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DBFZ Report No. 16 Algae Biorefi nery – Material and energy use of algae Ingolf Petrick, Lilli Dombrowski (Hochschule Lausitz (FH) Michael Kröger, Thomas Beckert (DBFZ) Thomas Kuchling, Sven Kureti (TU Bergakademie Freiberg) In Cooperation with: Funded by: Imprint / Approach Leipzig- Leipzig Radefeld Mitte Messegelände TauCha A 14 A 9 Leipzig-Nordost Taucha ThekLa 87 2 GOhLiS ße 6 SChöNefeToLrdgauer StPrearmoserstr.PauNSd6ORf LeipzOisgt- HBF 181 eisenbahnstr. zeNTRuM eNGeLSdORf 87 ReudNiTz GRüNau 2 STöTTeRiTz CONNewiTz Imprint Published by: © Copyright: DBFZ Deutsches Biomasseforschungszentrum gemeinnützige All rights reserved. This brochure may not be reproduced or GmbH, Leipzig, subsidised by the German Federal Ministry of distributed without the written permission of the publisher. Food, Agriculture and Consumer Protection (BMELV) based on This prohibition also refers in particular to the production of a decision of the German Bundestag copies for commercial purposes, the entering of contents into electronic databases and the copying on CD-ROM Responsible person under German Publishing Law: Paul Trainer authors: Ingolf Petrick, Lilli Dombrowski (Hochschule Lausitz (FH), Michael Kröger, Thomas Beckert (DBFZ), Thomas Kuchling, Sven Kureti (TU Bergakademie Freiberg) Contact: DBFZ Deutsches Biomasseforschungszentrum date of publication: gemeinnützige GmbH July 2013 Torgauer Straße 116 04347 Leipzig Phone: +49 (0)341 2434 - 112 Approach Fax: +49 (0)341 2434 - 133 [email protected] ... by train www.dbfz.de After arriving at Leipzig main station, take the tram line 3/3E (towards Taucha/Sommerfeld) until stop „Bautzner Strasse“. General Management: Cross the street, pass the parking-place and enter the gate to Prof. Dr. mont. Michael Nelles Torgauer Str. 116. Turn left after 100 meters. (Scientific Managing Manager) Daniel Mayer ... by car (Administrative Managing Manager) Leave highway „A 14“ at exit Leipzig Nord-Ost, Taucha. Drive towards „Leipzig-Centre“. After about 2 km you will see a „bft“- dBfz Report No. 16 petrol-station, after which you should turn left and enter the iSSN: 2190-7943 DBFZ-area (then follow the instruction as „by train“). Pictures: DBFZ, Title: Maja Dumat/pixelio.de (left), jutta wieland/ pixelio.de (right) … by tram Printing: Fischer druck&medien tram line 3/3E towards Taucha/Sommerfeld; Stop „Bautzner Straße“ (see „by train“) DBFZ, Leipzig 2013 Algae biorefinery - material and energy use of algae Report No. 16 Ingolf Petrick, Lilli Dombrowski (Hochschule Lausitz (FH)) Michael Kröger, Thomas Beckert (DBFZ) Thomas Kuchling, Sven Kureti (TU Bergakademie Freiberg) DBFZ Deutsches Biomasseforschungszentrum gemeinnützige GmbH Torgauer Straße 116 04347 Leipzig Tel.: +49 (0)341 2434-112 Fax: +49 (0)341 2434-133 www.dbfz.de [email protected] Ingolf Petrick Lilli Dombrowski Michael Kröger Thomas Beckert Thomas Kuchling Sven Kureti Auftraggeber oder Vattenfall Europe Generation AG Zuwendungsgeber Asset Development / R&D Projects (bei Forschungsförderung) Thermal & Biomass Technology Hermann-Löns-Straße 33 03050 Cottbus, Germany Ansprechpartner: DBFZ Deutsches Biomasseforschungszentrum gemeinnützige GmbH Torgauer Straße 116 04347 Leipzig Tel.: +49 (0)341 2434-112 Fax: +49 (0)341 2434-133 E-Mail: [email protected] Internet: www.dbfz.de Michael Kröger Tel.: +49 (0)341 2434-432 E-Mail: [email protected] Thomas Beckert Tel.: +49 (0)341 2434-575 E-Mail: [email protected] Erstelldatum: 03.05.2013 Projektnummer DBFZ: P3410009 Gesamtseitenzahl + Anlagen 164 III Algae biorefinery - material and energy use of algae Table of contents 1 Introduction ......................................................................................................................................................... 3 2 Algae production and species used .................................................................................................................. 4 3 Dewatering and drying ....................................................................................................................................... 7 3.1 Introduction ................................................................................................................................................................. 7 3.2 Dewatering ................................................................................................................................................................... 7 3.2.1 Gravity sedimentation .............................................................................................................................. 8 3.2.2 Filtration ..................................................................................................................................................... 8 3.2.1 Flotation...................................................................................................................................................... 8 3.2.1 Centrifugation ............................................................................................................................................ 9 3.2.1 Dewatering aids ..................................................................................................................................... 10 3.3 Drying ......................................................................................................................................................................... 12 3.3.1 Drying by solar energy ........................................................................................................................... 12 3.3.1 Flash dryers ............................................................................................................................................. 13 3.3.1 Spray dryers ............................................................................................................................................ 13 3.3.1 Drum dryers ............................................................................................................................................ 14 3.3.1 Conveyor dryers ...................................................................................................................................... 14 3.3.1 Freeze dryers........................................................................................................................................... 16 3.4 Assessment .............................................................................................................................................................. 16 3.4.1 Dewatering .............................................................................................................................................. 16 3.4.2 Drying ....................................................................................................................................................... 18 3.5 Manufacturers .......................................................................................................................................................... 19 4 Cell decomposition and extraction .................................................................................................................. 20 4.1 Introduction .............................................................................................................................................................. 20 4.2 Cell decomposition .................................................................................................................................................. 21 4.3 Solvent extraction .................................................................................................................................................... 29 4.4 Supercritical fluid extraction .................................................................................................................................. 33 4.5 Recovery of other compounds ............................................................................................................................... 