To appear in: Proc. Int.

Symp on Global Environment and Steel Industry

(ISES'03), June 24-26, 2003, Beijing, China The Chinese Society for Metals

Hydrogen as a reductant for iron ores

and the effects on CO2 formation

K.-H. Tacke* and R. Steffen **

*
Dillinger Hüttenwerke, Dillingen, **Steel Institute VDEh, Düsseldorf, Germany

Abstract: This study summarizes information on the use of hydrogen for iron ore reduction. Ideally, hydrogen re-
duction would imply zero CO2 emissions. Reaction capabilities of hydrogen and the existing processes are reviewed.
Available sources of H2 and the associated CO2 effects are discussed. Costs are estimated and compared.
Key words: Iron ore reduction, CO2 mitigation, steel industry, hydrogen reduction, direct reduction, fluidized bed,
cost of reductants, carbon-free hydrogen production

1 INTRODUCTION delivers is thus the appropriate basis for comparison

The questions of global warming and the current
political efforts to control greenhouse gas emission as
manifested in the Kyoto protocol motivate reconsid-
eration of the sources of CO2 and of the options for
abatement.
Steel is one of the most environmentally benign mass
products due to its high recycling rate. Iron ore reduc-
tion is today widely carried out with coke and coal in
the blast furnace. Steel industry contributes around 6 %
to the total anthropogenic emissions of CO2.
To apply hydrogen as a reductant could be an alterna-
tive. The resulting off-gas is H2O which can be sepa-
rated easily by condensation.
This contribution collects knowledge on the use of
hydrogen for iron ore reduction, starting with ther-
modynamic and kinetic aspects and the technical
process options. Also, the availability of hydrogen
from various sources is outlined; together with the cost
and the CO2 effects.
This paper can only capture the momentary status in
the fields of CO2 control and hydrogen technology
which are rapidly evolving.
2 ENERGY REQUIREMENTS
Energy is required to break the bonds between Fe and
O when extracting the metal from the ore. Per tonne of
reduced iron, 7.4 GJ (free enthalpy of formation) are
needed for Fe2O3 and 6.7 GJ for Fe3O4, independent of
the reductant. The amount of energy that a reductant
and will be used later in this text.
Direct reduction processes typically require 11 to 14 GJ
per tonne of solid DRI and the blast furnace 16 to 18 GJ
per tonne of liquid hot metal.
Carbon, the most widely used reductant, is first con-
verted by the solution loss reaction to CO, which per-
forms the reduction and is thereby oxidised to CO2.
The route blast furnace with basic oxygen steelmaking
generates about 1,500 kg of net CO2 per tonne of crude
steel [1].
3 THERMODYNAMICS AND KINETICS
The equilibria of iron ore reduction with the gases CO
and H2 are well known [2]. Above 850°C, hydrogen is
even stronger in reducing power than CO.
Hydrogen, atomically small and with high diffusivity,
has been noted as the faster reductant [3] and thus of-
fers the prospect of rapid reduction processes with no
greenhouse gas emission.
Figure 1 shows how close the limits of equilibrium can
be approached in the case of pellets [4]. Gas utilisation
is a function of temperature and depends on the degree
of reduction. The thermodynamic limit is not reached.
With ore fines in fluid bed reactors, kinetics are more
complex [5,6]. Figure 2 shows reduction characteristics
of Mt.-Wright hematite fines when reduced by a
50%H2-50%N2-gas mixture between 450 and 800°C in
a laboratory furnace.
Gas utilisation again depends on temperature and on
Figure 1: Gas utilisation of hydrogen as a function of tem-
perature and reduction degree. Pellets (hematite), dia. 3 to 30
mm, from Ref. [4, Figure 14]
the reduction degree. Initially, gas utilisation is high,
but drops after 50 to 60 % reduction, in particular at
temperatures around 700°C. The cause is the rate
minimum effect, which is attributed to morphological
changes of solid phases [6,7] and typically occurs
between 600 and 750°C.
The distance of measured curves from equilibrium is
known as insufficient gas utilisation. A reason is the
retarding effect of water vapour on the reaction
FeO+H2 -> Fe + H2O.
Another limiting factor in fluidised beds is sticking -
defluidization through adhesion between ore particles.
It leads to the breakdown of the fluid bed and also
depends on the type of ore fines and on the reduction
degree.
Hydrogen reduction in fluid beds can only be realised
when carried out in stages which are to be selected in
dependence on the degree of reduction, specific for
each fine ore. Similar diagrams have been established
for other hematite and magnetite ores.
4 HYDROGEN REDUCTION PROCESSES
Shaft furnaces The two most relevant direct reduction
processes are Midrex and HyL-III with several mod-
ules operating worldwide. They produce DRI from
pellets and lump ores. Natural gas is reformed to a
mixture of H2 and CO which is fed into the furnace as
the reducing gas.
Midrex typically applies H2/CO ratios between 1 and
1.5 but is capable of reducing iron ore with any com-
bination of H2 and CO. Improved reaction kinetics with
Figure 2: Gas utilisation of hydrogen as a function of tem-
perature and reduction degree. Ore fines (Mt.-Wright, hema-
tite), reduced in a laboratory fluidised bed, from [5,6]
H2 are expected to be offset from the lower burden
temperatures as a result of the endothermic reduction of
FeO. That there are currently no Midrex plants using
100 % H2 is only due to economic considerations [8].
HyL emphasizes the application of hydrogen as the
reducing gas [9]. The use of coke oven gas is promoted
for integrated iron and steel plants. Economic benefits
still remain to be proven.
The minimum effect seems to be no great obstacle in
such shaft furnaces owing to the temperatures which
