Environ Dev Sustain (2012) 14:529–540

DOI 10.1007/s10668-012-9342-z

Novel process concept for the production of H2

and H2SO4 by SO2-depolarized electrolysis

Anu Lokkiluoto • Pekka A. Taskinen • Michael Gasik •

Ilkka V. Kojo • Heljä Peltola • Michael H. Barker • Karl-Heinz Kleifges

Received: 9 November 2011 / Accepted: 23 February 2012 / Published online: 7 March 2012
Ó Springer Science+Business Media B.V. 2012

Abstract Outotec open cycle (OOC) is a new low-energy process linking together pro-
duction of hydrogen and sulfuric acid. While sulfuric acid is the world’s most widely
produced chemical by mass at approximately 200 Mt/a, the OOC gives the potential for
making 4 Mt/a of hydrogen gas as a by-product. H2SO4 manufacture requires a source of
sulfur dioxide. 30% of world production of H2SO4 is from the SO2 by-product of pyro-
metallurgical processing of sulfur containing concentrates of metals such as copper, nickel
and zinc. SO2 can also be made by direct combustion of sulfur. In OOC, a divided
electrochemical cell is used for SO2-depolarized electrolysis of water. SO2 is fed to the
anolyte and converted to H2SO4, while hydrogen gas is produced at the cathode. On the
industrial scale, the equipment will be in the form of a membrane electrolyzer assembly or
stack. A case is described where the OOC would be connected to a pyrometallurgical plant
smelting 1 Mt/a of nickel and copper concentrate, producing 1 Mt/a of H2SO4 and 20 kt/a
of hydrogen.

Keywords Hydrogen production  SO2 recovery  Metals production 

Sulfuric acid production

Readers should send their comments on this paper to BhaskarNath@aol.com within 3 months of publication
of this issue.

A. Lokkiluoto (&)  P. A. Taskinen  M. Gasik

Aalto University School of Chemical Technology, Vuorimiehentie 2, Espoo, PO Box 16200,
00076 Aalto, Finland
e-mail: anu.lokkiluoto@aalto.fi

I. V. Kojo
Outotec Oyj, Riihitontuntie 7 D, PO Box 86, 02200 Espoo, Finland

H. Peltola  M. H. Barker
Outotec (Finland Oy) Research Center, Kuparitie 10, PO Box 69, 28101 Pori, Finland

K.-H. Kleifges
Outotec (Oberursel), Ludwig-Erhard-Strasse 21, 61440 Oberursel, Germany

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1 Introduction

Hydrogen-powered vehicles are the key to maintain or obtain the mobility now available in
developed countries together with mitigation of CO2 emissions and reduction of our
dependence on fossil fuels. As an energy carrier, hydrogen can be used to store and
transport renewable energy produced at one location to be used in another time and place.
On the way to the hydrogen energy society, hydrogen can also be used to decarbonize
energy from fossil sources, for example, in the production of syngas (Winter 2009). Beside
its use as an energy carrier, hydrogen is a commodity needed for many industrial processes.
Environmentally and economically, one of the best known alternatives to alkaline
electrolysis or steam methane reforming for the large-scale hydrogen production is the
so-called hybrid sulfur process (HyS). The Nuclear Hydrogen Initiative of the US DoE has
identified the HyS cycle together with the sulfur-iodine cycle (IS) as the first priority cycles
for hydrogen production (Gorensek and Summers 2009). According to the analysis of these
two processes carried out within the International Energy Agency (IEA) Hydrogen
Implementing Agreement (HIA) Task 25 (High Temperature Production of Hydrogen), the
HyS is the more favorable one (Galzim et al. 2011).
In this article, the new Outotec open-cycle process will be introduced together with its
industrial background. The process has been developed based on the HyS process, but
unlike the HyS, it is connected to proven technologies from the fields of metals production
from sulfidic minerals and sulfuric acid manufacture. SO2 and water are used as feedstock
to produce hydrogen and sulfuric acid. The SO2 can come from nonferrous metal sulfides-
processing operations (flash smelting, roasting, etc.) and from spent acid regeneration, or it
may be produced by burning elemental sulfur.

