BioAlgaeSorb 2008-2

Call FP7-SME-

Enabling European SMEs to Remediate wastes, Reduce GHG Emissions and Produce Biofuels via Microalgae CultivationTo iu kin cho doanh nghip nh n cht thi chu u khc phc, gim pht thi kh nh knh v Sn xut nhin liu sinh hc thng qua vi to trng trt

BioAlgae Sorb

Table 1.1: Application Identifier Enabling European SMEs to Remediate wastes, Reduce GHG Application Title Emissions and Produce Biofuels via Microalgae Cultivation Application BioAlgaeSorb Acronym Coordinating Arnold Kyrre Martinsen Person Funding European Commissions Seventh Research Framework Programme Organization Call Title Research for SME Associations Call 2 Call Identifier FP7-SME-2008-2 Funding Scheme Research for the benefit of specific groups (in particular SMEs) Application Stage 2 Application stage Table 1.2: List of Participants Participant Participant Legal Name No. 1 Norwegian Bioenergy Association (NoBio) (Coordinator European Biomass Association (AEBIOM) 2 3 British Trout Association Ltd (BTA) 4 Sea Marconi Technologies s.a.s (Sea Marconi) BV (Ingrepro) 5 IngrePro 6 Varicon Aqua Solutions Ltd (VAS) 7 Value for Technology BVBA (VFT) 8 Swansea University (SU) 9 Teknologisk Institutt AS (TI)

Country Norway European United Kingdom Italy Netherlands United Kingdom Belgium United Kingdom Norway

Organisation Type AG AC SME European SME AG SME AG MS SMEP SMEP SMEP SMEP RTD RTD

1 0 1 1 2

Durham University (UDUR) Hellenic Centre for Marine Research (HCMR) University of Florence (UFL)

United Kingdom Greece Italy

RTD RTD RTD

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ContentsB1.1: SOUND CONCEPT AND QUALITY OF OBJECTIVES ............................................................................................... ........................................4 . B1.1.1: Overview and Aims ........................................................................................................................................................... .............4 B1.1.2: The Need for Capture and Remediation of Greenhouse Gases and Liquid Effluents ...................................................................5 B1.1.3: The Scale of GHG and Liquid Waste Emissions ...........................................................................................................................6 B1.1.4: The Role of Microalgal Biotechnology in Effluent Mitigation and Valorisation ...............................................................................8 B1.1.5: Markets of Microalgae Products ....................................................................................................................................................9 B1.1.6: Relevance and Improving Competitiveness of SME-AGs ...........................................................................................................11 B1.2: INNOVATIVE CHARACTER IN RELATION TO STATE OF THE ART ............................................................................................... ...................12 . B1.2.1: Overview ........................................................................................................................................................... ...........................12 B1.2.2: Effluent Remediation - Current State of the Art ...........................................................................................................................12 B1.2.3: Microalgae Production Technologies...................................................................................................................................... .....15 B1.2.4: Microalgal Cell Harvesting ........................................................................................................................................................... 17 B1.2.5: Microalgae Upgrading.......................................................................................................................................... ........................18 B1.3: CONTRIBUTION TO ADVANCEMENT OF KNOWLEDGE / TECHNOLOGICAL PROGRESS ....................................................................................21 B1.4: QUALITY AND EFFECTIVENESS OF S/T METHODOLOGY AND ASSOCIATED WORK PLAN ...............................................................................22 B1.4.1: Overall Strategy of the Work Plan ...............................................................................................................................................22 B1.4.2: Timing of Work Packages and their Components .......................................................................................................................23 B1.4.3: Work Package Descriptions....................................................................................................................................... ..................26 B1.4.4: Graphical Presentation of Work Packages ..................................................................................................................................41 SECTION B2: IMPLEMENTATION QUALITY AND EFFICIENCY OF THE IMPLEMENTATION AND THE MANAGEMENT ....................42 B2.1: QUALITY OF THE CONSORTIUM AS A WHOLE ............................................................................................... ............................................42 . B2.1.1: Management structure and procedures .......................................................................................................................................42 B2.1.2: Description of the Consortium .....................................................................................................................................................46 B2.2: RESOURCES TO BE COMMITTED ............................................................................................................................... .............................. . 53 SECTION B3: IMPACT THE POTENTIAL IMPACT THROUGH THE DEVELOPMENT, DISSEMINATION AND USE OF PROJECT RESULTS ...................................................................................................................................... ....................................................................57 B3.1: CONTRIBUTION, AT THE EUROPEAN AND/OR INTERNATIONAL LEVEL, TO THE EXPECTED IMPACTS LISTED IN THE WORK PROGRAMME UNDER THE RELEVANT ACTIVITY.................................................................................................................................................

.................................57 B3.1.1: Improving the Competitiveness of SME-AG Members ................................................................................................................57 B3.1.2: Markets for BioAlgaeSorb Technologies ..................................................................................................................................... 58 B3.1.3: Economic Justification ........................................................................................................................................................... ......63 B3.1.4: Societal Aspects and Regulatory Drivers ....................................................................................................................................65 B3.1.5: Time to market ........................................................................................................................................................... ..................67 B3.2: APPROPRIATENESS OF MEASURES ENVISAGED FOR THE DISSEMINATION AND/OR EXPLOITATION OF PROJECT RESULTS, AND MANAGEMENT OF INTELLECTUAL PROPERTY ............................................................................................................................................................. ..............67 B3.2.1: Project Results and Intellectual Property Rights..........................................................................................................................67 B.3.2.2 Dissemination and Use ........................................................................................................................................................... .....71 SECTION B4: ETHICAL ISSUES ....................................................................................................................................... ..............................73 SECTION B5: CONSIDERATION OF GENDER ASPECTS.......................................................................................................................... ...74 REFERENCES ................................................................................................................... ...............................................................................75

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TablesTABLE 1.1: APPLICATION IDENTIFIER ....................................................................................................................................... ....................1 TABLE 1.2: LIST OF PARTICIPANTS ....................................................................................................................................... ........................1 TABLE 1.3: RISK DESCRIPTION FOR THE PROJECT ..................................................................................................................................23 TABLE 1.4: TIMING OF WORK PACKAGES AND THEIR COMPONENTS ...................................................................................................24 TABLE 1.3A: WORK PACKAGE LIST ....................................................................................................................................... ......................26 TABLE 1.3B: DELIVERABLES LIST................................................................................................................................. ...............................26 TABLE 1.3C: WORK PACKAGE DESCRIPTION ....................................................................................................................................... .....27 TABLE 1.3D: SUMMARY OF STAFF EFFORT............................................................................................................................ ....................39 TABLE 1.3E: LIST OF MILESTONES ....................................................................................................................................... .......................40 TABLE 2.2: INDICATIVE BREAKDOWN OF THE OFFER FROM THE RTD PERFORMERS TO THE SME PARTICIPANTS.....................54 TABLE 2.3: BIOALGAECONSUMABLE COSTS PER PARTNER ..................................................................................................................55 TABLE 2.4: BUDGET ALLOCATION TABLE ....................................................................................................................................... ...........56 TABLE 4.1: ETHICAL ISSUES TABLE ....................................................................................................................................... .....................73

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B1.1: Sound Concept Quality of Objectives

and

B1.1.1: Overview and Aims This project addresses specific needs of several key European SME groupings, via integration of technologies for effluent water remediation and the production and exploitation of microalgae biomass for mitigation of climate change (renewable energy generation, carbon dioxide (CO2) capture, utilisation of organic wastes) and the production of valuable bio-products using a biorefinery approach. The BioAlgaeSorb concept is shown diagrammatically in Figure 1.1 below:

Figure 1.1 Microalgae are very small (microscopic) photosynthetic, single-celled organisms that play a key role in nature as a food source for higher animals (eg, zooplankton, fish), for transferring nutrients in aquatic food webs and for balancing the exchange of CO2 between the ocean and the atmosphere. They are a highly diverse group, ranging in size from several hundredths of a mm to several tenths of a mm, taking many different shapes and existing singly or in chains or groups. Microalgae occupy a very wide range of habitats, including forms that live in open water (phytoplankton) or on surfaces (benthic), and are adapted to extreme physical and chemical conditions (eg, extremes of temperature, salinity, pH). Well known natural phenomena involving these orgnaims include blooms of green algae in fresh wate r ponds or lakes during summer andred tides in the sea. Vi to rt nh (vi) quang hp, sinh vt n bo c vai tr quan trng trong t nhinnh mt ngun thc n cho ng vt bc cao (v d, ng vt ph du, c), chuyn cc cht dinh dng trong li thc n thu sn v cn bng s trao i CO2 gia i dng v kh quyn. H l mt nhm rt a dng, khc nhau v kch thc t vi trm ca mt vi mm n phn mi ca mt mm, mang nhiu hnh dng khc nhau v

hin n l hoc trong dy chuyn hoc cc nhm. Vi to chim mt phm vi rt rng ca mi trng sng, bao gm cc hnh thc sng trong nc m (thc vt ph du) hoc trn cc b mt (y), v ang thch nghi vi iu kin khc nghit vt l v ha hc (v d, thi cc nhit , mn, pH). Cng c bit n hin tng thin nhin lin quan n cc orgnaims bao gm hoa ca to xanh trong ao nc ngt, h trong ma h v thy triu trong bin.

