Technical Meeting to Examine the Techno- Economics Opportunities for Non-Electric Applications of Small and Medium Sized or Modular Reactors COGENERATION POSIBILITIES WITH THE ARGENTINEAN MODULAR NUCLEAR POWER REACTOR CAREM G.G. Fouga, D. Nassini, H.E. Nassini, A.E. Bohé fouga@cab.cnea.gov.ar May, 29 th - 31 st 2017 Vienna - Austria
Non-Electric Applications of Small and Medium Sized or Modular Reactors. 02/20 The wide spectrum of current reactors can cover all applications I. Khamis. Non-Electric Applications of Nuclear Energy.
CAREM Nuclear Reactor 03/20 IAEA SMR Booklet 2014 CAREM Nuclear Reactor Characteristic (Videos) CAREM Nuclear Reactor Under Construction (Videos)
Gasification 04/20 Gasification refers to a thermo-chemical process that converts solid carbonaceous fuels into either fuel gas (usually containing CH 4 and some N 2 ) or syngas (containing mainly H 2 and CO). C(s) + H 2 O(g) H 2 (g) + CO(g) C(s) + CO 2 (g) 2CO(g) C(s) + 2H 2 (g) CH 4 (g) H = 118.9 KJ/mol H = 159.7 KJ/mol H = -87.4 KJ/mol Gasification involves the possibility of co-generation of electricity, chemicals and fuels in the same energy facility. nco (2 n) H2 CnH2n nh2o nco (2 n) H C H OH ( n 1) H O 2 n 2n 1 2 nco (2n 1) H2 CnH2n 2 nh2o Alkenes Alcohols Paraffins
Gasification Tar + Pyrolysis gas Step 1: Pyrolysis Syngas Step 2: Gasification 05/20 Gasification is a two-step process The two-stage Pyrolysis Reactor Volatile components of solid fuels are rapidly released At T between 300 and 500 ºC Gasifier Reactor Ratelimiting step gasification concept makes full use of the high-value aromatic compounds contained Solid Fuel Char in the solid fuels. Coal Asphaltites petroleum coke Biomass, etc. Composed of fixed carbon and mineral matter Gasifying agent Steam; CO 2 In this way one can co-produce tar and fuel gas or syngas, (poly-generation).
Gasification 06/20 Gasification also involves the possibility of using a wide range of feed stocks including low-cost fuels like: petroleum coke, biomass and also municipal waste. Argentinean Natural Solid Fuels Evaluated Sub-bituminous coal: Rio Turbio Ortho-Asphaltite: F4 Meta-Asphaltite: EM Asphaltites are complex mixtures containing compounds ranging from nonpolar aliphatic and naphthenic hydrocarbons to highly polar aromatic molecules.
Natural Solid Fuels Deposits in Argentina 07/20 Natural Solid Fuels H 2 O + Volatile Material Pirólisis Fixed Carbon + + Char Ash Determinati on HT in air. (105 C) HT in Ar. (950 C) % of Char % of Ash HT in air. (950 C) ASTM standard ASTM D3173 03 ASTM D3175 07 ASTM D3174 04 Determination Coal (Río Turbio) EM (Meta) Asphaltites F4 (Ortho) Moisture (wt%) 3.5 11.47 0.26 Volatile Matter (wt%) 36.4 26.18 58.97 Fixed carbon (wt%) 51.2 68.67 40.57 Ash (wt%) 12.3 5.13 0.46 Density (g cm 3 ) 1.107 0.679 0.412 C T 59.8 64.3 78.0 N T 2.78 3.27 2.92 S T 0.86 2.36 4.5 Asphaltites Coal Peat Calorific Power kj/kg 25104 24895 39472
Experimental Program 08/20 Objective: characterize the behaviour of Argentine solid carbonaceous fuels under typical pyrolysis and gasification conditions, to identify the most suitable operational parameters in nuclear-assisted two-stage gasifiers. Scope: Theoretical and experimental studies designed to get the necessary information about the fundamental mechanisms and kinetic parameters of pyrolysis and gasification reactions, on laboratory scale.
