with High Oil Content ........................................................................................... 8 2.5.3 Phaeodactylum tricornutum ........................................................................................................ 8 2.5.4 Chlorella protothecoides ............................................................................................................. 9 2.5.5 Botryococcus braunii .................................................................................................................. 9 2.5.6. Nannochloropsis salina ............................................................................................................ 11 2.5.7 Choosing an Algae Strain ......................................................................................................... 12 2.6 Harvesting of Algae - Separation of Particles from Water ............................................................... 13 2.6.1 Flocculation .............................................................................................................................. 13 2.6.2 Gravity Sedimentation ............................................................................................................... 14 2.6.3 Centrifugal Recovery................................................................................................................. 14 2.6.4 Ultrasound................................................................................................................................. 14 2.6.5 Filtration ................................................................................................................................... 14 2.6.6 Dissolved Air Flotation ............................................................................................................. 15

2.6.7 Conclusion - Separation of Particles from Water ..................................................................... 15 2.7 Extraction of Microalgal Oil from Biomass ..................................................................................... 16 2.7.1 Bead Mills ................................................................................................................................. 16 2.7.2 Presses....................................................................................................................................... 17 2.7.3 Solvent Extraction ..................................................................................................................... 17 2.7.4 Cavitation .................................................................................................................................. 17 2.7.5 Less Known Methods................................................................................................................. 18 2.7.6 Conclusion - Extraction of Microalgal Oil from Biomass ........................................................ 18 2.8 Termochemical Liquefaction - an Alternative Path? ........................................................................ 18 2.9 Post Processing Crude Oil to Biodiesel ......................................................................................... 19 2.9.1 EN 14214 ................................................................................................................................... 19 2.9.2 Pretreatment of Crude Oil......................................................................................................... 19 2.10 Transesterification of Crude Oil to Biodiesel ................................................................................. 22 2.10.1 Heterogeneous Catalysis ......................................................................................................... 23 2.10.2 Supercritical Methanol ............................................................................................................ 23 2.11 Suitable Plant Location ................................................................................................................... 23 2.12 Conclusion ...................................................................................................................................... 24 3 Flow Diagram ......................................................................................................................................... 26 3.1 Main Process Alternative .................................................................................................................. 26 3.2 An Alternative Process ..................................................................................................................... 26 4 Cost Estimates ........................................................................................................................................ 29 4.1 Total Annual Cost ............................................................................................................................. 29 4.1.1 Capital Costs ............................................................................................................................. 29 4.1.2 Operating Costs......................................................................................................................... 30 4.2 General Assumptions ........................................................................................................................ 30 4.3 Mass Balances .................................................................................................................................. 31 4.4 Cost Estimates of Unit Operations ................................................................................................... 31 4.4.1 Cost of Photobioreactor Facility............................................................................................... 31 4.4.2 Cost of Sedimentation Equipment ............................................................................................. 34 4.4.3 Cost of Cavitation Equipment ................................................................................................... 36 4.4.4 Cost for Separation of the Water Oil Algae Mixture ................................................................. 38 4.4.5 Cost of Degumming Equipment................................................................................................. 39 4.4.6 Cost for Removal of Free Fatty Acids ....................................................................................... 40

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4.4.7 Cost for Spray Drying Equipment ............................................................................................. 41 4.5 Revenues and Costs not Directly Derived from Unit Operations ..................................................... 42 4.5.1 Byproducts................................................................................................................................. 42 4.5.2 Cost of Storage Tanks ............................................................................................................... 42 4.5.3 Labor Costs ............................................................................................................................... 43 4.6 Summarized Costs for the Base Case ............................................................................................... 43 4.7 Sensitivity Analysis of Production Cost ........................................................................................... 44 4.7.1 The Production Rate of Algae ................................................................................................... 45 4.7.2 Concentration upon Harvest ..................................................................................................... 46 4.7.3 Assumed Life Span of Facility and Interest Rate on Capital Investment .................................. 46 4.8 Conclusion ........................................................................................................................................ 47 5 Bibliography ........................................................................................................................................... 48 Appendix 1 ............................................................................................................................................. 55 Appendix 2 ............................................................................................................................................. 56 Appendix 3 ............................................................................................................................................. 57 Appendix 4 ............................................................................................................................................. 59 Appendix 5 ............................................................................................................................................. 63 Appendix 6 ............................................................................................................................................. 64 Appendix 7 ............................................................................................................................................. 68 Appendix 8 ............................................................................................................................................. 69 Appendix 9 ............................................................................................................................................. 70 Appendix 10 ........................................................................................................................................... 71 Appendix 11 ........................................................................................................................................... 72 Appendix 12 ........................................................................................................................................... 73 Appendix 13 ........................................................................................................................................... 77 Appendix 14 ........................................................................................................................................... 79 Appendix 15 ........................................................................................................................................... 80 Appendix 16 ........................................................................................................................................... 81

VII

1 Introduction
Petroleum products as the source of transport fuels have to be replaced soon by renewable biofuels/energy sources due to problems with global warming and limited availability. Today the renewable biofuels are bioethanol produced mainly by sugarcane, and biodiesel by oil crops like oil palm. One of the main reasons why ethanol and biodiesel is looked upon as an energy carrier in transport fuel is the possibility to use it with current drive trains and infrastructure. To replace the world demand of petroleum products by these crops is not a sustainable alternative. The productivity per hectare of land based crops is not sufficient for large scale production. In an example with biofuels replacing the petroleum products in the US, it is calculated that over 60 % of the agricultural land has to be used for biofuel production if the grown crop is oil palm. This would lead to insufficient land to produce food and fodder for the animal production. Microalgae production rates are much higher than land based crops, the calculation for the US biofuel replacement with biodiesel from microalgae states that only 3 % of the farmed area has to be used (2). The waste products of the biodiesel production can be used to produce animal fodder, heat or generating electricity. Bioethanol produced by sugarcane is a product that is competitive with petroleum products today, concerning the price. The productivity per hectare is however a problem for full scale replacement of petroleum fuels by bioethanol, about the same amount of agricultural land has to be used for total replacement as for oil palm. The problem with microalgae for biodiesel production is the economics, the prices for production today is substantially larger, almost ten times the price of petroleum diesel and even more expensive than biodiesel from oil crops. Today the microalgae production plants are mainly used for production of high value specialty chemicals such as pigments and virtually no biodiesel is derived from algae: the reduction of the costs for microalgae production has to be reduced substantially if competitiveness compared to petroleum products, can be achieved without the subsidies for renewable fuels found in Europe and the US (2). The aim of this study is to investigate the potential of large scale production of biodiesel from microalgae, as a student assignment for the Norwegian oil and gas company StatoilHydro. Since the technology is new and no large facilities exist to date, this report focuses on suitable technologies for future biodiesel production.

1.1 Why Algae for Production of Biodiesel?

Microalgae have been suggested as very good candidates for fuel production because of their advantages of higher photosynthetic efficiency; higher biomass production and faster growth compared to other energy crops (3). Algal biomass can be produced on lands not suitable for higher plants, therefore resulting in a more effective use of global land surface (4). Therefore 1

microalgae production does not compete with the production of food for a growing population and is the only viable alternative for a large scale biodiesel production seen today.

1.2 Technology State-of-the-Art

The algae industry has been present for a long time, but commercial biodiesel feedstock production is a new path. Earlier the industry has been specialized on producing high value products such as specific proteins, colorants or other substances that are highly valuable. Today, only small amounts of biodiesel are produced from microalgae (2). Several manufacturers have produced pilot plants and demonstration scale production but on their homepages they say that they can or have built plants for large scale production but when contacting them, no commercial production is yet operating on their system. The main problem found with microalgae for biodiesel today is the economics; biodiesel from microalgae is even more costly than biodiesel from other sources. Today the biodiesel is only an alternative in the US and Europe due to the high subsidies found on alternative fuel sources (2). Many scientific papers have been written on the subject of microalgae. Most of these are optimistic about further development of the algae industry, but it seems that many problems have to be overcome before biodiesel from microalgae can become a commercial alternative for petroleum products derived from fossil fuel, or other renewable fuel derived from land based crops.

1.3 Brief Description of Production System

In Figure 1 is a brief overview of the production system for biodiesel production from algae, including the system boundaries. The core of the production unit is the photobioreactor, where the algae grow in a water environment enriched with carbon dioxide and nutrients. The limiting growth factor is the incoming light. The algae are then separated from the water; the separated water is recycled and the algae continue to the next separation step. In this step the algae are crushed and the solid algae membranes and other solid constituents are separated from the algae oil. The algae oil contains free fatty acids and phosphorous that needs to be eliminated before transesterification; this is done in the pre-treatment. After the pretreatment the crude oil is ready to be used in a regular transesterification process for biodiesel production.

Figure 1 A block diagram showing the most important process steps in microalgal biodiesel production. The main steps is the photobioreactor (1), the water-algae separation step (2), the extraction of hydrocarbons from solid algae constituents (3), the removal of free fatty acids and phosphorous (4) and the transesterification (5).

2 Technology Suitable for Large-Scale Production

For algae to grow they need light, carbon dioxide, the right temperature conditions, fresh or salt water dependent on the string of algae and the right nutrients. From the articles read, the main problem for reaching higher yields is to maximize the light utilization, since this is the limiting factor in an efficient reactor. Therefore the main challenge is to make a large scale system that maximizes light utilization and that is economical. There have been much research done in this area, how to maximize light utilization and production, but most is on the laboratory scale, even though a few scaled up experiments and commercial systems exist. The main problem is the light saturation effect, which means that the algae growth is inhibited by the incoming light if this is too strong; this will be explained further below. Other problems, including oxygen oversaturation and pH will also be discussed. The algae industry has been present for a long time but it has produced high price products such as specific proteins, colorants or other substances that are highly valuable (5). Thus, this high price per weight ratio has made the industry profitable in the past, as well as allowed some costly processes to still be profitable. The new challenge for the algae industry is to get economy in a large scale production unit that produces bulk chemicals, such as crude oil for biodiesel production or biomass for energy purposes. There are two main groups of systems for cultivation of microalgae, open and closed systems. The open ponds have their surface open towards the atmosphere, while the closed photobioreactors are closed vessels made of a transparent material allowing the light to reach the microorganisms inside. Most of the closed systems can then be further categorized into one of the following two categories; tubular devices or flat panels (6).

2.1 Problems in Photobioreactors

There have been many suggestions of how to deal with the light saturation effect, the effect occurring when the microalgae get photo-inhibited due to solar irradiation above certain limits. Most of the solutions to this problem consist of partially shading the algae which leads to light loss. This is not a preferred method since light is often the limiting growth factor and hence all light should be used. Other methods concentrate on moving the light into the solution by using fiber optics or other high-tech equipment (7). Yet another method is to dilute the light by using a cone of transparent material, with the cone towards the solution, thus increasing the surface towards the algae culture compared to the incoming light surface. (8) While all these methods might work in the laboratory or when producing high value products they seem too complex and expensive to use for this project where the product is a low value bulk material. The light saturation effect can also be solved by exposing the alga with short flashes of strong light followed by long periods of darkness. In this way, the algae can efficiently use the short flashes of strong light (9) Subjecting alga to short flashes can be achieved by good agitation causing the 4

algae to be at the surface of the closed system only a short period of time before being shielded by other algae again. This together with the solution conducted by J.M Fernandez et al, in which the problem with photo-inhibition is minimized by having more optically dense cultures and thereby decrease the irradiance inside the reactor, seems to be a good alternative (10). 2.1.1 Oxygen Oversaturation During the photosynthesis the microalgae produce oxygen, in closed bioreactors this can be a problem since the oxygen is trapped in the solution and create an oversaturation that is harmful for the algae culture. This has been reported to be true for the microalga Phaeodactylum tricornutum, where the growth rate decrease when oxygen saturation levels approaches 400% compared with the levels reached by equilibrium with air. Values over 400 % caused the culture to collapse (11). This indicates that the oversaturation must be solved in a closed photobioreactor. 2.1.2 pH-value The pH value needs to be controlled within certain limits. The additional CO2 that needs to be added for the alga culture to grow rapidly lowers pH, while the respiration and usage of CO2 increases pH. Nutrients also have to be added without affecting the pH value too much. 2.1.3 Temperature Different alga strings prefer different temperatures, but most high producing algae prefers temperatures around 25 C. High temperatures can cause the culture to collapse, e.g. Phaeodactylum tricornutum collapsed at temperatures above 35 degrees in experiments done by Acin Fernndez et al 2003 (11). This indicates that the temperature should always be kept under a certain limit, either by a colder climate or an emergency cooling systems for days when the temperature are too high.

2.2 Open Pond System

The open pond can be compared with the natural shallow lake, but the artificial open pond has specific engineered solutions to deal with problems such as keeping the algae from sedimentation, keeping the stirring continuous and at the right rate.

