Anda di halaman 1dari 10

Applied Energy 178 (2016) 736–745

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Sulphuric acid production via Chemical Looping Combustion of


elemental sulphur
Francisco García-Labiano a,⇑, Luis F. de Diego a, Arturo Cabello a, Pilar Gayán a, Alberto Abad a, Juan Adánez a,
Gerald Sprachmann b
a
Instituto de Carboquímica (ICB-CSIC), Department of Energy and Environment, Miguel Luesma Castán 4, Zaragoza 50018, Spain
b
Shell Global Solutions International B.V., Amsterdam, The Netherlands

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A new process for H2SO4 production CHEMICAL LOOPING COMBUSTION CONVERTER ABSORBER
via CLC is proposed. Concentrated
 It has relevant techno-economic sulphuric acid
benefits versus current production Steam turbine/
generator SO2
process. ~ Concentrated Vanadium Waste gas
 The proof of concept was carried out
SO2 SO2 + O2 Oxide catalyst SO3
in a continuous 500 Wth CLC unit. 450 °C
 Elemental sulphur was burnt with an N2(+O2) Mixer Oleum
oxygen carrier by first time ever. AR FR H2S2O7
 A high sulphur-resistant Fe-based Water
oxygen carrier was used. Sulphuric
acid, H2SO4

Air Sulphur Air

a r t i c l e i n f o a b s t r a c t

Article history: A relevant objective of the sulphuric acid (H2SO4) production industry today is to obtain sulphur dioxide
Received 12 January 2016 (SO2) gas streams with the highest possible SO2 concentration after the elemental sulphur combustion
Received in revised form 31 May 2016 stage in order to reduce both capital and operating costs. A new technology, Chemical Looping
Accepted 18 June 2016
Combustion (CLC), is able to generate gaseous streams that are highly concentrated in combustion prod-
ucts by means of oxygen transfer from air to the fuel using a solid oxygen carrier. This work proposes a
new process for H2SO4 production via CLC and using elemental sulphur as fuel. An oxygen carrier with
Keywords:
high sulphur resistance should be used for this purpose. The analysis of this process has brought promis-
Sulphuric acid
Fe-based oxygen carrier
ing results, such as the easy integration of the CLC system into the entire H2SO4 production plant and the
Chemical Looping Combustion confirmation that this is a process in which the energy potential of sulphur is exploited to a very high
degree. Furthermore, the proof of concept was carried out by burning elemental sulphur in a 500 Wth
CLC unit with a high sulphur-resistant oxygen carrier based on iron oxide, Fe20cAl. This work presents
the first ever results of elemental sulphur combustion by an oxygen carrier. Complete combustion of sul-
phur to SO2 was achieved, and no deactivation of the oxygen carrier was observed. Considering all the
results obtained in this work, it can be concluded that the production of H2SO4 via CLC is a feasible tech-
nology which can provide a series of relevant techno-economic benefits in comparison with current
industrial production process.
Ó 2016 Elsevier Ltd. All rights reserved.

⇑ Corresponding author.
E-mail address: glabiano@icb.csic.es (F. García-Labiano).

http://dx.doi.org/10.1016/j.apenergy.2016.06.110
0306-2619/Ó 2016 Elsevier Ltd. All rights reserved.
F. García-Labiano et al. / Applied Energy 178 (2016) 736–745 737

