Session XIII: Biofuels & Biobased Products Sustainability assessment for the production of bio ‐ based products using by ‐ product streams derived from the pulp and paper industry Anestis Vlysidis, D. Ladakis, M. Alexandri, I. Kookos, A. Koutinas Department of Food Science and Human Nutrition Agricultural University of Athens Greece 23 rd – 25 th June 2016 Limassol, Cyprus Agricultural University of Athens, Greece
Our Research Group Biorefinery development based on renewable resources Industrial wastes and by ‐ Agricultural crops and residues Food waste and by ‐ products product streams Valorisation of renewable resources White biotechnology Bioprocess / biorefinery engineering Biorefinery Bioprocess / biorefinery design development Β ioprocess optimisation Antioxidants Chemicals Biopolymers Food Added ‐ value products Feed Biomaterials Biofuels Heat Agricultural University of Athens, Greece
Fermentation cases of Agricultural wastes integrated in biorefinery schemes A.A. Koutinas, Chem. Soc. Rev. , 2014,43, 2587 ‐ 2627 Agricultural University of Athens, Greece
The BRIGIT Project: Valorising SSL from pulp and paper mills Phenolic Extract LS Fermentation SSL N 2 Ultrafiltration Phenolic Extraction with Ethyl acetate Bioprocess optimisation Techno-economic evaluation Life Cycle Analysis Fireproof biopolymers Succinic acid production Polybutylene Succinic acid Separation succinate and Purification Agricultural University of Athens, Greece
SSL Production in Pulp and Paper Industry SO 2 WOOD CHIPS COOKING SSL Characterisation RECOVERY CHEMICALS SO 2 /MeHSO 3 Value St Dev (Me: Ca, Mg, Na, NH 4 ) pH 2.7 BLOW Density (g/mL) 1.277 0.007 TANK Viscosity (cP) 552 167 Dry Matter (g-DM/L) 816.5 0.6 +NaOH Plasticizers for concrete Current uses Lignosulphonates (g/L) 458.8 2.7 +Ca(OH) 2 WATER production among others Ash % (g/g-DM) 8.62 0.55 Phenolics % (g/g-DM) 1.55 0.04 DIGESTER WASHER Sugars are destroyed during precipitation after the addition of Carbohydrates (g/L) 176.41 calcium or sodium hydroxide THIN LIQUOR Xylose (g/L) 128.08 0.59 CELLULOSE Galactose (g/L) 21.47 5.50 FIBRES Glucose (g/L) 19.27 0.39 Mannose (g/L) 7.41 1.30 1 2 3 4 5 6 7 Arabinose (g/L) 0.18 0.05 SSL Acetic Acid (g/L) 6.91 0.49 THICK LIQUOR MULTIPLE EVAPORATION PROCESSES Agricultural University of Athens, Greece
Worldwide production quantity of bleached sulphite pulp in the last decade Global annual production of bleached sulphite pulp: 3,570,476 t/yr (FAO, 2012) 14% increase since 2009 − Annual production in United States of America: 989,074 t/yr (FAO, 2012) 21% increase since 2009 − Annual production in South America: 211,000 t/yr (FAO, 2012) 74% increase since 2009 − Annual production in European region: 2,056,902 t/yr (FAO,2012) 0,01% increase since 2009 Agricultural University of Athens, Greece
Formation of Sugars & Inhibitors During the Process Lignosulphonates Lignin Phenolic compounds Cellulose glucose Levulinic acid galactose 5 ‐ HMF mannose Hemicellulose xylose Formic acid arabinose Furfural Acetic acid Agricultural University of Athens, Greece
Detoxification / Pretreatment and fermentation of SSL SSL N 2 Ultrafiltration Phenolic Extraction with Ethyl acetate 45 0.63 g ‐ SA/g yield 40 Low by ‐ product 35 Concentration (g/L) 30 Total sugars formation 25 SA productivity Succinic acid Fermentations 20 A. succinogenes 0.31 g/L/h (0.5 15 B. succiniciproducens g/L/h @ 50 h) 10 ~ 40 g/L final SA 5 0 0 20 40 60 80 100 120 140 Time (h) Agricultural University of Athens, Greece
Process Design of the SA production & purification of SA from SSL lps (160 o C) Small scale plant Sterilization Inoculum 130 o C 140 o C Mixing tank Inoculum Annual Capacity of SSL: 15 kt Reactor V-103 Hourly rate of 2.14 t/h 20 o C E-104 E-105 Water II TSB R-102 140 o C 3 E-106 Medium Mixing tank V-102 A-101 20 o C Concentrated Detox 2 SSL from WP2 37 o C Fermentor lps (160 o C) R-101 4 Medium 72.9 o C Sterilization Mixing tank 1 130 o C 140 o C V-101 20 o C CO 2 37 o C Water I E-101 E-102 P-101 (Yeast Extr.) To Area 200 140 o C C-101 CO 2 compressor E-103 Agricultural University of Athens, Greece