2.2.1 Advantages Low cost construction that is easy to build. No cooling needed. No problems with solutions oversaturated with oxygen. 2.2.2 Disadvantages Low productivity per area and volume (8), due to the low light over volume ratio. The system can easily be contaminated by other microorganisms, which can harm the cultivation of the desired alga string. High loss of water through evaporation from the open surface. Diffusion of CO2 to the atmosphere. (12)

2.3 Closed Photobioreactors

The closed photobioreactor system consists of a number of transparent reactors. The reactors are designed to maximize the absorption of the incoming light and to minimize negative effects such as oxygen oversaturation. 2.3.1 Advantages High productivity per areal of land and per volume (5). High algae content per volume makes separation easier and cheaper, because less water per kg dry biomass has to be removed. Easier to prevent contamination from other microalgae, due to the fact that the system is closed to the environment. Small evaporative losses of water compared to open systems. 2.3.2 Disadvantages Cooling needed to prevent the system from overheating (5). Problems due to oversaturation of oxygen (5) Cleaning problems due to bio-adhesion on the inside of transparent surfaces. Expensive construction that is complex to build. 2.3.3 Comparison of Different Systems of Closed Photobioreactors The comparison between different types of reactors are hard to do, since they have different forms and thus also volume to surface ratio. Therefore when comparisons are made, the way these are made should always be examined. The usual comparison is made on one of the 6

following parameters: volumetric productivity, irradiance area productivity and land area productivity. When a tubular and a flat reactor are compared with reference to the photo efficiency during the day, it can be seen that the flat reactor suffers more from the light saturation effect. The photo efficiency of the tubular reactor was greater due to the dilution effect caused by the curved surface area. The experiments conducted by Tredici et al shows that the photo efficiency drops for the flat reactor during maximum illumination, which occurs at mid day. The tubular reactor had a significantly higher production and growth rate because of the higher photo efficiency. However, the flat reactor had a higher volumetric productivity (7), this shows how hard general conclusions are to make, and that many of the comparing values depend on the specific details of the reactor. Another reactor type with promising experiments is a reactor in polyethylene sleeves. These experiments have been done by Ephraim Cohen et al but since the sleeves in this case are very thin 0.2 mm they would most likely deteriorate from the forces of climate unless a protective greenhouse was build to shield from these forces (13). For large scale production this would be very expensive. For this reason and also that only a few articles has been found on this reactor type, this method is not investigated further at the moment. But in the future it might be an interesting possibility.

2.4 Conclusions - Type of Reactor

The preferred reactor will be the closed photobioreactor, since the open ponds suffer from contamination risks together with high evaporative losses of water and diffusion losses of CO 2. This means that the investment cost will be significantly higher, but also that the separation step will be easier, due to dense cell cultures. Land area unsuitable for agricultural activities are generally sparse on fresh water, why the loss of water should be minimized, this supports the closed reactor. Of the different kinds of closed reactors, tubular, flat and in polyethylene bags, the tubular reactor is chosen. The research on polyethylene bags is not sufficient for the bags to be an alternative. The tubular reactor has a better photo efficiency than the flat reactors, and will be the preferred choice.

2.5 Choosing the Right Algae

2.5.1 General Aspects to Consider There are many aspects to consider when choosing the right algae for biodiesel production. In order to achieve the highest possible production rate of oil, oil content has to be balanced against growth kinetics. Furthermore there are many advantages in having a robust species of alga since the system will be less sensitive to variations in parameters like temperature, pH and salinity. Size and oil composition are also important in order to achieve a simple separation and post 7

processing. Last but not least, it is important that the alga strain is well known and that sufficient research and information exists. 2.5.2 Algae Strains with High Oil Content Algae with high oil content from the list in Micro- and Macro- Algae: Utility for industrial applications by Anders S Carlsson et al 2007 (14) were investigated. When considering important parameters it resulted in further evaluation of the following three algae: Phaeodactylum tricornutum, Chlorella Protothecoides and Botryococcus braunii. After a conversation with the commercial company Algae Link the algae Nannochloropsis salina was also investigated. 2.5.3 Phaeodactylum tricornutum Phaeodactylum tricornutum has been considered as a possible algae strain for biodiesel production. The reasons for this can be summarized by the following: relative high oil content (15-20 % of dry weight), extensive research on this alga, ability to grow to high cell densities and high productivity. These characteristics lead to a more detailed search where the main interest was the conditions for cultivation, how to achieve maximum productivity and the composition of this strain. The growth rate and fatty acid composition of Phaeodactylum tricornutum is greatly affected on growth conditions such as nitrogen source and other inorganic nutrients. Generally the options which give the highest productivity give the lowest fatty acid content. This alga is a fresh water strain that is affected drastically with increased salinity. Many nutrients will change the pH of the growth media from the optimum pH. This will be a problem since the change in pH affects the production negatively. Temperature differences also affect the production rates significantly; the preferred temperature is in the range of 21.5-23 C. (15) Photoautotrophic growth in outdoor pilot scale photobioreactors give the following results. Temperatures above 35 C are lethal for the algal culture; temperatures above 30 C severely affect the growth rate but, by keeping the temperature below 28 C, significant growth occurs. In order to achieve maximum productivity of 1.3 g/L in batch mode the following measures needs to be taken: pH must be kept at 7.7 by automatic CO2 injection, nutrient limitation must be prevented and oxygen saturation kept at less than 350 %. For a continuous mode, productivity of 1.4 g/L d was achieved (10). The report by Garca et al 2004 examines how the carbon and nitrogen sources affect biomass production and fatty acid composition in mixotrophic growth. Mixotrophic growth, a combination of heterotrophic and photoautotrophic, in general gives higher productivity than 8

photoautotrophic growth. In the Garca report the results show that the combination of glycerol as carbon source and urea as nitrogen source gives the highest productivity in mixotrophic growth. This increase in productivity was 9-fold compared to photoautotrophic growth (16). By comparing mixotrophic and photoautotrophic growth in an outdoor pilot scale plant the following results were achieved: The results show that the growth rate increases with mixotrophic growth, up to 1.87 g/L and day, 4 times more than what can be achieved with photoautotrophic conditions. The biomass concentration supported in the reactor can be almost tenfold. The fatty acid concentration of the algae is also increased as well as the photosynthetic efficiency because of the higher algae concentrations (10). Due to the low oil content of this algae strain, another alga has been chosen to be used in this feasibility study. However because of the many favourable characteristics of this strain and more research being done the Phaeodactylum tricornutum could in future be a viable feedstock for the production of biodiesel from microalgae. 2.5.4 Chlorella protothecoides Chlorella protothecoides can grow both photoautotrophic and heterotrophic. Most literature found on Chlorella protothecoides was about heterotrophic growth, where the carbon sources can be constituted of acetate or glucose. When growing Chlorella protothecoides the lipid content in the cells reaches values about four times higher under heterotrophic- than under phototrophic conditions. Heterotrophic growth of Chlorella p. followed by transesterification resulted in biodiesel with a high heating value, 41 MJ/kg, which is comparable with that of conventional diesel (17). When grown under heterotrophic conditions, there is a disappearance of chlorophyll in the cells and therefore the algal cannot utilize the available energy from the sun (17). Because of this and the lack of information on phototrophic growth of Chlorella p. this alga is not used in this study. 2.5.5 Botryococcus braunii Botryococcus braunii is a green colonial microalga which produces high levels of lipids, mainly hydrocarbons and ether lipids. Metzger and Largeau define lipids as all compounds that are readily soluble in organic solvents but only sparingly soluble in water. (18) Botryococcus braunii is an alga that forms colonies. The sizes of these colonies have a wide range with volume average diameters ranging from 0.05-0.2 mm and are strongly dependent on light intensity in the experiments (19). Botryococcus braunii contains lower contents of nitrogen and phosphorus than many other algae on an organic basis, therefore the energy requirement for fertilizers are smaller (4). 9

B. braunii strains can be found in all climate zones except the Antarctic. There are three races, A and B which grow in alpine, continental, temperate and tropical lakes and L which has only been found in tropical conditions. The classification into different races depends on the hydrocarbon production. Race A produce C23-C33 odd numbered n-alkadienes, from mono- to tetraenes, where oleic acid is found to be precursor of the dienes and trienes. Race L produce only lycopadiene, which is a tetraterpenoid hydrocarbon. Algae of race B produce polymethylated triterpenoid hydrocarbons, called botryococcenes which range from C30 to C37. Other hydrocarbons, which the B race synthesizes in trace amounts, are squalene and C31-C34 methylated squalenes. Hydrocarbon contents of up to 61 % in algae of race A have been discovered. Race B usually gives hydrocarbon contents of 30-40 % while the L race has a hydrocarbon content of maximum 8 %. (18) For B. braunii, hydrocarbon productivity is optimal when growth is in the exponential or early linear phase, which means hydrocarbon production kinetics is growth associated. This also indicates that the optimal operating conditions are when maximum growth rate is obtained. In the linear growth phase the following empirical expression was obtained by Kojima et al.:

0.406
Production rate of hydrocarbons Specific growth rate The growth related hydrocarbon production is a special feature of B. braunii, compared to many other microalgae like Chlorella, which mainly produce fatty acids during nitrogen starvation. (20) In fact hydrocarbon production does not take place during nitrogen and phosphorus starvation of B. braunii (21) (22). Factors important for growth are CO2, light, nutrients and water, as well as temperature conditions and pH. Several studies have been performed on Botryococcus braunii to investigate the ability to affect growth rate and hydrocarbon yield by changing different parameters. It has been showed that air enriched with 1 % CO2 enhances growth; the doubling time of the biomass was approximately 2.7 days instead of about 7 days with non-enriched air. Hydrocarbon production also increased five times with CO2 enriched air. (23) B. braunii requires light intensities in the range 40-90 W/m2 for optimal hydrocarbon production (24) (25). It has been reported that B. braunii accepts irradiances between 15 and 180 W/m2 (24) although Li et al. found a slow growing Japanese strain that was not affected in growth or lipid content at the irradiance 300 W/m2 (25).

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Studies on B. braunii indicate that to achieve optimal growth the temperature of the medium should be around 25C. Li et al. made a comparison between three different strains from temperate to subtropical climate zones which all exhibited optimal growth at 25C (25). Furthermore most studies on B. braunii are performed at 25C (26) (27) (28) (20). However, differences between different strains and races are possible; especially since B. braunii can be found in most climate zones. Depending on the algaes ability to adapt to salinity, they are categorized in two groups. Halophilic algae that need salt to enhance growth and halotolerant algae which can survive in salinity. Both groups, however, produce metabolites to protect them from the salt. Ranga Rao et al showed that B. braunii (race A, strain LB 572 from University of Texas, USA) is adaptable to lower levels of salinity. The lower salinity levels also give an increased production of biomass, hydrocarbon content and fat. Maximum hydrocarbon content is 28 % w/w in the salinity range of 50-70 mM, while maximum biomass was achieved in 20-30 mM salinity. Total fat content was 24-28 % w/w where palmitic and oleic acids were the major fatty acids compared to the control culture where the major fatty acids were stearic and linoleic acids. (29) B. braunii does not seem to be particularly sensitive to changes in pH in the range of pH 6-11, although optimal growth seems to occur at pH 6. (30) Nutrients are also an important factor in growing the algae; the most commonly used growth medium in different studies of the different B. braunii races is a modified Chu-13 medium, see Appendix 1 (18) (28) (30). The effects of four major nutrients in this medium; potassium dihydrogen phosphate, potassium nitrate, magnesium sulphate and ferric citrate, were examined on a race A strain. The best combination was found to be concentrations of 0.0195, 0.05, 0.2 and 0.0185 g/l respectively. This composition gave a biomass yield of 0.65 g/l and a hydrocarbon production of 50.6 % (w/w) after four weeks of incubation. (27) Furthermore, there is a possibility to use treated wastewater as a source of nutrients. A study of the ability to remove nitrogen and phosphorus from secondarily treated piggery wastewater, using B. braunii, gave a dry cell weight of 8.5 g/l and hydrocarbon levels of 0.95 g/l after 12 days cultivation. (28) 2.5.6. Nannochloropsis salina When talking to Algae Link, information was received that they are using an algae strain of Nannochloropsis salina. Considering the problems encountered when using Botryococcus braunii and the fact that useful data was accessible for Nannochloropsis salina the decision was made to use the alga Nannochloropsis salina in the suggested process. This alga belongs to the class Eustigmatophyceae and is a yellow-green unicellular microalga with a cell shape of an ellipsoid and an average length of 3.3 and width of 1.9 m. The dry weight of N. salina cells reported by Volkman et al. is 8.3 pg. One has to bear in mind that these data are not absolute and changes with the algaes physiological state when harvested. This in turn will depend on many factors such as light regime, growth temperature, nutrients supply etc. (31) 11

A study conducted by Boussiba et al. showed that permitted growth temperature for Nannochloropsis salina (in laboratory experiments) ranged between 17-32 C with optima at 28C. The results from this study also pointed out that seawater did not have any effect on the lipid content of the cells. The same is true when considering the pH of the culture. Decreased productivity was observed only at the higher pH conditions in the permitted range of growth, pH 5-10.5. The study by Boussiba et al. also reports that to avoid contamination in a monoculture of Nannochloropsis salina with diatoms, it is possible to use urea as a nitrogen source. (32) From personal communication with the sales office at Algae Link the oil content of the cells when harvested is 50 % (dry weight). However, in calculations in this report the oil content used will be 40% (dry weight) since it is more consistent with other studies conducted on this subject. 2.5.7 Choosing an Algae Strain B. braunii is one of the most known hydrocarbon producing algae. This fact that its well known and thoroughly researched is one of its strengths. If an unknown alga strain is chosen, expert knowledge and extensive research are required to produce necessary data concerning oil composition and to properly dimension the equipment. The high hydrocarbon content of race B and the fact that the alga produces these hydrocarbons during growth and not starvation was one of the key factors for choosing this alga at first. The fact that the alga grows in colonies has several positive but also negative effects. One positive effect is easy separation since big particles (colonies) are easier to separate than small (cells). The negative effects are problems caused by the extracellular matter causing clogging, the need for fresh water as well as difficulties determining if the algae cellular material ends up in the water or oil phase. A supplier of photobioreactors for commercial use is Algae Link. For biodiesel purposes they use the algae strain Nannochloropsis salina. Nannochloropsis salina has the following advantages over Botryococcus braunii: Nannochloropsis grows in seawater, which means there is no need for desalination Nannochloropsis is no colony forming microalga (see Appendix 2), and has no extracellular matter Nannochloropsis is used in the photobioreactors produced by Algae Link; hence a more accurate approximation can be done concerning yield in these specific photobioreactors. Nannochloropsis salina is therefore the preferred algae strain in this feasibility study for use in large scale biodiesel production and the calculations in the report will be based on Nannochloropsis salina.