1. Introduction can be found elsewhere [5]. Sulphur is melt and fed in liquid state
into the furnace. The combustion of elemental sulphur is typically
Sulphuric acid (H2SO4) is one of the largest-volume industrial carried out in one-stage or two-stage sulphur combustion cham-
chemicals produced in the world, and indeed, a nation’s H2SO4 pro- bers at high temperature (1100 °C),
duction is a good indicator of its industrial strength [1]. The major
SðsÞ þ O2 ðgÞ ! SO2 ðgÞ DH0 ¼ 296:8 kJ=mol ð1Þ
end-use market for H2SO4 is the production of phosphate fertiliser
materials [2]. This compound is also used for the manufacture of a Air is passed through a drying tower to avoid the presence of
great variety of chemicals, to process metals, to act as electrolyte in H2O and so to prevent the furnace from corrosive atmospheres.
the lead-acid storage batteries commonly used in motor vehicles, The combustion air flow is controlled in proportion to a predeter-
and to remove impurities from gasoline and other refinery prod- mined sulphur feed rate so that gases of about 10–11 vol.% SO2 are
ucts in petroleum refining industry. produced. Combustion gas leaves the sulphur combustion furnace
Today, the industrial double-absorption plants for sulphuric acid at about 1100 °C and is cooled in a waste-heat boiler to the
production have capacities between 1000 and 3000 ton/day, which converter-inlet temperature of 420 °C [5].
correspond to thermal capacities between 60 and 200 MW. A The converter is the main part of the sulphuric acid plant and
typical industrial-scale H2SO4 production plant consists of the where SO2 is catalytically oxidised to SO3,
following main processes: (1) sulphur dioxide (SO2) production,
1
(2) conversion of sulphur dioxide into sulphur trioxide (SO3), and SO2 ðgÞ þ O2 ðgÞ () SO3 ðgÞ DH0 ¼ 99:0 kJ=mol ð2Þ
2
(3) absorption of SO3 into a 98 wt.% H2SO4 solution (the dissolved
SO3 reacts with the 2 wt.% fraction forming H2SO4) to obtain a final The constant for the SO2/SO3 equilibrium expressed in terms of
product with a purity above 99.7 vol.% [3]. All steps in the produc- partial pressures of gases, Kp, is given by the following equation
tion of sulphuric acid from elemental sulphur are exothermic. PSO3
Therefore, heat recovery in these plants is a key aspect both from Kp ¼ 1=2
ð3Þ
PSO2  P O2
economic and environmental point of view. This heat is used to
meet the energy requirements in other locations of the plants and where Kp can be calculated according to Bodenstein equation,
even to give extra energy for electricity production. This energy is
therefore obtained as a subproduct of the own process and has 5186:5
logK p ¼ þ 0:611 log T  6:75 ð4Þ
the additional advantage that no CO2 is produced during the com- T
bustion as it is normal when oil or natural gas are used as fuel. Nowadays, vanadium pentoxide (V2O5) is used almost exclu-
A wide variety of raw materials can be used for SO2 production sively as the catalyst. The most commonly used process to being
such as elemental sulphur coming from oil/natural gas desulphur- about this catalytic oxidation reaction is referred as the double
ization and from underground deposits by means of the Frasch absorption contact process. In this configuration, the acid mixture
process, pyrites, non Fe-based sulphide ores, spent acid, gases com- is passed through an intermediate absorption tower, where the
ing from different sources that contain sulphur compounds, generated SO3 is removed, in order to shift the equilibrium of the
sulphate-based salts, etc. Among these, the elemental sulphur oxidation reaction towards the formation of a higher amount of
recovered from oil and natural gas desulphurization is the predom- SO3. Finally, H2SO4 is obtained as final product with a purity higher
inant compound used as a raw material [4]. than 99.7 vol.% by absorbing SO3 in water in presence of a concen-
Fig. 1 shows a schematic flow diagram of a typical sulphur- trated H2SO4 solution (98 vol.%).
burning double absorption plant for H2SO4 production. A detailed
description of both the flow diagram and the production process SO3 ðgÞ þ H2 O ðlÞ () H2 SO4 ðlÞ DH0 ¼ 132:5 kJ=mol ð5Þ

Fig. 1. Schematic flow diagram of a typical sulphur-burning double-absorption plant for H2SO4 production.
738 F. García-Labiano et al. / Applied Energy 178 (2016) 736–745