are around 750 to 1000°C and thus above the critical
range.
Fluidized beds Such reactors are fed with ore fines and
thus no pelletizing is needed. Intensive mass and heat
transfer in fluid beds promise high productivity. In the
past, several concepts have been tried out but were
abandoned [10, 11, 12] with one exception: the FIOR
process [13] has been operative since 1976 (temporar-
ily shut down in 2001).
FIOR has been further developed in collaboration with
VAI into the FINMET process [14,15] which converts
iron ore fines (<12 mm) in a series of four fluidized bed
reactors to HBI.
FINMET plants have been built in Port Hedland, Aus-
tralia, and in Puerto Ordaz, Venezuela, each with a
design capacity of ~2 million tonnes of HBI per year.
Port Hedland, initially with problems [16], now ap-
proaches the rated capacity [15]. The Orinoco plant is
able to produce good briquettes [16] but its start-up was
overshadowed by a partner bailing out and by a low
HBI market.
Lurgi's Circored fluid bed process [17, 18] reduces ore gasification [9, 20, 21]. These figures are not expected
fines with hydrogen in a circulating fluid bed at 630°C to drop significantly in the future.
and a stationary bed at 680°C. The first industrial plant
has been built in Trinidad for a capacity of 500,000 t
6 LOW-CARBON HYDROGEN PRODUC-
HBI/year. After initial problems were resolved, the
TION
plant was operative between March and October 2001
at 90 % capacity. It was stopped due to an unfavourable Fossil sources with CO2 separation and disposal
HBI market, but is kept idle since Lurgi Metallurgie is Carbon dioxide can be captured and stored when pro-
confident in the potential of Circored. ducing hydrogen from fossil media. This relieves the
atmosphere of CO2 while dumping it on other locations.
Such technologies are pursued and developed.
5 AVAILABILITY AND CO2 EFFECT OF
For capturing carbon dioxide from gas streams chemi-
HYDROGEN
cal solvent absorption (with MEA as the most widely
About 500 Gm3 of hydrogen are produced annually used absorbent), adsorption on a solid, pressure swing
from natural gas, oil or coal [19]. The most widely used adsorption, membranes and other concepts are avail-
technology is steam reforming of natural gas. able.
Hydrogen can be generated from other fossil media. As Storage of CO2 has been proposed in geological res-
Table 1 shows, such sources are associated with sub- ervoirs, in saline aquifers or in the deep ocean. CO2 can
stantial mass fractions of carbon. The leanest is meth- be stored in gas or oil fields; in active fields, the pres-
ane with a ratio C/(C+H) of 75 mass%. sure of CO2 may be used for Enhanced Oil Recovery
Table 1: Fossil sources: carbon and hydrogen content, CO2
(EOR). Examples of large scale CO2 storage are the
formation on combustion and on hydrogen production Weyburn [23] and the Sleipner West projects [24]. CO2
can also be injected into coal beds, where it
Stoich.C,H C/(C+H), CO2, kg/GJ CO2, kg/GJ displaces methane and can enhance methane
(approx) mass% combustion hydrogen recovery.
Carbon C 100 111.7
World-wide storage capacities for CO2 seem
Coal CH0.8 94 88 - 115 136 - 170
more than adequate [25], although the suit-
Wood CH1.44 89.3
Biomass CH2 85.7 98 ability of reservoirs for storage varies greatly.
Oil CH1.5-2 85.7 - 88.3 74 - 76 115 - 121 The cost of carbon dioxide capture and
Propane C3H8 81.8 65 long-term storage is today in the order of 40 to
Natural gas CH3.75 76 60 - 65 55 - 80.5 60 $ per tonne of CO2 [26]. Future costs are
Methane CH4 75 55
estimated between 5 and 10 €per tonne of CO2
by IISI [27] while the US DOE supports the goal of 3 $
The next column in the table contains the mass of CO2
per tonne CO2 [28].
released per unit energy when the substance is oxidized.
When about 70 kg of CO2 need to be disposed per GJ of
With natural gas, the quantity of CO2 is still about half
hydrogen from natural gas (Table 1), capture and
of that for carbon.
storage of CO2 at 50 € per tonne will add 3.5 € to the
The manufacture of hydrogen from fossil sources re-
price for a GJ of hydrogen, and only 0.3 € at storage
quires some extra process energy and thus leads to the
costs of 3 €per tonne of CO2.
estimates of CO2 formation in the rightmost column.
Coal-based hydrogen making involves more CO2. Cost
To produce hydrogen from natural gas in the steam
estimates with CO2 venting are 10 $/GJ [23] and 11 to
reforming process costs about 2 €/GJ [9]. When natural
13 $/GJ [23, 29] with CO2 removal. The higher storage
gas is available at 4 €/GJ (as in Europe), the hydrogen
cost may be offset by the lower base medium price. For
price is 6 €/GJ [9, 20, 21, 22]. In cheap energy coun-
the future, more economical processes are anticipated
tries hydrogen will cost less than 3 €/GJ.
with costs of 6.4 $/GJ [30].
Hydrogen from partial oxidation of oil costs about 6 to
9 €/GJ [9, 20, 21], and 7.5 to 10.8 €/GJ from coal
Biomass Hydrogen can be produced by gasification of CO2-COST DIAGRAMS
biomass [31, 32]. Since biomass is composed of hy-
Figure 3 summarises the data collected in the previous
drocarbons, the emitted quantities of CO 2 are not low.
section. The figure shows how cost increases when
However, the overall cycle is viewed as CO2-neutral
CO2 emission is mitigated - cleanness has a price.
when such CO2 is released into the atmosphere because
all this carbon dioxide is eventually recovered by the
growth of new biomass through photosynthesis. If CO2
is separated during hydrogen making and disposed, the
lifecycle emissions will even be negative - an overall
extraction of carbon dioxide from the atmosphere.
Hydrogen from biomass will cost about 9 to 11 $/GJ
[32, 33, 34] and 7 €/GJ are projected for 2020 [33].
Scepticism remains with the large-scale feasibility of
this approach.