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2.6 Harvesting of Algae - Separation of Particles from Water

Harvesting of microalgae is a major contributor to the total cost of algal biomass and might contribute as much as 20-30 %. The harvesting method must handle large volumes due to dilute culture broths, sometimes less than 0.5 grams dry algal biomass per litre broth. The small size of microalgae, typically ranging from 3-30 microns in diameter makes the process complex. Many separation processes could be used for the harvesting of microalgae, the choice of method depends on a number of parameters such as algal species, cell density and culture conditions (13). The level of moisture is dependent on the harvesting method. Since mechanical dewatering is less expensive than thermal drying, any thermal drying should be preceded by an effective mechanical dewatering step (33). 2.6.1 Flocculation Flocculation is a method that can be used to aggregate particles to increase the particle size and thereby easing other separation methods such as sedimentation, filtration and centrifugation. To aggregate microalgae cells the net negative charge of the cells must be neutralized or reduced by adding a so called flocculants such as multivalent cations or cationic polymers. Some of these flocculants may not be acceptable when the biomass is to be used in certain ways, such as feedstock for animals. Higher cell concentrations and gentle mixing helps flocculation since this makes the cell encounters more frequent. Excessive shear force as can be found in centrifugation can disrupt the flocks (34). Changing the pH of the solution by adding acids or bases can also act as a flocculent since the ionization of functional groups on the algal cell surface are highly pH dependent. A combination of cat ions and pH can also be used. For many algae such as Botryococcus braunii the most efficient method of flocculation seems to be to change pH to around 11. A method suggested is to change pH to 11 with potassium hydroxide to flocculate 85 % of the algae, and then treat the water and remaining 15 % of algae back to appropriate pH with nitric acid after the removal of the flocs. (34). The water-algae mixture is then recirculated and hence no major loss of algae occurs. These chemicals are chosen since the salts they produce will function as nutrients which are needed downstream in the process.

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2.6.2 Gravity Sedimentation Gravity sedimentation is a process that separates particles from liquids on the base of their density difference and the particle diameter. If the solids that are to be separated consists of individual particles of sizes of only a few micrometer in diameter the settling rates will be low (35). The chosen alga, Nannochloropsis salina, is a unicellular alga culture. After flocculation the cells aggregate which makes the sedimentation faster due to the larger effective diameter. However, since the flocks are porous the rate of sedimentation will not be as fast as non porous particles would be, due to the water content. 2.6.3 Centrifugal Recovery Centrifugal separation uses the same principles as gravity sedimentation but enhances the settling rate by centrifuging the particles. This method often replaces the gravity separators, since their higher efficiency and smaller apparatus size for a given capacity (34). Centrifugal recovery is often a preferred method for recovery of algal cells. High concentration factors as well as high percentages of solids in concentrate can be obtained. Centrifugal recovery is a rapid method but also an energy intensive method (33). The use of centrifugation for harvest of low concentration of suspended solids is limited by the power cost of handling large quantities of water. In the experiments conducted by T.-S Sim et al. the energy demand is 1.3 kWh/m3 of pond water in order to produce 4-5 % of dry solid content by weight from pond water containing 0.04-0.07 % of total suspended solids (36). 2.6.4 Ultrasound Ultrasound is a method that can be used to harvest microalgae. The ultrasound process is based on acoustically induced aggregation and enhanced sedimentation. Concentration factors of 20 can be reached with low biomass concentrations and low flow rates. This method uses more energy than centrifugation, has less efficiency and lower concentration factors. Some benefits by using ultrasound compared to centrifugation can be found at lab or pilot scale when other parameters are important than for industrial scale (35). 2.6.5 Filtration There are three main groups of filters; two of the main groups of filters may be used to recover algal cells from a broth. These are: cake filtration in which the broth is filtered through a filter, leaving a cake behind and cross flow filters, in which the suspension flows across the filter medium at high velocities and pressure, leaving a more concentrated suspension behind. The

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third main group is clarifying filters, but these do not suit the need of the harvesting methods, since they are used to remove small amounts and the particles get trapped inside the filter (37). In cake filtration the particles get immobilized in the filter and soon a cake is formed on the filter surface, this cake has to be removed periodically. Cake filtration can be performed continuously or discontinuously with pressure applied either upstream (positive pressure) or downstream (vacuum) (37). Both filter presses and rotary drum filters operating under pressure or vacuum are satisfactory for recovering relatively large microalgae, but not satisfactory when the algae size approaches bacterial dimensions. Pre-coating the filter with filter aid is possible to make the filtration easier, but not suitable when contamination of the biomass cannot be tolerated (36). In experiments conducted by T.-S Sim et al., using 12 m mesh filter, the power requirement ranged from 0.3-0.5 kWh per m3 broth giving about 3 % solids, the power consumption is thereby much lower than their experiments with a centrifuge. Their experiments suggest insignificant or small improvement in performance when flocculants were used. With small algae the filter can clog and the flow through can get much lower (36). Cross flow filtration may be applied to concentrate suspensions of fine particles. Cross flow filtration can be useful for suspensions of very small particles as an alternative to normal filtration since cakes formed by small particles give a high resistance to flow and thereby low filtration rates (37). Cross flow filtration is not an economical method for larger production volumes where centrifugation is a more economic method (34). 2.6.6 Dissolved Air Flotation In dissolved air flotation, air bubbles are passed into a solution in order to increase the buoyancy and cause the particles to float by adhering themselves to the algal particles. For this method the particle-size is crucial, the size is therefore often increased by flocculation. From the results of T.S Sim et al tests, they found that dissolved air flotation is an economical method, but that filtration is a better method when the size of the algae is not a problem (36). 2.6.7 Conclusion - Separation of Particles from Water First flocculation as a pre-treatment method is used to increase the particle size by aggregating the algae cells. This is necessary since Nannochloropsis salina grows in a unicellular manner. Gravity sedimentation is used since it is a method that has low capital costs even if large scale basins are needed. Centrifugal separation of dilute solution is rejected due to the large energy 15

costs. The use of ultrasound is not a viable option for large scale operations because of the extremely high operating costs. Cross flow filtration as a harvest method rejects due to the large scale of harvesting. Dissolved air flotation is a good and economical method for harvest of microalgae. Although, after a discussion with Professor Jes la Cour Jansen, Department of Chemical Engineering, Faculty of Engineering, Lund University, concerning flotation experiments conducted on unicellular algae where the micro bubbles did not stick to the algae, this is not used. The used method is flocculation followed by gravity sedimentation.

2.7 Extraction of Microalgal Oil from Biomass

In general, all separation methods of oils and fats from animal and vegetable materials share the following common objectives: to obtain the fat or oil intact and free from undesirable impurities, to gain the highest yield possible and at the same time not to interfere with the economy of the process, to produce a residue with as high value as possible. (38) To disrupt microorganisms, such as algae, may at first seem as an easy task to be done, but Wimpenny among others refers that this is not true. Microorganisms are in fact more robust than is generally believed. For example Wimpenny points out that the internal pressure inside the organisms (studied organism were Micrococcus lysodeikticus and Sarcina lutea) can be as high as 20 atmospheres. The structures, cellular walls and membranes, which resist this high pressure, are in fact about as strong, weight for weight, as reinforced concrete. (39) Most of the cell disruption methods developed for use with non-photosynthetic microorganisms can also be applied to microalgae (39). For choosing the right extraction method for the large scale recovery of algal oil from the cells certain parameters have to be considered. Among those are: the ease with which the cells disrupt, the cost of method, the speed of the extraction method applied etc. In the following sections some of the more promising extraction methods are discussed. 2.7.1 Bead Mills One way to disrupt the cells is by agitation in presence of small glass, steel or ceramic beads, approximately 0.5 mm in diameter, in bead mills (39). Cell disruption in bead mills is regarded as one of the most efficient techniques for physical cell disruption. These mills consist of either a vertical or a horizontal cylindrical chamber with a motor-driven central shaft supporting a collection of off-centered discs or other agitating element. The chamber is filled to the desired level of beads which provide the grinding action. (39)

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2.7.2 Presses There are a many different presses available on the market, i.e. screw, expeller, piston. Suitable press configuration for the extraction is largely dependent on which algae strain that is being used, since there is a vast variation among different strains in their physical attributes such as cell dimensions, rigidity in the cell structures etc. The amount of oil recovered from the cells depends on many factors. Among those is the rate at which pressure is applied, the maximum pressure attained, the time allowed for oil drainage at full pressure, and the temperature or the viscosity of the oil. (38) Screw presses are used for extracting oils and fats from soybeans, cottonseed, peanuts and are possible to use with almost any other variety of oil seed. This method for extraction can give as low oil content as 3-4 % in the resulting cake. (38) Information about applying this extraction method to algae cells is missing in literature, but could emerge as a viable alternative if the low oil content in the cake is true when applying this technique on microalgae instead. 2.7.3 Solvent Extraction Solvent extraction of oil in algae can be performed with a two solvent system. When allowing algae to be in short contact with hexane experiments conducted by P. Metzger showed an extraction yield of up to 70 % of the total hydrocarbons contained in the cells (18). The disadvantages when using solvent extraction in commercial large scale is that the process requires an extra energy input because the solvent needs to be distillated of, but also the risk for the solvent used to contaminate the products, thereby limiting the options for their end use. (40) One way to overcome the problems mentioned above could be to use the final product biodiesel as the solvent. By recirculation of the final product to be used as the solvent, distillation would not be necessary since the biodiesel can follow the crude oil through pretreatment and transesterification. This would eliminate the large energy input needed to distillate the solvent but also solve the problem related to contamination of the product biodiesel. 2.7.4 Cavitation Cavitation is a method that uses pressure differences and the resulting cavities collapses as a result of the shifting pressures. The collapses cause high shock waves in the micro environment and this causes the algaes cell membranes to break. There are two types of cavitation, one using ultrasonic cavitation and the other hydrodynamic cavitation. Ultrasonic cavitation utilizes sound to create the oscillating pressure, causing the formation and collapse of cavities. The other is

17

hydrodynamic cavitation, where the pressure drop over simple geometrics like venturi pipes or orifice are used. (41) 2.7.5 Less Known Methods In lab scale there exists many ways to disrupt microbial cells, some of which are supercritical CO2 extraction, osmotic shock, enzymatic and chemical lysis. However, none of these have been object for further studies for large scale production of micro-algal-oil. The reason for this is probably due to the high processing cost. 2.7.6 Conclusion - Extraction of Microalgal Oil from Biomass The chosen method for the extracting the oil is the utilization of cavitation, since this is the most viable method to disrupt the algae cell membranes. This method also eliminates the need of adding solvents, which thereby lower the costs. The most suitable method of cavitation would be hydrodynamic cavitation, since this is a safer and requires less energy than the ultrasonic cavitation.

2.8 Termochemical Liquefaction - an Alternative Path?

By thermochemical liquefaction, it is possible to obtain greater amount of liquid fuel than just the hydrocarbons, since other materials in the algal cells such as protein and fiber can be converted to liquid fuel. The reaction can be performed in the temperature range of 200-350 C with or without a catalyst, such as sodium carbonate (4). In the thermochemical liquefaction the algal mass is treated in a sealed autoclave with 20-30 MPa. Thermochemical liquefaction has the advantage of being able to treat wet material, with water contents above 60 % based on total weight, meaning no drying process is needed (5). Thermochemical liquefaction is best conducted at 300 C, the highest yield of fuel over mass achieved in this process, is well above the maximum yield in any extraction step. With higher temperatures than 300 C, thermochemical degradation occurs (4). The reaction mixture from the liquefaction is separated in a series of steps. The gas mixture, mainly consisting of CO2 that could be sent back to the process, is easy to collect. Solvent extraction is used to separate the oil and water phase, the solid residues are filtered and may be dried if necessary. The solvent is separated from the oil by evaporation under low temperature and pressure (4). There is a possibility to save money by reusing the waste water from the liquefaction stage since it contains large parts of many of the inorganic nutrients supplied to the algae as a fertilizer (5). Solid energy yield of the liquefaction process can be as high as 5 %, the yield decreases with increased catalyst and increased temperature (42). The solids should be taken care of to increase the total energy yield of the process.

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When conducting thermochemical liquefaction on Botryococcus braunii, three separate fractions are formed. One fraction is hydrocarbons with mean molecular weights in the range of 200-300; this fraction is probably degraded products from the oil substances. The second fraction is the botryococcenes, the oil produced from the algae. The third fraction is fairly large polar substances. The first two fractions are suitable as energy feedstock. The third fraction might be suitable for a feedstock for boiler fuel (43). Thermochemical liquefaction might be an alternative to more conventional extraction steps. The higher yield possible in this step as well as ability to threat wet materials might make this process step a viable alternative even though large amounts of heat energy has to be supplied. No further calculations were made on this alternative due to the complexity of this process step with multiple purification steps, high temperature and pressure as well as problems finding any data concerning the needs of this process.

2.9 Post Processing Crude Oil to Biodiesel

2.9.1 EN 14214 The common European standard for biodiesel is EN 14214. This standard sets specific demands on the physical and chemical properties on the biodiesel for use in compression ignition motors. The standard can be seen in Table 1. (44) 2.9.2 Pretreatment of Crude Oil In order to minimize losses in further refining and fulfill the EN 14214 standard the algal oil will most likely need some kind of pretreatment. The most important purification steps will be removal of free fatty acids and degumming, which will remove phosphorous content. 2.9.2.1 Degumming Removal of Phospholipids Just like vegetable oils, oil from microalgae contains phosphorus in the form of phospholipids. Phospholipids consist of hydrophilic heads and hydrophobic tails and will form reversed micelles in non-aqueous systems (45). Since phosphorous will cause losses due to formation of emulsions in the further refining of the oil (46) and a decrease in the efficiency of the catalytic converters in diesel vehicles (47), phosphorous content of more than 10 mg l-1 is not allowed according to the EN 14214 standard. It is important to remove the phospholipids, just after the extraction step, otherwise the phospholipids will settle out in the containers when the oil is stored (46). The phospholipid content will differ depending on which algae strain is used.

