Metal oxide based redox couples for hybrid thermochemical hydrogen production

Debasis Saran1, R. Singh1+, A. Anand1, S. Pati1, K. K. Sahu1, S. Swain2, Y. S. Chaudhary2

School of Minerals Metallurgical and Materials Engineering, Indian Institute of Technology, Bhubaneswar
2
Colloidal and Materials Processing Div., Institute of Minerals and Materials Technology, Bhubaneswar
+
Contact: randhir@iitbbs.ac.in

Introduction

Standard cycle:

Post industrialisation, fossil fuels are being used to

meet the ever-increasing demand for the primary
energy. However, the fossil reserves are finite (Table
1). A pragmatic replacement to fossil fuels in future
would be hydrogen, derived from renewable or
semi-infinite sources of energy such as nuclear
fission/fusion. In fact, the drastic increase in the
atmospheric CO2 level warrants an imminent
alternative to fossil usage.
Table 1. Estimated depletion time for worlds fossil fuels (Shafiee et
al., Energy Policy 37, 181189, 2009).

Fossil resource

Depletion time, y

Oil
Coal
Gas

35
107
37

The present work presents a novel hybrid (thermal

and electro-chemical) route to fuel such as hydrogen
with a much less carbon footprint (Fig. 1).

T>2000K
Thermal
Reduction:
Fe3O4 = 3FeO +
O2

Disadvantages:
Non-isothermal (more losses)

Material out: O2
Material in: H2O

T900K
H2 production:

Problem of powder sintering

3FeO+H2O =
Fe3O4 + H2

High Temp (>1500 K)

Crushing of FeO at each cycle

Vacuum/Inert atm requirement

Material out: CO/H2

Fe2O3: to recycle

Material loss

Proposed cycle:

Advantages:

T~1000K
Molten Salt
Electrolysis:
Fe3O4 = 3FeO +
O2

Material out: O2
Material in: H2O

Material out: CO/H2

Fe2O3: to recycle

Pseudo-isothermal
No sintering
Fixed bed reactor
Low Temp (<1000 K)
Electricity is needed / dispensed
depending on inert or C electrode

T900K
H2 production:
3FeO+H2O =
Fe3O4+ H2

Min material loss

Fig 1. Comparison between conventional & proposed cycle.

The objective of this work was to use of iron oxide redox couple in a hybrid thermochemical cycle for H 2 production. The work constituted the following
main steps: 1) Oxide foam preparation; 2) Electrolytic reduction of Fe2O3 to FeO using the FFC Cambridge process and 3) FeO-hydrolysis to generate H2.

Experimental

Results

The sol-gel method of foam making consisted

of slurry preparation , addition of initiator &
catalyst, foaming by stirring and polymerisation
(casting & settling ).
Techniques like XRD & SEM were used to
characterise the samples. For molten salt
electrolysis, the furnace was programmed
according to a particular schedule for the FFC
process reduction. The overall experimental
plan is shown in the flow diagram below.

H2 production unit

(a) As gel-cast

10mm

Fig 3. Iron oxide foams: (a) before sintering (b) after sintering.
A diameter reduction of about 33% is recorded after sintering.
(a)

Fig 4. SEM image of foams

sintered in closed atmosphere:
(a) macroscopic BS image of
pores at low magnification
(100 X) (b) intra strut pores
revealed
at
a
high
magnification of 50000 (back
scattered) and (c) high
resolution SE image of the
strut.

Iron oxide foams making

Bubbler (water trap)

()

H 2 ( g ) H 2O ( g )

FeO regeneration
unit
O2 ( g )
3

2
Cathode: Fe e Fe

Reaction:

3FeO H 2O( g )
Fe3O4 H 2 ( g )

Fe3O4

( )

FeO

Fe3O4

FeO

O 2 O2 2e or

Anode:
2

C Fe3O4 3FeO CO( g )

1
2

Overall: Fe3O4 3FeO O2 ( g )

Molten salt: in

H 2O ( g )

Fig 5. Schematic of Hydrogen generation and FeO regeneration unit.

electrolysis

100m

(c)

(a)

Drying and sintering

500 nm

Hydrolysis of FeO at 600 C to produce

H2
Reduction of Fe3O4 to FeO by electrolysis

(b)

Fig 2.(a) Schematic of FFC Cambridge (A) Fe2O3 foam

cathode (B) Graphite Anode C) Electrolyte (Eutectic
mixture of LiF, MgF2, CaF2) (D) Ti cathode for pre
electrolysis ( E) Outlet for exhaust.
(b) Experimental set up FFC Cambridge

(b)

Fig 6. Iron oxide foam (a) as sintered in air and (b) after electrolysis.

Sintering of the oxide foams in a closed atmosphere resulted in partial reduction of the oxide into the reduced
form of the iron oxides as was confirmed by the XRD pattern. Figure 3 and 4 show the presence of requisite
pore sizes at various length scales which results in an increase in surface area for hydrolysis reaction.
It is proposed to use a single fixed bed reactor as: 1) H2 production unit, and 2) FeO regeneration unit. Water
vapour will be passed through the bottom of the fixed bed of porous FeO foam at hydrolysis temperature of
900 K and the hydrogen will be collected from the outlet stream at the top (See Fig 5). Fig 6 shows the
colour change observed after electrolysis, which indicates conversion of Iron(III) oxide to FeO. Further
characterisation and hydrolysis of the reduced foam is yet to be performed.

Conclusions

(a)

FischerTropsch process
(H2+CO = hydrocarbon (liq.))

Dierite (sorption of
water residue)

(b)

Reduction of the sintered foams to

FeO by the FFC process at 810 C.

H2 (g)

(b) Post-sintering

A novel method for production of hydrogen is proposed.

A fixed bed reactor concept for a hybrid thermochemical
process is envisaged.
The process is isothermal and offers many advantages:
o Minimum material and heat loss
o Fuel products: H2 and CO

Future work
Hydrolysis of the reduced (i.e.,
FeO) foam.
Process cycling
Process optimisation
Scale up