Recent Developments and Current Situation of Cellulosic Ethanol R&D in Brazil Research Center in Applied Chemistry Department of Chemistry Federal University of Paraná (UFPR), Brazil www.quimica.ufpr.br/paginas/luiz-ramos luiz.ramos@ufpr.br
Renewable fuels Estimation of the world biofuel production By type By Country Source: Brazilian Energy Report - REN 21-2016 2
BR energy matrix Etanol Hidratado Ethanol (hydrated) Etanol Anidro Ethanol (anhydrous) Coal and firewood Cane bagasse Biodiesel 3
Biofuels in Brazil RenovaBio 43% reduction in GHG emissions by 2030; Zero tolerance for illegal deforestation in the Amazon basin; Up to 45% renewable energy in the Brazilian energy matrix; Bioenergy contributing with 18% of the total renewable energy; New biofuels: 2G ethanol, green diesel, HVO, biohydrogen, biogas, biomethane and biokerosene, among others National program launched in December 2016 by the Brazilian Ministry of Mines and Energy to expand the production of biofuels in Brazil, having as main foundations its predictability, compatible scaling according to the market demand and its social, environmental and economic sustainability. 4
Biofuels in Brazil RenovaBio for 1G ethanol New policies will be needed to raise our ethanol production from the current 30 to more than 50 billion liters per year: o Innovative financial mechanisms to reduce the risk of commercialization o Tax differentiation and incentives based on sustainability Social and environmental externalities Regulation of bioelectricity production and use o Decarbonization of light fuels Reduction in annual CO 2 emissions New policies for stimulating clean renewable energy Creation of an effective program for monitoring and control Commercialization of emission certificates (trading) Improvements of engine performance in flex fuels 5
Biofuels in Brazil RenovaBio for 2G ethanol Proposed strategic planning to reach an annual production of 50 billion liters of ethanol by 2030: o Market development = premium of R$ 1.00 per liter until 2030 or until production reaches 2.5 billion liters year -1 o Creation of an high-level advisory committee for industrial biotechnology involving government and stakeholders o Establishment of new policies involving tax incentives, subsidies, warranties and grace period for financing o Establishment of a regulatory regime for carbon trading o Economic valuation of environmental externalities that are associated with the use of low carbon biofuels o Attention to the food vs. fuel dilemma and to sustainability issues such as availability of arable land, effect on soil fertility and impact on biodiversity 6
Biofuels in Brazil RenovaBio for 2G ethanol Proposed strategic planning to reach an annual production of 50 billion liters of ethanol by 2030: o 2G ethanol is one of the most important doors way towards a solid and advanced bioeconomy in Brazil o Roadmap challenges: the current technological gaps must be overcome, a dedicated market share must be consolidated and the annual production capacity must be expanded o Goal: one new medium-size plant (60 million liters year -1 ) per year speeding up to progressively to ten new plants per year to reach 120 plants in operation by 2030, with the production capacity ascending to 110 million liters year -1 7
Sugarcane 8
First generation (1G) or saccharinic ethanol Simplified flowsheet Steam 2.5 bar CO 2 Ethanol 1G CANE HARVESTING CRUSHING CLARIFICATION EVAPORATION FERMENTATION (1G) YEAST RECOVERY DISTILLATION Vinasse HOT WATER WASHING Residue YEAST ACID WASH Nutrients BAGASSE HANDLING BOILER WTT BIOGÁS 2016/17 harvesting: Electricity STEAM TURBINE 691 million ton cane 30.3 million m 3 ethanol 37.5 million ton sugar ~184 million ton trash Autonomous distillery (75-80 L/ton sugarcane) Adapted from Macrelli, S.; Mogensen, J.; Zacchi, G. (2012) Biotechnology for Biofuels 5, 22. 9
