Gasification of bagasse to Syngas and Advanced Liquid Biofuel Production

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1 Gasification of bagasse to Syngas and Advanced Liquid Biofuel Production Prof. Dr. Rubens Maciel Filho School of Chemical Engineering Laboratory of Optimization, Design and Advanced Process Control-LOPCA National Institute of Biofabrication-BIOFABRIS State University of Campinas UNICAMP Brazil Fapesp/Bioen- Process Engineering Coordination PLA-CTBE L O PCA Laboratório de Otimização, Projeto e Controle Avançado Brazil-EU-Workshop:Coordinated Call on Advanced Biofuels

2 HORIZON 2020 (H2020) Work Programme Secure, Clean and Efficient Energy LCE : International Cooperation with Brazil on Advanced Lignocellulosic Biofuels Coordinated Call

3 Sub-challenge 1: Gasification of bagasse to syngas and advanced liquid fuel production, including biofuels for aviation. Sub-challenge 2: Applied research to biomass production logistics and applied research for feedstock diversification for advanced biofuels. Sub-challenge 3: Development of new fermentation and separation technologies for advanced liquid biofuels and applied research to increase the energy efficiency of advanced biofuel processes. Proposals shall aim at moving technologies from TRL 3-4 to TRL 4-5.

4 Energy Consumption & Human Well Being are Linked Impact on Sustainable Process Development Biofuel processes should be energetically efficient, if possible, to export energy and necessarilly to be sustaintable. By Bruce Dale Michigan State University

5 Renewable Feedstock for Biofuels, Energy and Chemicals (Brazil is in prime position) Sugar cane, Soya bean, Palm, Coconut Orange, Agriculture residues, Animal Fatty among others. Any lignocellulosic material. Many alternatives to use such raw materials production scale and logistic has to be accounted for Saccharose Bagasse Tips and Straw Sugar Cane More or less 1/3 Saccharose, Bagasse Tips and straw Residues from biodiesel industries and by-products from bioethanol Urban waste advantage in terms of logistic and price and difficulties from standardization

6 Sugarcane numbers in Brazil Energy-cane to come ( ton/hectare) 2011/12: 8.5 million ha Cane production 2011/12: 595 Mt 52% for ethanol and 48% for sucrose Ethanol: 23 billion L Sucrose: 36 Mt 434 mills (250: sucrose + ethanol 168: exclusive for ethanol) 1 ton of sugar cane (80 ton/hectare) produce: 250 Kg of bagasse 120 Kg of Sugar 85 Liters of ethanol 2014/15 Use less than 1 % of arable land Production of sugar cane 630 Mt 70,000 growers 1.2 million jobs Annual revenue: US$ 48 billion Exports: US 15 billion 6 Updated from Cantarella, 2013

7 Possible Routes to Process Biomass Sugar extracted from sugar-rich crops fermentation Biomass Fermentation of residues and waste to Biogas

8 Preliminary proposal for the Brazil-EU joint call on Advanced Lignocellulosic Biofuels- Fast Pyrolysis and Gasification Feedstock Conversion/energy densification Upgrading Advanced liquid biofuels Agroforestry residues Gasoil(s) from crude oil fractionation Co-processing in FCC/ hydrotreating units Energy crops sugarcane, energy-cane, others Biomass Fast pyrolysis Bio-oil Biochar H 2 Catalytic hydrodeoxygenation/ hydrogenation Green gasoline Green diesel Biojet fuel Urban residues Hydrothermal treatment Cellulignin Gasification/ catalytic conversion C5 liquor Stabilization/ physical upgrading Bio-oil (direct use) Biochemical conversion Ethanol Butanol Microbial lipids Biogas Catalytic dehydration/ oligomerization Catalytic hydrogenation Ethanol Biojet fuel Butanol Biojet fuel Biogas Field Decentralized units Centralized units Use

9 Evolutionary Process Engineering and the 1G Learning Curve Learning curve of Thermochemical Route from other raw materials important knowledge 70 s 1G (40 years) Today 2G Biochemical In 10 years? 82 % % /ha. US$ cents production cost of 1 liter of ethanol (70% sugar cane)

