Mass balance of algae biomass treatment with ionic liquids

Transcription

1 Mass balance of algae biomass treatment with ionic liquids Ricardo Pezoa Conte Supervisor: Jyri-Pekka Mikkola Päivi Mäki-Arvela OPTIFU Monosaccharides Microorganisms Bioethanol 1 Summer Course - Saaremaa, Estonia

2 Millions of years of evolution 0.2 4,500 3,600 3,400 2,000 1, Formation of Earth Prokaryote cells Cyanobacteria performing photosynthesis Eukaryote cells Multicellular Life (algae) millions of years Simple animals Land plants Mammals Primates Homo sapiens 2 Summer Course - Saaremaa, Estonia Today

3 Cyanobacteria Cyanobacteria are prokaryotic organisms. They use photosynthesis to produce oxygen from water and take carbon dioxide to produce carbohydrates. Sun light is caught by pigments such as phycocyanin, which gives them their bluish color. 3 Summer Course - Saaremaa, Estonia

4 New atmosphere Prokaryote organisms are mainly anaerobic, thus they do not require oxygen to live. New atmosphere rich in oxygen, due to photosynthetic organisms, led the formation of more evolved and complex microorganisms known as eukaryotic. 4 Summer Course - Saaremaa, Estonia

5 Eukaryotic domain Prokaryotic domain 5 Summer Course - Saaremaa, Estonia

6 Eukaryotic domain Algae 6 Summer Course - Saaremaa, Estonia Cyanobacteria

7 Algae They use sunlight to capture inorganic and organic carbon and store it as food source via photosynthesis. Approximately 50 % of biomass is believed to be grown up in marine environments. Algae has a high production rate between dry ton/ha/year, meanwhile forest biomass is between dry ton/ha/year 7 Summer Course - Saaremaa, Estonia

8 Algal subdivision Microalgae Most of them are unicellular. Reach in lipids, protein and carbohydrates. Macroalgae They are more like plants on earth Carbohydrates content is up to 70 %. Seaweed Peter 8 Summer Course - Saaremaa, Estonia

9 Macroalgae Green algae Brown algae Red algae 9 Summer Course - Saaremaa, Estonia

10 Carbohydrates in algae Brown algae Laminarin Mannitol Alginate Fucoidin Cellulose Red algae Carrageenan Agar Cellulose Lignin Green algae Starch Cellulose Sulphated polysaccharides Containing: Gluc. acid Arabogalactans 10 Summer Course - Saaremaa, Estonia

11 Aim of this work Use photo-chemo and enzymatic processes in order to obtain bioethanol from agae. Investigate new processes to obtain different products from algae under a biorefinery concept. 11 Summer Course - Saaremaa, Estonia

12 Algae used in this work Macrocystis pyrifera Brown algae Main carbohydrate: alginate Biomass yield: 50 dry ton/ha/year Ulva rigida Green algae Main monosaccharide: glucose Biomass yield: 23 dry ton/ha/year 12 Summer Course - Saaremaa, Estonia

13 Macrocystis pyrifera La Chiloé Herradura Islands Bay 13 Summer Course - Saaremaa, Estonia

14 Ulva rigida La Herradura Bay 14 Summer Course - Saaremaa, Estonia

15 World production in 2006 of wild stock harvested and cultured algae Harvest of wild stock Aquaculture Source Production Production % of total Source [wet Mton] [wet Mton] % of total World total 1,143, World total 15,075, China 323, China 10,867, Chile 305, Philippines 1,468, Norway 145, Indonesia 910, Japan 113, South Korea 765, Russian Federation 65, Japan 490, Ireland 29, North Korea 444, Mexico 27, Chile 33, Iceland 20, Malaysia 30, France 19, Vietnam 30, Australia 15, Cambodia 16, Morocco 14, Taiwan 5, South Korea 13, India 4, Canada 11, Kiribati 3, Indonesia 9, South Africa 3, South Africa 6, South Africa United States 6, Russian Federation Madagascar 5, Tanzania Peru 3, Solomon Islands Italy 1, Fiji Islands Ukraine 1, Mali Others 3, Others Summer Course - Saaremaa, Estonia Roesijadi, G. et al. Macroalgae as a Biomass Feedstock: A Preliminary Analisis. US Department of Energy, September 2010

