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LOGO
Sorption enhanced production of hydrogen in industrial processes
using two chemical loops J.R. Fernández*, I. Martínez, J.C. Abanades
jramon@incar.csic.es
CO2 Capture Group
INCAR-CSIC (Spanish Research Council)
TCCS-9, June, 12th-14th, 2017, Trondheim
Outline
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
1. Introduction
2. The Ca-Cu looping process for H2 production
3. The Ca-Cu looping process in steel industry
4. SER combined with an iron oxide chemical loop
5. Conclusions
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
Conventional Steam Methane Reforming (SMR)
Feed
CH4+H2O
Reforming Reaction CH4(g) + H2O(g) ↔ CO(g) + 3H2(g) ∆Hr
o = 226 kJ/mol CH4
Shift Reaction CO(g) + H2O(g) ↔ CO2(g) + H2(g) ∆Hr
o = -38 kJ/mol CO
HTS
LTS
WET SCRUBBER
PSA UNIT REFORMER SHIFT
REACTORS
99.5% H2
95% H2
Trace CO, CO2
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
Conventional Steam Methane Reforming (SMR)
Feed
CH4+H2O
Reforming Reaction CH4(g) + H2O(g) ↔ CO(g) + 3H2(g) ∆Hr
o = 226 kJ/mol CH4
Shift Reaction CO(g) + H2O(g) ↔ CO2(g) + H2(g) ∆Hr
o = -38 kJ/mol CO
HTS
LTS
WET SCRUBBER
PSA UNIT REFORMER SHIFT
REACTORS
99.5% H2
95% H2
Trace CO, CO2
Supplemental
Energy Fuel + Air
PSA
Off gas
T=800-950ºC
P=20-40 bar
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
Equilibrium is shifted to H2 production
Operation at lower temperatures
Reforming process in one single stage
Process almost thermally balanced
Thermodynamics
Sorption Enhanced Reforming (SER)
Fuel+ Steam
H2 rich gas
CO2 sorbent
(CaO)
SER
600-700 ºC
up to 15 bar
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
Sorption Enhanced Reforming (SER)
CaCO3 calcination
900 ºC
1bar
CO2
HEAT
CaCO3
CaO Fuel+ Steam
H2 rich
gas
SER
600-700 ºC
up to 15 bar
High T for calcination (around 900ºC)
Efficiency penalties
Unsurmountable challenge???
Proposed solutions for sorbent regeneration
Oxy-combustion of additional fuel in a regenerator
External heating through high-temperature heat transfer surfaces
Direct heating by contact with hot solids or hot gases obtained from additional fuel
combustion
Use of the waste heat from a fuel cell coupled to the SER process
Low thermal efficiencies
and/or
High equipment cost
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
TCCS-9, 2017 J. R. Fernández , I. Martínez, J. C. Abanades
Outline
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
1. Introduction
2. The Ca-Cu looping process for H2 production
3. The Ca-Cu looping process in steel industry
4. SER combined with an iron oxide chemical loop
5. Conclusions
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
CuO Reduction CaCO3 Calcination
Cu Oxidation
SER CH4+H2O H2
Air
N2
Fuel gas
CO2+H2O
CaCO3 Cu (Ni)
CaO Cu (Ni)
CaCO3
CuO (NiO)
The Ca-Cu looping process
(Abanades & Murillo, CSIC, EP09382169.2, 16th Sep 2009)
CH4+H2O
A B B’
Air
GT
H2-rich gas
H2
PSA off-gas (CH4, H2, CO2,CO)
PSA ~
C
N2(CO2)
N2 (CO2)
CO2
C’
CH4+H2O
N2(CO2)
N2(CO2) Syngas (CO,H2,CO2,H2O)
H2O
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
The Ca-Cu looping process
TCCS-9, 2017 J. R. Fernández , I. Martínez, J. C. Abanades
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
Plant performance indexes for H2 production processes with and without CCS
Equiv H2 production efficiency (LHV, electricity, heat exchanges with exterior)
Reference FTR= 83% FTR with MDEA=72% (CO2 capture penalty) Ca-Cu process=77% (CO2 capture penalty)
CO2 capture efficiency
Reference FTR= 0% FTR with MDEA=85% Ca-Cu process=93%
FTR plant FTR+MDEA Ca-Cu process
S/C molar ratio 2.7 4.0 3.0 Thermal input, MW 121.9 130.8 113.5
Steam turbine output, MW 3.3 3.8 0.3 ASU consumption, MW - - -
CO2 compression, MW - 2.2 2.1
H2 compression, MW - - 1.0 Other plant auxiliaries, MW 1.0 1.4 0.2
Heat output, MW 8.6 4.1 4.3 Net electric plant output, MW 2.4 0.3 -4.1
H2 production efficiency,% 73.9 68.8 78.6 Eq. H2 production efficiency,% 83.3 71.6 77.1
Equivalent CO2 emission, gCO2/MJH2 68.4 9.3 6.5
Carbon capture ratio, % - 84.9 93.0 SPECCA, MJ/kg CO2 - 3.3 1.6
(*)
Reference plant:
30,000 Nm3H2/h
(*) Martinez et al. Appl Energ 114:192−208 (2014)
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
TCCS-9, 2017 J. R. Fernández , I. Martínez, J. C. Abanades
Experimental validation of the Ca-Cu looping process (ASCENT Project)
TEST RIG AT INCAR-CSIC
Material: Inconel
Internal diameter: 0.038 m
External diameter: 0.042 m
Height: 1 m
Solids mass: around 1 kg
Multipoint type K termocouple (15 points)
Insulating material: quartz wool
IR and Paramagnetic Gas Analizers
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
TCCS-9, 2017 J. R. Fernández , I. Martínez, J. C. Abanades
CuO reduction/CaCO3 calcination stage
High reactivity of H2 (and CO) with CuO even at low temperatures (around 400ºC)
(rapid increase in temperature, total fuel consumption during pre-breakthrough)
Negligible calcination of CaCO3 below 800 ºC