10 A point to be considered is its possible integration with the first generation units and this may lead to a careful choice of the process that leads to economically and robust solution to use byproducts as feedstock for energy and chemicals. Flexibility of Thermochemical route, in terms of raw material should be addressed- any lignocellulosic material and use of Solid Municipal Waste Decision making couple with different alternatives Brazilian concept of Biofuel Production requires to be energetically selfsufficient and even Electricity Exporter Thermochemical Routes Challenges 1-) Ecoomic Syngas production 2-) Gas purification 3-) Catalyst development for efficient process (Lower T and P) 4-) Separation an purification Biochemical Route 2G Challenges 1-Pre-treatment in large scale 2-Delignification 3-Enzymes- costs and on site production 4-Fermentation time 5-C5 fermentation 6- Separation and purification To other raw materials -Impact of Logistic ( Near Brussels )

11 Concept of the Integrated Plants take advantage of the First Generation competitiveness process (Good starting point)- share facilities (lower CAPEX and OPEX) and raw material available in the production site Typical Industrial Plant size: Thermochemical Biofuel Plants Sharing some facilities Sugarcane bagasse available 35,000 to 40,000 ton/sugar cane/day Amounts of ethanol, sugar and electricity depend upon the business model

12 Pretreatment BIOCHEMICAL PLATFORM Hydrolysis Fermentation Downstream processing Biomass Bioproducts Gasification Clean-up/ Conditioning THERMOCHEMICAL PLATFORM Catalytic conversion Downstream processing Biomass+ O 2 /Ar (limited) CO + H 2 + CO 2 + CH 4 + H 2 O vapor + N 2 syngas Convertion of Themochemical Process T = C High pressre

13 Sugar Cane Bagasse characterization Ultimate analysis Ultimate analysis Heating value Heating (MJ/kg) value Proximate Proximate analysis (wt analysis %) (wt %) (dry and free (dry Ultimate of and ashes free wt of analysis ashes %) Low wt %) Low High Proximate analysis C (wt %) C Moisture content Moisture 2.00 content 2.00 H H (dry and free of ashes wt %) Ash content Ash content O* O* C Heating Moisture value content (MJ/kg) 2.00 N N Volatile matter Volatile matter t %) Low High H 5.9 Cl Cl Fixed Ash Heating carbon content Fixed value carbon 3.36 (MJ/kg) S S O* t %) Low High N 0.2 Heating Volatile value matter (MJ/kg) Cl 0.3 t %) Low High Fixed carbon 3.36 S For example: Wood 25 aprox Most significant differences of sugar cane bagasse compared to coal: moisture (requires more heat) and higher amount of volatiles

14 Gasification /Pyrolysis Wet biomass Drying Drying Dry biomass H2O Wet biomass Dry biomass H2O Pyrolysis Dry biomass Pyrolysis gas (Gas +Tar) Char Tar (Priority) CH4 HEAT Combustion Combustion C+O2 CO2 2 H2+O2 2 H2O CnHm+(n/2+m/4) O2 nco2 + m/2 H2O CO2 H2O Process Conditions Pressure,Temperature, Residence Time, etc. Reduction Reduction C+CO2 CO 2 C+H2O CO+ H2 CnHm+nH2O nco + (m/2+n) H2 CnHm+nCO2 2nCO + m/2 H2 CO H2 Syngas

15 Thermochemical process Bagasse Pyrolysis Thermochemical process Gasification In the absence of oxygen Combustion In the presence of oxygen (Air or steam) It uses an amount of oxygen lesser than that required stoichiometrically Bio-Oil (Tar) C Char Gas >700 C Electricity gas turbine in combined cycle to produce energy in larger scale Syngas (H 2 /CO) (Priority)

16 Fixed Bed and Fluidized bed gasifier + steam reforming Gasifier Reformer reactor Laboratory scale gasifier Gas cleaning systems (filter and cooler) Fluidized bed reactor showed higher performance when compared to Fixed bed reactor

17 SUGARCANE BAGASSE AS RAW MATERIAL TO SYNGAS PRODUCTION: PLANT DESIGN BY COMPUTATIONAL FLUID DYNAMIC AND GASIFICATION PROCESS DEVELOPMENT Study cases Figure 1. Mesh of Bubbling fluidized bed gasifier of bagasse. CFD simulation Simulations validity Table 1. Comparison between experimental results and those obtained with the CFD simulation. Figure 2. Dry composition of Syngas obtained in bubbling fluidized bed gasifier of bagasse. * * Stoichiometric air ratio (AR) and the steam to bagasse ratio (SR) Figure 3. Velocity profile.: a) Solid phase and b) Gas phase. T = 900 C, AR = 0.29 and SR = In the simulation presented in this work, the gasifier was operated at temperature of 900 C with AR= 0.29 and SR = 0.34, obtaining dry compositions of 22.25, and vol% for H 2, CO and impurities, respectively.