16 World wide farmed seaweed production in 2004 Taxa Common name Wet metric tons Laminaria japonica Japanese kelp 4,519,701 Plantae aquaticae Aquatic plant 2,605,107 Undaria pinnatifida Ealkame 2,519,880 Porphyra tenera Laver (Nori) 1,397,660 Eucheuma spp. Eucheuma seaweeds 1,264,438 Gracilaria spp. Gracilaria seaweeds 948,292 Rhodophyceae Red seaweeds 410,570 Sargassum fusiforme Fusiform sargassum 131,680 Kappaphycus alvarezii Elkhorn sea moss 44,906 Phaeophyceae Brown seaweeds 23,030 Monostroma nitidum Green laver 11,514 Caulera spp. Caulerpa seaweeds 4,252 Enteromorpha prolifera Dark green nori 3,280 Gelidium amansii Japanese isinglass 1,150 Asparagopsis spp. Harpoon seaweeds 12 Total 13,885, Summer Course - Saaremaa, Estonia Roesijadi, G. et al. Macroalgae as a Biomass Feedstock: A Preliminary Analisis. US Department of Energy, September 2010

17 Wet algae, metric tonnes Brown algae Brown algae production in Chile Phaeophyta Lesonia spp. Macrocystis spp. Durvillaea antarctica 17 Summer Course - Saaremaa, Estonia Buschmann, A.H. et al. Int. J. Environment and Pollution, Vol. 33, No. 4, 2008

18 Wet algae, metric tonnes Macrocystis pyrifera landings Macrocystis pyrifera landings Macrocystis spp. Macrocystis for alginate 18 Summer Course - Saaremaa, Estonia Buschmann, A.H. et al. Int. J. Environment and Pollution, Vol. 33, No. 4, 2008

19 Commercial uses Macrocystis pyrifera Alginate for use in human food and as aditives. Feed for abalon cultures (seafood). For bioremediation New products Organic fertiliziers. Compounds with health activity, such us anticoagulant and antiinflamatory. Bioethanol Ulva rigida Food in Asia. New products Formation of gels Bioethanol 19 Summer Course - Saaremaa, Estonia

20 Experimental Summer Course - Saaremaa, Estonia 20

21 Experiments Dilute acid hydrolysis treatment Reagent Acid Water H 2 SO % v/v distilled water Biomass loading 10 % w/w Temperature 125 C Pressure Time Samples 1.5 atm 60 min duplicate 21 Summer Course - Saaremaa, Estonia

22 Experiments 22 Ionic liquids treatment Reagent SIL DBU/MEA/SO 2 IL TMG-CO2Et Biomass loading 10,% w/w Temperature C Pressure Stirring Time Samples Summer Course - Saaremaa, Estonia atmospheric magnetic 6 20 h duplicate TMG : 1,1,3,3-tetramethylguanidine CO 2 Et : propionic acid

23 Methodology for ILs Fresh algae Ionic liquid Ethanol Freeze drying IL treatment Filtration Evaporation Precipitation Washing (DI water) Filtration & Washing Remaining mass Precip. Mass from IL IL + EtOH Carbohydrates anylizes by acid methanolysis and acid hydrolysis methods 23 Summer Course - Saaremaa, Estonia

24 Methodology for ILs Fresh algae Ionic liquid Ethanol Freeze drying IL treatment Filtration Washing (DI water) Evaporation Precipitation Filtration & Washing Remaining mass Precip. Mass DI water Remaining IL + EtOH Carbohydrates anylizes by acid methanolysis and acid hydrolysis methods 24 Summer Course - Saaremaa, Estonia

25 Methodology for ILs Fresh algae Ionic liquid Ethanol Freeze drying IL treatment Filtration Evaporation Precipitation Washing (DI water) Evaporation Precipitation Filtration & Washing Filtration & Washing Remaining mass Precip. Mass DI water Remaining IL + EtOH Precip. Mass from IL IL + EtOH Carbohydrates anylizes by acid methanolysis and acid hydrolysis methods 25 Summer Course - Saaremaa, Estonia

26 Methods Acid methanolysis for determination of hemicelluloses, pectins and alginate. Acid hydrolysis for determination of cellulose. FTIR for qualitative analyzis of relevant picks. TEM pictures of treated and untreated samples. 26 Summer Course - Saaremaa, Estonia