2 The hybrid sulfur (HyS) cycle

The HyS or Westinghouse cycle was patented by Brecher and Wu (1975) and described by
Brecher et al. (1977). It is a two-step process, first a low-temperature electrochemical step
and second a high-temperature, thermochemical step. The process flow sheet is shown in
Fig. 1.
In the electrochemical step of the HyS cycle, sulfuric acid and hydrogen are produced
by sulfur dioxide-depolarized electrolysis of water. In the thermochemical part, the sulfuric
acid formed in electrolysis is concentrated and decomposed thermally to SO2 and O2. The
SO2 is circulated back to the electrolysis step for hydrogen generation. The most energy-
demanding part of the HyS cycle is the decomposition of sulfuric acid; high temperature is
needed due to fundamental thermodynamic reasons, and the stabilities of sulfuric acid and
sulfur trioxide.
To be feasible, the process was designed to be coupled to a very high temperature
nuclear power plant, which would supply both the heat needed for the sulfuric acid con-
centration and decomposition steps and the electricity required for the electrochemical part
(Brecher and Wu 1975; Brecher et al. 1977). Very high temperature reactor belongs to the
group of so-called Generation IV nuclear power plants, which have yet to be constructed
(Kruger 2008; Charit and Murty 2010). One example of the Generation IV is a pebble bed
modular nuclear reactor, for which the outlet temperature of the cooling helium would be
950°C (McLaughlin et al. 2006). The BWR (boiling water reactor) and PWR (pressurized
water reactor) type reactors used nowadays produce steam, the temperature which is less
than 319°C and thus far below the feasible temperature range for decomposing sulfuric

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Fig. 1 HyS flow sheet schematic. Drawn after Brecher et al. (1977)

acid and sulfur trioxide further to SO2 (Forsberg 2009). Later coupling of the HyS cycle to
a solar heat source has also been studied for achieving sufficiently high temperatures for
sulfuric acid decomposition (O’Brien et al. 2010).
In the sensitivity studies carried out by Carty et al. (1977), the optimal process con-
ditions for the high-temperature step of the HyS cycle were analyzed to be T = 1,144 K,
the acid concentration post the electrolyzer 65–85 wt% and the SO3 decomposition
pressure 75–150 psia. Besides of the studies carried out in the USA, the Jülich Nuclear
Research Center in Germany studied the HyS process (Struck et al. 1980). Recently, few
research groups in different countries have been focusing on the HyS. Flow sheets for the
process were published by Gorensek and Summers (2009). Modeling results concerning
especially the coupling to a nuclear energy heat source were published by Jeong and
Kazimi (2007). Updated flow sheets were also discussed by McLaughlin et al. (2006).

3 Outotec open-cycle process

The novelty of the new process is the co-production of hydrogen and sulfuric acid by SO2-
depolarized electrolysis, where the SO2 used in the process can be obtained from flash
smelting, sulfides roasting, sulfur combustion or any other similar operation. Contrary to
the HyS/Westinghouse process, here the cycle is open and sulfuric acid is not decomposed,
as it is a commercial product with wide industrial use. The process is described in a patent
(Rauser et al. 2010). The process is shown in Fig. 2. The incoming SO2 gas stream is

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Fig. 2 Outotec open-cycle

process schematic

divided in two sub-streams, where the first sub-stream is routed to the SO2-depolarized
electrolyzer (SDE) and the second is routed to the acid plant to produce SO3. The SO3 is
used for concentrating the sulfuric acid produced in the electrolyzer as described below.