18 Biomass Gasification Syngas Thermochemical route Fuels and Chemicals Source: Ebert, Focus on ethanol production with lower temperature and pressure compared to FT 2-electricty generation using turbine powered by gas from biomass (forest residues from pulp and paper residues- nowadays bar boilers for sugar cane ) 3-Syngas fermentation to ethanol and organic acids which are platforms for other biofuels

19 Conventions of fuel names and compositions and some criteria for catalyst selection Name Synonyms Components Gasoline C 5 C 12 Naphtha C 8 C 12 Kerosene Jet fuel C 11 C 13 Diesel Fuel oil C 13 C 17 Middle Light gas oil C 10 C 20 distillates Soft wax C 19 C 23 Medium wax C 24 C 35 Hard wax C 35+ Parameters Cobalt Iron Cost More expensive Cheap Timely Resistant to deactivation Low resistance (coke, carbon deposit, carbides) Probability of chain growth Max. 0,94 Max. 0,95 Reaction gas-water There isn t significant Significant Sulfur tolerance <0,1 ppm <0,2 ppm Inflexible. Influence on the selectivity Flexibility (temperature and pressure) Flexible, low formation of CH 4 inhigh temperature Resistance to abrasion Resistance Low resistance H 2 /CO ratio ~2 0,5-2,5 Focus on biodiesel and Kerosene (Jet fuel) with lower process pressures and temperatures compared to Fisher-Tropsch.

20 Catalytic conversion of syngas via direct synthesis ETHANOL Ethanol formation Methanation 2CO (g) + 4H 2(g) C 2 H 5 OH (g) + H 2 O (g) CO (g) + 3H 2(g) CH 4(g) + H 2 O (g) r EtOH 6, e 126,7/ RT p 0,90 H 2 p 0,76 CO r CH 4 9, e 156,8/ RT p 0,79 H 2 p 0,60 CO Flowsheet Catalyst Rh-Mn-Li-Fe/SiO 2 Thermodynamic model: PRSV- (Patent requested 2015) Production of 500 m3/day of ethanol 20

21 Thermochemical Routes to Produce Advanced Biofuels and Electricity

22 Syngas Fermentation Pretreatment BIOCHEMICAL PLATFORM Hydrolysis Fermentation Downstream processing Biomass New hybrid platform Bioproducts Gasification Clean-up/ Conditioning THERMOCHEMICAL PLATFORM Catalytic conversion Downstream processing

23 BIOMASS Gasification SYNGAS Fermentation ETHANOL C + 1/2 O 2 CO C + O 2 CO 2 H 2 + 1/2 O 2 H 2 O C + CO 2 2 CO C + H 2 O CO + H 2 C + 2 H 2 CH 4 CH 4 + H 2 O CO + 3H 2 CO + H 2 O CO 2 + H 2 anaerobic bacteria 6 CO + 3 H 2 O C 2 H 5 OH + 4 CO 2 2 CO H 2 C 2 H 5 OH + 3 H 2 O 4 CO + 2 H 2 O CH 3 COOH + 2 CO 2 2 CO H 2 CH 3 COOH + 2 H 2 O

24 BIOMASS Gasification SYNGAS Fermentation ETHANOL Thermochemical conversion of biomass Full conversion of carbon Feedstock flexibility Mature technology Presence of contaminants in gas Expensive clean-up Biochemical conversion of syngas Higher resistance to contaminants Moderate temperature and pressure higher selectivity Inefficient gas-liquid mass transfer High dilution

25 Proposed Conceptual Design for Syngas Fermentation to Ethanol Flue gas Flue gas Process electricity Geração de eletricidade Surplus electricity Hot flue gas syngas CO 2 Biomass Drying and Gasification Hot syngas Flue gas Heat Recovery Steam Generator Cold syngas Bioreactor product Ethanol recovery Ethanol Water recycle Ashes Steam Steam wastewater (Medeiros et al., 2015)

26 How to decide on the technology Feedstock availability and logistic Domain of technology, costs of royalties, human resources Need to attend the market regulations Energy and water supply restrictions or limitations Sustainability analysis economic, social and environmental evaluation is necessary ( e.g. BVC-CTBE) Several scenarios have to be considered Economic viability is essential society, in general, is not to pay more because is renewable

27 Brazilian Consortium Coordinated by CTBE/CNPEM UFPE UNICAMP