27 Results Summer Course - Saaremaa, Estonia 27

28 Proximal analysis Proximal analysis (Macrocystis pyrifera) Proximal analysis (Ulva rigida) 10,18 7,30 3,77 10,01 42,61 46,42 18,09 1,03 36,16 Humidity Protein Ash Fatty material Carborhydrates¹ 5,36 19,06 Humidity Lipid Ash Protein Insoluble Fiber Carborhydrates 28 Summer Course - Saaremaa, Estonia

29 Carbohydrates in M. pyrifera Res (std) Fuc (2) Alg (5) Alg (6) Mnt (1) Monosaccharides Alg : alginic acid Fru : fructose Fuc : fucose Gal : galactose GlA : glucuronic acid Glu : glucose Mnt : mannitol Rha : rhamnose Xyl : xylose Standard (std) Res : resorcinol Sor : sorbitol Mnt (3) Sor (std) Rha (1) Fuc (1) Alg (1) Fuc (3) Fuc (4) Xyl (1) Xyl (2) Alg (2) GlA (1) Alg (3) Alg (7) Alg (8) Fru (1) Gal (1) Alg (9) Gal (3) Gal (2) Mnt (2) Alg Gal (10) (4) Glu (1) GlA (2) Glu (2) 29 Summer Course - Saaremaa, Estonia Time [min]

30 Carbohydrates in M. pyrifera Component (mg/g of dry algae) Macrocystis pyrifera Alginic acid ± 4.03 Arabinose 0.15 ± 0.02 Fucose ± 0.95 Galactose ± 0.13 Galacturonic Acid 0.34 ± 0.02 Glucose ± 7.85 from acid hydrolysis ± 7.85 from acid methanolysis ± 1.43 Glucuronic Acid 9.03 ± 0.18 Fructose 6.61 ± 0.01 Mannose < 0,1 Mannitol ± 2.12 Rhamnose 0.50 ± 0.02 Xylose 2.80 ± 0.01 AVG ± STD Difference in glucose amount reported for these two methods suggests some cellulose content in this alga. 1 acid hydrolysis method is meant to release all glucose in biomass, included from cellulose. 2 acid methanolysis method method is meant to atack hemicelluloses and pectins, leaving free cellulos e fra ction. 30 Summer Course - Saaremaa, Estonia

31 Carbohydrates in U. rigida Monosaccharides Glu (1) Gal : galactose GlA : glucuronic acid Glu : glucose Rha (1) Rha : rhamnose Xyl : xylose Standard (std) Res : resorcinol Sor : sorbitol Glu (2) Res (std) Xyl (1) Xyl (4) Xyl (3) Rha (2) Xyl (2) GlA (1) Gal (1) Gal (2) Gal (3) Gal (4) GlA (3) GlA (2) Sor (std) 31 Summer Course - Saaremaa, Estonia Time [min]

32 Carbohydrates in U. rigida Component (mg/g of dry algae) Ulva rigida Alginic acid ± 6.11 Arabinose 0.69 ± 0.03 Fucose < 0,1 Galactose ± 0.14 Galacturonic Acid 1.38 ± 1.50 Glucose 182,75 ± 7,76 from acid hydrolysis 1 182,75 ± 7,76 from acid methanolysis 184,22 ± 1,09 Glucuronic Acid ± 0.88 Fructose 1.36 ± 0.10 Mannitol 0.93 ± 0.77 Rhamnose ± 2.46 Xylose ± 1.06 No difference in glucose amount reported for these two methods suggest there is no cellulose content in this alga. AVG ± STD 1 acid hydrolysis method is meant to release all glucose in biomass, included from cellulose. 1 acid methanolysis method method is meant to atack hemicelluloses and pectins, leaving free cellulose fraction. 32 Summer Course - Saaremaa, Estonia

33 Carbohydrate content in Algae Monosaccharides content [mg/g dry algae] 300 Carbohydrate content of algae Alginic acid Fucose Galactose Glucose Glucuronic Acid Monosaccharides Fructose Mannitol Rhamnose Xylose Summer Course - Saaremaa, Estonia Macrocystis pyrifera Ulva rigida 33