Important features of interest for the commercial exploitation of microalgae include their rapid rate of cell division (very high growth rate compared to terrestrial plants), their ability to grow using just light and a simple nutrient mix (like plants), and their synthesis of a wide range of useful and valuable compounds (including oils, pigments and antioxidants). These attributes have encouraged the development of commercial techniques for microalgae mass cultivation and downstream processes for the extraction of value-added products, which will be extended and directed towards effluent remediation for European SME-AG members within the BioAlgaeSorb project. tnh nng quan trng ca li sut chovic khai thc thng mi ca cc vi to c tc nhanh chng ca h phn chia t bo (tc tng trng rt cao so vi thc vt trn cn), kh nng ca h pht trin ch s dng nh sng v mt hn hp cht dinh dng n gin (nh thc vt), v tng hp ca h v mt nhiu loi hp cht hu ch v c gi tr (bao gm c loi du, bt mu, v cht chng oxy ha). Nhng thuc tnh ny khuyn khch s pht trin ca k thut canh tc thng mi hng lot vi to v cc quy trnh h lu tch cc sn phm gi tr gia tng, s c m rng v ch o khc phc hu qu i vi nc thi cho cc thnh vin chu u SME-AG trong d n BioAlgaeSorb.

The overall aims of the project are to: Increase knowledge on the bioconversion of industrial and agricultural/aquacultural effluents to microalgae biomass, as a sustainable raw material for biofuels and other value added applications; Provide new carbon neutral fuel sources for biomass power plants and biodiesel manufacture; Provide new sources of sustainable and carbon neutral high quality fine chemicals extracted from microalgae biomass; 4

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Reduce the discharge of CO2 to the atmosphere from biomass and fossil fuel power plants and other industrial processes reliant on combustion of fossil fuels; Reduce the nutrient loading of effluent waters from livestock production systems which are responsible for the largest proportion of organic waste in Europe, including most ammonia emissions. Increase know how and competence within a range of European SME-dominated industries. The specific Scientific and Objectives of the project are to: Technological

Optimise parameters for the rapid growth of (especially carbon-rich) microalgae, using waste-water nutrients and/or CO2- rich industrial flue gases, to high densities and in scalable cultivation systems; Develop efficient and reliable microalgae harvesting and dewatering processes; Develop effective processes for the conversion of dewatered microalgal biomass into biofuels and/or directly into energy; Optimise physical and chemical fractionation and transformation methods for those biomass components not directly converted to biofuels or energy; Assess the viability of the new processes and products developed, incorporating coupled process and financial models; Develop an industry-based model to assess a variety of strategies that maximise the value of the microalgal biomass in a changing market environment.

B1.1.2: The Need for Capture and Greenhouse Gases and Liquid Effluents

Remediation

of

Greenhouse Gas (GHG) Emissions For the past two decades, reduction of GHGs has been high on the political agendas for the European Union, individual Member States and worldwide organisations such as the United Nations. Recognizing that anthropogenic activities contribute significantly to climate change, the EU has adopted ambitious targets for reducing GHG emissions in the coming decades. This has led to current and emerging GHG mitigation agreements and incentives such as: The Kyoto Protocol, The EU2020, ref Directive 2003/87/EC, Greenhouse Gas Emissions Trading and national agreements such as the UK Carbon Reduction Commitment. The current target of 20% reduction in EU GHG emissions by 2020 will not be achieved without significant reduction of CO2 emissions from power production, where the use of fossil fuels, primarily coal and gas, leads to approximately 40% of all CO2 emissions EU-wide, and totalled almost 5,000 million metric tonnes in 2005 (Europa report; International energy annual, 2006). These decreases are expected to be attained by reducing the carbon footprint of existing fossil fuel-based power generation and by developing alternatives to fossil fuels. Geological carbon capture and storage (CCS) from fossil fuel-based power plants is a current focus for technology development in the EU (e.g., proposed EC Directive on Geological Storage of CO2) and globally, however geological CCS will not be adaptable to all scales of operation or localities (e.g. where seismic events and other geological failures may cause broken pipes): additional technologies are needed to reduce GHG emissions from fossil fuel-based power plants. The BioAlgaeSorb project will benefit SMEs and other enterprises by developing technologies for biological carbon capture using microalgae. Biofuels Production The EC is committed to a target of 20% energy production from renewable sources by 2020. As part of this scheme, biofuels are to comprise 10% of European transport fuels by 2020, however biofuels have recently been the subject of much criticism within the EU

and globally, for diverting human food supplies and arable land to fuel production (euobserver.com). Photosynthetic microalgae can be cultured to produce biofuels that do not directly compete with food crop-based commodities, as they are not typically grown in arable land areas, nor is microalgae biomass a major food source for humans (although it is a high quality food supplement). Furthermore, microalgae naturally tend to produce a lipid fraction suitable for the manufacture of second generation transport biofuels that are compatible with current transport infrastructure and do not require vehicle modification. Also, microalgae produce higher oil yields (up to 50 % of algal body weight) than oil-palm trees (up to 20 % body weight) which are currently the largest producer of oil to make biofuels (Research and Markets). It is therefore very timely to develop technologies for microalgae mass cultivation in Europe as a source of environmentally sustainable, carbon neutral biofuels. Waste Water Treatment In parallel to measures to decrease European GHG emissions, the discharge of aqueous effluents is increasingly regulated across diverse business sectors within the EU. Eutrophication is caused by several industrial activities (Tusseau-Vuillemin (2001) and it has long been suggested that water pollution should become an international priority (Duda, 1993). There are some 20 EU Directives encompassing all aspects of water quality, including those affecting water abstraction and effluent discharge from agriculture and land-based aquaculture, municipal waste water treatment and food and drink production. Key 5

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legislation affecting businesses that produce soluble organic wastes include the Water Framework Directive (2000/60/E), the Urban Waste Water Treatment Directive (91/272/EEC, amended by Commission Directive 98/15/EC); The Nitrates Directive (91/676/EEC) and the Integrated Pollution Prevention and Control Directive (2008/1/EC). These regulations are driving both better conservation of water (e.g. water re-use and recycling in land-based aquaculture systems) and upgrading of effluent treatment infrastructures, all of which have significant cost implications for SMEs and large enterprises in Europe. As an example, the EU Court of Auditors estimate the Europe-wide cost of constructing new sewer pipelines and secondary treatment plants in compliance with the Urban Waste Water Treatment Directive to be about 200 billion (The information centre, Scottish Parliament 1999). There is clearly a need to develop innovative, cost effective approaches to the treatment of effluents, preferably incorporating valorisation of wastes. Critically, as the global cost of fertilizers increases (N is fixed by the Haber process at great energetic cost, while natural P reserves are fast being exhausted) it will become all the more important to recover and reuse these nutrients rather than to deal with them as wastes. The EC Water Framework Directive and related legislation place great pressures upon the removal of this valuable resource; it is logical to combined the removal of nutrients with the production of biofuels. The BioAlgaeSorb project will provide EU SME groups in the livestock production sectors with new technologies implementing microalgae for effluent treatment phycoremediation yielding a valuable by- product in the form of microalgae biomass. B1.1.3: The Scale of GHG and Liquid Waste Emissions Power Generation (Fossil Fuels and Biomass) Based on average world data, fossil fuels currently supply over 85% of the worlds ener y needsand will remain g in abundant supply well into the 21st century (International Energy Agency, 2001). Simultaneously, Biomass energy production is the fastest growing renewable energy resource in Europe (European Biomass Association, 2007), and in 2004 had contributed up to 66% of the total renewable energy. The carbon dioxide emissions from the exhaust gases of the biomass/fossil fuel-fired power plants are one of the major emitters of GHG, accounting for about a third of global CO2 emissions, and have been increasing in recent decades (Andrade and Zaparoni Survey, 2009). Data for 2004 show that within the EU 27 member community, a total of 5142 Mt of CO2 was emitted of which about 1700Mt came from power plants emissions (EEA, 2009) This elevation of CO2 and other greenhouse gases concentrations in the Earths atmos phere is leading to changes in the global climatic conditions caused by the rise in the terrestrial surface average temperature. Therefore there is need for stabilization of GHG: However, this will be difficult to achieve if coal-fired plants remain, unless carbon capture and storage emissions from coal fired stations becomes viable. Heavy Industry Nearly a third of the worlds energy consumption and 36% of CO2 emissions are attributable to manufacturing industries. The large primary materials industries, i.e., chemical, petrochemicals, iron and steel, cement, paper and pulp, and other minerals and metals, account for more than two-thirds of this amount. The industrys use of energy has grown by 61% between 19 7 12004, although if the industry adopted advanced technologies, there would be a significant reduction in CO2 emissions (Global Warming Report, 2004). The cost of CO2 mitigation is expected to rise. The EU Emissions Trading Scheme covers CO2 emissions from the power sector (all fossil fuel generators over 20MW). Member States are required to develop a National Allocation Plan, setting targets for emissions

