Renewable hydrogen production methods based on biomass processing
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1 Renewable hydrogen production methods based on biomass processing Scientific supervisor: Prof. Dr. Eng. Paul Șerban Agachi PhD. Student: Tasnádi-Asztalos Zsolt Cluj-Napoca,2014
2 Thesis objectives Thermodynamic study of hydrogen production via bioethanol catalytic steam reforming Kinetic modeling of bioethanol catalytic steam reforming Analysis of different types of concepts of 100MW thermal power production from bioethanol Thermodynamic analysis of hydrogen production via bioglycerol catalytic steam reforming Kinetic modeling of bioglycerol catalytic steam reforming Analysis of different types of concepts of 100MW thermal power production from bioglycerol Dynamic simulation of hydrogen production from bioglycerol steam reforming in continuous tubular reactor
3 Achived results
4 Thermodynamic study of hydrogen production via bioethanol catalytic steam reforming Thermodynamic analysis is important before implementing a new process flow, because must know the most important parameters that influence the new process. In the calculation of the gaseous mixture composition at equilibrium a mathematical model developed in CHEMCAD process simulator was used.
5 The most important reaction for bioethanol steam reforming 1. CH 3 CH 2 OH+ 3 H 2 O 6 H CO 2 2. CH 3 CH 2 OH + H 2 O 4 H CO 3. CO + H 2 O CO 2 + H 2 4. CH 3 CH 2 OH H 2 + CO + CH 4 5. CO + 3 H 2 CH 4 + H 2 O 6. CH 3 CHO + 3 H 2 O 5 H CO 2 7. CH 3 COCH H 2 O 3 CO + 6 H 2 8. CH 3 COOH + 2 H 2 O 2 CO H 2 9. CH 3 CH 2 OH H 2 + CH 3 CHO 10. CH 3 CH 2 OH C 2 H 4 + H 2 O 11. CH 3 CHO CH 4 + CO 12. C 2 H 4 2 C + 2H CO CO 2 + C Zsolt Tasnadi-Asztalos, Ana-Maria Cormos, Árpád Imre-Lucaci, and Clin C. Cormos, Thermodynamic Evaluation of Hydrogen Production via Bioethanol Steam Reforming, AIP Conference Proceedings 1565, 175 (2013)
6 Compositon at equilibrium on dry basis (mol %) 80 Results of thermodynamic study via bioethanol steam reforming H 2 CH4 CO 2 CO Temperature ( o C) FIGURE 1. Composition at equilibrium reported to dry gas function of temperature at: a) r=3 and p=1 bar; b) r=25 and p=1 bar. 2.a) 2.b) Concentration profiles at equilibrium for the major products of the bioethanol stream reforming process at r=25. Zsolt Tasnadi-Asztalos, Ana-Maria Cormos, Árpád Imre-Lucaci, and Clin C. Cormos, Thermodynamic Evaluation of Hydrogen Production via Bioethanol Steam Reforming, AIP Conference Proceedings 1565, 175 (2013)
7 Kinetic study of bioethanol catalytic steam reforming There are few papers in the literature on kinetic studies of ethanol steam reforming, because the system is complex. Some kinetic studies have been published in which power law, Eley Rideal (ER), Langmuir Hinshelwood (LH) and Langmuir- Hilnshinwood-Hougen-Watson-(LHHW) model kinetic expressions are reported.