The different stages in the production of H2SO4 by means of the to the sulphur combustion in industrial units. In addition, the cor-
combustion of elemental sulphur are all exothermic reactions. The responding proof of the concept in a 500 Wth continuous CLC pilot
heat generated can be used to melt the elemental sulphur fed, to plant using an iron-based oxygen carrier with high sulphur-
meet the energy requirements (heat and electricity) of the entire resistance will be carried out.
H2SO4 industrial plant and to produce electric power that is sup-
plied to the grid.
A key parameter of the H2SO4 production process from a 2. Assessment of sulphur combustion process via CLC to
techno-economic standpoint is the concentration of SO2 resulting produce H2SO4
from the elemental sulphur combustion stage [5]. At this point, it
should be considered that this value of SO2 concentration will The process herein showed represents a new process for sul-
determine the total volume of gases to be handled in the subse- phur combustion via CLC to be implemented inside current sul-
quent processes. The size of the plant units, such as the SO2/SO3 phuric acid plants with several advantages with respect to the
converter, heat exchangers and absorption towers, greatly depends state of the art of current technology. Fig. 2 illustrates the flow dia-
on the gas volume handled. Therefore, the generation of concen- gram of the proposed H2SO4 production process. Sulphur is fed into
trated SO2 streams would be advantageous for the process of pro- a melter and liquid sulphur is pumped to the Fuel Reactor (FR) of
ducing sulphuric acid. A current objective of the H2SO4 industry is the CLC unit where it is instantaneously vaporised. Liquid fuels
to process SO2 gas streams with the highest SO2 concentrations have been successfully burnt in continuous CLC units in recent
possible in order to reduce capital and operating costs and further years [9–11]. The gaseous sulphur makes possible FR fluidization
increase the extent of high-temperature energy recovery from the without the presence of any other gas. Later, sulphur is oxidised
entire production process [5]. to SO2 by means of the reduction of the active metal oxide present
In this regard, there is a new combustion technology, known as in the oxygen carrier particles. It must be remarked that, on con-
Chemical Looping Combustion (CLC), which is able to generate gas- trary to conventional combustion with air, no gaseous oxygen is
eous streams that are highly concentrated in combustion products present in the FR and negligible amounts of SO3 are produced, as
by means of oxygen transfer from air to the fuel using a solid oxy- will be later shown. In addition, no H2O is fed into the reactor;
gen carrier that circulates in dual fluidized bed systems: the fuel therefore no gaseous sulphuric acid can be produced. This has rel-
and the air reactors [6–8]. As air is not mixed with the fuel, a evant consequences regarding equipment selection (materials of
nitrogen-free stream is obtained at the outlet of the fuel reactor, construction) in the flue gas cooling section.
which increases the concentration of the main combustion prod- The reduced oxygen carrier particles are reoxidized with pre-
ucts such as CO2, H2O, and SO2 in the aforementioned stream. heated air in the air reactor (AR), so that they are ready to start a
The CLC process is primarily being developed to perform the com- new cycle. The heat released during the oxidation process is used
bustion of carbonaceous fuels, mainly in gaseous and solid phase to produce steam in a series of heat exchangers place inside the
with inherent CO2 capture, which reduces the economic cost and AR. The steam is then sent to a steam turbine (power generator)
the energy penalty of the CO2 capture process. However, the devel- to produce electricity. Moreover, a waste heat recovery unit is set
opment of sulphur-resistant oxygen carriers offers the possibility at the AR outlet to recover heat from the corresponding hot flue
of using CLC technology to burn sulphur-based fuels with an inher- gas stream. The highly concentrated stream of SO2 obtained at
ent capture of the SO2 generated. Therefore, the objective of this the FR outlet (100 vol.% SO2) is sent to an adiabatic mixer where
work was to evaluate the feasibility of the sulphur combustion pro- it is mixed with preheated air in order to achieve a gas stream at
cess via CLC to produce a highly concentrated SO2 stream ready to the converter inlet with the adequate temperature (420 °C) and
be used in a sulphuric acid plant. This would represent also a rel- the optimum O2/SO2 ratio (1/1) for the catalytic oxidation process
evant issue from the point of view of the energy process associated from SO2 to SO3, which corresponds to twice the stoichiometric

Power
Generator Electricity

Q net,CLC
-0.75 MW
Q5 Q4 Q3 Tail gas
-0.393 MW -0.686 MW 0 MW SO2 SO2 SO3
100 vol.%) (18 vol.%) (18 vol.%)
CLC 900 °C 420 °C
Final
N2 (O2) Waste heat Absor H2SO4
Mixer Converter p-on 98 vol.%)
25 °C recovery T=900 °C 19.42 mol/s
unit Adiabac tower
Adiabac H2SO4
AR FR Q7
SO2: 3.37mol/s (> 99.7 vol.%)
O2: 3.37 mol/s SO2/SO3
0 MW Final product
S (g) N2: 12.68 mol/s

Absor
p-on H2SO4
Q1 Q2 tower 98 vol.%)
+0.198 MW +0.031 MW Q6
S (l) +0.102 MW
400 °C 150 °C 240 °C
Preheater Melter Preheater H2O

Air S (s) Air


25 °C 3.37 mol/s (1MW) 25 °C
25 °C

Fig. 2. Schematic flow diagram of a double-absorption H2SO4 plant with sulphur combustion through CLC technology.
F. García-Labiano et al. / Applied Energy 178 (2016) 736–745 739