4 Sulfur dioxide-depolarized electrolysis

Sulfur dioxide-depolarized electrolysis (SDE) is a common step in both the HyS and the
new open cycle. In standard water electrolysis, the cathode reaction is hydrogen evolution
according to the reaction (1a). The anode reaction is oxygen evolution (1b).
4Hþ þ 4e ! 2H2 ðgÞ ð1aÞ
2H2 O(l) ! 4Hþ þ 4e þ O2 ðgÞ ð1bÞ
The overall reaction is:

2H2 O(l) ! 2H2 ðgÞ þ O2 ðg)E ¼ þ1:23 V vs: SHE ð2Þ
The idea of SDE was reported for the first time for hydrogen production by Juda and
Moulton (1967). In SO2-depolarized electrolysis, the cathode reaction is also hydrogen
evolution, (1a) but the anode reaction is the oxidation of dissolved sulfur dioxide, which
takes place at far lower anodic potentials according to reaction (3).

SO2 ðaqÞ þ 2H2 O ! 4Hþ þ 2e þ SO2

4 ðaqÞ ð3Þ
The overall cell reaction in SDE is then (4):

SO2 ðaqÞ þ 2H2 O ! H2 SO4 ðaqÞ þ H2 ðgÞE ¼ þ0:158 V vs: SHE ð4Þ
The clear advantage of the SDE process is that the reversible voltage E8 of the net cell
reaction (4) is only 0.158 V at 25°C (Gorensek et al. 2009), versus the reversible voltage of
E8 = 1.23 V (2) needed in water electrolysis realized with alkaline or polymer electrolyte
membrane (PEM) technologies. In laboratory-scale tests, the realized cell voltage of SDE
has been 0.5–1.2 V, depending on the current density (O’Brien et al. 2010; Lu and Ammon
1982; Steimke and Steeper 2006; Staser and Weidner 2009), versus 1.8–2.0 V of the
commercial alkaline water electrolysis (Stolten and Krieg 2010). Thus, the HyS process
would require only 25–60% of the electrical energy needed for the direct water splitting by
conventional electrolysis. Research groups at the Savannah River National Laboratory
(SRNL) at the University of South Carolina (USC) and at CSIRO (O’Brien et al. 2010;

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Steimke and Steeper 2006; Staser and Weidner 2009) as well as Jomard et al. (2008) have
recently studied and modeled the SDE. At Aalto CHEM, studies have been carried out to
replace the traditional catalyst material for SDE, platinum, with a cheaper material. The
results obtained thus far have encouraging.

5 Existing technology related to the new process

5.1 Flash smelting of sulfidic minerals

In a flash smelting furnace (FSF), the exothermic oxidation processes of sulfur and iron in
sulfide minerals produce the thermal energy needed to melt the metal-bearing concentrate
and slag-forming additives known as fluxes (Kojo et al. 2000). Gaseous SO2 formed during
smelting, and the subsequent converting step is cooled and cleaned of solids, for example,
by wet electrostatic precipitation. SO2 purification is followed by its capture and sulfuric
acid production at an acid plant (Kojo and Storch 2006).
The world’s first flash smelting furnace was commissioned in Harjavalta, Finland, in
1949 by Outokumpu Oy (today Outotec Oyj; Bryk et al. 1958), and the plant is still in
operation today by Boliden Harjavalta Oy. In Fig. 3, a schematic flow sheet of a flash
smelting plant producing copper is shown. 75–85% of world copper production is based on
sulfidic minerals, and for them, flash smelting is the dominant technology used (Anthony
et al. 2004). Besides copper smelting, the flash smelting technology is also used for nickel
smelting, as well as for continuous converting of solidified copper matte to blister copper
(Mäkinen and Taskinen 2006; Tuominen and Kojo 2005).
A typical example of a sulfide mineral is chalcopyrite CuFeS2, which is used for
producing the majority of copper in the world. Oxygen-enriched air or oxygen is used for
the oxidation of the fine concentrate mixture in a gas–solid suspension. The overall
reaction can be written as:
2CuFeS2 þ 4O2 ðgÞ ! Cu2 S þ 2FeO þ 3SO2 ðgÞ ð5Þ
and
6CuFeS2 þ 13O2 ðgÞ ! 3Cu2 S þ 2Fe3 O4 þ 9SO2 ðgÞ: ð6Þ
In a similar way, iron sulfides in the feed mixture react with oxygen-forming ferrous and
ferric oxides as well as gaseous sulfur dioxide. In the case of pyrite (FeS2), the overall
reactions are:
2FeS2 þ 5O2 ðgÞ ! 2FeO þ 4SO2 ðgÞ ð7Þ
3FeS2 þ 8O2 ðgÞ ! Fe3 O4 þ 6SO2 ðgÞ ð8Þ
In the settler part of the FSF, pressure of SO2(g) generating in the slag and matte formation
reactions is equal to the prevailing total pressure. It is not linked with the atmospheric
sulfur dioxide pressure of the process gas in the smelting vessel. The copper flash smelting
furnace temperature is 1,250–1,300°C.