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Table 1 EN 14214 Biodiesel standard with courtesy of Christian Hulteberg (44)

In the removal of phospholipids it is important to minimize formation of free fatty acids. Formation of free fatty acids occurs when the heated oil comes in contact with oxygen. It is also important to dry the oil if it contains water since hydrolysis will produce free fatty acids (46). Initial degumming of crude solvent extracted oil is performed by adding a small amount of water (4 %) or a weak acidic or salt solution to the oil at 80 C (46). The phospholipids will then coagulate (47) and can be removed through centrifugal separation in continuous centrifuges. These centrifuges are hermetical, which is important in order to avoid oxidation of the oil at the required temperature. After this step the oil will still contain about 0.5 % of phospholipids. In order to obtain a higher purity, this first degumming step has to be followed by another 20

degumming step. Then, the oil is treated with 0.25-0.3 % (v/v) of 85 % phosphoric acid; the remaining impurities will form a precipitate that is removed by a separator. After this step neutralization is necessary to get stable oil. Neutralization is performed by adding the oil to a 0.1-0.3 M sodium hydroxide solution in a neutralizing column. The neutralized oil will then contain traces of soap which will be removed by adding a water solution containing 0.05 % (w/w) citric acid before drying the oil. When drying the oil, small amounts of free fatty acids and sodium citrate are formed instead of citric acid and soap. Citrate has to be removed in a bleaching step. (46) Another way of degumming the oil is to use acetic anhydride. A small amount of acetic acid is added to the oil together with water to hydrate the gum. The solution is heated before the hydrated gums are centrifugally separated. To remove all of the acetic anhydride, the oil has to be washed with water, before it is vacuum dried. This process will produce oil which needs no neutralization with alkalis to obtain a stable product (38). There is also a possibility of removing the phospholipids through ultrafiltration of crude oil. Fluxes achieved in experiment are however too small for large scale production. Reported numbers are; 0.75 kg/m2h with 3 MPa pressure and roughly 95 % removal of phospholipids (48), 20 l/m2h with 5 bar pressure and a retention on phospholipids of 73 % (48). Therefore it will not be possible to use ultrafiltration in this case. A final possibility would be to remove the final phospholipid content by distillation, since phospholipids have a higher molecular weight than the crude oil they will remain in the residue from the distillation. It is recommended to use wiped-film short-path evaporators with 10-200 Pa operating pressure. (47) 2.9.2.2 Purification of Free Fatty Acids Oil derived from algae such as Botryococcus braunii might contain high levels of free fatty acids (FFA). Kalacheva et al. has shown that B. braunii Ktzing contains about 10 % of total lipid content. Although it is disputed that this particular strain belongs to B. braunii, analysis of the oil composition suggests that this strain instead belongs to B. sudeticus. (49). In regular transesterification of the oil into biodiesel by using base catalysts and methanol, the free fatty acids will react with the base catalyst to produce soap. This will deactivate the catalyst or cause a lower production yield. (50) This reaction will cause problems at levels as small as 0.5 % of total lipid content. (51) To prevent this reaction, the FFAs should be either removed or converted into an inert or useful material. Studies have been made to convert the FFA to fatty acid methyl esters through esterification using heterogenic acid catalysts and methanol. Batch reactions with catalysts in powder form showed that the catalysts which gave the highest FFA conversion were WO3/ZrO2 and 21

SO42-/ZrO2. The WO3/ZrO2 catalyst was chosen for a longer operation test in packed-bed since loss of SO4-2 from the SO42-/ZrO2 catalyst was likely. The longer operation test lasted for 140 hours and showed an FFA conversion of 65 %, which rose to 85 % after 20 hours just to decrease back to 65 %. The increase after 20 h was due to the generated biodiesel, which improved the miscibility of oil and methanol. Normally, increased temperature would lead an increased catalyst activity; in this case however, catalyst activity only rose by 5 % between 75 C and 200 C due to the vaporization of methanol. With reaction time the catalyst structure changed, although this was due to deposition of soybean oil, which is regenerable, and not due to W leaching. This means it is possible to regenerate the catalyst. Powder catalysts gave a FFA conversion of 85-90 % for both catalysts and the pellet-type WO3/ZrO2 catalyst a conversion of 65 %. (51) Many different catalysts can be used for the esterification reaction, the best homogenous phase catalyst choice might be ferric sulfate due to the easier separation and lower cost than for sulfuric acid, and this reaction setup can produce conversions up to 97% at 3 hours residence time and 95 C (52). The downside with this reaction is that the catalyst has to be separated from the reaction mixture to be recirculated. Heterogeneous catalysts such a WO3/ZrO2 catalyst give a conversion of 65-70% at one hour residence time and a high methanol to FFA ratio and a 75 C (51) Higher conversions can be achieved by increasing the residence time in the reactor, 3 hours give a yield about 80% and 10 hours almost 100% yield for a tungsten-zirconia catalyst at 120 C (53) Another solution to the problem would be to have a pre-treatment process using a homogeneous catalyst. FFA is converted into esters by mixing the crude oil with methanol in a 0.60 w/w methanol-to-oil ratio and using 1 % w/w H2SO4 as catalyst. The reaction takes place at a temperature of 50 C and reaction time is one hour. (54)

2.10 Transesterification of Crude Oil to Biodiesel

The most common process for transesterification today uses a base catalyst, either sodium hydroxide or potassium hydroxide, in a homogenous phase reaction. The reaction takes place at atmospheric pressure, just below the boiling temperature of methanol; the reaction time is about two hours. (55) This process has some major drawbacks like the undesired saponification reaction in which the base catalyst is consumed by the free fatty acids present in the oil. Another drawback is the complicated purification when the products and catalyst has to be separated (56). Due to these major drawbacks of the homogenously catalyzed transesterification step, many other methods have been investigated and some seem promising. The main types of processes

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possible for transesterification described in the literature are base catalyzed, acid catalyzed, enzyme catalyzed and supercritical processes. 2.10.1 Heterogeneous Catalysis One of the main reasons for considering heterogeneous catalysis is that the post processing with heterogeneous catalysis is less complicated than for homogenous catalysis. But due to diffusion, the three phase system often gives low reaction rates in experiments. Compounds suitable as catalysts are alkaline earth metal hydroxides, oxides and alkoxides (57). 2.10.2 Supercritical Methanol Transesterification can be conducted by a supercritical methanol process; this process is conducted at high temperature in the range of 200-350 C and at pressures around 35 MPa. Supercritical processes have some advantages compared to catalytic processes that make them interesting. One of the most striking differences is the absence of a catalyst. This leads to the following: no saponification, less after-process separation, less sensibility to water content, no problems with corrosive environment and fewer waste products. The reaction time for the supercritical process is extremely short, only 4 min (58), compared to other transesterification processes (59). This means that a smaller reaction vessel is required which, together with easier post treatment and no catalyst cost, may compensate for the more expensive process equipment and costs for higher temperature and pressure.

2.11 Suitable Plant Location

Biodiesel production of microalgae can be cultivated in many different environments. If biodiesel from microalgae are to be the large scale solution for our growing energy demand, food production for a growing population might be affected if farmland is used for fuel production. Therefore the location should preferably be land with no major farming opportunities. Microalgae, as all photosynthetic life forms need sunlight to grow. The production facilities are costly and therefore it is important to have a high total production of the plant, in order to achieve this, sunlight must be readily available. Most microalgae prefer water temperatures around 25 C but need to have water temperatures below 30 C to survive. In closed photobioreactors the temperature of the system increases by the incoming sunlight and cooling of the growth medium is therefore extremely important. Possibility to cool the growth medium to optimal temperature is an extremely important parameter when choosing the location, if the natural temperature is not optimal. The daily variation and seasonal changes in weather, as well as the availability, price and temperature of cooling water, limits the location to coastal areas or inland areas with readily available water. Since microalgae need large amounts of carbon dioxide and other inorganic nutrients, the availability and price of these products are important. Large industrial complexes can supply carbon dioxide as flue gas from combustion of various organic 23

substances. Other necessary nutrients must be purchased and transported to the site, if not acquired for free as partially treated waste water from a large city. Many algae strains suitable for biodiesel production are fresh water strains. If no freshwater is available, desalination must be performed since the used algae can be freshwater strains which do not grow optimally and sometimes not at all in saline water. The perfect location has many hours of sunlight per year and low seasonal variations in temperature, suitably a desert. The location should also be next to a power plant which is a source of free carbon dioxide. There is also need for a secure source of water for both cultivation and cooling. Is there such a place on earth? Probably not, but the sunlight must be the most important factor closely followed by the possibility to cool the growth media with sufficiently cool water. One alternative would be to locate the facility in Qatar. Firstly Hydro is building two large aluminum smelting plants in Qatar which solves the problem with free access to carbon dioxide. Secondly Qatar has a lot of land area that would not compete with areal for food production. It is also one of the best places in the world when comparing sun-hours, though a big drawback would be the high day temperatures from March to December. The Persian Gulf might also have a too high temperature in order for Qatar to be a perfect choice for a plant location. Future molecular level engineering of the algae strain can possibly solve this problem through increased temperature tolerance (2). When considering other options South Africa seems like a favorable alternative. There are aluminium smelting plants in South Africa as well. South Africa has lower air and sea temperatures than Qatar although one downside is less hours of sun. Locations that might be suitable are coastal areas in Qatar, South Africa and Australia. The main reasons for choosing these places can be summarized by the following factors: Suitable climate, sunlight and temperatures, for microalgae production. Production facilities that releases CO2 Access to water Non-expensive land

2.12 Conclusion
The location of the production facilities for microalgae cultivation needs land with suitable characteristics such as many sunlight hours and cooling possibilities if the temperature gets too high. Readily available carbon dioxide as well as excess energy from other industrial processes is also important aspects to consider when choosing the location. Three suitable places for algae cultivation are Qatar, South Africa and Australia. When considering the factors above South 24

Africa was chosen. Qatar has too high temperatures and it is concluded that it would be difficult to find a cooling system that would handle such large quantities of water without affecting the overall feasibility. However, if this problem is solved Qatar would be the best alternative considering the number of sun-hours. The cultivation should be carried out in closed tubular photobioreactors since they provide the most favorable characteristics. The separation step is carried out through flocculation and sedimentation. This is the most suitable alternative, considering the dilute solutions which will make other separation techniques energy consuming. The method of choice for the extraction, where the crude oil from the microalgae is derived, is hydrodynamic cavitation. Since the phospholipid content of Nannochloropsis salina is unknown, it is assumed that the crude oil needs some pre-treatment to remove phospholipids. The chosen method is the most common method of using phosphoric acid. The crude oil contains free fatty acids; these are removed by converting the FFA to fatty acid methyl esters through esterification using heterogenic acid catalysts and methanol. The pre-treated crude oil is converted to biodiesel through homogenous phase base catalyzed transesterification. This is a well known process and is the same whether upgrading soybean oil, oil from oil palm or crude oil from micro algae.

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3 Flow Diagram
In Flowsheet A, the process chosen in the conclusion of the chapter above Technology Suitable for Large-Scale Production is presented; this is the process that was designed and cost estimated. Another process alternative is also presented in Flowsheet B, but it is not investigated through calculations in this report. It could have been interesting to compare the two processes cost effectiveness, but no calculations of the alternative process have been made; this mostly due to the limited time available for the project.

3.1 Main Process Alternative

The chosen method for producing algae oil from N. salina consists of a number of unit operations. The algae are cultivated in a closed photobioreactor consisting of multiple pipes and the algae-water mixture is separated by a flocculation-sedimentation unit. 85% of the algae is separated, the water containing the remaining algae is recirculated and hence no major loss of algae occurs. The algae cells are disrupted by a hydrodynamic cavitation unit, the disrupted cells and water are separated from the oil phase in a stirring settling tank unit followed by an oil water separator. The phosphorous content of the oil is removed in a degumming step and the free fatty acids are reacted with methanol in order to esterify the FFAs into methyl esters. All these main unit operations can be seen in Flowsheet A.

3.2 An Alternative Process

Before the disruption method of algae cells using hydrodynamic cavitation emerged as an alternative way for disruption of algae cells, an alternative process including a bead mill was looked upon. This process can be seen in Flowsheet B. One of the main reasons why it was not the chosen process was due to missing information, both on the wet bead mills ability for large scale operation but also the lack of data for making it possible to calculate the energy needed for operating the unit. Today wet bead mills are, to the principal investigators best knowledge, only used for small scale disruption of microalgae, where high value products are extracted. The main unit operation differing from the chosen process seen on Flowsheet A, is the use of a wet bead mill instead of a cavitation equipment. Because a wet bead mill operates with a dry weight of approximately 50 %, a larger amount of water has to be removed. Equipment for this task have been suggested to include a centrifuge operating parallel with a spray dryer using the flue gas from the facility feeding the photobioreactor with carbon dioxide. Here the spray dryer is used to increase the dry weight of the algae before disruption occurs, while in the chosen process the flue gas in the dryer is used to dry the byproduct constituted of crushed cell walls.