Bringing 1G and 2G cellulosic ethanol together Simplified flowsheet Steam 2.5 bar CO 2 Ethanol 1G CANE HARVESTING CRUSHING CLARIFICATION EVAPORATION FERMENTATION (1G) YEAST RECOVERY DISTILLATION Vinasse HOT WATER WASHING Residue YEAST ACID WASH BAGASSE HANDLING FILTRATION ENZYMATIC HYDROLYSIS SOLID/LIQUID SEPARATION FERMENTAÇÃO (2G) YEAST RECOVERY PRETREATMENT C5 stream Enzymes DISTIlLATION Electricity STEAM TURBINE BOILER DRYING Vinasse Ethanol 2G WTT BIOGÁS 1G/2G process integration Adapted from Macrelli, S.; Mogensen, J.; Zacchi, G. (2012) Biotechnology for Biofuels 5, 22. 10
Bringing 1G and 2G cellulosic ethanol together Hydrolysis at 20 wt%, 200 rpm, 0.1 g Cellic CTec2 g -1 cellulose released of 76.8 g L -1 of GlcEq in 72 h (equivalent to 39.2 g L -1 ethanol from cane bagasse) Based on this, the ethanol production from sugarcane could be increased by 40 %, from 80 to 115 L ton -1 The use of cane straw (leaves and tops, also referred to as cane trash) and C5 sugars may improve these numbers even further Ramos et al. (2015) Bioresour. Technol. 175, 195-202. 11
Sugarcane Bagasse Straw (trash) Szczerbowski et al. (2014) Carbohydr. Polym. 114, 95-101. 12
Pretreatment Cellulose Pectins Hemicelluloses Lignin Adapted from Silveira et al. (2015) ChemSusChem 8, 3366-3390 13
Enzymatic hydrolysis Synergism among cellulases and auxiliary proteins such as swollenins and GH61 (AA9) TrCel12A GH61 Glucose bg Cellobiose Swollenins CBM Cellobiose TrCel6A TrCel7A TrCel5A Silveira, M. H. L. et al. In: S. S. Silva and A. K. Chandel. Biofuels in Brazil. Switzerland: Springer International, 2014. p. 151-172. 14
Enzymatic hydrolysis Typical hydrolysis profile of cellulosic materials SHF pssf Substrate TS > 20 wt.% 12 72 (h) Arantes, V. and Saddler, J. N. (2011) Biotechnology for Biofuels 4, 17. 15
Fermentation Typical SSCF profile Pre-hydrolysis at 20 wt% TS C5/C6 fermentation with 2 g/l of yeast cells (Nedalco) 16
Fermentation Inhibitory compounds arisen from pretreatment Cellulose Hemicelluloses Lignin Glucose Mannose Galactose Xylose Arabinose Acetic acid Phenolics Formic acid Levulinic acid HMF Furfural Adapted from Palmqvist, E.; Hahn-Hagerdal, B. (1999) Bioresour. Technol. 74, 25-33. 17
Ethanol 2G in Brazil Costa Pinto mill Piracicaba SP 40 mi L ethanol year -1 18
Ethanol 2G in Brazil Bioflex 1 São Miguel dos Campos AL 82 mi L ethanol year -1 19
First Cellulosic Ethanol Plant of the South Hemisphere Set/2014 20
Cane Extraction Bagasse CoGen Electricity (grid) Juice Lignin Steam & energy Ethanol 1G EtOH Straw 2G EtOH Vinasse First Cellulosic Ethanol Plant of the South Hemisphere Set/2014 21
Sugarcane straw 22
Large scale storage of cane straw 23
Conventional sugarcane Energy cane Cane plantations after 7.5 months Average rainfall: 350 mm 24
> 164% > 1200% > 450% Production / Productivity Energy Bagasse (10 6 ton) / (ton ha -1 ) (MW year -1 ) Production Consumption Surplus 951 22 3 495 (10 6 ton) Sugarcane Energy cane 385 360 70 185 17 90 60 110 30 25
> 164% < 31% > 232% Fibers / Sugars Ethanol Ethanol (%) / (%) (10 6 L) (10 9 L year -1 ) 135 93 20 per ha 47 per year Sugarcane Energy cane 53 26 13 26 6 1G 4 2G 26
Green biomass (ton ha -1 ) Biomass productivity Average Energy cane Average Sugarcane Harvesting (years) 27