Process Design of the SA production & purification of SA from SSL (cont’) 6 7 AREA 3 ‐ Phase Wastes 100 2 ktons of SA / year Evaporator AC-201 4 IER-201 F-201 Hourly rate: 300 kg/h V-202 E-201 130 o C 37 o C 5 Biomass residues CR-201 9 8 SD-201 Air E-202 Succinic Acid Air Crystals compressor Fluidized bed C-102 Dryer Agricultural University of Athens, Greece
Using process simulation software UNISIM Simulation of SA production & purification Triple effect Evaporator Spray drier Crystallizer Fermentation Activated carbon Resins Cell mass removal Downstream • Combine hot and cold stream Heat Integration • Energy minimization • 65% less consumption of steam Agricultural University of Athens, Greece
Techno ‐ economic evaluation of SA bioprocess • C BM = M$ 9.7 Development of the Process Flow Diagrams • 47% Triple effect evaporator • 37% the three fermenter Sizing of the equipment and we find • Together with their agitators their characteristic values • FCI = M$ 15.6 • Utility Cost was remarkable Calculation of the equipment cost through empirical costing equations • High requirements for steam • M$ 0.85 per year Conversion to 2015 prices by using the CEPCI The Total Production Cost: (CHEMICAL ENGINEERING PLANT COST INDEX) 0 . 18 2 . 73 1 . 23 TPC FCI C C C C woD OL RM UT WT Calculation of the installation cost TPC = M$ 11.1 per year (C BM ) via installation factors F BM 5.39 $/kg ‐ SA produced Current prices: Calculation of the fixed capital 2.94 for biobased SA * investment FCI=1.6*C BM 2.5 for petroleum derived SA * Agricultural University of Athens, Greece * E4tech (UK) Ltd
LCA for the production and purification of SA System boundaries “Gate to gate” approach Materials Emissions 6 7 4 3 5 Concentrated Detox 2 SSL from WP2 9 8 4 1 Energy Succinic Acid Crystals Wastes Agricultural University of Athens, Greece
LCA of SA bioprocess Gabi software from PE International Agricultural University of Athens, Greece
Identification of “hot spots”: SA Production and Recovery Total of SA New resin for downstream process Power for Agitation in the fermentor Regenaration of Resins with sulphuric acid Abiotic resource depletion includes depletion of nonrenewable resources, i.e. fossil fuels, metals and minerals. Global warming potential (GWP) is calculated as a sum of Process steam for sterilisation emissions of the greenhouse gases (CO2, N2O, CH4 and VOCs) Process steam for evaporation Carbon Dioxide Requirements for fermentation Activated Carbon 0,00% 20,00% 40,00% 60,00% 80,00% 100,00% 120,00% Primary energy demand from ren. and non ren. resources (gross cal. value) MJ CML2001 ‐ Apr. 2015, Abiotic Depletion (ADP fossil) MJ Environmental Impact UNITS GWP (100 years), excl biogenic carbon kg ‐ CO2 eq GWP 6.33 kg ‐ CO2 Eq/kg of SA produced ADP (MJ) 136.06 MJ /kg of SA produced Energy Demand (MJ) 155.22 MJ /kg of SA produced Agricultural University of Athens, Greece
Main Conclusions & Future recommendations • SSL is a by-product of the pulp and paper industry that can be used as a substrate in microbial fermentations – Needs to be pretreated first (remove the inhibitors) – Extract LS by nanofiltration – Extract phenolic compounds by solvent extraction • Succinic acid can be produced in high yields and adequate productivities and final SA concentrations • Techno-economic evaluation gave a higher TPC of SA from current SA costs – 5.3 instead of 2.9 $/kg – Under the same order of magnitude – Scale up designs (2 10 50 ktons) will significantly decrease the TPC • The carbon footprint of the SA process showed a 6.3 kg-CO 2 Eq./kg-SA – Mainly due to the downstream process – The LCA results will be compared with petrochemical SA production Agricultural University of Athens, Greece
The AUA team Thank you for your attention The research leading to these results has received funding from the European Union’s Seventh Framework Program for research, technological development and demonstration under grant agreement n o 311935 Agricultural University of Athens, Greece
Phenolic compounds Determination of the main phenolic compounds in the extracts by HPLC ‐ DAD Phenolic pH =2 pH =3.4 compound (mg/L) ratio 1:3 v/v ratio 1:3 v/v Gallic acid 1038 525 Isorhamnetin 41 21 Syringic acid 252 106 Syringaldehyde 32 127 Vanillic acid 50 17.8 Acetosyringone 16 ‐ Lariciresinol 142 ‐ Ellagic acid 1165.5 534 Caffeic acid 3.2 4 Vanillin 115 120 Catechin 127.6 53 Agricultural University of Athens, Greece
Recommend
More recommend