26

1. Photobioreactor 2. Sedimentation 3. Pump 4. Cavitation 5. Stirring Settling Tank

Biodiesel from microalgae FLOWSHEET A

Ftot = 7774 ton/h Water = 7768 ton/h

6. Centrifuge 7. Degumming 8. Removal FFA 9. Spray Dryer

[V]
Flue gas

5 3
Disrupted algae

[C]
1 2

[D]

[E]

[U]

Ftot = 8760 ton/h Water = 8754 ton/h

[G]

Cell paste = 373.1 ton/h Cell walls = 18.66 ton/h

Water = 973.8 ton/h

Water = 318 ton/h

[B]

[I]
Ftot = 334.8 ton/h Cell walls = 16.74 ton/h

Flue gas = 1.425 million Nm3/h, water = 36.46 ton/h

[H] [R]
Cell paste = 38.38 ton/h Cell walls = 1.920 ton/h

Ftot = 24.88 ton/h Algae oil = 12.44 ton/h

Nutrients

Ftot = 9145 ton/h Algae = 36.58 ton/h

Ftot = 1372 ton/h Algae = 31.09 ton/h

[A]

[F]

[F]

[J] [K]
Water = 12.44 ton/h

Dry cells = 1.920 ton/h

[T] [L]
9

Algae oil = 12.44 ton/h

[S]
Flue gas = 1.425 million Nm3/h

[O] Algae oil = 12.44 ton/h [Q]

7 8

Crude oil = 12.44 ton/h + MeOH + water = approx. 4.28 ton/h

[M]
Phosphorus acid and NaOH

[N]
Phospholipids = 0.12 ton/h

[P]
MeOH = approx. 4.28 ton/h

Figure 2 Flowsheet A over the main process

27

1. Photobioreactor 2. Sedimentation 3. Spray Dryer 4. Centrifuge 5. Wet Ball Mill

Biodiesel from Microalgae FLOWSHEET B

Flue gas + water

6. Stirring Settling Tank 7. Centrifuge 8. Degumming 9. Removal FFA

Algae + water 50 % w/w

3
Water + algae recycled

Algae + water

Algae + water

Crushed algae

Water

Algae + water

Algae + water

Water recycled

6
Cell walls

4
Water recycled

Crude oil + MeOH + water

Algae oil Phosphorus acid and NaOH

9
Flue gas

MeOH

Phospholipids

Figure 3 Flowsheet B over alternative process

28

Algae oil

Nutrients

Algae + water

Water recycled

4 Cost Estimates
4.1 Total Annual Cost
The total annual cost for algae oil production facility is summarized as the capital cost and the operating cost. The results are summarized in Appendix 6. 4.1.1 Capital Costs The capital investment is calculated by summarizing the cost of all process equipment found in Appendix 3. Depending on the method used for cost estimation or the status of the equipment, different add-on factors are used to the bare module costs. For turnkey equipment and module factors calculated by the Ulrich method, the adding factors were contingency and contracting (15%) and on site infrastructure/auxiliary facilities (5%). For the non-turnkey equipment, where the cost was given by a commercial company, all add on factors described in the book Projekteringsmetodik (60) with the given rule of thumb approximations were used. These factors include; Installation, building, land improvement, transportation and insurance as well as social benefits and overtime, engineering, contractor, contingency and support equipment. The results are summarized in Appendix 4. In the estimations of capital costs for the different equipment in the process a method described in Ulrich, G. D., A guide to Chemical engineering Process Design and Economics, Wiley, 1984 is used (61). In this method the equipments total contribution to both the direct and indirect construction cost, CBM , is calculated using Equation 1.
Equation 1

(1) CBM is the installed bare module cost, Cp the purchased equipment cost and finally which is a factor taking into consideration both the type of material and deviations from normal temperature and pressure as well as including installation, buildings, land improvement, transportation and insurance, social benefits and overtime and engineering. The depreciated capital cost for the algae oil production facility is calculated with the well know annuity factor model (62), the results are summarized in Appendix 5. The total value of the factory at the end of its expected useful life span is set to zero when calculating the capital cost. The tanks and equipment built in metal should have a positive value at the end of its useful life

29

span, but the main cost that is the photobioreactor mainly built in plastics could well result in a net negative value. 4.1.1.1 Cost Estimation of Land Requirement Estimations on cost of land requirement are usually not done, due to the increasing value of the land making compensation for decreasing value unnecessary. A brief estimation also shows that it is negligible. A search for available land in South Africa in the province Kwazulu Natal gave a price of 9.950 000 ZAR for a land area of 350 Ha (63). This is less than half of what the photobioreactors require (750 Ha). Considering that the price of 350 Ha of land is 896 658 Euro and the difficulty to set an exact valid price due to large uncertainties on location, the cost of land are seen as negligible at this stage. The cost of land is only a few percent or smaller of the total capital cost. For exchange rates, see Appendix 9. 4.1.2 Operating Costs The operating costs for producing algae oil is calculated by the method described in the book Projekteringsmetodik (60) with the given rule of thumb approximations (60). The results are summarized in Appendix 6.The major energy consumption units can be found in Appendix 3 and are summarized in Appendix 4. The electricity costs for large scale consumption in South Africa can be approximated as 0.1 ZAR/kWh according to Dr. Christian Hulteberg (64). The total energy consumption of the facility is calculated by multiplying the energy consumption of the large scale consuming equipment with a small factor. Extra equipment adds a total of 2 % to the total energy consumption.

4.2 General Assumptions

In order to make a cost approximation, certain assumptions have been made regarding our base case. The algae contain 40% (w/w) oil Nannochloropsis salina is possible to flocculate No loss of algae biomass, since the water containing 15% of the algae is recirculated from the sedimentation into the photobioreactors The production in our photobioreactor is 500 g/(m3) day Facility operating 335 days a year Useful life span of factory is 15 years

30

The production facility is in close proximity to a 400 MW NGCC plant providing carbon dioxide as well as support equipment Production costs are calculated for South African conditions Algae cultivation are performed in Algae Links photobioreactors All process units are viable for their operation, for example the cavitation equipment can process high dry weight content and disrupt the algae cell The rate of interest for the capital investment is 10 %. It should be noted that if any of these assumptions prove to be false this will have extensive effects on the overall process. Therefore, a sensitivity analysis is performed and presented later in this feasibility study,

4.3 Mass Balances

Calculations of the different flow rates in the process were performed on the base case, 0.4 % concentration of algae when harvesting and a daily production rate of 500 g m -3 day-1. The oil content of the algae was set to 40 %. The calculated flow rates in the process, needed to meet the required yearly production of 100 000 ton crude oil, can be seen on Flowsheet A and in Appendix 7. Assumptions made in the calculations of the flow rates are: Degree of separation of algae from water in the flocculation/sedimentation step is set to 0.85 Flow ratio stream [D]/[E] = 0.85 Oil content in dry algae is set to be 40 % (dry weight) Dry weight of cell paste in stream [H] = 0.05 100 % degree of separation in the centrifuge step (6) is assumed Stream [N] is assumed to be 1 % of stream [L], resulting in 0.12 ton/h of phospholipids Flow rates of H3PO3 and NaOH needed in the degumming stage (7) are not calculated and neglected due to no large quantities are needed

4.4 Cost Estimates of Unit Operations

4.4.1 Cost of Photobioreactor Facility No estimations are performed regarding the system for sterilization of the incoming seawater. This might lead to an underestimation of the production costs. The cost of the photobioreactor system is based on the commercial company Algae Links photobioreactors. This technology is not yet proven in large scale facilities, why production 31

estimates are seen as future technology performance. The performance estimated in this feasibility study therefore compensates for differences between future and current technology by dividing the future performance value by 3. Using this estimation from a commercial company with the current technology gives a more accurate price than if the facility should be estimated without any commercial connection. If the cost should be estimated without using Algae Links tubular photobioreactors, a number of questions arise; questions which are very hard to answer without extensive laboratory and pilot scale experiments. The questions involve: suitable diameter on the tubing, how agitation in the tubing is solved, how cleaning of the inside of the photobioreactor is secured. Further questions are; how the produced oxygen is removed to prevent the algae culture from suffering from oxygen oversaturation and how the insertion of CO2 is solved. These are just a few of the questions encountered while looking at tubular photobioreactor systems. Therefore the estimates will be carried out as follows: Algae Link, has given an approximate price for a facility producing 100 tons of dry algae mass per day. Algae Link stresses the fact that they cannot give a real price until a pilot plant has been run on the chosen location. This is due to the fact that the algae growth and hence the size of the facility varies greatly dependent on the growth conditions on site. Information on Algae Links homepage estimates a 100 tons facility to have a photobioreactor volume of 66 667 m3. Simple calculations give that the growth rate per m3 and day should be in the order of 1500 grams/(m3day). This is theoretical values which is not possible to achieve today. When talking to Algae Link the following estimations were given.
Table 2 Table showing growth rates of the algae at different sun radiation

Sun radiation Intermediate (production indoors, in the Netherlands) Good Very Good Exceptionally good Theoretical

g/m3 day 300 600 900 1200 1500

An assumption of reaching 500 g/m3day is made, thus the growing facility needs to be three times as big as the theoretical value given by Algae Link. This gives the approximate values for a 100 ton/day dry algae mass facility: Purchase price: 15 million Euro 3 = 45 million Euro Energy demand pumps: 327 kW 3 = 981 kW 32

Volume: 66 667 m3 3 = 200 000 m3 Meters of piping: 213 864 m 3 = 640 000 m Installation area: 332 700 m2 3 = 1 000 000 m2 Price and numbers recalculated for a facility producing 746 tons of dry algae mass per day: Volume: 200 000 m3 7.46 = 1 490 000 m3 Price: 45 million Euro 7.46 = 336 Million Euro Energy demand: 981 kW 7.46 = 7320 = 7.3 MW Meters of tubing: 641 592 m 7.46 = 4 810 000 m Installation area: 998 100 m2 7.46 = 7 490 000 m2 Area specific production: 99.6 g/m2day To compare Algae Links given cost for the photobioreactors, the raw material cost for polycarbonate which is used in the photobioreactor tubes, was calculated. The tubes were estimated to consist of pipes with 1.2 cm thick, 5 m long with a circumference of 2 m. This gave a total material volume of 58 000 m3 polycarbonate for the entire system. The density for polycarbonate is 1200 kg/m3 (65), thus giving a weight of 69 500 ton. The price of moulding polycarbonate in Hong Kong was $2800 CIF (cost, insurance, freight) in November 2007 (66). This means the total cost of the polycarbonate material in the system is 268 million. This price compares well with the 336 million calculated above and shows that the profit made by Algae Link is reasonable. 4.4.1.1 Nutrients Data of necessary amounts of nutrients were found at Algae Links homepage (67), see Appendix 8. In seawater there are low contents of magnesium (0.128%), calcium (0.041%) and potassium (0.040%) (68). If ca 350 tons of seawater is added every day, the magnesium content in the seawater will be sufficient to grow the algae and no further addition of magnesium will be necessary. Furthermore, the potassium and calcium levels will cover 25% and 35% respectively of total amount required. The cost of the nutrient was calculated in two different ways, one by calculating the required amount of fertilizers and another by calculating the required amount of suitable chemicals.

33

Fertilizers used were Yara Suprasalpeter N27 and Yara OptiCrop 21-3-10, since current market prices for these fertilizers were available. The compositions of N27 and 21-3-10 were found at Yaras homepage (69). The price of Yara OptiCrop 21-3-10 was 449 /ton, found at ATLs homepage (70). The price of Yara Suprasalpeter N27 was 0.341 /kg in 750 kg bags, information given by Lantmnnen direkt (71). In order to achieve sufficient amounts of nitrogen, 114 tons of N27 and 145 tons of 21-3-10 per day is needed. This will also cover the required amount of potassium and magnesium and most of the calcium and phosphorous. A similar, better suited fertilizer can most likely be found at a similar price, and our calculations of fertilizer cost are therefore based on the prices above. The total fertilizer cost will be 104 000 /day which gives a cost of 0.348 /kg algae oil. When calculating with prices of basic chemicals, the following chemicals are used; prices from 2005 were found in Chemical Market Reporter (72) and were recalculated to the price value today using a fertilizer index for the U.S. (73), see Appendix 9. Nitric acid and potassium hydroxide are used when flocculating the algae and the main part of this water is recycled. The calculations are performed with 85% recirculation. See Appendix 8 for calculation of nutrients from chemicals. When using base chemicals the cost was 84 500 /day giving a cost of 0.283 /kg when using the prices of base chemicals and sufficient amounts of nitrogen, potassium, calcium, phosphorous and iron were added, magnesium is assumed to be sufficient in the added seawater. The most economic solution would therefore be using base chemicals for nutrition, if possible.
Table 3 Photobioreactor Capital Cost and Operating Cost

Purchased equipment cost [] Capital cost Photobioreactor, turn-key Operating costs Energy demand Nutrients 335 733 500

/year

501 043 28 307 500

4.4.2 Cost of Sedimentation Equipment The equipment necessary for dewatering of the algae broth by flocculation followed by sedimentation is approximated as a facility to produce drinking water using factors from Ulrich (61).

34

The following assumptions were made in the flocculation and sedimentation steps: 85 % of the algae are separated in this step 85 % of the water is removed from the algae broth The added flocculants does not contribute to the liquid volume The algae concentration in the dilute algae broth is set to, either 0.4 kg/m3 according to literature, or 1.0 kg/m3 according to Algae Link, and the costs for the different concentrations are compared. The calculations and results shown are calculated with the Ulrich method (61).
Table 4 Cost comparison for different harvesting concentrations

0.4% algae Module Cost [] 26 900 000

1% algae 11 100 000

As can be seen, the size and cost for this equipment is extremely sensitive to the algae content. A small decrease in the harvesting concentration lead to a large increase in the facility costs. 4.4.2.1 Consumption of Flocculants One easy way to flocculate microalgae is to increase the pH of the solution to around 11. To do so, a base is added to the solution. After the flocculation, the solution has to be neutralized by a strong acid before recycling the water and nutrients. The byproduct in the flocculation is the salt produced from the strong acid and strong base. A suitable base in this case would be potassium hydroxide and a suitable acid would be nitric acid, since both potassium and nitrogen is needed as nutrients. This means accumulation of byproduct from this step is avoided in the same time as nutrient costs are somewhat lowered. The following assumptions were made in the chemical price calculation of the flocculants: The same assumptions as for the flocculation sedimentation equipment The strong acid and base deprotonate completely The added flocculants does not contribute to the liquid volume The initial OH- in the dilute algae broth is neglected The same amount of H+ ions is needed to neutralize the water after sedimentation No buffering capacity is observed by the initial salts The activity of the OH- ions equals the concentration The amount of OH- ions needed per m3 for pH 11 equals 0.001 kmole.