Properties Sugarcane a Energy cane Fiber (%) 17.4 35 Sugars (%) 12.6 7 Productivity (green biomass, ton ha -1 ) b 92 250 Productivity (fiber, ton ha -1 ) 16 88 Productivity (sugars, ton ha -1 ) 12 18 Annual energy gain (%) 1.5 3 Demand for fertilizers High Low Plague/disease resistence Low High Harvesting cycles 5 10 Propagation rate 1:10 1:400 Breeding cycle (years) 8 to 12 4 to 6 a 80 tons ha -1 containing 50% straw in harvesting b State of São Paulo, low fertility soil 28
Pretreatment o Sugar yields o Accessibility o Inhibitors o Cost Severity factor (log R o ) * SF = log Ro = e T 100 14.75. t * Overend, R. P., Chornet, E., Gascoigne, J. A. (1987) Phil. Trans. R. Soc. Lond. A, 321, 523-536. 29
Pretreatment optimization o Severity factor (log R o ) vs. sugar recovery Xylose Glucose 30
Yield (%) Pretreatment optimization o Severity factor (log R o ) vs. total sugar yield 100 A B C D 90 80 E F 70 60 50 A B C D E F Hydrolysis efficiency Fermentable sugars 31
Enzyme dosage (relative values) Enzymatic hydrolysis o Optimal enzyme dosage 120 100 80 60 U$90 U$100 U$70 Substrate accessibility New (accessory) enzymes Customization Production system Offsite Onsite 40 60 65 70 75 Efficiency (%) Integrated Activity enhancement 1 Gen 2 Gen 3 Gen 32
Ethanol production o Process: Hemicellulose Cellulose C6 C5 Integration at low cost Flexible (feedstock agnostic) o Enzymatic hydrolysis: Xylose Total solids > 20%; time < 70h Efficiency > 70% Xylulose o Fermentation: C5/C6 C6 G-3P Ethanol Efficiency > 90% o Yield from 100 g: Sugars PT EH F EtOH 0.68 0.90 0.65 0.45 17.9 0.60 0.45 16.5 33
Current situation and future challenges So far, the plant has operated without interruption for a total of 5 months, from October 2016 till February 2017, reaching 50% of its total production capacity The plant stopped its operation in March 2017 due to the end of the cane harvesting season The cane productivity in the last harvest was far below the initial predictions due to a severe draught in the Northeastern region of the country There was a major shortage of biomass supply for the entire process: bagasse for the industrial boilers and straw for cellulosic ethanol production Current challenges: reduce production costs, improve yields and increase production close to the full production capacity 34
Glucose (%) Alkali delignification Experiment AnGlc (%) AnXyl (%) AnAra (%) Lignin (%) Insoluble Soluble Total AWB 52.15 ±0.27 19.70 ±0.29 1.99 ±0.15 15.42 ±0.56 0.01 ±0.00 15.45 ±0.56 SEB 59.73 ±0.42 3.59 ±0.07 bdl 33.44 ±0.23 0.04 ±0.23 33.48 ±0.23 SEB-AW 77.25 ±2.00 5.50 ±0.38 bdl 10.42 ±0.20 0.01 ±0.20 10.43 ±0.20 Hydrolysis at 4 wt% TS, 50 C, 150 rpm for 96 h, with 33 mg of Cellic CTec3 (Novozymes) g -1 TS or 7.1 FPU g -1 TS in a 50 mmol L -1 acetate buffer, ph 5.2. Analysis by HPLC in an Aminex HPX-87H. 100 80 60 40 20 SEB-AW SEB AWB Torres da Silva et al. (2016) Catalysis Today 269, 21-28. 0 0 24 48 72 96 Time (h) 35
Torres da Silva et al. (2016) Catalysis Today 269, 21-28. Glucose (%) Glucose (g L -1 ) Ethanol (g L -1 ) Alkali delignification Experiment AnGlc (%) AnXyl (%) AnAra (%) Lignin (%) Insoluble Soluble Total AWB 52.15 ±0.27 19.70 ±0.29 1.99 ±0.15 15.42 ±0.56 0.01 ±0.00 15.45 ±0.56 SEB 59.73 ±0.42 3.59 ±0.07 bdl 33.44 ±0.23 0.04 ±0.23 33.48 ±0.23 SEB-AW 77.25 ±2.00 5.50 ±0.38 bdl 10.42 ±0.20 0.01 ±0.20 10.43 ±0.20 100 80 60 40 20 0 SEB SEB-AW AWB Hydrolysis at 4 wt% TS, 50 C, 150 rpm for 96 h, with 33 mg of Cellic CTec3 (Novozymes) g -1 TS or 7.1 FPU g -1 TS. 0 24 48 72 96 Time (h) 70 60 50 40 30 20 10 0 0 3 6 9 12 15 18 21 24 Time (h) 30 25 20 15 10 5 0 36
Yield (%) Alkali delignification 100 80 60 40 20 0 Total solids Glucan Ethanol AWB6 SEB SEB-AW Torres da Silva et al. (2016) Catalysis Today 269, 21-28. 37
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Thank you! luiz.ramos@ufpr.br