Experimental Setup for Pyrolysis 09/20 Effects of pyrolysis conditions as temperature, heating rate and holding time on: Microstructure and gasification reactivity of chars. Yield and composition of the evolved tar and pyrolysis gas. Fixed bed reactor after pyrolysis Drop tube reactor Fixed bed reactor
M/Mi (%) Experimental Setup for Pyrolysis 10/20 Pyrolysis heat treatments at temperatures above 500-600 ºC produce a significant reordering of the carbonaceous char matrix, increasing the crystalline carbon fraction and consequently decreasing their reactivity. 0-10 -20 EM -30-40 Rio Turbio -50 LHR: 4 C/min -60 Mass: 10 mg F4 0 200 400 600 800 1000 Temperature ( C) Initial Asphaltite sample Asphaltite char after pyrolysis at 950ºC during 60 minutes Kinetics of the Gasification of a Rio Turbio Coal Under Different Pyrolysis Temperatures. G. De Micco, A. Nasjleti, A.E. Bohé. Fuel 95 (2012) 537 543. Effects of pyrolysis conditions on the structure of chars prepared from an Argentine asphaltite. D. Nassini, G. G. Fouga, H. E. Nassini, A. E. Bohé. Fuel 182 (2016) 623 631
Experimental Setup for Gasification with CO 2 11/20 THERMOGRAVIMETRIC ANALYSIS SYSTEM: This equipment is applied to follow the kinetic of gasification reaction by measuring the temporal evolution of relative mass changes of the char. The gasification rate, R, is evaluated as: (t) is the reaction degree at time t, m 0 is the initial char mass, α t = m 0 m t m 0 m ash m(t) is the char mass at time t, m ash is residual mass at the end of the gasification reaction. R = dα dt = 1 m 0 m ash dm dt
Alfa Ln t -ln t( ) Alfa Alfa EM Asphaltite Gasification Efecto de la Masa 12/20 1.0 0.8 0.6 0.4 0.2 0.0 1.0 0.8 0.6 0.4 0.2 0.0 T: 950 C PCO 2 : 80 kpa M i : 10 mg 20 (l h -1 ) 15 (l h -1 ) 10 (l h -1 0.2 0.2 T: 950 C CO ) 2 Flow Mass PCO 5 (l h -1 PCO : 80 kpa ) 0.0 2 Caudal: 5 ls/h 0.0 2 0 600 1200 1800 2400 3000 3600 4200 4800 Tiempo (seg) Efecto de la Temperatura Temperature 0 3600 7200 10800 14400 18000 21600 Tiempo (seg) 950 C 925 C 900 C 875 C 850 C 825 C 800 C 775 C PCO 2 : 80 kpa Caudal: 10 ls/h Masa: 2,5 mg 1.0 0.8 0.6 0.4 10 9 8 7 6 5 1 mg 2,5 mg 5 mg 10 mg 20 mg 40 mg 0 900 1800 2700 3600 4500 5400 875 C 900 C 925 C 950 C Tiempo (seg) 850 C 825 C 800 C 775 C Det. Ea: 185 kj/mol 4 8.0x10-4 8.5x10-4 9.0x10-4 9.5x10-4 d 2 3 Rate 1 1.1x10 exp PCO dt R T 1/T 1 5 185 kj mol 0.5 Kinetic Study of Argentinean Asphaltite Gasification Using Carbon Dioxide as Gasifying Agent. G.G. Fouga, G. De Micco, and A.E. Bohé. Fuel. Vol. 90, (2011), pp 674-680. ISSN: 0016-2361. 2 1.0 0.8 0.6 0.4-5.2-5.6-6.0-6.4-6.8-7.2-7.6-8.0 80 kpa 70 kpa 60 kpa 50 kpa 40 kpa 20 kpa 10 kpa T: 950 C Caudal: 5 ls/h Masa: 2,5 mg 0 1800 3600 5400 7200 1 2 Tiempo (seg) = 0,3 = 0,4 = 0,5 = 0,6 = 0,7 = 0,8 2.4 2.8 3.2 3.6 4.0 4.4 4.8 3 ln (PCO 2 (g)) Order: 0,5 4 5 6 7
Río Turbio Coal Gasification 13/20 CO 2 Flow Mass PCO 2 Temperature effect Ea: 190 kj/mol Order: 0,85 Coal Gasification Studies Applied to H 2 Production. G. De Micco, G.G. Fouga and A.E. Bohé. International Journal of Hydrogen Energy. Vol. 35, Issue 11, 2010, pp 6012-6018.
