sorption enhanced production of hydrogen in industrial ......sorption enhanced production of...

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Sorption enhanced production of hydrogen in industrial processes

using two chemical loops J.R. Fernández*, I. Martínez, J.C. Abanades

[email protected]

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


two chemical loops


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


two chemical loops


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


two chemical loops


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


two chemical loops


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


two chemical loops

TCCS-9, 2017 J. R. Fernández , I. Martínez, J. C. Abanades

Outline


two chemical loops


1. Introduction




5. Conclusions


two chemical loops


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


two chemical loops

The Ca-Cu looping process



two chemical loops


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)


two chemical loops


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


two chemical loops


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)


two chemical loops


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


two chemical loops


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


two chemical loops


1. Introduction




5. Conclusions


two chemical loops


(*) 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


two chemical loops


(*) 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


two chemical loops


1. Introduction




5. Conclusions


two chemical loops


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


two chemical loops


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


two chemical loops


1. Introduction




5. Conclusions

Conclusions


two chemical loops


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.

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TCCS-9, June, 12th-14th, 2017, Trondheim

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sorption enhanced production of hydrogen in industrial ......sorption enhanced production of...

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