35

Table 5 Total amount of OH- ions

0.4% algae kmole/day 200

1% algae 80

The price of the flocculation chemicals are calculated as nutrients. The calculations and results shown are calculated with the Ulrich method (61).
Table 6 Flocculation and Sedimentation Capital Cost and Operating Cost

Module cost [] Capital cost Flocculation and Sedimentation Operating cost Energy demand Flocculants
*

/year

26 900 000

neglected not calculated*

Assumed to be included in the nutrient costs.

4.4.3 Cost of Cavitation Equipment As this project has progressed, an idea of using pressure differences to disrupt the algae has emerged. This idea came from a conversation with Professor Gunnar Lidn (74), and also from an article using ultrasonic cavitation for cell disruption (75). When later inquiring some specific details regarding Algae Links (76) photobioreactors they revealed that they use cavitation technology for cell disruption. Due to the fact that they currently have a patent pending in this field they did not give any more details, except that its not ultrasonic cavitation, but it will be revealed soon when they build and show their large scale plant in Spain (2 tons a day). (76) The two references, Gunnar Lidn and Algae Link, have set us on the path of cavitation. Unfortunately no extensive research was found when searching on cavitation on microalgae and specifically hydrodynamic cavitation since this is the method most likely used by Algae Link. Some research was found on extracting proteins from a kind of brewers yeast (77), but this experimental setup was not suitable for large scale processes. The cavitation process for disruption of microalgae is seen as a black box operation where the cost is estimated from a process from the German commercial company, Hielscher (78). This process is an ultrasound cavitation process, the most similar process found. To conclude, since the hydrodynamic cavitation is relatively new in this context and extensive research is missing, as an approximation, the cost of ultrasonic cavitation is used. 36

Personal communication with Mr. Walter Staudenrauss (79) gave the approximate price of 12 000 for an ultrasonic equipment that can handle approximately 200-750 liters per hour. Considering that the flow is 1370 m3/h a number of 2744 units are required if used at 500 liters/hour. The result is a capital investment of 32 923 617 only for the cavitation equipment. Pumps delivering a pressure of 2 barg are also required. This cost can most likely be reduced in a large scale facility but as a conservative estimate the full cost is used. The cost of the required pumps is estimated using Ulrichs method (61) (60).
Equation 2

This gives

when assuming an electrical efficiency of 0.85.

Module cost is estimated to 15 000 dollar mid 1982 and the bare module factor is estimated to (61). Thus will the total price be 15 000 7 = 105 000 dollar in 1982 value. This is translated into Euros in current value, by first translating to SEK 1982 exchange rate 6 SEK/dollar and then corrected for the Swedish price index and finally translated into Euro at current exchange rates.

Total cost 32 923 617 + 166 148 33 100 000 and this is only the equipment for generating the ultrasonic cavitation and the pump for giving the required pressure for this step only. This shows that ultrasonic equipment is very expensive and that hydrodynamic cavitation is cheaper (80), but how much cheaper is unknown at this stage; however, the main cost should consists of pumps to build the necessary pressure. However as mentioned before this is not calculated in this study due to lack of data. Other issues that need to be considered is how the equipment reacts to a large percent of dry weight content, will clogging and other problems occur? How effective is the cell disruption? To solve these issues it is necessary to start with a laboratory or pilot plant facility.

37

Table 7 Cavitation Capital Cost and Operating Cost

Purchased equipment cost [] Capital cost Cavitation Operation cost Energy demand 33 090 000

/year

195 500

4.4.4 Cost for Separation of the Water Oil Algae Mixture The separation of the oil, water and algae mixture from the cavitation unit is performed in a mixing settling tank followed by a centrifuge. The cost of this apparatus is approximated as the cost of one process vessel used for sedimentation, followed by one centrifuge. The following assumptions were made in the calculation: 85% of the initial water in the algae broth is removed by the sedimentation The density of the mixture is the same as for pure water 30 minutes residence time is sufficient for the oil-water separation After the settling tank, the oil phase contains 50% water to be removed by a centrifuge The calculations and results shown are calculated with the Ulrich method (61).
Table 8 Cost estimation for a settling tank

Module cost $ 1982 Algae 1% Algae 0.4% 80 000 150 000

MF 4.50 4.50

FBM 8.50 8.50

Total cost $ 1982 680 000 1 280 000

Table 9 Cost estimation for an oil-water separator

Module cost $ 1982 30 000

FBM 5

Total cost $ 1982 150 000

38

Table 10 Separation of oil from water Capital Cost and Operating Cost, conversion has been made from $1982 to 2008 for the algae concentration of 0.4%.

Module cost Capital cost Settling tank Centrifuge Operating cost Energy demand settling tank Energy demand centrifuge 2 020 000 237 000

/year

neglected 2 540

4.4.5 Cost of Degumming Equipment The degumming is performed by adding phosphorous acid in order for the phospholipids to form a precipitate. Then lye is added to neutralize the oil, the impurities are separated and the oil is washed with water and dried. To get a fairly accurate assessment of the cost of this process, Westfalia Separator AB Sweden was contacted and an approximate cost of 1.3 Million was given for their TOP degumming process, not including installation, piping and tanks, see Appendix 10. The energy consumption in the degumming stage is due to the separators, heating of the oil and the wash water as well as mixing and pumping the fluids. The following assumptions have been made when calculating the total costs of this step. The phospholipid content is assumed to be 1% (47) The cost for tanks needed is neglected since it is much smaller than the cost for the heatexchanger, separators and vacuum-dryers Costs for installation and piping are added according to the Ulrich method (60) Energy consumption due to mixers and pumps is neglected since this is relatively small compared to the power required for the separators (81) Power required running a PX 80 separator handling 18.75 ton/h is 18 kW (82). Energy required for heating the oil was calculated using the heat capacity of soybean oil at 60C, 2.0 kJ/kgC (83). T was assumed to be 40C, considering that the oil is heated from 28C to 60-90C in the degumming reaction (47). Energy required to heat wash water was set to be 1/3.5 of the energy required to heat the oil (81). For calculations see Appendix 11.

39

The cost of the degumming unit is 1.3 Million. Energy spent in this process is 279 kW to heat the oil, 80 kW to heat the wash water. Power usage of approximately 36 kW derives from the two separators.
Table 11 Degumming Capital Cost and Operating Cost

Purchased equipment cost [] Capital cost Degumming Operating cost Energy demand 1 300 000

/year

27 110

4.4.6 Cost for Removal of Free Fatty Acids The residence time needed for treatment of algae oil from N. salina cant be calculated since the amount of FFA in the produced oil is unknown. For B. braunii 10 hours would be sufficient, since the final concentration is dependent on the initial concentration. Since the initial concentration of FFA from N. salina is unknown, calculations are presented at both 3 and 10 hours of residence time. For the economic calculations a 10 hour residence time is used. The following assumptions were made as a base for the calculations: The algae oil is considered to have the same density as rapeseed oil, 0.92 ton/m3 (83) The algae oil is considered to consist of only saturated c18 triglycerides for the calculation No density changes occurred due to the reaction The amount of free fatty acids in the oil is not taken into account when calculating the volume of the reaction vessel The calculations and results calculated with the Ulrich method (61) are found in Appendix 14.
Table 12 Removal FFA Capital Cost and Operating Cost

Module cost [] Capital cost Removal FFA Operation costs Energy demand 941 500

/year

neglected

40

4.4.7 Cost for Spray Drying Equipment

The plant location is planned to be close to a larger industry facility, supplying large amount of low grade heat and carbon dioxide for free. With this assumption, spray drying seems like a good alternative for drying part of the flow consisting of water and algae waste, after the oil has been extracted. The benefits are: the equipment is cheap compared to other process choices. The exhaust gas used in the spray tower needs to be cooled before it can be used to enrich the algae culture with carbon dioxide. If the gas has to be cooled it can be done by using it as drying media in a spray tower, hence at the same time getting benefits of drying the algae. A typical 400 MW NGCC (Natural Gas Combined Cycle) has exhaust volumes in the dimension of 1.8 million Nm3 per hour. If the plant location should be near the Aluminum smelting plant in Qatar operated by Norsk Hydro, the power is 1000 MW of the NGCC (84). Considering the fact that there are other problems that make Qatar a doubtful choice concerning plant location, calculations will be based on having access to exhaust from a 400 MW NGCC plant. The temperature of this exhaust is estimated to 90C and the water content to 8% by volume. The temperature after leaving the spray tower is approximately 58C; this is calculated by using a psychometric chart for humid air. Calculations can be seen in Appendix 12. These calculations show that the total drying capacity of 1.8 million Nm3 of flue gas per hour is approximately 36 tons of water per hour. This is less than the facilitys total need for drying, but this can be used as a part of the drying need. Considering how a spray tower works the slurry entering the spray tower should be dried until surface dry, to prevent problems in the outward transport of the algae in the bottom. Therefore the flow is split into two before the spray tower in order to send an appropriate amount to the spray dryer. The calculated cost is 5.9 million for 7 spray dryers calculated with the Ulrich method.
Table 13 Spray dryer Capital Cost and Operating Cost

Module cost [] Capital cost Spray Drier Operating cost Energy demand 5 980 000

/year

neglected

41

4.5 Revenues and Costs not Directly Derived from Unit Operations
4.5.1 Byproducts When producing oil from microalgae, the main byproduct formed is the algae meal. This algae meal consists mainly of proteins, carbohydrates, remaining lipids and micro nutrients. The algae meal has a range of income bringing process alternatives, which can be investigated thoroughly first when the properties of the flour are known. The three main alternatives are: Dry the algae flour and sell it as animal fodder Dry the algae flour and use it in direct combustion. Nutrients can be re-circulated back into the process. Use the algae flour to produce methane by anaerobic bacteria. Nutrients can be recirculated back into the process. The price for animal fodder depends on the available energy and nutrients, the heating value will affect the energy production. Which one of these steps that are the most economical alternative and the economy of these steps are not investigated, but the revenue from the byproducts should at least cover the cost of fertilizer. The general assumption in this report is that the income from the byproducts cancels the cost of fertilizers/flocculants. 4.5.2 Cost of Storage Tanks 4.5.2.1 Algae Culture Storage Tank Algae Link recommends a tank capacity equal to half of the photobioreactor culture volume. Therefore tanks of this volume are accounted for. Information on exactly how many and their individual volume are missing, why 15 rubber lined tanks of 50 000 m3 each are used. They are rubber lined to be able to withstand the growing medium seawater. The cost of these are 28 400 000 . For calculations please see Appendix 13. 4.5.2.2 Product Storage Tank The product will be transported by boat to the biodiesel refinery, calculations are made that 2 weeks production should be able to be kept in storage, and in case of delays 1 week extra storage is calculated for. If this is a good solution can be discussed, but the alternative is that trucks have to transport the product that cannot be contained in the tanks in case of delays. The required volume is 7 300 m3 and the construction material stainless steel. The cost for this oil storage tank

42

is 98 700 . This is without any additional costs added for installation and other expenses connected to the tank. 4.5.2.3 Other Tanks Needed Other tanks for storage of fertilizer, flocculent chemicals etc. are not specified at this stage; these are considered to be small in comparison and not specified. Further due to the large scale of the factory some of the tanks calculated above may be available for these purposes. 4.5.3 Labor Costs Personnel required for running the factory have been estimated to be 30 persons. The process operators are assumed to be working in shifts of 5 persons in each. Due to their uncomfortable working hours, they are given a slightly higher salary than the day personnel. All salaries are estimated using information from the web page mywage.co.za (85). As can be seen in Appendix 15 the salaries in South Africa are low, which contributes to keeping the costs of running the factory down. Total personnel costs for the plant will be 27 200 /month, see Appendix 15.
Table 14 Costs not directly derived from operation Capital Cost and Operating Cost

Module cost *+ Capital cost Algae culture storage tank Product storage tank Other tanks Operating cost Labor cost 28 400 000 99 000 neglected

/year

330 000

4.6 Summarized Costs for the Base Case

The estimated capital cost was depreciated using an expected useful life span of 15 years and an interest rate of 10%. The estimated operating cost was then added to the depreciated capital cost to obtain the total annual cost. The summarized cost is based on the assumption that the cost for nutrients/flocculants is covered by the income from sold algae meal.

43

Table 15 Total cost including add on factors for the different unit operations

Origin

Photobioreactor Flocculation + Sedimentation Ultrasound Settling tank Centrifuge Degumming Removal FFA Spray dryer Storage tanks product+algae culture
Total capital investment:
Table 16 Summary of base-case costs

Cost turnkey equipment Ulrich module cost Purchased equip. cost Ulrich module cost Ulrich module cost Purchased equip. cost Ulrich module cost Ulrich module cost Ulrich module cost

Add on factor 1.21 1.21 3.45 1.21 1.21 3.45 1.21 1.21 1.21

Cost including add on factors 405 000 000 32 500 000 114 000 000 2 440 000 287 000 4 480 000 1 140 000 7 220 000 34 300 000 603 000 000

Estimated costs Capital cost [106] Operating cost [106 / year] Depreciated capital cost [106 / year] Total annual cost [106 / year] Production cost [/L]

603 17 79 97 0.87

4.7 Sensitivity Analysis of Production Cost

The main factors considered to affect the profitability of this project, and to be included in the sensitivity analysis, are: Production rate of algae, g/(m3 day) Concentration upon harvest, dry weight in % Additional cost estimations on capital investment using higher factors from the rule of thumb, given by Hans Karlsson. Assumed life span of facility and the interest rate on investment Income from byproducts The calculated production cost for all the cases varied can be seen in Figure 2 and in Appendix 16.