5.2 Roasting of sulfidic minerals

In the roasting of metal sulfide concentrates, sulfide minerals are typically converted in
fluidized bed reactors to oxides, from which the metals are more easily liberated at the next

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Fig. 3 Flow sheet of a flash smelting plant using the direct-to-blister technology for iron-lean raw
materials. Blister = blister copper, acid plant = sulfuric acid plant. Process gas stream contains SO2

process stages, which usually include leaching and other hydrometallurgical extraction
steps.
About 90% of the world’s zinc is produced from sulfidic minerals, and from this, the
main part is produced by electrowinning with roasting as the first step, for eliminating
sulfur from the sulfidic raw materials (Graf 2008). Roasting is also used for desulfurization
for copper, nickel and gold concentrate processing circuits. There, it is for example used to
produce SO2 for making sulfuric acid and iron oxide calcine and to recover gold from
pyrite (FeS2). A typical roasting process is the oxidation of sphalerite (a-ZnS), which is
converted into zinc oxide ZnO (9). The roasting reactions take place between the solid
sulfide concentrate and oxygen-enriched air, and the metal-bearing oxide product remains
in the solid state. Similarly with flash smelting, roasting of sulfide minerals is an exo-
thermic process (Goodwin 2006).
2ZnS þ 3O2 ðgÞ ! 2ZnO þ SO2 ðgÞ ð9Þ

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The roasting temperature for zinc is 900–950°C (Graf 2008). Gaseous SO2 is liberated
during the process, similarly to the flash smelting technologies, and off-gas handling and a
sulfuric acid production unit complete the modern roasting plant (Taskinen et al. 2008).

5.3 Sulfuric acid manufacture

Almost 30% of sulfuric acid is produced as by-product of metallurgical operations, while

60% of sulfuric acid produced originates from burning of elemental sulfur or from roasting
of pyrite carried out for that purpose. Annual production of sulfuric acid divided in cat-
egories by raw material is shown in Fig. 4.
The contact process is currently the most widely used method for the production of
sulfuric acid (Müller 2008a). In this process, gaseous SO2 is oxidized catalytically to SO3
at catalyst temperatures 400–620°C.
SO2 ðgÞ þ 1=2O2 ðg) $ SO3 ðgÞ ð10Þ
The typical catalyst used is vanadium pentoxide V2O5 doped with potassium or cesium
sulfate. The SO3 generated is absorbed in concentrated [98% sulfuric acid. SO3 reacts
with existing or added water, and more sulfuric acid is produced:
SO3 þ H2 O ! H2 SO4 ð11Þ
The absorption of SO3 can be realized in a single step or with an intermediate step. The
methods are called the single-absorption process and the double-absorption or double-
contact process, respectively. Single-absorption plants are used nowadays only for pro-
cessing of dilute smelter off-gases (SO2 \ 2%). The conversion efficiency is 98–99%.
Double-absorption plants need smaller equipment compared to the single-absorption
plants, and their efficiency in sulfur recovery can reach 99.9%. Double absorption is the
most common sulfuric acid production process and is suitable for gases containing 5–12%
SO2. The adsorption temperature ranges from 70 to 120°C (BREF Document 2007). The
contact method is an exothermic process, and large amounts of heat are being collected and
utilized. Both high- and low-pressure steam and hot water are produced, with the heat
export about 6 GJ/t of sulfuric acid (BREF Document 2007).