34 Sugars in algae(released) [mg/g dry algae] Dilute sulfuric acid treatment U. rigida Monosaccharides obtained for Ulva rigida 125 C - 1,5 atm - 60 min - 5 % w/w Summer Course - Saaremaa, Estonia 0 Alginic acid Galactose Glucose Glucuronic Acid Rhamnose Xylose Monomers Fresh algae Liquid phase Distilled water 125 C - 1 h Liquid phase Acid 1 % v/v 125 C - 1 h 34

35 Sugars [mg/g of dried algae] Mass after treatment [%] IL treatments M. pyrifera Macrocystis pyrifera SIL2 treatments - 20 h - 10 % w/w Cellulose content analysis by acid hydrolysis method has not been performed to treated samples, so glucose content migh be higher than those here presented for treated samples. Values for treated algae have been corrected to their respective wheight after treatment Summer Course - Saaremaa, Estonia 0 Alginic acid Fucose Galactose Glucose Glucuronic Acid Fructose Mannitol Mass Monosaccharides / Mass 0 fresh algae solid residue 100 C solid residue 130 C 35 35

36 Sugars [mg/g of dried algae] Mass after treatment [%] SIL2 treatments U. rigida Ulva rigida SIL2 treatments - 20 h - 10 % w/w Values for treated algae have been corrected to their respective wheight after treatment Summer Course - Saaremaa, Estonia Alginic acid Galactose Glucose Glucuronic Acid Rhamnose Xylose Mass Monosaccharides 0 fresh algae solid residue 100 C solid residue 130 C 36 36

37 Methodology for ILs Fresh algae Ionic liquid Ethanol Freeze drying IL treatment Filtration Evaporation Precipitation Washing (DI water) Evaporation Precipitation Filtration & Washing Filtration & Washing Remaining mass Precip. Mass DI water Remaining IL + EtOH Precip. Mass from IL IL + EtOH Carbohydrates anylizes by acid methanolysis and acid hydrolysis methods 37 Summer Course - Saaremaa, Estonia

38 Methodology for ILs Fresh algae Ionic liquid Ethanol Freeze drying IL treatment Filtration Evaporation Precipitation Washing (DI water) Evaporation Precipitation Filtration & Washing Filtration & Washing Remaining mass Precip. Mass DI water Remaining IL + EtOH Precip. Mass from IL IL + EtOH Carbohydrates anylizes by acid methanolysis and acid hydrolysis methods 38 Summer Course - Saaremaa, Estonia

39 Untreated algae Treated algae Precipitated from wash water Precipitated from IL 39 Summer Course - Saaremaa, Estonia

40 Results mass balance 40 Summer Course - Saaremaa, Estonia

41 FTIR FTIR U. rigida - treated amd untreated biomass Untreated Treated at 100 C Treated at 120 C 41 Summer Course - Saaremaa, Estonia

42 FTIR FTIR U. rigida C Untreated Remaining mass Precipitated from IL 42 Summer Course - Saaremaa, Estonia

43 Conclusions 43 Summer Course - Saaremaa, Estonia

44 Conclusions Algae have high potential for biofuels production, due to high presence of carbohydrates, which can also lead to obtaining byproducts under a biorefinery concept. M. pyrifera has high content of alginic acid which results a challenge how to obtain this carbohydrate for the food industry and even use remaining sugars for bioethanol production. U. rigida has a high content of glucose (18 %), probably coming from starch. Also it has high amounts of rhamnose (9 %) and xylose (6 %) which can lead bioethanol production or e.g. production of polyols (sugar hydrogenation). 44 Summer Course - Saaremaa, Estonia

45 Conclusions Sulfuric acid treatment for U. rigida shows high hydrolysis of carbohydrates. Furfural compounds must be quantified in order to see how techno-economically feasible this treatment really is. Mass have been obtain for Ils treatments for U. rigida. Nevertheless characterization of products, principally remaining biomass and precipitated mass from Ils must be performed. 45 Summer Course - Saaremaa, Estonia

46 Acknowledgements This works is part of the project Optimal production of bioethanol from macroalgae via photo-chemo-enzymatic processing OPTIFU. Akademi of Finland AKA and Comisión Nacional de Investigación, Ciencia y Tecnología de Chile CONICYT are greatfully acknowledged for funding this project. 46 Summer Course - Saaremaa, Estonia

47 47 Summer Course - Saaremaa, Estonia