ln( t ) -ln(t ) F4 Asphaltite Gasification 14/20 1,0 0,9 0,8 0,7 0,6 0,5 0,4 T = 1400 ºC Mass = 1 mg pco 2 = 1 atm CO 2 Flow 0,3 9 L/h 8 L/h 0,2 6 L/h 0,1 4 L/h 2 L/h 0,0 0 60 120 180 240 300 360 420 480 540 600 CO 2 Flow 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 1200 C 1250 C 1300 C 1350 C 1400 C Time (seg) 1150 C 1100 C Temperature effect 0 1800 3600 5400 7200 9000 Time (s) 1.0 Experimental coditions: 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 8.0 7.5 7.0 6.5 6.0 5.5 5.0 T = 1400 ºC CO 2 (g) Flow = 6 L/h pco 2 = 1 atm Mass Char Mass 1 mg 2 mg 4 mg 10 mg 15 mg 20 mg 0 120 240 360 480 600 720 Time (s) Ea: 183 kj/mol 0.00060 0.00064 0.00068 0.00072 T -1 (K -1 ) 1.0 0.8 0.6 0.4 0.2 0,73 atm 0,82 atm 0,90 atm 1 atm 0,45 atm 0,55 atm 0,64 atm PCO 2 0,18 atm 0,27 atm 0,36 atm T= 1300 C Q CO 2 = 6 Lh -1 m o = 2 mg 0.0 0 1800 3600 5400 7200 9000 10800 12600 14400-4.5-5.0-5.5-6.0-6.5-7.0-7.5-8.0-8.5-9.0 0,091 atm 0,182 atm Time (s) 0,91 atm 0,728 atm = 0,2 0,546 atm = 0,3 0,364 atm = 0,4 = 0,5 = 0,6 = 0,7 = 0,8 0,273 atm 0,455 atm 0,819 atm 0,637 atm -9.5-2.5-2.0-1.5-1.0-0.5 0.0 0.5 ln(pco 2 ) Order: 1 Gasification for Practical Applications. ISBN 980-953-307-245-1. Chapter Number 2. Gasification Studies on Argentine Solid Fuels. Fouga, G. G., De Micco, G., Nassini H. E. & Bohé A. E. Editorial InTech.
Experimental Setup for Gasification with Steam 15/20 The gasification with steam needs a more complex experimental setup: it consist of a steam generator, a gasification reactor and a water condenser; coupled in series with a GC and a FTIR.
Analysis setup for gaseous components. 16/20 Infrared Spectrometer Perkin Elmer, Model: Spectrum 400 Gas Chromatograph CG/MS Perkin Elmer. Model Clarus 600/680 TCD: H 2 ; METANIZER-FID: CO, CO 2 Gasification reaction kinetics Characterised CO(g) concentration Peak areas Gas cell α t = n CO t n CO t f In chromatograms registered every 5 minutes n CO (t) is the number of CO(g) moles formed from the beginning until time t. n CO (t f ) is the number of total moles formed during the whole reaction.
Steam vs CO 2 Gasification 17/20 H 2 O GASIFICATION CO 2 GASIFICATION These results show that Argentinean solid carbonaceous fuels tested are susceptible to be gasified since their reactivities are comparable with those of low-rank coals used in large-scale gasifiers. Rate (E) > Rate (RT) > Rate F4 Reactivity Rank
Fluidized bed reactor for solid fuel gasification Parameter Int Bed mass Height of the bed Height of the bed (mfc) R mf P fr 18/20 FBR 25,8 mm 40 g 5 cm 8 cm 30 l/min No detected
Concluding Remarks 19/20 Coal gasification assisted by nuclear energy is a promissory process to utilize the residual heat from a nuclear reactor providing heat and steam for the natural solid fuels pyrolysis and gasification reactions respectively For this purpose, a theoretical and experimental program on laboratory scale is underway with the objective of characterizing the behaviour of selected feed materials under typical pyrolysis and gasification conditions. The research program included the development of specially-designed experimental setups for gasification using CO 2 and steam as gasifying agents. These studies allow to get relevant information about the reaction mechanisms and kinetic parameters of the pyrolysis and the gasification reactions, in order to be used in large-scale gasifier design.
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