Fig. 4 Global sulfuric acid production by raw material, 2009–2010 based on data of Sulphuric Acid on the
Web (2010)

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5.4 Spent acid regeneration

The spent acid is impure sulfuric acid, which has been used in organic and inorganic
chemical, petrochemical or metallurgical industries. It can be regenerated to recycle the
SO2 to decrease the amount of waste. Depending on its source, the spent acid may contain
organic and inorganic impurities like metals or their sulfate salts. In the regeneration
process, the concentrated acid and the possible sulfates are decomposed thermally at
temperatures close to 1,000°C (Müller 2008b).
H2 SO4 ! SO2 ðgÞ þ H2 O(g) þ 1=2O2 ðgÞ ð12Þ
The decomposition product, SO2, is used as a raw material in the contact process for
sulfuric acid manufacture, as shown above. The decomposition of spent acid is similar to
the decomposition step of the HyS process.

6 Demand and use of sulfuric acid, metals and hydrogen

6.1 Sulfuric acid

Sulfuric acid is the world’s most produced chemical by mass (BREF Document 2007). The
current global sulfuric acid production is about 200 Mt/a (Sulphuric Acid on the Web
2010). In 2020, the sulfuric acid production is forecasted to be 285 Mt/a (ICIS Sulphur
2010). Sulfuric acid is used in fertilizers production, in the petrochemical industry, in
mining for leaching and in the steel industry for pickling (Müller 2008a). The annual
global demand on sulfuric acid in 2009 is shown in Fig. 5.

Fig. 5 Global use of sulfuric acid based of data of ICIS Sulphur (2010)

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Novel process concept 537

6.2 Metals production in future

The consumption of metals, especially that of copper, is forecast to increase also in future.
Historically, increasing metals consumption correlates with economic growth and espe-
cially with industrialization and urbanization. In 2006, developing countries accounted for
close to 50% of the global demand for metals (Armstrong et al. 2006). The global con-
sumption of the most important industrial metals like copper, lead, nickel and zinc together
already exceeds 35 Mt/a, according to CRU (former Commodities Research Unit) data
(Armstrong et al. 2006), with average annual growth rates 2–3%. These metals as shown
above are essentially originated from sulfidic minerals, and thus, this growth affects also
sulfuric acid production.
The per capita consumption of metals in many developing countries is less or about
25% of that in the developed countries, while the population of all developing countries is
five times higher (Armstrong et al. 2006). In the developed countries, metals demand
growth has leveled off and demand is forecasted to grow slowly in future. In future, the
resource base is not likely to be the major constraint of metals production, but increasing of
energy costs and declining ore grades are likely to affect production costs and thus metals
prices.