Non-fossil sources In this case, hydrogen is generated Figure 3: CO2-cost diagram of various energy sources and reduc-
by electrolysis of water. To split water into oxygen and tants, present status and near future
hydrogen thermodynamically requires 286 kJ per mol
of H2. Since the energy efficiency of large scale elec- Figure 4 is the same diagram, but with future projec-
trolysis is 70 to 90% [31] the production of 1 GJ of tions for a range of about 10 to 30 years. It is uncertain
hydrogen requires 1.1 to 1.4 GJ of electricity. if these lower costs can be reached. Especially for
low-carbon sources the shift toward lower prices is
Therefore the cost of H2 is closely tied to the price of
electrical energy. If electricity costs 0.05 €/kWh (14 obvious.
€/GJ), a hydrogen price reaching 20 €/GJ is the con-
sequence. This limits the competitiveness of non-fossil
sources for hydrogen.
Published cost estimates of hydrogen from alternative
concepts are 22 to 44 €/GJ for wind power [20, 33], 42
to 55 €/GJ from solar thermal units [20, 33] and 47 to
104 €/GJ for photovoltaic energy [20]. Future projec-
tions are as follows: hydrogen from wind energy in
2020: 10 to 16 €/GJ [33], from solar thermal in 2020:
about 28 €/GJ [33], photovoltaic (optimistic): 17 €/GJ
[29].
Figure 4: CO2-cost diagram, future projections (about 10 to
Nuclear power is in principle carbon-free but imposes
30 years)
the same efficiency factor when electrolysing water to
hydrogen.
Under special and localized conditions, hydrogen from
CONCLUSIONS
electrolysis may become competitive, for example
Iron ore reduction with hydrogen is feasible from
when low cost hydro-electric power is available [31], 7
thermodynamics and kinetics, although difficulties in
to 14 €/GJ from large scale hydro-electricity are esti-
processing may originate from the minimum effect,
mated in Ref. [33].
from insufficient gas utilization and sticking of ore
Where low-cost low-carbon electricity is available,
fines. Such phenomena need more R&D for a deeper
direct electrolytic reduction of ores [35] might be an
understanding.
alternative to the longer hydrogen route.
Large scale use of hydrogen for iron ore reduction is
not realistic at present with a worldwide production of
 608 Mio. tonnes of hot metal in 2002. The supply of
hydrogen is limited and the cost is not competitive in
most countries. Today's fossil sources involve consid-
erable CO 2 formation during hydrogen production.
Future developments will lead to a larger supply of
low-carbon hydrogen. While non-fossil sources of
hydrogen remain burdened with the loss of efficiency
through water electrolysis, fossil media with carbon
capture and disposal may provide a path with limited
cost. As Figure 4 shows, this is still not competitive
with coal-based ironmaking.
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