from the relevant sectors and allocating allowances to installations for the relevant periods. All installations (representing about 40% of EU emissions) are thus set an absolute emission cap (6,600 Mt CO2in Phase I of the scheme). Allowances are freely tradable installations may buy or sell allowances as they see fit. Phase II of the EU ETS began in 2008 and imposes tighter restrictions, as well as auctioning the allowances instead of distributing them freely. The UK Carbon Reduction Commitment is a mandatory emissions trading scheme targeting large commercial and public sector organisations using more than 6,000MWh of electricity through mandatory half hourly meters. Organisations will have to buy allowances for emissions at an auction, with the total number of allowances set by the Government. Revenue from the auction will be recycled to scheme participants. The scheme is expected to begin in 2010. Aquacul ture The cultivation of finfish and shellfish is a substantial and expanding European industry. Following current and anticipated trends, sectoral growth is expected to enlarge markedly over the coming decades, as global population and the demand for seafood increases whilst harvest from wild stocks stabilises or declines. The systems used for finfish production can be broken down into three main categories: open ponds/tanks/ raceways, cages (typically marine) or closed water recirculation systems (Table X). Throughout the EU Member States, salmonid species (e.g. trout) dominate in terms of production and number of farms. In 2007, approximately 1600 thousand tonnes of fish were produced across Europe, of which approximately 81% (1274 thousand tonnes) were salmonids or eels (FEAP/Finfish News 2009). In the UK alone, there were over 240 individual farms producing rainbow trout in 2007 (Finfish news, 2009). The quantity and precise constituents of aquaculture waste vary between 6

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production system and species farmed, with some studies (Ackefors & Enell, 1994; Chopin et al. 1999; Olsen et al., 2008) estimating that 44 - 78 kg N/ton of fish/year is released into the water column. Number of Quant Typical Member ity producti States (metric on Tilapia Tan 2 115 ks 0 African Catfish Tan 4 706 ks 1 Ponds, Sturgeon 6 207 tanks or 7 raceway Carp Ponds or tanks 8 703 41 Other coarse fish Ponds or tanks 2 124 1 European Eel Ponds or tanks 4 532 0 Freshwater salmonids (trout Ponds or tanks 2 3415 and Charr 2 64 Marine salmonids (Salmon Sea or loch 7 9271 and sea trout)fish cages 40 Other marine Sea cages or 1 2244 RAS 3 04 TOTAL 1580 More than 400,000 T of farmed fish pa are currently produced on land 298the EU, in conferring significant organic loading on receiving waters, while disposal of solid fish manures in many cases incurs a charge to operators and, in some situations (eg, where the manures contain a high salt content), is physically unsuitable for conventional land spreading practices. Increasingly stringent discharge regulations, driven principally by the EU Water Framework Directive, have furthermore encouraged greater water re-use and the adoption of water recycling technologies by land-based fish farms, in order to reduce total discharge water volumes and to enable more efficient separation of solids. These trends provide greater incentive and greater technical capacity for aquaculture SMEs, including members of the British Trout Association, to capture and valorise soluble aquaculture effluents via BioAlgaeSorb technologies. Fish There is industry wide apprehension of EU Water Framework Directive demands. To reach good ecological status by 2015, regulators may demand reduction of water abstraction and/or an increase in the cost of licences. The quantity and quality of water or effluent discharge, such as Phosphorus, may also be restricted with the threat that, for example, regulations governing livestock production industries may be amalgamated with heavy industry. Today, the precise demands are unknown but are likely to increase the cost of compliance (currently about 25 Euro/tonne trout BTA, pers. comm.). In the UK, the Environment Agency is responsible for enforcement of environmental legislation and offences committed under such laws and regulations. Since 2000, there have been 1600 cases (including approximately 800 prosecutions) per year. The fine varies between 4,250 7,700 EURO, and in some circumstances leads to a jail term Intensive Agriculture Due to an increase in intensity of agriculture, ammonia concentrations have doubled in the last 50 years in Europe (http://www.ukpollutantdeposition.ceh.ac.uk/ammonia_network). There is an estimated 230kt ammoniaN per year produced from agricultural sources in the UK; in common with many other European countries, this accounts for about 80% of the total emission (Pain & Jarvis, 1999) and a substantial part of the anthropogenic emissions of methane and nitrous oxide (Duxbury, 1994, Philips & Pain, 1998), as well as being responsible for the largest part of the nutrient load put on the surface waters. Pig slurry has up to twice the Biological Oxygen Demand (BOD) as cattle slurry (SEPA, 2009). To illustrate, around 160 million pigs and 100 million cattle produce 220 and 1200 million tonnes of fresh excrement annually with a nominal concentration of 10 % dry matter (FAO, 2000; Eurostat, 2007). This is often diluted with water and mixed with bedding: including wastes from other animal types, terrestrial livestock farming in Europe is currently producing in excess of 2

billion tonnes of organic wastes annually. The hygiene impact potentially can affect all aspects of food production as well as presenting a broad threat to public health from land spreading practices (Guan & Holley, 2003). Anaerobic Digesters This technology processes organic waste, reducing overall volume, producing biogases suitable for fossil fuel replacement and nutrient rich liquid wastes. In recent decades, anaerobic digestion has been a major development in waste treatment technology across Europe. Consequently, it has captured a significant share of the market for the biological treatment of solid waste. In 2006, the European commission reported that for biological treatment of organic waste in general a total of 6 000 installations have been identified, including 3 500 composting and 2 500 anaerobic digestion (AD) facilities (mostly small scale on-farm units). 124 AD installation for treatment of bio-waste and/or municipal waste with a total capacity of 3.9 million tonnes, were operational in 2006 and this number is expected to grow. While AD technology is effective in producing combustible biogas from digested organic waste, it does release a nutrient-rich liquor as a by-product that must be dealt with appropriately to avoid contamination of receiving waters. 7

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Municipal Waste Water Waste water from dwellings constitutes grey water (from appliances, showers and sinks) and foul toilet water (sewage). The characteristics of both waste streams differ. Grey water contains less nitrogen and pathogens and thus has more potential applications (Li et al., 2003). The published literature indicates that the typical volume of grey water varies from 90 to 120 L/person/day in developed countries (Morel and Diener, 2006) while that of sewage (sludge only) per European country varies between ca. 30 250 million kg (Eurostat, 2009). Food Processing In 2006, 233,344 thousand tonnes of animal and vegetal waste and food processing waste (not including excreta) were produced in the 27 Member States of the EU (Eurostat, 2009). Waste material from food processing contributes significantly to environmental degradation such as eutrophication (Tusseau-Vuillemin, 2001). The composition of food waste varies but a recent review (Digman & Kim, 2008) categorised 5 different types of food waste with biological oxygen demands between 300 100,000m g/L. B1.1.4: The Role of Microalgal Biotechnology in Effluent Mitigation and Valorisation Effluents that pose a burden of environmental loading need not be regarded as an expensive, challenging problem without value. Using microalgae, BioAlgaeSorb will assist SMEs to reducethe costs associated with effluent discharge and will generate new markets for microaalgal products, enabling current operations to offset their costs of discharge and to diversify operations. Feasibility of Microalgae Mass Cultivation Participants in this project include European SMEs with leading technologies for intensive microalgae cultivation in closed photobioreactors (Varicon Aqua Solutions Ltd) and in open raceways (Ingrepro BV). Working collaboratively with experts in water quality management, nutrient dynamics and process modelling (Swansea University & HCMR,), a range of improved products and processes will be developed for combined waste remediation and microalgae biomass production. Feasibility of Biofuel Production from Microalgae The biological characteristics of microalgae are favourable as biomass for biofuel in terms of their high areal productivity and biochemical composition (Chisti Y, 2007). They do not directly compete with food crop-based commodities and are typically grown in non-arable land areas (Patil, V et al (2008). Microalgae typically contain a much higher percentage of extractable oil than other oil crops in excess of 50% compared to, e.g., 25% from rapeseed, and contain more long chain polyunsaturated fatty acids which can be converted to biofuels by pyrolysis or catalysis (Greenwell et al., 2008?). Biomass composition will be optimised within the BioAlgaeSorb project not only by selecting appropriate microalgae species, but also by manipulating the physico-chemical environment in which the microalgae are grown, e.g. by depleting nitrogen and phosphorous at key stages in the growth process to induce maximal hydrocarbon production. Feasibility of Waste Remediation Using Microalgae Microalgae are photosynthetic aquatic microorganisms that require inorganic nutrients

and CO 2 for growth (Carvalho, et al; ,2008; Eriksen, 2008). They are therefore well suited for fixing nutrients (especially inorganic nitrogen and phosphorous, which are a large, but often unconsidered cost in microalgae biotechnology) from effluent waters and are capable of capturing CO 2 from industrial flue gases (Doucha et al (2005) Wang et al 2008). RTD providers within the project have the resources to characterise the compositions of gaseous and aqueous effluents from industrial and agricultural processes and to perform experimental and dynamic modelling studies to identify the most suitable microalgae species and operating conditions for remediating and valorising the chosen waste categories. Feasibility of Harvesting Microalgae on Large Scale Chemical flocculation (e.g. using aluminium sulphate) is a relatively inexpensive and efficient method for separating microalgal cells from water and is used in municipal waste water treatment plants. The principles of large scale microalgae harvesting are thus well established, although it is desirable to exclude residual metals that may interfere with subsequent chemical or enzymatic conversion of biomass to valuable compounds. Among the participating SMEs, online centrifugation is successfully used as an alternative to chemical flocculation for harvesting freshwater microalgae. However, this method is considered inefficient at the larger scales required for algal biofuel production and is also less compatible with marine microalgae species (due to equipment corrosion). Well established separation methods will therefore be adapted to the current purpose within BioAlgaeSorb, involving a sequential dissolved air floatation and mechanical filtration process. Ozonation and pH manipulation will be tested as alternatives to chemical flocculants and process optimisation will take into account the physiological status of the microalgae during harvest.