6.3 Hydrogen: current situation and future expectations

The current amount of hydrogen produced for sale is about 50 Mt/a, with an annual
increase of 10% (Winter 2009). The major users of hydrogen are electronics and electronic
equipment industries, glass and food manufacturers, oil refineries and chemical industry as
well as space mission programs. Hydrogen is also used as a reducing agent in many
hydrometallurgical processes, and it is the major energy carrier for fuel cells (Kruger
2008).
The replacement of fossil fueled vehicles by hydrogen-fueled vehicles would require a
substantial increase in hydrogen production (Winter 2009; Kruger 2008). Since currently
the majority of pure hydrogen is produced by water electrolysis (the electricity coming
from renewable sources or not), it would mean an additional demand of supply of electrical
energy. Hydrogen production by steam methane reforming of natural gas is clearly not
compatible with mitigation of CO2 emissions.
Taking the Boliden Harjavalta smelter in Finland as an example, the annual input of
copper and nickel concentrate is approximately 1 Mt/a, which produces 600 kt/a SO2. The
SO2 is captured and fed to the H2SO4 production plant, producing approximately 1 Mt/a of
sulfuric acid. With the Outotec open-cycle process, approximately 20 kt/a of hydrogen
could theoretically be produced from this amount of SO2 in addition to the sulfuric acid.
Assuming a refill of 5 kg of hydrogen, up to 400 fuel cell cars could be fueled per hour
with this hydrogen production rate.
Therefore for worldwide production of sulfuric acid of 200–250 Mt/a, global potential
for the new Outotec open cycle means additional opportunity for 4–5 Mt/a hydrogen
supply, without affecting the total acid production.
A comparison of the new cycle with other thermochemical and combined processes
using expert evaluation method (Galzim et al. 2011) shows that it has a substantial costs
reduction with an excellent trade-off with efficiency, process maturity and environmental
threats, Fig. 6, whether other processes use nuclear (Nucl), solar (Sol) or geothermal (Geo)
heat inputs. Here, new Outotec OC process is compared with HyS cycle, alkaline elec-
trolysis (AE), sulfur-iodine cycle (IS), high-temperature electrolysis (HTE), zinc oxide

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Fig. 6 Comparison of normalized hydrogen costs, process efficiency, maturity, maximal process
temperature and environmental threat for major hydrogen production cycles based on data of Galzim
et al. (2011). All the parameters here are normalized by the range (0—minimum, 1—maximum)

(ZnO), cadmium oxide (CdO) and iron oxide (FeOx) options (Galzim et al. 2011). It is seen
that sulfur-iodine cycle has prohibitive costs versus other methods, CdO cycle has too high
environmental risks and together with ZnO and FeOx has too high processing temperature
requiring special material solutions.
A brief comparison of the new open-cycle capital costs would be reasonable with
similar evaluation made for hybrid sulfur process (McLaughlin et al. 2006). In that
example, hydrogen production of 3 t/d is linked with 400-MW nuclear power plant, which
also produces heat necessary for acid decomposition and recycling. This plant concept
resulted in capital costs contribution as 2.06$/kg H2 (McLaughlin et al. 2006). With new
Outotec open cycle, identical plant design would not anymore require acid decomposition
units, intermediate SO2 storage tanks and associated balance of plant (sulfuric acid pro-
duction is unaffected, so there is no changes in the capital costs at this side). Applying the
same approach and the unit costs as shown by McLaughlin et al. (2006), the investment
would contribute to costs as 1.19$/kg H2 only, presenting nearly twofold capital costs
decrease. The readers interested in more economic details are encouraged to explore the
article by McLaughlin et al. (2006). In this context, implementation of Outotec open-cycle
process fulfills the balance between energy saving, environmental demands and hydrogen
by-production costs while satisfying demands for metals and sulfuric acid at the same time.

7 Conclusions

With the Outotec open-cycle process, hydrogen could be produced together with sulfuric
acid and metals economically and in an environmentally friendly way. New and existing
flash smelting furnaces and roasters could be equipped with this new technology. This
process coupled with a sulfur-burning step, or a pyrite roaster would be also suitable for
joint production of sulfuric acid and hydrogen from these feedstocks. On the way to the

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hydrogen energy society, the Outotec open-cycle would offer a valuable option for
hydrogen production, without the need of technical solutions, which do not yet exist.

7.1 Future work

Aalto CHEM and Outotec are carrying out materials and catalysts development together
with detailed techno-economical analysis of the OOC process, the results of which will be
published later.

Acknowledgments Support from Outotec and Tekes (Finnish Funding Agency for Technology and
Innovation) within the framework of IEA HIA Task 25 is gratefully acknowledged.

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