36 5 Hydrothermal liquefaction (HTL) ..................................................................................................................... 37 5.1 Introduction .............................................................................................................................................................. 37 5.2 State of the art of hydrothermal liquefaction ..................................................................................................... 38 5.3 Hydrothermal liquefaction with algae .................................................................................................................. 43 5.4 Pilot and demonstration plants ............................................................................................................................. 46 5.5 Preliminary HTL experiments................................................................................................................................. 50 6 Hydrothermal carbonisation (HTC) .................................................................................................................. 53 6.1 HTC literature research ........................................................................................................................................... 53 6.1.1 Method ..................................................................................................................................................... 53 6.1.2 Products................................................................................................................................................... 54 6.1.3 HTC coal from micro-algae ................................................................................................................... 55 IV Table of contents 6.1.4 HTC market overview ............................................................................................................................. 56 6.2 Preliminary HTC experiments ................................................................................................................................ 56 6.2.1 Objective .................................................................................................................................................. 56 6.2.2 Material and methods ........................................................................................................................... 56 6.2.3 Results ..................................................................................................................................................... 58 7 Motor fuel production processes ..................................................................................................................... 62 7.1 Fuel requirements .................................................................................................................................................... 62 7.2 Transesterification ................................................................................................................................................... 64 7.3 Pyrolysis / Cracking ................................................................................................................................................. 68 7.4 Hydrocracking ........................................................................................................................................................... 72 7.5 Hydrogenation .......................................................................................................................................................... 73 7.6 Gasification ............................................................................................................................................................... 77 8 Biogas production ............................................................................................................................................. 79 8.1 Introduction ............................................................................................................................................................... 79 8.2 Overview of biogas production ............................................................................................................................... 79 8.3 Suitability of micro-algae for biogas production ................................................................................................. 81 8.4 Yield prediction ......................................................................................................................................................... 83 8.5 Recovery paths ......................................................................................................................................................... 84 8.5.1 Digestion of the complete algal biomass ........................................................................................... 85 8.5.2 Digestion of individual fractions .......................................................................................................... 86 8.5.3 Linkage with biogas cleaning ............................................................................................................... 86 8.6 Summary ................................................................................................................................................................... 87 9 Algae as animal feed ....................................................................................................................................... 88 9.1 Poultry ........................................................................................................................................................................ 88 9.2 Pigs ............................................................................................................................................................................. 89 9.3 Aquaculture ............................................................................................................................................................... 89 9.4 Legal aspects ............................................................................................................................................................ 91 10 Assessment of product lines ........................................................................................................................... 92 10.1 Fundamentals........................................................................................................................................................... 92 10.1.1 Aims of the assessment ........................................................................................................................ 92 10.1.2 System constraints ................................................................................................................................ 92 10.2 Process chains .......................................................................................................................................................... 94 10.2.1 Base case ................................................................................................................................................ 96 10.2.2 Biogas path ............................................................................................................................................. 97 10.2.3 HTC path .................................................................................................................................................. 99 10.2.4 HTL path .................................................................................................................................................101 10.2.5 Direct hydrogenation ...........................................................................................................................103 10.3 Assessment and comparison of product lines ..................................................................................................110 10.3.1 Base case: Production of biodiesel ...................................................................................................112 10.3.2 Biogas path: ..........................................................................................................................................112 10.3.3 HTC path ................................................................................................................................................113 V Algae biorefinery - material and energy use of algae 10.3.4 HTL path ................................................................................................................................................ 