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Feasibility of a Microalgaebased Biorefinery A biorefinery approach will be used to develop optimal biomass processing pathways tailored to local conditions and market opportunity. The development of an integrated biorefinery for microalgae biomass is a central innovative feature of the BioAlgaeSorb project, designed to maximise the numbers of usable microalgae products and economic return per unit biomass produced. The constituent processes are each well established, but will require adaptation for the particular raw materials and intended end uses. The elements of this biorefinery are: direct thermo-chemical conversion of intact biomass (or biomass residue following oil extraction) to liquid biofuel, physical separation of intact biomass into major fractions (protein, lipid, carbohydrate), upgrading of the lipid fraction into current generation biodiesel (trans-esterification) and into g r e n e biodiesel (decarboxylation and decarbonylation of fatty acids), and extraction of specific valuable pigments (phycobiliproteins). A new microalgal biorefinery will be developed within BioAlgaeSorb to provide a series of processing options that can be tailored to the needs of different SME-AG sectors and individual SMEs. The biorefinery will furthermore offer a template for the broader microalgal biotechnology sector internationally, raising the impact of the investment beyond the immediate consortium and providing opportunities to SMEs for licencing, etc. Feasibility of Optimising and Evaluating New Processes The configuration and management of processes and products to be developed within BioAlgaeSorb will be optimised via computer modelling. The approach to be taken is to start with an established mechanistic model of microalgal growth. This model is a dynamic (not steady-state) photoacclimative description of temperature-light-multinutrient limited growth. This type of model is essential to properly consider the cost-benefit implications of the process (for example, to properly include nutrient consumption, selfshading of suspensions etc.). The model is not a crude thermodynamic, Monod or Droop quota model. Rather it is founded on well-grounded physiological understanding, with feedback interactions describing nutrient transport (N, P, Fe, Si etc; differentiating between N-sources, for example), photosynthesis and photoacclimation (with changes in light and nutrients), respiration, and changing chemical stoichiometry (e.g. with changes in nutrient status). This modelling structure will be employed within BioAlgaeSorb to provide a mechanistic basis for a thorough and transparent analysis for the design, geometries and efficient operation of coupled microalgae photobioreactors and raceways at SME-AG member locations. B1.1.5: Markets Microalgae Products of

Established Markets Microalgal biomass production for established markets has approximately doubled recently from 5,000 to 10,000 tonnes per year dry weight, excluding live microalgae produced and used in marine aquaculture hatcheries (Pulz and Gross, 2004; Algal Industry Survey, 2008). Briefly, the particular markets include: Aquaculture and Agriculture feeds, Pigments, antioxidants, Functional foods and nutraceuticals, Cosmetics and cosmeceuticals and Omega 3 oils. In 2006, these markets had an estimated value of $5-6.5 billion per year (Pulz and Gross, 2004, Table 1.1). Table 1.1 summary of microalgal product markets Current Product Prod Group uct Biomass Health Food Functional Food Feed additive Soil conditioner

Retail value (millions EURO) 180 0 57 0 21 5 50 0

Colouring substances

Antioxidants

Special products Emerging Product Group

Astaxan thin Phyocya nin phycoerythrin BCaroten Tocoph erol Antioxidant extract AR A DH A PUFA extract Toxi ns Isotop es Prod uct Biofuels and bioenergy C0 2 Effluent Remediation 9

11 0 7 1. 5 20 0 N/ A 11 0 1 5 107 5 7 2 3. 5 Retail value (millions EURO) N/A N/A N/A

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Around half of this production takes place in mainland China, with substantial commercial production also in Japan, Taiwan, U.S.A., Australia and India, and smaller volumes produced elsewhere. Aquaculture Feeds Microalgae are used ubiquitously as a feed source in the commercial hatchery production of juvenile marine fish and shellfish. There are thousands of marine hatcheries globally, producing billions of juvenile fish and shellfish annually. A relatively small number (~6-10) of easy-to-rear microalgae species have been adopted for this purpose. In most cases, the microalgae are cultured on site by hatchery personnel and presented live to the fish / shellfish larvae (see Fig x). Under this scenario, sales opportunities to hatcheries mainly consist of the equipment and consumables required for microalgae production: photobioreactors, pumps, lights, nutrient mixes, etc. However, there is a growing trend for hatcheries to purchase proprietary microalgae concentrates in order to simplify on-site operations. These concentrates are supplied by companies specialising in the large scale production and processing of microalgae. This market segment had an estimated value of EURO 500 million globally in 2004 (see Table 1) and has grown steadily since. There is further scope to develop the sector by introducing better quality products, since it is widely acknowledged that existing concentrated products still do not match live microalgae for hatchery applications (nutritional composition; physical attributes; product stability). Dried microalgae biomass (esp Arthrospira) is also widely used as an ingredient in formulated feeds for aquaculture species and terrestrial animals (farmed livestock, poultry, pets), where it has been demonstrated to have health promoting effects. Pigments & Antioxidants Microalgae produce a range of valuable compounds including carbohydrates, proteins, essential amino acids, pigments and vitamins, as well as bioactive molecules. The major pigments include chlorophyll a, b and c, - carotene, phycocyanin, xanthophylls (astaxanthin, canthaxanthin, lutein) and phycoerythrin. These pigments have existing applications in food, feeds, pharmaceuticals and cosmetics, and there is an increasing demand for their use as natural colours in textiles and as printing dyes. The value of these pigments lies not only in their colorant properties, but also as antioxidants with demonstrated health benefits. The worldwide market value for all commercially-used carotenoids was estimated at EURO 640 million in 2004 and is expected to rise at an average annual growth rate (AAGR) of 2.9% to just over EURO 730 million by the end of the decade. Although the synthetic forms of carotenoid are less expensive than their natural counterparts, microalgal carotenoids have the advantage of supplying natural isomers in their natural ratio and are generally accepted as being superior to synthetic all-trans forms. The largest commercial outlet of carotenoids (synthetic and natural) is in feeds, mainly because of the outstanding importance of astaxanthin and canthaxanthin, eg for colouring the flesh of farmed salmon. Increasing demand for organically farmed fish has expanded the market for microalgaederived astazanthin. The big carotenoid marketing success in recent years has been lutein, when it was demonstrated that it can help reduce age-relatedm acular degeneration. This pushed luteins m arket valu eup to EURO 100 million in 2004. Functional Foods & Nutraceuticals The documented bioactive properties of microalgae have led to a well developed market for dried biomass as a human nutritional supplement, sold in different forms such as capsules, tablets and liquids. The most important microalgae species for this purpose are Dunaliella salina, Arthrospira sp, Chlorella sp and Aphanizomenon flos- aquae. These are mainly produced in outdoor ponds or shallow raceways, but also in closed photobioreactors at more northerly latitudes including Europe. Certain cyanobacteria, for example Arthrospira platensis and A. maxina (formerly Spirulina) are also marketed as whole food, being particularly protein-rich (up to 77% dry mass) and containing all essential amino acids, a number of important essential fatty acids (EFAs) and vitamins of the B, C, D and E groups. This microalgae market segment is expected to grow in line with that of the wider nutraceuticals sector, which had a total global value of approximately EURO 58 billion in