requirement [5]. The remaining stages of the H2SO4 production Given these remarkable results, Fe-based oxygen carriers pre-
process would be similar to the ones currently found in the con- pared by the impregnation method using Al2O3 as support, such
ventional process but smaller in size. as the Fe20cAl material, could be adequate candidates for the
The implementation of a CLC system to burn elemental sulphur burning of elemental sulphur in a CLC system integrated into an
increases the operational difficulty of the combustion process H2SO4 production plant.
resulting from the use of particulate material that circulates
between two interconnected fluidized beds, in contrast with the 2.2. Thermodynamic study
conventional process where a furnace is used. Nevertheless, flu-
idized bed technology is mature and widely used at industrial Initially, a thermodynamic study using HSC Chemistry 6.1 soft-
scale, up to 460 MWe [12]. Although CLC has been demonstrated ware [22] was conducted to evaluate the possible interaction of
at 3 MW scale and needs further improvements, there are several sulphur compounds with the iron present in the oxygen carrier.
designs of CLC plants up to 1000 MWt [13,14]. Therefore, CLC units This software obtains the equilibrium composition by using the
of similar size to the current sulphuric acid plants could be then method of minimization of the Gibbs free energy in the system.
incorporated in the medium term. In addition, environmental The calculations were conducted in a range of temperatures from
aspects associated with the spent solid oxygen carriers must now 800 °C to 1000 °C and at atmospheric pressure. Fig. 3 shows the
be considered. Apart from the mentioned drawbacks, the imple- thermodynamic equilibrium of the sulphur compounds existing
mentation of a CLC system into the overall process of H2SO4 pro- in the FR as a function of the oxygen carrier-to-fuel ratio (/)
duction also provides a series of important advantages, such as: when the redox pair considered is Fe2O3 (Al2O3)–FeAl2O4. The
temperature selected for this example was 900 °C. The values
(1) The gaseous stream sent to the converter is more concen- obtained are expressed as the molar percentage of sulphur spe-
trated in SO2 (18 vol.%) than in the conventional process cies present in the products in relation to the sulphur fed into
(10–11 vol.%). The high reduction in the flow to be processed the CLC system.
downstream along with higher reaction rates as a conse- The oxygen carrier-to-fuel ratio, /, which is defined as the ratio
quence of the higher SO2 partial pressure in this unit implies between the flow of oxygen supplied by the oxygen carrier and the
a significant reduction in the capital and operational costs of oxygen needed to react stoichiometrically with the sulphur flow, is
the whole H2SO4 plant [5]. calculated by Eq. (6) as follows:
(2) The heat recovery equipment, including heat exchangers
F Fe2 O3
and the waste heat recovery unit, are set in non-corrosive /¼ ð6Þ
locations (air atmosphere) in contrast with the high sul- 2  FS
phurous atmosphere existing in the furnace of the conven- where FFe2O3 is the molar flow rate of Fe2O3 in the CLC unit calcu-
tional process. This allows the lifetime of the heat lated from the corresponding solids circulation rate, and FS is the
exchangers equipment to be extended, which also allows inlet molar flow rate of elemental sulphur in the FR. Note that ele-
this equipment to be manufactured using standard materi- mental sulphur is the fuel in this CLC process. A value of / = 1 cor-
als, thus reducing the corresponding costs. responds to the stoichiometric relation between Fe2O3 and sulphur
(3) Lower production of nitrogen oxides (NOx), since the AR in the combustion reaction (7).
operates at 900–920 °C, which is a much lower temperature
than that existing in the furnace used in the conventional S þ 2Fe2 O3 þ 4Al2 O3 ! 4FeAl2 O4 þ SO2 DH0r ¼ 70:76 kJ=mol
H2SO4 production process (1100 °C). ð7Þ
(4) The need for a drying tower, used to prevent the presence of
water in the furnace in the conventional process, is avoided. At / values above 1, the main stable sulphur species present is
(5) Increased electricity production. SO2, with very small amounts of SO3. However, at sub-
stoichiometric conditions, additional sulphur compounds can be
formed depending on the amount of oxygen supplied by the oxy-
2.1. Selection of oxygen carriers for solid sulphur combustion gen carrier to the CLC system. As the value of parameter /
decreases, the SO2 concentration at equilibrium diminishes and
A crucial aspect for the successful implementation of CLC tech- elemental sulphur, S2, appears. A stable iron sulphide, Fe0.877S, is
nology into the H2SO4 production process lies in the selection of an formed at / < 0.5 through reaction (8). Here, FeS is considered
adequate oxygen carrier with an extremely high resistance to the the stable iron sulphide instead of Fe0.877S in order to facilitate
presence of sulphur compounds. The presence of sulphur in the the adjustment of the chemical reaction.
fuel is normally detrimental for many oxygen carriers based on 1
NiO or CaMnO3 [15,16]. The poisoning of an oxygen carrier can FeAl2 O4 þ S () FeS þ Al2 O3 þ O2 ð8Þ
2
be reflected through SO2 release in the spent air stream due to
Finally, at very low / values (/ < 0.1), the oxygen carrier pro-
sulphides formation in the FR, an increase of the risk of agglomer-
vides a very small amount of oxygen to react with the fuel. Conse-
ation, or a drop in the overall combustion efficiency as a conse-
quently, the main compound that appears in the equilibrium is
quence of the reduction in its reactivity and oxygen transport
unburnt sulphur in the form of S2.
capacity. In contrast, Fe-based oxygen carriers seem to be the most
The reduced oxygen carrier particles obtained in the FR move
adequate materials to be used when sulphur is present in the fuel
towards the AR, where iron aluminate (FeAl2O4) is reoxidized to
[17–21]. In fact, excellent results were previously obtained with an
hematite (Fe2O3), releasing heat:
Fe-based oxygen carrier prepared by the impregnation method
using alumina (c-Al2O3) as support in a continuous 500 Wth CLC 4FeAl2 O4 þ O2 ! 2Fe2 O3 þ 4Al2 O3 DH0o ¼ 367:57 kJ=mol
unit fed with sour and acid gases that contained high H2S concen-
ð9Þ
trations (up to 20 vol.%) [19–20]. This oxygen carrier, designated as
Fe20cAl, was able to completely burn the sour and acid gases; SO2 Furthermore, the possible iron sulphides formed in the FR can
was not detected in the AR gas outlet stream; iron sulphides or sul- react with the oxygen fed into the AR to produce iron sulphate
phates were not formed; and the material maintained a high reac- (Fe2SO4), or Fe2O3 with SO2 release depending on the working
tivity through both experimental campaigns. operating temperature:
740 F. García-Labiano et al. / Applied Energy 178 (2016) 736–745

