Synergistic Natural Gas Biomass Co-processing to Produce Hydrogen

Synergistic Natural Gas  Biomass Co-processing to Produce Hydrogen

Synergistic Natural Gas Biomass Co-processing to Produce Hydrogen Rich Syngas Amoolya D. Lalsarea Jianli Hua Ali C. Sivrib Cosmin E. Dumitrescub a: Chemical and Biomedical Engineering b: Mechanical and Aerospace Engineering West Virginia University Outline Motivation Results and discussion Gasifier reactor Proposed reaction pathway configuration Process Scale-up and Path Natural gas-biomass co-processing Design of experiments to Commercial Application Conclusions Future Work 2 Motivation Lab scale scale-up of gasification reactor to bench scale

fluidized bed reactor Complexity of fluidization hydrodynamics Complex reaction engineering of biomass / coal gasification Gasification process development to improve efficiency Process intensification 3 Gasifier Reactor Configuration Fixed Bed Reactor Setup Bubbling Fluidized Bed Reactor Setup 4 Natural gas Biomass Co-processing Biomass Utilization Challenges Highly variable composition of feedstock 2 Complexity of solid biomass handling3 Low energy density and high oxygen content 1,2 Lignin representation HDO of phenolic (COH), carbonyl (C=O) functional groups, and fufurals Advantages of Shale gas / Natural gas Abundant availability, low prices High energy density4 High H / Ceff ratio of methane (4) as compared to biomass (0.3) 5 1. Ref.: https://www.eia.gov/outlooks/aeo/ 2. S. V. Vassilev, D. Baxter, L. K. Andersen, C. G. Vassileva, Fuel 2010, 89, 913 933 3. M. R. Wu, D. L. Schott, G. Lodewijks, Biomass and Bioenergy 2011, 35, 20932105 4. A. Demirba, Energy Sources 2002, 24, 601610 5. K. Bukowska, E. Klimiuk, in Biomass for Biofuels, 2016, 121153

5 Design of Experiments Fixed Bed Reactor Setup Fluidized Bed Gasifier Setup Reaction temperature: 850oC to 950oC CH4: 5 to 15 vol.%, CO2: 1 vol.% Balance: Nitrogen (N2) Catalyst to Biomass wt. ratio 3:4 Catalyst FeMo / ZSM-5 FeMo / CNF Mo 4 wt.% 4 wt.% Fe Support 0.5 wt.% Zeolite 0.5 wt.% Carbon nanofiber Hardwood Biomass Weight % Carbon (C) Hydrogen (H) Oxygen (O) Moisture Ash 45.25 4.65 49.2 7.16 0.32

Product Analysis: Inficon Fusion Micro-GC 6 Results and Discussion 100 Fixed bed reactor studies 80 Biomass gasification at 900oC gasification Methane - carbon dioxide activated synergistic biomass gasification Fluidized bed reactor studies Non-catalytic biomass gasification at 900oC No catalyst % Conc. Methane activated synergistic biomass Hydrogen Carbon Monoxide Carbon Dioxide Methane 60 0.5 % Fe - 4% Mo / ZSM-5 84

ZSM-5 55 44 32 40 25 20 24 19 16 14 12 13 08 10 06 01 01 0 Feed1 Feed1 Feed2 Feed3 H2/CO: 0.35

H2/CO: 0.57 H2/CO: 5.9 H2/CO: 1.94 Feed1: Biomass, Feed2: Biomass + 5% CH4, Feed3: Biomass + 5%CH4 + 1% CO2 7 Biomass Gasification on FeMo catalyst in absence of methane 70% Hardwood biomass gasification at FeMo/ZSM-5 catalyst High methane concentration due to reverse steam methane reforming in FeMo/ZSM-5 H2:CO ratio < 1 Normalized Conc. 850oC, 950oC on ZSM-5 support and 60% H2 CO CO2 CH4 55% 54% 50%

44% 40% 30% 25% 19% 20% 10% 24% 24% 16% 16% 11% 5% 6% 0% 950 ZSM-5 850 FeMo1 950 FeMo1 o Temperature ( C), Catalyst 8

Biomass Gasification on FeMo/ZSM-5 with 5 to 15% CH 4 Biomass CH4 reaction at 850oC 100% H2 CO CO2 CH4 84% 81% 100% 80% H2 CO CO2 CH4 77% 80% Normalized Conc. Normalized Conc. 76% 80% Biomass CH4 reaction at 950oC