113 10.3.5 Direct hydrogenation ........................................................................................................................... 114 11 Summary ......................................................................................................................................................... 115 Appendix ........................................................................................................................................................................ 117 Overview of HTL .................................................................................................................................................................... 117 Overview of transesterification ........................................................................................................................................... 122 Hydrocracking and hydrogenation ..................................................................................................................................... 124 Overview of pyrolysis ............................................................................................................................................................ 125 Algae data sheets ................................................................................................................................................................. 127 Base data of assessment .................................................................................................................................................... 132 Literature references .................................................................................................................................................... 133 VI List of abbreviations List of abbreviations AA Arachidonic acid BOD Biological Oxygen Demand COD Chemical Oxygen Demand CED Cumulative Energy Demand DHA Docosahexaenoic acid EPA Eicosapentaenoic acid FAME Fatty Acid Methyl Ester FCC Fluid Catalytic Cracking FPA-PBR Flat Plate Airlift Photobioreactor FA Fatty Acid(s) GLA γ-linolenic acid HHV Higher Heating Value HMF Hydroxymethylfurfural HRT Hydraulic Retention Time HTC Hydrothermal Carbonisation HTL Hydrothermal Liquefaction HVP High Value Product IRR Internal Rate of Return wt.% weight percent MSW Municipal Solid Waste PBR Photobioreactor p Critical pressure c PUFA Polyunsaturated Fatty Acid(s) RON Research Octane Number sc-CO Supercritical CO 2 2 SFE Supercritical Fluid Extraction TAG Triacylglycerol(s) T Critical temperature c VII Algae biorefinery - material and energy use of algae dm Dry matter Vol.% Percent by volume VS Volatile Solids ρ Critical density c VIII List of tables List of tables Table 3.1 Coagulants compared ................................................................................................................... 12 Table 3.2 Assessment of the dewatering methods ...................................................................................... 17 Table 3.3 Assessment of drying methods..................................................................................................... 18 Table 3.4 Manufacturers of drying/dewatering plants ................................................................................ 19 Table 4.1 Coarse chemical composition of selected alga species (% of dry matter) (Becker 1994) ....... 21 Table 4.2 Selected decomposition and extraction methods for algae ....................................................... 23 Table 4.3. Comparison of various extraction and conversion methods to generate 10,000 MJ of biodiesel (Brentner 2011) ....................................................................................................... 28 Table 4.4 Hydrocarbon yields and photosynthesis activity following extraction (Frenz et al. 1989) ........ 32 Table 4.5 Comparison of supercritical CO and conventional solvent extraction (Hosikian et al. 2 2010; Mercer and Armenta 2011) ......................................................................................... 33 Table 4.6 Physical-chemical data of some gases used for extraction (Stahl et al. 1987) ........................ 34 Table 4.7 Examples of studies on supercritical extraction of micro-algae with different extraction agents ....................................................................................................................................... 35 Table 5.1 Water properties under selected conditions (adapted according to Toor et al. 2011) ............ 37 Table 5.2 Possible degradation products of glucose/fructose under hydrothermal conditions ............... 42 Table 5.3 Results of hydrothermal treatment of various biomasses .......................................................... 42 Table 5.4 Oil yield and energy consumption rate of oil production in hydrothermal liquefaction of micro-algae (Tsukahara and Sawayama 2005) ..................................................................... 44 Table 5.5 Overview of the hydrothermal liquefaction of various micro-algae ............................................ 45 Table 5.6 Overview of the elemental composition and calorific value of the bio-oil HTL .......................... 46 Table 5.7 Overview of HTL processes in pilot plants (Toor et al. 2011) ..................................................... 47 Table 6.1. Overview of HTC process developers in Germany ...................................................................... 56 Table 6.2 Analysis methods ........................................................................................................................... 58 Table 6.3 Analysis results for the solid matter before and after hydrothermal treatment ........................ 58 Table 6.4 Analysis of the liquid products ...................................................................................................... 60 Table 7.1 Requirements for motor fuels and typical composition (ARAL 1995; ARAL 2000) ................... 62 Table 7.2 Lipid contents of some alga species (Demirbas 2010) .............................................................. 64 Table 7.3 Composition of the biodiesel (Li et al. 2007) .............................................................................. 66 Table 7.4 Comparison of speed constants in 10-2 l/(mol min) with and without ultrasound assistance (Gole and Gogate 2012) ...................................................................................... 67 Table 7.5 Overview of pyrolysis conditions and product yields (Brennan and Owende 2010) ................. 69 Table 7.6 Composition of fast pyrolysis oil from algae (Miao et al. 2004) ................................................. 69 Table 7.7. Results of catalytic cracking of oil of the alga Botryococcus braunii compared to FCC of a heavy crude oil fraction (Kitazato et al. 1989) ................................................................... 71 Table 7.8 Composition of the micro-alga Chlorella pyrenoidosa (wt.%) (Chin 1979) ................................ 75 Table 7.9 Product distribution and elemental composition of products in hydrogenation of algae (wt.%) (according to Chin 1979) ............................................................................................. 76 IX

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Spirulina platensis. 46-63. 8-14. 4-9. Free fatty acids (FAs) and triglycerols (TAGs) can be separated from the algal biomass by a wide variety of methods (Amin 2009). Ikenaga, Na-oki; Ueda, Chiyo; Matsui, Takao; Ohtsuki, Munetaka; Suzuki, Toshimitsu (2001): Co- liquefaction of Micro Algae with
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