2008, nearly EURO 6 billion of this being European. Helping to protect the sector during the economic downturn is the strong preven tive health care angle of nutriti nal supplements and the markets sizeable component of better-off o demographics, including an aging population. The sector is currently maturing beyond basic and sometimes unproven supplements to one of delivering more subtle benefits that aid absorption of nutrients, and prevent a range of conditions relating to energy metabolism, such as diabetes. Welsh HEIs and SMEs are well placed to deliver the appropriate applied science and to develop verified microalgae-based functional foods in response to this evolving marketplace. Cosmetics & Cosmeceuticals A number of microalgae species (esp Chlorella and Arthrospira) have become established in the cosmetics market. Some cosmetics companies (eg, Louis Vitton) have even invested in their own microalgae production capacity. Microalgae extracts can mainly be found in face and skincare products, eg anti-ageing cream, refreshing or regenerant care products, emollient and as an antiirritant in peelers. Microalgae are also represented in sun protection and hair care products. Omega 3 Oils The major source of omega 3 is from fish oils and they contribute about 85% of the market by volume. However, the supply of marine sourced omega 3 is being threatened by adverse environmental conditions that have contributed to lower DHA levels in fish oil especially from fish species from South American waters which are the major suppliers of fish oil and also depleting global fish stocks. The adverse environmental factors coupled by depleting fish stocks can aid the global market 1 0

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growth of algal based omega 3 which is currently contributing about 3% of the total omega 3 market. It is estimated that the EU market for algal-sourced omega 3 is currently at EURO 40 million and 90% of the total volume is being used for infant health products. Analyst have also revealed that omega 3 ingredients market is set to grow at 24.3% annually and projected all the way to 2014 when it will be worth EURO 1.2 billion and this figure is for both marine and microalgal sources omega 3. Over the years, the growth of microalgal based omega 3 has been hampered by a network of patents that have only allowed a few players in the market i.e. Martek Biosciences (US) and Lonza (EU). However, it is anticipated that M art ks paten will begin to expire in the next decade, and this will e ts encourage more players into the market and ultimately the global microalgal omega 3 market share will increase. Furthermore, the microalgal omega 3 market can appeal as a vegetarian source of omega 3.

Emerging Microalgae Markets Current global, European and national regulations suggest that algaculture will expand into future markets such as Biofuels and bioenergy, CO2capture and Effluent Remediation. Biofuels: The main types of biofuel currently in use can be divided into those based on ethanol from carbohydrate breakdown, e.g. from corn and sugar cane, and those based on fatty acid methyl esters (FAME) or fatty acid ethyl esters (FAEE) of lipid fractions, e.g. from rape seed oil or palm oil. Microalgae naturally tend to produce a lipid fraction of which a significant portion is suitable for fuel applications. First generation biofuels from algae are based on FAMEs, whilst second generation fuels will be based on de-oxygenated fatty acids. Second generation biofuels will be compatible with current transport infrastructure with no modification to vehicles. Carbon abatement / mitigation: Biofuels are a carbon neutral technology and therefore eligible for funding and tax breaks from governments as renewable sector revenue. Biofuel crops use CO2 to grow and therefore mitigate levels of CO2 in the atmosphere. Strains of microalgae have been shown to grow optimally under CO2 concentrations of 5-10% (Lee and Lee, 2003). Other strains grow well at CO2 saturations of 30-70% (Hanagata et al. 1992; Iwasaki et al. 1996; Sung et al. 1999). By controlling the pH and solution CO2 release algae could potentially grow at 100% CO2. (Olaizola, 2003), Carbon capture: Algae capture and store CO2 so can also be used directly reduce the discharge of industrial CO2 to the atmosphere. (Hall and House, 1993; Benemann, 1997; Hughes and Benemann, 1997; Sheehan et al., 1998; Chisti, 2007; Huntley and Redalje, 2007). Studies have reported on microalgae sequestering CO2 emissions from coal fired power plants, which are likely to dominate in energy generation throughout India and China (Sheehan et al, 1998). B1.1.6: Relevance and Improving Competitiveness of SME-AGs The innovative nature of BioAlgaeSorb creates a cost effective solution to the economic and environmental demands of sectors that produce gaseous and liquid effluents, while providing a cheap, constant and plentiful supply of raw materials to produce microalgae and associated value added products for a diversifying market. Participating SME AGs Members within the livestock (agriculture and aquaculture) production sector will gain a competitive advantage by improving the cost effectiveness of their waste treatment processes by generating a valuable by-product (microalgae biomass). Meanwhile, SME-AG s representing biomass power generation will additionally benefit by re-using processed microalgae biomass for on- site energy production, as well as offering the potential for gaining carbon credits (directly or indirectly) by reducing their GHG emissions. Participating SMEs will undertake industrial validation of the microalgae production techniques and biomass

conversion processes developed by the RTD performers (Chaumont D, 1993). The technology is also transferable to other sectors - such as heavy industry, anaerobic digester operators, food processors and municipal water companies. Participating SME Technology Providers Those SMEs involved in developing the microalgae production and processing technologies will acquire IP that is exploitable both within Europe and globally, in addition to direct sale of processes and value added microalgal products. This includes SMEs such as bioreactor manufacturers and lighting specialists, fluid handling and clarification, chemical conversion and fractionation, biofuel manufacturers and specialized food supplement and pharmaceutical manufacturers. Indeed, the opportunities for export of expertise are increased by the fact that lower latitude countries have ambient environmental conditions (light and temperature) that may make them highly appropriate as locations for commercial microalgal production. There is without doubt a European and global opportunity for this industry (Farrell et al., (2008). Benefits of the Project Partnership The SME categories represented in the project (microalgae technologists; biofuel producers; agriculture and aquaculture producers) have limited in-house RTD capacity to resolve problems or meet the needs of their respective sectors, and less so to identify and exploit cross-sectoral opportunities. Current global economic conditions place further constraints on the 1 1

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resources available for in-house RTD. The higher level of private sector and government funding in this arena beyond Europe (approximately EURO 170 million, mainly from Californian investors Biofuels International) represents a very real risk to the EU Member States, in terms of being able to compete economically and technically within this very important developing sector. The participating SME-AGs provide an important mechanism for collating, prioritising and conveying the needs and problems of their members to local, regional and EU funding agencies and RTD performers.

B1.2: Innovative Character in Relation to State of the ArtThe overall aims of the project are to increase knowledge on the bioconversion of industrial and agricultural/aquacultural effluents to microalgae biomass, as a sustainable raw material for biofuels and other value added applications; B1.2.1: Overview A review of current remediation practices and recent research investigating phycoremediation is described below, followed by methods employed to grow and process algal biomass. The current and future markets for algal products are then described. Currently, there are a limited number of applied research publications investigating phycoremediation for individual industries, primarily at small (i.e. laboratory) scale. B1.2.2: Effluent Remediation Current State of the Art -

Power Generation (Fossil Fuels and Biomass) and Heavy Industry The increased awareness on the adverse consequences of global warming has resulted in the imposition of a number of policies with the objective of reducing emission greenhouse gases. Currently, power plants are reducing their CO2 emissions by improving on thermal efficiencies of the plants. However, current global CO2 emissions still need further reduction in order to meet with the GHG emission strategic requirements. Consequently, a number of carbon dioxide mitigation strategies have been investigated and these have been broadly classified under chemical reaction based and biological CO2 mitigation categories. These concentrated sources of CO2 can be potentially captured and a number of commentators indicate that it can technically be feasible. The most common removal processes that have been investigated for CO2 capture from flue gas can be classified in two general categories - post-combustion separation and pre-combustion separation. Post-combustion and pre-combustion separations: Post-combustion separation is the most established technique to remove CO2 from flue gases. In this procedure, the CO2 capture processes are based on chemical absorption where the CO2 is absorbed in a liquid solvent by formation of a chemically bonded compound and is removed after the flue gas combustion. This process has proven to be expensive due to large volumes of 'solvents' required and also the energy requirements in CO2 absorption process. Precombustion separation involves reacting CO2 with oxygen and/or steam to give mainly carbon monoxide and hydrogen. Combustion with oxygen, however, yields temperatures too large such that expensive specialised material would be required. Chemical reaction based strategies are known to be expensive because they involve a 3 stage process of separation, transportation and sequestration with cost of separation and compression. It has been reported that this technology may cost in the range between EURO 40-90 per avoided ton of CO2 for natural gas combined cycle plants and coal fired power plants (Amann et al, 2009). Therefore, because of the costly nature of the strategy, the mitigation benefits become marginal.