60% 40% 74% 60% 40% 21% 20% 0% 14% 1%1% 5% CH4 H2:CO = 6 17% 1%1% 10% CH4 H2:CO = 5.0 18% 20% 3%3% 15% CH4 H2:CO = 4.2

20% 11% 5%5% 1%1% 0% 5% CH4 H2:CO: 7.4 10% CH4 H2:CO: 3.7 2%4% 15% CH4 H2:CO: 3.7 9 Temperature effect on methane activated biomass gasification Biomass and 5% CH4 reaction 100% H2 CO CO2 CH4 84% 80% 80% 81%

H2 CO CO2 CH4 77% 80% Normalized Conc. Normalized Conc. 100% Biomass and 10% CH4 reaction 60% 40% 20% 0% 60% 40% 21% 20% 14% 11% 5% 5%

1% 1% 850 H2:CO = 5.9 Temperature (oC) 17% 950 H2:CO = 7.5 0% 1% 1% 850 H2:CO = 5 Temperature (oC) 1% 1% 950 H2:CO = 3.8 10 CH4 CO2 Activated Biomass Gasification High temperature catalytic 60 methane carbon dioxide activation

Zeolite and carbon nanofiber catalyst support Gas yieldZSM-5 < Gas yieldCNF 55.9 50 % Conc. Catalyst: FeMo/ZSM-5, FeMo/CNF H2:CO = 2 Hydrogen Carbon Monoxide Carbon Dioxide Methane 40 30 20 10 31.6 29.3 16.3 16.3 8.36 10.3

6.36 0 ZSM-5 H2/CO: 1.94 Catalyst Support CNF H2/CO: 1.97 11 Proposed Reaction Pathway Adsorption of biomass components like phenols, furfurals, and carbonyl oxygen on oxophilic Mo active site Decoupling of carbon oxygen bond to form steam adsorbates 12 Synergistic Steam Methane Reforming Synergistic Bi-reforming 13 Hydrogen Carbon Monoxide Carbon Dioxide

Methane 100 Feed1: Biomass Feed3: Biomass + 5% CH4 + 1% CO2 FB Fixed bed BFB Bubbling fluidized bed 80 % Conc. Feed2: Biomass + 5% CH4 83.8 55 60 38.4 42.1 31.6 40 20 19 12 13 8.72 8.67

16.3 14.2 8.36 10.3 0.93 0 F1 / FB F1 / BFB F2 / FB F3 / FB Feed (F#) / Reactor Type (FB: Fixed Bed, BFB: Bubbling Fluidized Bed) H2/CO: 0.35 H2/CO: 0.91 H2/CO: 5.9 H2/CO: 1.94 14 70 Hydrogen

Carbon Monoxide Carbon Dioxide 55 Methane 50 60 38.4 Fluidized Bed Product Gas Composition % Conc. 50 42.1 40 30 17 15 19 20 16 12 13 8.728.67

10 0 Biomass_fixed bed H2/CO: 0.35 Biomass_fixed bed Coal - 10% Steam_BFB H2/CO: 0.91 H2/CO: 3.23 Biomass and coal gasification at 900oC 15 Conclusions Natural gas biomass and natural gas carbon dioxide - biomass synergy Hydrogen rich syngas for applications like fuel cells and conventional processes like ammonia synthesis Synthesis gas for value added chemical synthesis Process scale-up is achievable by continuous feeding of biomass-catalyst in a fluidized bed or moving bed reactor 16 Future Work Replicating all the fixed bed experimental conditions on bubbling fluidized bed setup Achieve continuous streamlined feeding of coal / biomass Extended continuous operation of fluidized bed reactor 17 Publications

1. Hydrogen Rich Syngas Production through Synergistic Methane Activated Catalytic Biomass Gasification; Amoolya Lalsare, Yuxin Wang, Qingyuan Li, Ali C. Sivri, Cosmin E. Dumitrescu, Jianli Hu (under review at ACS Sustain Chem Eng) 2. Syngas (H2:CO = 2) production through methane carbon dioxide activated synergistic bi-reforming in catalytic biomass gasification; Amoolya Lalsare, Ali C. Sivri, Ryan Egan, Roman J. Vukmanovich, Cosmin E. Dumitrescu, Jianli (submitted to ChemSusChem) 18 Acknowledgements Authors are pleased to acknowledge U.S Department of Energy and National Energy Technology Laboratory, Morgantown along with Leidos Research Support Team for the continuous support and cooperation for the specific work and broadly for the NETL Gasifier Support Stand Project 19 Thank you! Questions? 20 Gas Yield 100 12.5 9.9 3 13 Tar

5 8 15 12 80 80 Char 2 10 5 7 11 11 84 82 Yield (mole%) 80 60 40

87.5 90.1 84 850, 0 950, 0 850, 5 88 20 0 850, 10 850, 15 950, 5 950, 10 950, 15 Temperature (oC), CH4 (vol.%) 21

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