44

/L
2 1,8 1,6 1,4 1,2 1 0,8 0,6 0,4 0,2 0 Base case 1 500g/(m3 day), 0,4% harvest, 15 years, 10 % intrest Base case 2 Best case Best case 2 500g/(m3 900g/(m3 900g/(m3 day), 1% day), 1% day), 1% harvest, 15 harvest, 15 harvest, 15 years, 10 % years, 5% years, 10% intrest Worst case 300g/(m3 day), 0,4% harvest, 10 years 15%

High Factors Low Factors

Figure 4 Sensitivity analysis with regard to harvesting concentration, production rate, interest rate, expected useful life spans using lowest and highest adding factors according to Hans T. Karlsson

As can be seen in Figure 2, the production cost varies greatly dependent on the factors investigated in the sensitivity analysis. The rule of thumb factors given by Hans Karlsson (60) has a wide span, the low factors presented in the sensitivity analysis are the lowest value from the span and the high factors are the highest value from the span. If no income from selling the byproducts is possible to achieve, for instance due to oversaturated market and the recycling of chemicals is impossible or non profitable, the production cost shown in Figure 2 will increase by 0.26 /l for all process alternatives. However, if the possibility to sell algae flour at a higher price than expected, the production price can be decreased substantially. 4.7.1 The Production Rate of Algae The production rate of algae depends on a number of variables, including: Type of algae string Sun conditions - may vary from year to year Temperature - optimum for Nannochloropsis salina is 28C (32) If the tubes would lose some of their transparency, the production will decrease. This can be expected sooner or later due to aging of the plastic material they are made of. A number of other conditions which can be controlled to give the maximum production such as nutrients etc. 45

The following information regarding productivity was received through personal communication with Algae Link (86).
Table 17 Productivities dependency on weather conditions

Weather conditions Intermediate (indoors, in the Netherlands) Good Very Good Exceptionally good Theoretical

g/m3day 300 600 900 1200 1500

Algae Links calculations are made on the theoretical value and are hence very optimistic. In the calculations made, the production is estimated to be 500 g/(m3 day) which the principal investigators regard as a conservative number that most likely will be possible to attain. However a pilot plant has to be built to verify this. To check how an increase in production affects the production cost, calculations are also made for the case of 900 g/(m3 day). This growth rate directly affects the size of the photobioreactor which is a large part of the overall cost. In the sensitivity analysis, the calculations from the base case are multiplied by 500/900, giving a new lower cost if the 900 g/(m3 day) growth conditions are attained. 4.7.2 Concentration upon Harvest The concentration upon harvest has a large effect on the downstream costs associated with the separation of algae from the growth medium. Two cases are calculated, the base case with 0.4% and the 1% case: One with a harvesting concentration of 0.4% dry algae weight. This estimation is from a number of articles that give concentrations in the interval 0.2-0.8% dry weight. One with a harvesting concentration of 1 % dry algae weight. This concentration was given by Algae Links sales office and should be viewed with caution. 4.7.3 Assumed Life Span of Facility and Interest Rate on Capital Investment The life span of the polycarbonate pipes used in Algae Links photobioreactor is 10-15 years; this information was given by Algae Links sales office (76). Considering the whole facility; the pipes can probably last for 15 years, and other processing equipment will most likely last longer, making a 15 year life span a reasonable approximation for the base case. A case with only 10 years life span is also calculated. An interest rate of 10 % is used in the base case since this is the standard used in chemical industry (87). Cases with 5 % and 15 % interest rate are also investigated. 46

4.8 Conclusion
This feasibility study of large scale biodiesel production shows large variation of production cost depending on some key factors. The production cost in this study lies in an interval between 0.38 and 1.95 /L with the base case of 0.87 /L, for details please see sensitivity analysis above. The calculated costs are considerably lower than the estimation earlier made by Y. Chisti (2) where the production cost was approximately a factor nine higher when compared to fossil fuel ($100 per barrel). No income from biomass residues were considered in Chistis approximation. The price of comparable bio-based crude oil is today 122 $ barrel (palm oil) (1), which is approximately 0.49 per liter. This shows that even though profitability is still not achieved but it is concluded that profitability is not far away. Molecular level engineering of the algae may have the answers to lowering the cost, photosynthetic efficiency, increase biomass growth rate, increase of oil content and improved temperature tolerance are some of the areas that would lower the cost if solved (2). When estimating the capital and operating cost it was found that the capital cost is the major part of the total cost. This means that the life span of the plant, as well as the interest rates paid on the initial investment will have a large impact on the estimated costs. Another important factor will be the productivity, since this directly affects the size of the photobioreactors and thereby the capital cost. The large variation in production cost is to a large extent dependent on the weather conditions present at the plant location, such as temperature and sun availability, the yield these conditions give cannot easily be estimated. Therefore, it is vital to build a pilot plant to verify growth rates and harvest concentration. When these values are given, a more accurate estimation can be made. Another issue that should be addressed is the approximation that nutrient/flocculant cost and algae meal revenue will balance each other. If the algae meal turns out to be worthless this will increase the algae oil price with 0.26 /L. The increasing climate threat is another big issue that favors projects like this one. However, from an environmental perspective, additional analysis has to be made to verify if and how much this production method really decreases greenhouse gas emissions compared to fossil fuel. For this an LCA of algae biodiesel originating in a plant similar to this one is suggested. From the result of this feasibility study some general conclusions can be drawn. The production of biodiesel from algae grown in photobioreactors could become a reality, with increasing fossil fuel prices and a maturing algae technology the future might be a bright one. However, the effect of increasing oil price on the construction cost has to be kept in mind.

47

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87. Karlsson, Hans. Departement of chemical engineering. Personal communication. 05 05, 2008. 88. SCB. Konsumentprisindex (1980=100), faststllda tal - Statistik frn SCB. Statistiska centralbyrn Statistics Sweden. [Online] April 14, 2008. [Cited: May 07, 2008.] http://www.scb.se/templates/tableOrChart____33847.asp. 89. AlgaeLink. Sales Department. E-mail communication. January 31, 2008.

54

Appendix 1
Table 18 Contents of modified Chu-13-medium (28)

Substance KNO3 K2HPO4 MgSO4*6H2O CaCl2*2H2O Fe-citrate Citric acid (1 ml microelement solution per l of Chu-13) Substance H3BO3 MnCl2*4H2O ZnSO4*7H2O Na2MoO4*2H2O CuSO4*5 H2O Co(NO3)2*6 H2O

mg per l Chu-13 371 80 200 107 20 100 g added per l microelement solution 2.86 1.81 0.22 0.39 0.08 0.05

55

Appendix 2

Figure 5 Picture of Nannochloropsis salina from Plankton Net (2008-04-24)

Calculation of the Cell Density: The shape of the cell can be seen as an ellipsoid and hence as a prolate spheroid due to the fact that the equatorial radius are roughly the same.

56

Appendix 3
Table 19 Cost per unit operation

Cost per unit operation

500 g/m3 day 1. - Photobioreactor cost energy demand 2. - Flocculation + Sedimentation $1982 Cost for 0.4 % Cost for 1 % energy demand 3+4. - Ultrasound cost for 0.4 % cost for 1 % energy demand pump energy demand sonification 5. - Settling tank $1982 cost for 0.4 % cost for 1 % 1 280 000 680 000 2008 2 020 000 1 080 000 1 080 000 2 020 000 33 100 000 13 332 000 2008 kW 89.7 2 744 33 100 000 13 300 000 35.9 1 097 13 300 000 35.9 1 097 89.7 2 744 33 100 000 17 000 000,00 7 000 000,00 neglected 2008 2008 neglected 26 900 000 11 100 000 neglected 11 100 000 neglected neglected 26 900 000 335 700 000 7 318 2008 kW for 0.4 % 335 700 000 7 318 500g/m3 day for 1 % 335 700 000 7 318 900g/m3 day for 1 % 186 500 000 4 065 300 g/m3 day for 0.4 % 559 500 000 12 197

57

Continuing Table 19

6. Centrifuge $1982 cost PX90 energy demand 7. - Degumming cost (without tanks, pipes and installation) energy demand heating energy demand centrifuges energy demand vaccum dryer 8. - Removal FFA $1982 2008 cost (residence time 10 h) Energy 9. - Spray dryer cost 10. - Storage tanks product + algae culture Cost 2008 28 400 000 28 400 000 28 400 000 28 400 000 2008 5 980 000 5 980 000 5 980 000 5 980 000 595 000 942 000 neglected 942 000 neglected 942 000 neglected 942 000 neglected 1 300 000 359 36 neglected 2008 kW kW kW 1 300 000 359 36 neglected 1 300 000 359 36 neglected 1 300 000 359 359 neglected 1 300 000 359 359 neglected 150 000 37.00 2008 kW 237 000 37 237 000 37 237 000 37 237 000 37

58

Appendix 4
Table 20 Cost per unit operation minimal costs MIN Process equipment NON Ulrich On Process equipment auxiliary equipment Installation Buildings Land improvement Direct cost Process equipment and auxiliary equipment Transportation and insurance social benefits + overtime Engineering Module cost Contractor contingency Direct and indirect cost 4-11% 0.15 0.04 0.15 102 500 000 43 490 000 43 490 000 102 500 000 3-5% On installation 0.70 On direct cost 7-10 % 0.07 4 863 000 86 130 000 2 063 000 36 540 000 2 063 000 36 540 000 4 863 000 86 130 000 0.70 10 350 000 4 392 000 4 392 000 10 350 000 0.03 1 444 000 612 800 612 800 1 444 000 40-160 % 43-63 % 6-70 % 13-16 % 0.40 0.43 0.06 0.13 69 470 000 29 470 000 29 470 000 69 470 000 Total sum: 34 390 000 14 590 000 14 590 000 34 390 000

59

Continuing Table 20 Support equipment TOTAL COST NON Ulrich apparatus Total COST photobioreactor TOTAL Capital COST Total energy consumption of unit operation equipment kW Total energy consumption of unit operation equipment kWh (335 days 24 hours) 17-25% 0.17 119 900 000 483 300 000 603 200 000 10 580 85 090 000 50 880 000 463 000 000 513 900 000 8 883 71 420 000 50 880 000 282 800 000 333 700 000 5 953 47 870 000 119 900 000 753 500 000 804 400 000 15 790 126 900 000

60

Table 21 Cost per unit operation maximal costs MAX Process equipment NON Ulrich On Process equipment auxiliary equipment Installation Buildings Land improvement Direct cost Process equipment and auxiliary equipment Transportation and insurance social benefits + overtime Engineering Module cost Contractor contingency Direct and indirect cost 4-11% 0.15 0.11 0.15 219 700 000 93 210 000 93 210 000 219 700 000 40-160 % 43-63 % 6-70 % 13-16 % 1.60 0.63 0.70 0.16 140 700 000 59 680 000 59 680 000 140 700 000 Total sum: 34 390 000 14 590 000 14 590 000 34 390 000

3-5% On installation 0.70 On direct cost 7-10 %

0.05 0.70 0.10

4 471 000 15 170 000 14 070 000 174 400 000

1 897 000 6 435 000 5 968 000 73 980 000

1 897 000 6 435 000 5 968 000 73 980 000

4 471 000 15 170 000 14 070 000 174 400 000

61

Continuing Table 21 Support equipment TOTAL COST NON Ulrich apparatus Total COST photobioreactor TOTAL Capital COST Total energy consumption of unit operation equipment kW Total energy consumption of unit operation equipment kWh (335 days 24 hours) 85 090 000 71 420 000 47 870 000 17-25% 0.25 274 600 000 116 500 000 116 500 000 274 600 000

483 300 000 757 861 818.91 10 580

463 000 000 579 500 000 8 883

282 800 000 399 400 000 5 954

753 500 000 1 028 000 000 15 790 126 900 000

62

Appendix 5
Table 22 Annuities and Capital Costs per Year

Annuity 5% 10 % 15 % Capital cost per year EUR 2008 5% 10 % 15 %

10 years 0.1295 0.1627 0.1993

15 years 0.0963 0.1315 0.171

10 years 78 110 000 98 130 000 120 200 000

15 years 58 080 000 79 320 000 103 100 000

The annuity factors are taken from the book Investeringsbedmning en introduktion (62)

63

Appendix 6
Table 23 Costs for running the factory using the lowest estimation Lowest factors Harvest concentration Bound capital Keeping of raw material Keeping of products Spare parts Direct mobile costs Raw material Byproducts help chemicals. solvents Electricity Water Steam Disposal Maintenance and reparations Labor Normal conditions 0.01 Euro/year 4 380 256 000 1 210 000 Normal conditions 0.004 Best Case 1 1 % 900 g/m3 15 years 5 % Best Case 2 1 % 900 15 years 10 % Worst Case 0.4% 300 10 years 15 %

4 380 256 000 1 210 000

2 190 49 100 667 000

4 380 12 400 667 000

6 570 20 800 1 610 000

2 280 000 2 280 000 -2 280 000 -2 280 000 neglected neglected 609 000 726 000 Neglected Neglected Heating degumming calculated as electricity neglected neglected 12 000 000 327 000 12 100 000 327 000

2 280 000 -2 280 000 neglected 408 000 Neglected neglected 6 670 000 327 000

2 280 000 -2 280 000 neglected 408 000 Neglected neglected 6 670 000 327 000

2 279 000 -2 280 000 neglected 1 080 000 Neglected neglected 16 100 000 327 000

Licenses Land interest

515 000 neglected

519 000 neglected

294 000 neglected

293 000 neglected

678 000 Neglected

64

Continuing Table 23 Indirect mobile costs Overhead Administration Distribution and sales R&D Sum almost all MOBILE costs Capital investment annuity 15 years 10 % Sum ALL costs Annual production tons Annual production kilos Annual production liter Production price (/liter) 100 000 100 000 000 111 111 111 0.76 0.87 0.38 0.48 1.65