Geological carbon capture and storage (CCS): Geological carbon capture and storage from fossil fuel-based power plants is a current focus for technology development in the EU (eg, proposed EC Directive on Geological Storage of CO2) and globally, however geological CCS will not be adaptable to all scales of operation or localities (eg, where seismic events and other geological failures may cause broken pipes). The long term CCS economics has come under scrutiny because of the uncertainties regarding implications of CO2 leaking back into the atmosphere. Van der Zwaan and Smekens (2009) maintain that CCS would constitute a meaningful climate change mitigation option if leakage rates are 10,000 m 3 per day) (Crossley et al 2002). The main disadvantage of this approach is the contamination of the materials with the floc agent which may significantly reduce their value (Molina Grima et al 2003). Although these methods have not been proven in saline environments on a large scale, the integration of floatation into the bioreactor has been demonstrated. Using an integrated reactor and foam fractionator under appropriate conditions, up to 90% of a Chaetoceros sp. could be removed (Csordas and Wang 2004). Filtration There are many modes of filtration that can be used to concentrate cells, the most simple of which is dead end filtration. This is achieved with large quantities of dilute microalgae by using packed bed filters (mixed media or sand). T his type of filtration is limited by the rheological properties of the algae as these form compressible cakes which easily blind filters. This technique has been used successfully in the separation from reservoirs, where the algae concentrations are relatively low. The amount of water that can be processed is severely limited by the characteristics of algal materials, e.g. compressible cakes and the presence of extra-cellular foulant materials. These processes involve relatively very low energy consumption but the frequency of washing with loading increases energy costs and reduces filter productivity. Pressure or vacuum filtration can be used but concentration of the alga is required for these processes to be effective. Power consumptions for these operations are in the order of 0.3 to 2 kWh.m-3. To avoid problems in dead end filtration, cross flow filtration can be used; several studies have been published and demonstrate that high concentrations of algal cell can be attained (up to 100 kg.m 3). These filtration systems are easily upscaled, with rapid advances being made in their use and operation. Several studies have been carried out on laboratory scales and have shown that these systems are capable concentrating the algae and be used in downstream fractionation (Rossignol et al, 1999; Vandanjon et al 1999 and Rossi et al 2004). Reducing the process volume by at least a factor of 100 significantly reduces the costs of disruption and fractionation stages downstream. Although a definitive study on large scale algae harvesting has yet to be published, work has shown that the costs of the microfiltration river water are as low

0.2 kWh.m-3 of water processed. Several variables associated with the choice of membranes and type of organisms could increase this cost and there is considerable scope for optimisation of this process. As a guide to potential improvement, th e costs of desalination by reverse osmosis, where a far higher pressure process is used, have fallen dramatically (85%) over the past decade to less than 1/m-3 and with energy costs being a as low a 3 kWh.m-3. This is largely down to better membrane technology, greater membrane longevity; increase scale of operation and better system management. Project innovations, microalgae harvesting methods: Novel rapid separation technologies and separation schemes will be developed, exploiting the unique properties of microalgae to provide stable high quality concentrates and commodity materials e.g. protein and lipid fractions that will go for further refinement and purification to produce high value products; New methods of preservation and storage will be developed to allow high value algae-derived materials to be kept for long periods, thus maintaining their value and simplifying marketing and distribution.

B1.2.5: Microalgae Upgrading Cell disruption To maximise the value of the materials obtained from the processes, rapid and precise mechanical disruption of the cells is chosen in most cases as this avoids further chemical contamination of the algal preparation whilst preserving most 1 8

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of the functionality of the material within the cell. There are two processes proven on large scale, homogenisation and bead milling. Cell homogenisation involves the process fluid being forced through an orifice; this creates rapid pressure change as well high liquid shear impinges on the algae causing disruption. The second approach is the use of bead mills, these are vessels packed with small glass beads that are agitated at great speed. The result is that cells are disrupted, but the level of disruption is usually dependent upon the residence time in the system (Doucha and Livansky (2008). Cell strength size and shape of cells affect the performance of both methods. Optimisation of breakage is important as this involves the use of large amounts of energy and also affects the physical and chemical nature of the end product (e.g. extent to which lipid membranes are disintegrated). Scale up of these devices brings about some efficiency gains based on improved pump performance. Bead mills give an equivalent performance but design of the milling chamber and fluid mixing can have a significant affect, while disrupter requiring multiple passes are inefficient and allows poor mixing to given uneven process treatment of the cells. There is considerable scope to study these processes to find the correct breakage procedure, particularly the manipulation biological factors (cell wall strength and possible pre-treatments to achieve this) associated with this process. Fractionation and oil recovery After cell disruption, microalgal cells are fractionated. Generally, the principles of separation of materials from disrupted cells are well established and it is only the development of specific optimised protocols that recover all parts of the microalgae at maximum value. Many specific one-product protocols exist, for example the use of solvents (such as hexane) and salt precipitation of proteins which contaminate the fractions and require further remediation. It is for these reasons that methods of separation based upon size, charge and density are preferred: Fat droplet separation can be achieved by microfiltration, while the soluble proteins, using a diafiltration process, will pass through a microfiltration membrane creating a fat-free, soluble protein fraction that can be concentrated and dried. This material can be used as source for further refining (enzymes functional protein etc) alternatively the density differences may be exploited using centrifugation which is more effective in the absence of emulsifying soluble proteins. Further fractionation of the cell debris is also possible so that the cell wall materials (carbohydrates and silica) and other organics such as pigments may be isolated. Thermo-chemical conversion pyrolysis Pyrolysis is a technique used to upgrade biomass at reasonably large scales through the slow heating in the absence of oxygen to produce gaseous, oil and char products. Cracking is a technique used to breakdown larger hydrocarbons, and other molecules, into smaller, more desirable hydrocarbons in the presence of a size selective catalyst and the absence of oxygen and can be used to further upgrade the oil fraction from pyrolysis processes. In a recent study Grierson et al (2008) investigated the pyrolysis of dried and finely ground algae biomass using a slow pyrolysis method; it was found that up to 43% by volume heavy bio-oil could be produced for Tetraselmis and Chlorella species. Catalysts used for cracking include zeolites (Twaiq 1999) and other mesoporous aluminosilicates (Twaiq 2003). A number of 3- dimensional structures called pillared clays containing various metals have also been investigated for their ability to crack vegetable oils such as canola oil, palm oil and sunflower oil into biofuels (Kloprogge 2005). During the last two decades pyrolysis has been optimised for a number of algal species using temperatures of up to 600C, yielding liquid components of up to 70wt% of organics in the algal cell (3-10). Of primary importance is the Energy Consumption Ratio (ECR) for the process (defined as the energy required to heat the algal cells up to the reaction temperature over the available energy of oil produced). For microalgae, the process is more economical than processing lignocellulosic materials and is more easily manipulated. Weimin et al. (7) investigated the slow vacuum pyrolysis of dried samples of Chlorella protothecoides. The amount of oil and gas produced during pyrolysis was greater than the content of crude oil in the cells, indicating that other chemicals such as protein and water soluble carbohydrate were converted into fuel oil or gas by thermochemical techniques. In a successive study Miao et al. (10) compared the product of the fast pyrolysis of autotrophic and heterotrophic Chlorella p. They found that heterotrophic Chlorella has a stable bio-oil yield 3.4 times higher than autotrophic sample of the same cells, and double that of wood - suggesting that there is a commercial potential for large-scale production of liquid fuels from microalgae by fast

pyrolysis. In general, pyrolysis can be a useful approach for dried, or even untreated biomass and biomass residues, or for use in local co-firing of biomass. However, in pyrolysis of entire algal biomass, it remains unclear whether the return in oil in any way improves the yield that might be extracted from the biomass for upgrading. There is also the question of the high commercial value biochemicals; pyrolysis would destroy these. However, there may well be a place for pyrolysis of the residual biomass after oil and high value product extraction to maximize the yield from the biomass. Catalytic Trans-esterification Biodiesel is produced via trans-esterification, where triglycerides present in vegetable oils are catalytically esterified, usually with methanol (methanolysis), to yield the corresponding FAME and glycerol. Both homogenous (same phase) and heterogenous (different phase) catalysis can be used to drive this reaction. The main distinction between these two types is the possible recovery and recycling of the (solid) catalyst in heterogenous catalysis, potentially reducing the overall conversion costs. Homogeneous acid or base catalysis: Homogeneous acid or base catalysis have the advantage of the catalyst being in constant contact with the reaction mixture leading to increased rates, and is a generally used method for biodiesel production from seed oils. A problem with homogeneous (acid or base) catalysts is that they suffer from the requirement of a neutralisation step to remove the catalyst. Additionally, plant and algal oils can contain free fatty acids (FFAs) at; concentrations of up to 25% 1 9

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(Dunstan et al. 1994). If these are not pre-treated (esterified) then they can react with homogeneous base catalysts during trans-esterification and form the corresponding soaps, leading to downstream separation problems (Huber et al 2006). FFAs may also be formed from water reacting with FAME during storage; FAME fuels have a tendency to hydrolysis or undergo oxidative decomposition and storage of the fuel product must be maximized for longevity (Paligov et al 2008). Project innovations, microalgae-based products: The adoption of a biorefinery approach will increase both the numbers of products and the overall financial return per unit microalgal biomass compared to present processing techniques (e.g., by combining oil extraction for transport fuel with pyrolysis of residue for electricity generation); Biofuel production efficiency will be increased by using microalgal rather than traditional plant biomass, owing to higher areal productivity of microalgae and the ability to utilise the entire biomass; The screening of microalgal biomass fractions for useful chemical compounds and, vitally, as feedstock compounds for the traditional chemical industry will be extended. Pigments, PUFAs and other high value compounds have been identified and may be separated out with the oils suitable for upgrading to fuel and lubricant components (the latter fractions having received relatively little attention to date); The conversion of microalgal lipids to biofuels has been almost exclusively centred around the conversion to fatty acid methyl esters (FAME). A much smaller field is the production of decarboxylated fuel, which unlike FAME may directly replace current road transport and heating fuels. Within the project new solid catalysts will be investigated for the efficient production of both FAME and deoxygenated biofuels; Fractionated materials will be assessed for their suitability in food and feed applications. Efficient heterogeneous (solid) catalysts: Efficient heterogeneous (solid) catalysts offer economic benefits in producing biofuels since, unlike homogeneous catalysts, they are easily separated after trans-esterification, and so can be readily recycled, lowering production costs. The precise protocols have yet to be optimised but advances offer potentially robust and FFA tolerant catalysts for trans-esterification catalysts for microalgae lipid feedstocks.