8 Zsolt Tasnádi-Asztalos a, Árpád Imre-Lucaci a, Ana-Maria Cormoş a, Mihaela Diana Lazăr b, Paul-Șerban Agachi a, Thermodynamic Study and Kinetic Modeling of Bioethanol Steam Reforming, Studia UBB Chemia, LVIII, 4, 2013 Kinetic model parameters Table1.Kinetic parameters with we started the optimization k i(t) = k i(898.15k) e -(Ea,i/R) ((1/T) (1/ K )) [mol/min mg] Ea i, ΔH i [kj/mol] K i(t) = K i(898.15k) e (ΔHi/R) ((1/T) (1/ K)) [dimensionless] k E1,(898.15K) Ea E k E2,(898.15K) k R1,(898.15K) k R2,(898.15K) K Et(898.15K) K CHO(898.15K) K CH2(898.15K) K CH(898.15K) K CH3(898.15K) K H2(898.15K) Ea E2 Ea R1 Ea R2 ΔH Et ΔH CHO ΔH CH2 ΔH CH ΔH CH3 ΔH H2O Table2.Global kinetic coefficient after optimization Parameters Calculated parameters Exp 1-5 k E1sim 3.64*10-5 k E2sim 1.44*10-5 k R1sim 0.55*10-3 k R2sim 4.33*10-2 K OH(898.15K) ΔH OH K CH4(898.15K) ΔH CH K CO(898.15K) ΔH CO 83.1 K H(898.15K) ΔH H K CO2(898.15K) ΔH CO K H2(898.15K) ΔH H
9 The results of kinetic model of bioethanol Zsolt Tasnádi-Asztalos a, Árpád Imre-Lucaci a, Ana-Maria Cormoş a, Mihaela Diana Lazăr b, Paul-Șerban Agachi a, Thermodynamic Study and Kinetic Modeling of Bioethanol Steam Reforming, Studia UBB Chemia, LVIII, 4, 2013 catalytic steam reforming Table3. Experimental and calculated values of components concentration Figure3. Measured and simulation data of steam reforming of bioethanol (with symbols are shown the experimental data and with lines and symbols the simulation results)
10 Zsolt Tasnadi-Asztalos, a * Arpad Imre-Lucaci, a Calin-Cristian Cormos, a Ana-Maria Cormos, a Mihaela-Diana Lazar, b Paul-Serban Agachi a, Thermodynamic Study of Hydrogen Production via Bioglycerol Steam Reforming, Proceedings of the 24 th European Symposium on Computer Aided Process Engineering ESCAPE 24 June 15-18, 2014 Thermodynamic study of hydrogen production via bioglycerol catalytic steam reforming The main reaction of bioglycerol catalytic steam reforming: 1. C 3 H 8 O 3 + 3H 2 O 3CO 2 + 7H 2 2. C 3 H 8 O 3 4H 2 + 3CO 3. CO 2 + CH 4 2H 2 + 2CO 4. CO + H 2 O H 2 + CO 2 5. CO + 3H2 CH4 + H2O 6. CO 2 + 4H 2 CH 4 + 2H 2 O 7. 2CO CO 2 + C 8. CH 4 2H 2 + C 9. CO + H 2 H 2 O + C 10. CO 2 + 2H 2 2H 2 O + C
11 Results of thermodynamic study via bioglycerol steam reforming a) Variation of H 2 concentration with temperature and pressure b) Variation of C concentration with temperature and pressure c) Variation of CH 4 concentration with temperature and pressure d) Variation of CO 2 concentration with temperature and pressure Zsolt Tasnadi-Asztalos, a * Arpad Imre-Lucaci, a Calin-Cristian Cormos, a Ana-Maria Cormos, a Mihaela-Diana Lazar, b Paul-Serban Agachi a, Thermodynamic Study of Hydrogen Production via Bioglycerol Steam Reforming, Proceedings of the 24 th European Symposium on Computer Aided Process Engineering ESCAPE 24 June 15-18, 2014
12 In progres Kinetic modeling of bioglycerol catalytic steam reforming Analysis of different types of concepts of 100MW thermal power production from bioglycerol Bioglycerol autothermal reforming Bioglycerol steam reforming Chemical looping
13 In future plan Analysis of different types of concepts of 100MW thermal power production from bioethanol Dynamic simulation of hydrogen production from bioglycerol steam reforming in continuous tubular reactor
14 Dissemination of results Zsolt Tasnadi-Asztalos, Ana-Maria Cormos, Árpád Imre-Lucaci, and Clin C. Cormos, Thermodynamic Evaluation of Hydrogen Production via Bioethanol Steam Reforming, AIP Conference Proceedings 1565, 175 (2013) Zsolt Tasnádi-Asztalos a, Árpád Imre-Lucaci a, Ana-Maria Cormoş a, Mihaela Diana Lazăr b, Paul-Șerban Agachi a, Thermodynamic Study and Kinetic Modeling of Bioethanol Steam Reforming, Studia UBB Chemia, LVIII, 4, 2013 Zsolt Tasnadi-Asztalos, a * Arpad Imre-Lucaci, a Calin-Cristian Cormos, a Ana-Maria Cormos, a Mihaela-Diana Lazar, b Paul-Serban Agachi a, Thermodynamic Study of Hydrogen Production via Bioglycerol Steam Reforming, Proceedings of the 24 th European Symposium on Computer Aided Process Engineering ESCAPE 24 June 15-18, 2014
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