212 000 81 600 1 720 000 127 000 14 800 000 67 600 000 84 700 000

212 000 81 600 1 730 000 128 000 14 900 000 79 300 000 96 600 000

212 243.46 81 632.10 979 306.32 72 429.50 8 420 000 32 100 000 41 900 000

212 243.46 81 632.10 975 287.64 72 132.27 8 390 000 43 900 000 53 600 000

212 243.46 81 632.10 2 258 891.39 167 067.61 19 400 000 160 000 000 183 000 000

65

Table 24 Cost of running the factory using the highest estimation Highest factors Harvest concentration Bound capital Storing raw material Storing product Spare parts Direct costs mobile 2 280 000 -2 280 000 neglected 609 000 Neglected Neglected 15 200 000 327 000 2 280 000 -2 280 000 Neglected 726 000 Neglected neglected 15 200 000 327 000 2 280 000 -2 280 000 neglected 408 000 Neglected Neglected 11 600 000 327 000 2 280 000 -2 280 000 Neglected 408 000 Neglected neglected 11 600 000 327 000 2 280 000 -2 280 000 Neglected 1 080 000 Neglected neglected 7 990 000 327 000 Normal conditions 0.01 Euro/year Normal conditions 0.004 Best Case 1 1 % 900 g/m3 15 years 5 % Best Case 2 1 % 900 15 years 10 % Worst Case 0.4% 300 10 years 15 %

4 380 256 000 1 520 000

4 380 256 000 1 520 000

2 190 49 100 1 160 000

4 380 12 400 1 160 000

6 570 20 800 799 000

Raw material Byproducts help chemicals. solvents Electricity Water Steam Disposal Maintenance and reparations Labor

Heating degumming calculated as electricity

Licenses Land interest

634 000 neglected

638 000 neglected

482 000 neglected

481 000 neglected

367 000 neglected

66

Continuing Table 24 Indirect mobile costs Overhead Administration Distribution and sales R&D Sum almost all MOBILE costs Capital investment annuity years 10 % 212 000 81 600 2 110 000 156 000 18 200 000 212 243.46 81 632.10 2 130 000 157 000 18 300 000 212 000 81 600 1 610 000 119 000 13 800 000 212 000 81 600 1 600 000 119 000 13 800 000 212 000 81 600 1 220 000 90 400 10 500 000

15 76 200 000 Sum ALL costs 97 300 000 99 700 000 121 000 000 38 500 000 54 500 000 52 500 000 68 500 000 205 000 000 217 000 000

Annual production tons Annual production kilos Annual production [l] Production price [/l]

100000.00 100000000.00 111111111.11 0.88 1.09 0.49 0.62 1.95

67

Appendix 7
Mass balance calculations
Flow rate crude oil [ton/h] Flow rate algae [ton/h] (0,4%) Flow rate algae [ton/h] (1%) Flow rate with 0.4% algae [ton/h] Flow rate Flow rate with 1% cell walls algae [ton/h] [ton/h] Flow rate cell walls + water [ton/h] Flow rate water [ton/h] (0,4%) Flow rate water [ton/h] (1%) Flow rate Flow rate Flow rate crude oil + methanol Flue gas water [ton/h] [Nm3/h] [ton/h] Flow rate phospholipids [ton/h]

STREAM [A] [B] [C] [D] [E] [F] [G] [H] [I] [J] [K] [L] [M] [N] [O] [P] [Q] [R] [S] [T] [U] [V]

318,02 14,63 12,44 36,58 5,49 31,09 31,09 36,58 5,49 31,09 31,09 9145,45 7773,63 1371,82 1371,82 3658,18 3109,45 548,73 548,73 18,66 12,44 16,74 12,44 334,75 373,13 9108,87 7768,14 1340,72 1340,72 973,81 354,48 12,44 318,02 12,44 3621,60 3103,97 517,63 517,63 150,72 354,48 12,44 318,02 12,44 24,88

0,12
12,44 4,28 12,44 1,92 1,92 5,49 5,49 8759,88 3272,61 8754,39 3267,12 38,38 36,46 36,46 4,28

1,43E+06

not calc.

[letter] = refers to the stream in the process. See FLOWSHEET A

Separation grade of algae, stage (2): Flow ratio stream [D]/[E]: Flow ratio stream [E]/[D]: Oil content in dry algae:

0,85 0,85 0,15 0,40

Dry weight of cell paste: 0,05 Flow rates of phosphorous acid and NaOH 100% separation in centrifuge is assumed are not calculated and neglected due to 1 mass-% of stream [L] is assumed to be phospholipids: 0,01 no large quantities are needed. For calculations of required amount of nutrients, se Appendix 8.

68

Appendix 8
Nutrients required per day to grow 746 ton of dry algae according to Algae Link.
Table 25 Nutrients required, producing 746 tons per day

Nutrient CO2 N K Ca P Mg Fe Zn Mn Cu Mo
*
*

Amount required [kg/day] 2 150 000 60 600 13 700 9050 7 840 2 140 540 270 223 52.2 2.80

The required amount of CO2 is 2881 kg / ton dry algae

Chemical substance Urea Nitric acid Lime Monobasic sodium phosphate Tetrabasic potassium pyrophosphate Potassium hydroxide Ferric chloride TOTAL Added [kg/day] 130 000 7 860 16 700 13 900 23 100 9 330 1 570 202 000 Price 2005 [$/kg] 0.198 0.248 0.082 1.83 1.74 0.344 0.398 Total price 2005 [$/day] 25 300 1 500 1 400 25 800 13 900 3 200 630 71 800 Total price 2008 */day+ 29 800 1 800 1 600 30 400 16 400 3 800 740 84 500

Table 26 Chemicals needed per day, cost per day

69

Appendix 9
Cost Calculations All prices in the final calculations in this report are given in Euro [] for 2008. Costs in other currencies will be recalculated into . Costs from earlier years will be recalculated using cost price indexes. Two different cost indexes have been used in this study. Process equipment costs have been recalculated using the Swedish consumer price index (88), considering the uncertain rate of the USD today. Nutrient costs have been calculated using the U.S. fertilizer index (73), in order to consider the price development on the chemical market. The indexes can be seen in Table 27 and 28 below. When recalculating a process equipment cost from $1982, a currency rate from 1982 of 7 SEK/USD was used. The price in SEK from 1982 was then transferred into current price using the Swedish consumer price index. Finally the cost was converted from SEK into using current exchange rate.
Table 27 Cost index for calculation of process equipment

From US$ of year 1982 to of 2008 Exchange rate [SEK/$] KPI KPI KPI factor Exchange rate [SEK/] US$ 1982 to 2008 Exchange rate ZAR to
Table 28 Cost index for calculation of nutrients

6.00 121.50 298.00 2.45 9.30 1.58 0.0853

mid 1982 mid 1982 march 2008

factor

Price index regarding nutrients Fertilizer index (USA) Currency rate */$+ 2005 164.00 feb 2008 260.00 0.74

70

Appendix 10

Figure 6 TOP Degumming process from Westfalia Separator, with courtesy of Westfalia Separator

71

Appendix 11
Table 29 Degumming Calculations of heating energy and power consumption

Degumming
Amount of oil / year [ton] Operating days / year Hours / day Oil flow [ton/h] Part phospholipids Phospholipid content Total inflow [ton/h] Total inflow [kg/h] Heating Heat capacity [kJ/kg*K] DeltaT [K] Energy consumption heating [kJ/h] Energy consumption heating [kW] Rate energy consumption washing/heating Energy consumption washing [kW] Separation Separator Capacity [ton/h] Energy consumption [kW]/separator Number of separators Total consumption [kW] 2.00 40 1 001 000 279 0.286 79.8 100 000 335 24 12.44 0.01 0.12 12.56 12560

PX80 18.75 18 2 36

Cost of equipment 2008 *+

1 300 000

72

Appendix 12
Calculations of spray dryer Rules of thumb by Prof. Hans T Karlsson (87) Gas velocity Nm3/s Meter in diameter Meter high Residence time of seconds on Nm3 Ulrichs method Estimate as process vessel Transporter bottom Atomizer with air Pump delivering the necessary pressure Available exhaust gas 400 MW NGCC Nm3/h Nm3/s m2 to achieve 2.7 m/s Area of cylinder radius 3 m. in m2 Number of spray dryers 3 m in diameters residence time in spray dryers per Nm3 Calculation of Capital cost Ulrich method has no process vessels of this size (6 m), see reference (61) Interpolate Material factor Nickel clad Pressure factor (normal pressure) Number of spray towers Total investment dollars mid 1982 120 000 4.50 1.00 7.00 3 780 000 1 800 000 500 185 28.3 6.55 5.56 ~7 Done below Neglected Neglected Neglected 2.70 6 15 5-6 Conversion from Nm to m (pV=nRT) From 0 to 90 degrees centigrade conversion factor (Volume) 2.7 Nm3/s corresponds to m3/s at 90 degrees centigrade 1.33 3.59
3 3

Conversion factor dollar 1982 to euro 2008 Euro march 2008

1.58 5 981 472.00

73

Calculation of drying capacity of exhaust gas

Constants Gas constant J/(K mol) Conversion Celsius to Kelvin + 273.15 1 atm in Pa Value 8.31 273.15 101 325

Calculations based on e-mail communication with Hans Ragnar Eklund, Statoil Hydro (84). The exhaust composition from a 400 MW NGCC plant Exhaust temperature 90 C, no consideration is taken to the high temperature at the site which might increase the exhaust temperature. This way the estimation is very conservative. Composition % M g/mol 1 Mol exhaust gas weight Re-scale to 1 kg number of moles per kg Weight per substance in 1 kg (g) Part of total Kg water/kg exhaust gas C02 4.00 44.01 1.76 62.04 0.06 0.11 O2 13.00 32.00 4.16 146.6 N2 75.00 28.02 21.02 740.56 H2O 8.00 18.02 1.44 50.80 100.00 122.05 28.38 35.24 1 000

From Psychometric chart for humid air Diagram moist air kg/kg in Diagram moist air kg/kg out absorbed kg per kg (difference in-out) in kg 0.11 0.13 0.02

74

From a psychrometric chart for humid air the following values were obtained. Using 90 degrees and 0.11 kg/kg for the first point, and then picking the second point at 95 % humidity. These two point give a difference of 0.016 kg/kg see the psychometric chart below.

75

Drying capacity of 1.8 million Nm3 Mol/Nm3 (pv=nRT) Molar mass Density kg/Nm3 Absorbed per Nm3 Drying capacity ton/h based on 1 800 000 Nm3 44.61 28.38 1.27 0.02 36.46

Need of CO2 per 100 tons a day facility (kg/day) Total need (746 tons a day) of CO2 kg/dag Number of kilos exhaust gas kg/day Number of Nm3 day Number of Nm3/h Assume 25 % excess Total need Nm3/h 288 100 2 149 000 34 640 000 27 360 000 1 140 000 1 425 000

76

Appendix 13
Table 30 Tank for storage of crude oil to be shipped

Concentration upon harvest annual production days of production per year Production/production day A tanker arrive every second week + 1 week of marginal Size of tank needed for crude oil storage Density biodiesel (EN14214) Density biodiesel (EN14214) Size of tank (m3)

0.004 100 000 335 299 21 6 270 0.86 0.86 7 300

0.01 100 000 335 299 21 6 270 0.86 0.86 7 300 ton days ton/day days ton g/ml ton/m3 m3

ULRICH 5-61 bin stainless steel gives the cost

62 400

62 400

$1982

or

98 700

2008

Description of tank: Stainless steel tank with a capacity of 7300 cubic meter

77

Continuing Table 30

Tank requirements for production unit Total volume Algae Link recommends half the production volume (89) Size of tanks Rubber lined cone roof 50 000 m3 cost Number of tanks Material factor rubber lined at atmospheric pressure Total cost re-calculated to euro 2008 1 492 000 746 000 50 000 500 000 15 2.40 17 900 000 28 300 000 1 492 000 746 000 50 000 500 000 15 2.40 17 900 000 28 300 000 US $ 1982

Description of tanks: approx 15 tanks of 50 000 cubic meters each.

Total cost for storage tanks crude oil + production tank euro 2008 28 400 000

28 400 000

Other tanks are neglected do to their very small size compared to these, large scale effect may also make it possible to use some of these tanks for other purposes although their construction material and hence the cost will change.

78

Appendix 14
Table 31 Calculations FFA removal

FFA Removal
Density [ton/m3] Molar weight [kg/kmole] Moles / ton Mole ratio Amount [ton/h] Residence time Volume [m3] W [ton] Economy 3 Hours Vertically oriented 10m length 1.8m diameter Basic cost $ 15 000 MF 4.5 FBM 8.5 Tot 1982 $ 127 500

Methanol 0.791 32 31 250 10 4.28 3 hours 56.8 1.12 Economy 10 Hours Vertically oriented 20m length 3m diameter Basic cost $ 70 000 MF 4.5 FBM 8.5 Tot 1982 $ 595 000

Oil 0.92 855 1 076 1 12.44 10 hours 189 3.73

79

Appendix 15
Table 32 Labor costs calculated using South African salaries

Personnel

Number

Salary (ZAR/month)

Salary (ZAR/month)

Salary (/month)

Salary (/month)

Head of factory Process operators Engineer Electrician Mechanic Laboratory assistant

1 25 1 1 1 1 30

30 000 10 000 15 000 8 000 8 000 8 000 79 000

30 000 250 000 15 000 8 000 8 000 8 000 319 000

2 559 853 1 280 682 682 682 6 739

2 559 21 325 1 280 682 682 682 27 211

80

Appendix 16
Table 33 Sensitivity analysis

Base case 1 Base case 2 Best case 1 Best case 2 Worst case

Harvest concentration [w/w] 0.004 0.010 0.010 0.010 0.004

Production rate [g/(m3 day)] 500 500 900 900 300

Annuity factor 15 years, 10% 15 years, 10% 15 years, 5 % 15 years, 10 % 10 years, 15%

Factors lowest factors highest factors lowest factors highest factors lowest factors highest factors lowest factors highest factors lowest factors highest factors

Production cost 0.87 1.09 0.76 0.88 0.38 0.49 0.48 0.62 1.65 1.95

81