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B1.3: Contribution to Advancement of Knowledge / Technological ProgressAs reported in the preceding Section, there is unprecedented global interest in cultivated microalgae for biofuels and other applications, coincident with tighter than ever EU regulation of industrial and agricultural emissions to mitigate climate change (GHGs) and maintain high water quality (soluble nutrients). Substantial work has been carried out in the past on specific aspects of effluent bioremediation (gaseous and aqueous) and on microalgae exploitation for different purposes, but the available technologies have not yet been combined or extended in the integrated manner proposed by BioAlgaeSorb for the benefit of diverse groups of SMEs. The BioAlgaeSorb approach will be developed from the existing knowledge base by an expert team of RTD performers in collaboration with well established commercial microalgae technology providers, acting on behalf of European SME AG members in the bioenergy and food production sectors. An integrated knowledge platform will be founded and synergistic links established between currently disparate SME AG sectors and between SME-AGs / RTDs. The main contributions to advancement of knowledge / technological progress will be provided through: Enhanced understanding of requirements for microalgae mass cultivation using industrial and aquacultural/ agricultural effluents as nutrient sources. A novel approach will be developed to ensure that the effluents produced at SME-AG member locations are suitable for microalgae cultivation. Following characterisation of the different effluent streams, pre-treatment processes will be developed for each effluent category, followed by reformulation into a consistent nutrient package for microalgae. This will enable microalgae cultivation systems installed at SME-AG member locations to maintain consistent output despite variations in effluent abundance and composition and will furthermore yield a valuable source of nutrients for other applications such as plant growth. Development of reliable, scalable microalgae production processes tailored to particular effluent sources, guided by a mechanistic modelling approach. In order to capitalise on the remediation potential of microalgae, there is a pressing need to develop scalable biomass production processes for implementation at SMEAG member sites. The importance of this is reflected in the high abundance of scientific literature (often lab scale studies) and patents in the area of microalgae cultivation, contrasting with the relatively low numbers of processes and systems adopted commercially. BioAlgaSorb will be developed from the well proven microalgae production systems provided by participating SMEs. Uniquely, the configuration and management of these systems will be optimised for pre-treated effluents via computer modelling. The approach to be taken is to start with an established mechanistic model of microalgal growth. This model is a dynamic (not steady-state) photoacclimative description of temperature-light-multinutrient limited growth. This type of model is essential to properly consider the cost-benefit implications of the process (for example, to properly include nutrient consumption, self-shading of suspensions etc.). The model is not a crude thermodynamic, Monod or Droop quota model. Rather it is founded on wellgrounded physiological understanding, with feedback interactions describing nutrient transport (N, P, Fe, Si etc; differentiating between N-sources, for example), photosynthesis and photoacclimation (with changes in light and nutrients), respiration, and changing chemical stoichiometry (e.g. with changes in nutrient status). This modelling structure will be employed within BioAlgaeSorb to provide a mechanistic basis for a thorough and transparent analysis for the design, geometries and efficient operation of coupled microalgae photobioreactors and raceways at SME-AG member locations.

Enhanced understanding of microalgae harvesting and stabilisation methods. The harvesting of microalgae cells from dilute solutions (~1-5 kg biomass/m3 process water) poses a considerable technical challenge for large scale cultivation. The costs of current harvesting methods restrict commercial microalgae production to high value applications (eg, production of nutritional supplements PUFA, pigments and vitamins). A number of established harvesting methods exist, but each of these has limitations, eg traditional approaches include dissolved air floatation (DAF) incorporating poly- ionic flocculants (Al, Fe or ionic polymers), centrifuges and flocculation. Most processes add materials to the system that are undesirable and devalue the quality of the material, and/or are reliant on very expensive equipment that is intolerant of saline solutions. BioAlgaeSorb will develop a series of processes that avoid the limitations of other harvesting methods and determ their most approprate usage in relation to various o p e r ngt ienvelop e encountered by SME-AG ine i a s members. These operating envelopes are based upon the physical conditions associated with the process water (chemical and physical characteristics), the microalgae species (structural and physical properties) and the economics of the local operations. The following specific processing methods will be investigated and their potential for cost effective implementation evaluated: electroflocculation (EF); dissolved air flotation (DAF) using ozone as a pre-treatment; microfiltration; centrifugation; hybrid processes (combinations of the above). Once harvested, pre-treatment and preservation procedures (freezing of concentrates and spray drying) will be developed to provide high quality stable materials. Development of efficient processes for microalgae fractionation and biorefining, to yield biofuel and bioenergy substrates, food- and feedstuffs and fine chemicals. The development of an integrated biorefinery for microalgae biomass is a central innovative feature of the BioAlgaeSorb project, designed to maximise the numbers of usable microalgae products and economic return per unit biomass produced. The elements of this biorefinery are shown 2 1

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schematically in Figure 1 (Section 1) and encompass direct thermo-chemical conversion of intact biomass (or biomass residue following oil extraction) to liquid biofuel, physical separation of intact biomass into major fractions (protein, lipid, carbohydrate), upgrading of the lipid fraction into current generation biodiesel (trans-esterification) and into gee n biodiesel (decarboxylation and decarbonylation of r fatty acids), and extraction of specific valuable pigments (phycobiliproteins). This new microalgal biorefinery will provide a series of processing options that can be tailored to the needs of different SME-AG sectors and individual SMEs. The biorefinery will furthermore offer a template for the broader microalgal biotechnology sector internationally, raising the impact of the investment beyond the immediate consortium and providing opportunities to SMEs for licencing, etc. Advancement of knowledge on the economic viability of phyco-remediation technologies for European SMEs. Of crucial importance, the BioAlgaeSorb project will examine the whole life cycle costs of the processes developed, requiring the coupling of a description of the processes themselves with that of an economic model. This will take into account not only the economics of running the new processes, but also the cost/benefit of not having to otherwise handle the previously unremediated effluents. A new coupled technical-economic model will be developed and run under different physical forcings (e.g., meteorological data, waste water stream composition) and also under different economic scenarios (cost of fertilizers, of land, energy, and of the engineering plant). From this analysis will emerge data that will indicate under which conditions the operation of the whole system will be cost negative, positive, or neutral, hence informing the SME-AGs and their members sector on where greatest leverage is to be gained in applying new BioAlgaeSorb technologies.

B1.4: Quality and Effectiveness of S/T Methodology and Associated Work PlanB1.4.1: Overall Strategy of the Work Plan Introduc tion The participating SME AGs and AGs have identified complementary challenges and key areas of opportunity and have recruited an experienced RTD partnership to develop new processes and products on their behalf. The project work plan has been organised into an integrated series of work packages, A thorough scientific and technological foundation will be developed in WP 1 to guide the definition of specifications based on the needs and regulations in the industry and in regions of the EU. Based on the outputs from WP 1, the RTD performers with input from the SME-AGs and SMEs will in WPs 2-5 carry out RTD activities to define system and process specifications and to design & build prototypes, test and optimise and finally validate (WP 6) and implement the process into the industry by various activities including the establishment of demonstration, training and dissemination activities (WP7 & 8). Research and Technological Development Activities The work plan has been structured to exploit the skills of the participating RTD performers, namely SU (microalgae production technologies; mechanistic modelling; bio-process engineering), TI (fluids handling; process control, mechanical enginering, prototype design and manfacture), UDUR (upgrading of biomass lipids to biofuels, in particular via heterogeneous catalysts); HCMR (microalgae production technologies; microalgae-based effluent remediation) and UFL (thermo-chemical biomass conversions [incl pyrolysis]; liquid biofuels). All RTDs will be involved in building up the scientific and technological understanding in