Rapid calcination when T profile achieves 850 ºC (dramatic increase in CO2 out)
Relatively short breakthrough period
Dynamic model describes reasonably well temperature and composition profiles, breakthrough curves
(*) Fernandez et al. Ind Eng Chem Res 55: 5128-5132 (2016)
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
TCCS-9, 2017 J. R. Fernández , I. Martínez, J. C. Abanades
Cu oxidation stage
The recirculation of a large fraction of the product gas moderates the temperature profile (Tmax=800 ºC)
Low O2 content and high flow rate make heat front advances much faster than the oxidation front
Rapid oxidation despite the very low content in the feed (i. e. 3 vol%O2)
Dynamic model describes reasonably well temperature and composition profiles, breakthrough curves
(*) Alarcon et al. Chem Eng J 325: 208-220 (2017)
OF
HF
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
TCCS-9, 2017 J. R. Fernández , I. Martínez, J. C. Abanades
SER stage in micro fixed-bed under conditions of the Ca-Cu process
H2 contents above 90 vol.% on a dry basis (SER equilibrium)
Negligible presence of CO2 during prebreakthrough
Good agreement between modelling and experimental results
(SER, breakthrough and SMR periods) (*) Grasa et al. Chem Eng J 324: 266-278 (2017)
Reforming catalyst+CaO sorbent over Ca12Al14O33
Catalyst subjected to 200 redox cycles
Operation up to 9 bar
Outline
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
1. Introduction
2. The Ca-Cu looping process for H2 production
3. The Ca-Cu looping process in steel industry
4. SER combined with an iron oxide chemical loop
5. Conclusions
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
(*) Martinez et al. Int J Hydrog Ener 42: 11023-11037 (2017)
The Ca-Cu concept to decarbonize the blast furnace gas (BFG)
Use of an arrangement of 3 fluidized-bed reactors operating at atmospheric pressure
SEWGS of the blast furnace gas (22% vol.CO) and production of a H2-enriched gas (higher LHV)
Fuel gases for sorbent calcination: N2-free fuel gases from the steel mill and/or natural gas
Segregation step: reduction in solids circulation
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
(*) Martinez et al. Int J Hydrog Ener 42: 11023-11037 (2017)
The Ca-Cu concept to decarbonize the blast furnace gas (BFG)
Using COG as reducing gas about 28% of BFG can be decarbonized (35% vol H2 for power generation and DRI)
After segregation the CaO required for steelmaking is obtained (avoiding the lime plant)
About 31% of carbon emissions are avoided
Around 60% of thermal input can be recovered as high-T heat to produce electricity
Outline
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
1. Introduction
2. The Ca-Cu looping process for H2 production
3. The Ca-Cu looping process in steel industry
4. SER combined with an iron oxide chemical loop
5. Conclusions
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
SER combined with a Fe3O4/Fe2O3 chemical loop
Heat required for CaCO3 calcination (and OC reduction) is supplied by a high-T stream of Fe2O3 coming from AR
PSA-off gas as reducing agent avoids the need for additional NG in the calcination and improves CO2 capture efficiency
-(*) Fernandez and Abanades,
Chem Eng Trans 52:535-540 (2016)
-(**) Fernandez and Abanades,
Accepted for publication App Therm Eng
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
Effect of active content of Fe-carrier on process performance
High-purity carriers result in higher H2 efficiencies and lower energy inputs
Lower circulations of solids are feasible and higher temperatures in the AR are achieved (lower thermal ballast)
For 50 wt% Fe2O3 85% H2 eff (based on LHV) S/G ratio in AR= 10 1,050 ºC in AR
For <20 wt% Fe2O3 <83% H2 eff (based on LHV) S/G ratio in AR>30 <950 ºC in AR
Outline
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
1. Introduction
2. The Ca-Cu looping process for H2 production
3. The Ca-Cu looping process in steel industry
4. SER combined with an iron oxide chemical loop
5. Conclusions
Conclusions
Sorption enhanced production of hydrogen in industrial processes using
two chemical loops
J. R. Fernández , I. Martínez, J. C. Abanades TCCS-9, 2017
The Ca-Cu looping process is a feasible alternative to carry out the regeneration of calcium
carbonate with moderate energy penalty
The key reaction stages of the Ca-Cu process have been experimentally validated at TRL4
The Ca-Cu concept applied to steel plants allows about 28% of BFG to be decarbonized using
COG, and avoids 31% of CO2 emissions and the need for the lime plant
A SER process combined with an iron oxide chemical loop can theoretical produce virtually pure H2
with energy efficiencies up to 87% (on LHV basis) and CO2 capture efficiencies close to 100%.
However, a more detailed investigation is required to demonstrate the feasibility of this process.
LOGO
THANKS FOR YOUR ATTENTION!
Any questions…..?
TCCS-9, June, 12th-14th, 2017, Trondheim
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