WP1, with assistance from the SME- AGs who will contact their members and facilitate an information flow between SMEs and the RTDs. Preliminary characterisation of different effluent streams will also be performed in WP1 to guide the specific direction of the subsequent WPs. The next 4 WPs will develop technologies for each part of the value chain, involving combined inputs from the RTDs and SMEs. In WP2, HCMR will lead the RTD on microalgae biomass production aided by VAS and Ingrepro; SU will develop biomass harvesting processes for these SMEs in WP3; UDU will lead the development of biomass upgrading methods on behalf of VFT in WP4; and UFL will devise thermo-chemical conversions to biofuels for Sea Marconi in WP5. In WP6 include system integration to ensure focus on the whole value chain from micro-algae production to thermo-chemical conversion to biofuels. WP6 furher include industrial validation/benchmarking, economic evaluations as well as risk assessment and contingecy management of the RTD activities. Demonstration Activities Within WP7, the SME AGs will arrange demonstrations to their members as well as include the broader audience. The participating SMEs will further extend the audience for demonstration activities via their contact networks and existing custumer base. The demonstration will include the business of prototype equipment and processes for microalgae biomass production, harvesting, upgrading and thermo-chemical conversion that have been developed in the preceding WPs and will be coordinated with the running of lab and fulls scale tests of the different systems. 2 2

BioAlgaeSorb 2008-2

Call

FP7-SME-

Other Activities WP8 include Innovation Related Activities and Training. The SME-AGs will play a major role in the dissemination and exploration activities and a primary target for the activities will be their members across Europe. The dissemination channels will be input to publications, promotion and demo CDs, leaflets and other printed material, web based activity, online courses and exhibitions, conferences, seminars, especially towards enduser communities and associations in the relevant industrial sectors and especially the bio-energy sector. The success depends on the industry sector driving the system itself and that the system specifically targets the needs of the ME companies in the relevant sectors. Management Activities Co-ordination between the EC and project consortium ensuring that all milestones, reports, and project financial administration is prepared in accordance with the contractual requirements. Integration of effort between RTD performers and partners. Monitoring that each of the partners and the RTD performers use their own resources effectively through internal project management. Development of a technology implementation plan to aid the dissemination and exploitation process. Prepare Dissemination and Utilization plan (DUP). Ris ks Having undertaken an analysis for each of the project activities, the following risks have been identified and contingency measures put in place to minimise any impacts on delivery of the new BioAlgaeSorb technologies. Table 1.3: Risk Description for the Project Imp Prob act Risk Description ab. (L1 (L1 M2 M2 MANAGEMENTChanges to consortium members or key personnel during Management disagreements among partners TECHNICAL Failure to develop effective methods for microalgae biomass production using pre-treated Failure to provide sufficient samples of microalgae biomass for Failure to develop novel biomass harvesting methods Failure to develop effective novel refinery and upgrading Failure to tailor pyrolysis processes for microalgae Failure to provide effective technical & economic appraisals of new BioAlgaeSorb INNOVATION-RELATED Mediu m Mediu m Mediu m Mediu m

Ris k Sco re4

Preventive ActionsThe consortium has the resources necessary for substitution Conflict resolution processes in place and conveyed from start of project Work plan focuses on effluents, systems and species that are known to fit criteria Selection of partners and technologies with proven track record New harvesting methods developed from proven of partners Selection and technologies with proven track record Pyrolysis methods will be extension of proven technologies Selection of partners and evaluation methods with proven track record i related

SolutionsAppoint new consortium members / assign replacement staff Follow conflict resolution rules and handle the conflict at appropriate level Adjust work plan for the most suitable effluent sources Obtain biomass samples from outside the Adjust work plan towards more conventional Confine the scope of RTD on refinery and upgrading to most Adjust pyrolysis RTD to fewer microalgae species Extend evaluation tasks more broadly within the consortium

4

Low

High

3

Low Mediu m Mediu m Low

High Low Mediu m Mediu m Low

3 3 4 3

High

3

IPR disagreements Ineffective dissemination

Mediu m Low

Mediu m Mediu m

4 3

IPR policy clear within consortium agreement from outset SME AGs suitably resourced for dissemination

Adhere to agreed written procedures Extend dissemination activities more widely within the

B1.4.2: Timing of Work Packages and their Components The timing of Work Packages and their components is summarised in Table 1.4, below.

2 3

BioAlgaeSorb 2008-2 Table 1.4: Timing of Work Packages and Their ComponentsN WP 1 T 1.1 T 1.2 T 1.3 T 1.4 Task Time Scientific Understanding and Advancement of Operational Parameters Physico-chemical Requirements for Optimal Microalgae Production Microalgae Harvesting Processes Microalgae Biomass Conversion Processes Critique of Modelling Approaches for Technical and Economic Evaluations Lea SU SU SU UFL SU D HCM R SU HCM R HCM R T I SU SU SU SU SU SU SU UDU R SU SU UDU R UF L UFL UFL UFL UFL T I T I T I SU T I T I T I T I D D D D 1 2 3 4 5 Year 61 7 D D M 8 9 1 0 1 1 1 2 1 3 1 4 1 5 1 6 1 7 Year 12 1 8 9 2 0 2 1 2 2 2 3 2 4 2 5 2 6 2 7 2 8 2 9

Call FP7-SME-

Year 33 3 0 1

3 2

3 3

3 4

3 5

3 6

WP Optimization of Microalgae Cultivation on Effluents 2 T 2.1 T 2.2 T 2.3 T 2.4 T 2.5 WP 3 T T 3.2 T 3.3 T 3.4 T 3.5 WP 4 T 4.1 T 4.2 T 4.3 WP 5 T T 5.2 T 5.3 T 5.4 WP 6 T 6.1 T 6.2 T 6.3 T 6.4 WP 7 T 7.1 T 7.2 Effluent Characterization, Upstream Processing and Reformulation as Microalgae Nutrients Define Culture Conditions for Selected Microalgae Species Using Pretreated Aqueous and Gaseous Effluents Define Bioreactor and Raceway Operating Conditions for Selected Microalgae Species, Effluent Sourcesof Nutrient Delivery and Optimisation of Transfers in Microalgae Control and Operating Locations Cultivation Systems for Technical Evaluations Modelling Approaches Microalgae Harvesting Technologies Colloidal Characterisation of Selected Microalgae to Facilitate Optimal Optimisation of Conventional Harvesting Technologies in the Context of Microalgae Culturing Systems Concentrates and Their Preservation Characterisation of Microalgae Investigation of Hybrid Harvesting Technologies: Electro-Flocculation Development and Assessment of a Novel Flotation Technique Without the Use of Deleterious Additives Refinery and Upgrading Processes for Microalgae Biomass Disruption of Microalgae Physical Separation / Fractionation Schemes for Fractionation of Disruptates to Produce Stable Materials Conversions Chemical Thermo-chemical Conversions of Microalgae Biomass Design and Construction of a Laboratory Scale Pyrolysis Reactor Installation, System Set-up and Testing Chemical-Physical Characterisation of Products Preliminary Tests for Heat and Power Production System Integration and Industrial Validation System Integration Industrial Validation / Benchmarking Modelling Approaches for Economic Evaluations Risk Assessment and Contingency Management Demonstration Activities Demonstrations to SME Staff Demonstrations to IAG Staff

D

M

D

D

D

M

D M

D

D

D

D

D

24

BioAlgaeSorb 2008-2

Call FP7-SME-

WP 8 T 8.1 T 8.2 T 8.3 T 8.4 WP 9 T T 9.2 T 9.3 T 9.4

Innovation Related Activities / Training Protection of IPR Uptake of Results by Proposers Dissemination of Knowledge / Promotion of Knowledge Training Consortium Management Consortium Management Technical Management IRA Management Organise Meetings

NoB io AEBI OM NoBi o AEBI OM AEBI OM NoB io NoBi NoBi o AEBI OM NoBi o

D

d

d

d

d

D

d

d

d

D

d

D

D D

25

BioAlgaeSorb 2008-2 B1.4.3: Work Package Descriptions Table W P N WP 1 WP 2 WP 3 WP 4 WP 5 WP 6 WP 7 WP 8 WP 9 Table Del iv. No D 1.1 D 1.2 D 2.1 D 2.2 D 2.3 D 2.4 D 2.5 D 2.6 D 3.1 D 3.2 D 3.3 D 3.4 D 4.1 D 4.2 D 4.3 D 4.4 D 4.5 1.3a: Work Package List Work Package Title Scientific Understanding and Advancement of Operational Parameters Optimization of Microalgae Cultivation on EffluentsHarvesting Technologies Microalgae Refinery and Upgrading Processes for Microalgae Biomass Thermo-chemical Conversions of Microalgae Biomassand Industrial System Integration Validation Demonstration Activities Innovation Related Activities / Training Consortium Management TOTAL 1.3b: Deliverables List Deliverable Title Reference document on current technologies for microalgae mass cultivation and biorefinery approaches suitable for BioAlgaeSorb applications Report reviewing existing modelling approaches suitable for technical and economic evaluation of microalgae-based effluent remediation Report on the composition, formulation and costs of effluent-derived microalgae nutrient media and gases the efficacy of pre-treated / reformulated Report on microalgae effluents and gases for microalgae cultivation - /laboratory Report on the efficacy of pre-treated reformulated microalgae effluents and gases for microalgae cultivation - photobioreactor and raceway studies Report on engineering processes for the controlled delivery of microalgae nutrients and efficient mixing and transport of microalgae within cultivation the technical feasibility of the methods Report on systems developed for effluent remediation and microalgae biomass