FeAl2O4 Fe2O3 (Al2O3) - FeAl2O4

Sulphur in products (mol. %)


100
SO2
80

60

40 Fe0.877S
S2
20
S3 SO3 (< 0.2 %)
0
0.0 0.5 1.0 1.5 2.0
Oxygen carrier-to-fuel ratio (φ)

Fig. 3. Thermodynamic calculations for the system Fe2O3 (Al2O3) - FeAl2O4/sulphur. T = 900 °C.

FeS þ 2O2 () FeSO4 ðT < 700  CÞ ð10Þ 16 kg s1 MW1 [23]. This value is approximately equivalent to that
of an oxygen carrier-to-fuel ratio of 3 according to Eq. (13) when
7 complete combustion of fuel (gc = 1) is considered.
2FeS þ O2 () Fe2 O3 þ 2SO2 ðT > 700  CÞ ð11Þ
2 gc
As the AR temperature is always higher than 700 °C in conven-
/¼ ð13Þ
DX S
tional CLC systems, the iron sulphides formed would be decom-
This result entails that the CLC unit should operate with values
posed in this reactor, releasing SO2 to the atmosphere.
of parameter / ranging between 1 and 3, which is a usual operating
Nevertheless, as the FR of the CLC unit integrated into an H2SO4
range in CLC processes for the Fe20cAl material [18–20,23].
plant will operate at oxygen carrier-to-fuel ratios above the stoi-
The energy balance in a CLC unit acquires remarkable relevance
chiometric conditions, formation of iron sulphides is never
when the reaction that takes place in the FR between the active
expected to occur during operation.
metal oxide and the fuel is endothermic, as in the case of the
reduction of Fe2O3 with sulphur, see reaction (7). In this case, the
2.3. Mass and energy balance circulating solids that come from the AR at a higher temperature
supply the needed heat to the FR. To avoid a large temperature dif-
Any H2SO4 industrial plant must be designed to be extremely ference between both reactors, suitable variation values for solids
efficient in terms of not only SO2 conversion and H2SO4 production, conversion can be limited [23].
but also in terms of energy recovery [5]. Therefore, the CLC system In addition, a check must be made as to whether the Fe20cAl
included in the H2SO4 plant must present an optimal thermal inte- material can transfer enough heat from the AR to support the
gration in order to maximise the energy exploitation of sulphur as endothermic reaction (7) in the FR under the solids circulation
fuel. This will depend on different operational factors such as the restrictions previously indicated. At this point, it must highlighted
material selected as oxygen carrier and the solids recirculation that the variation in enthalpy involved in the reduction and oxida-
rate, which is correlated with the oxygen carrier-to-fuel ratio, / tion reactions, see reactions (7) and (9), that take place in the FR

[23]. The solids recirculation rate in a CLC unit, mOC , can be calcu- and AR, respectively, is equivalent to the heat released during the
lated as follows: combustion of one mole of solid elemental sulphur in direct con-

tact with air, see reaction (1).
 mO An energy balance to the CLC system was established taking
mOC ¼ ð12Þ
ROC  DX S into account the following assumptions: the FR was adiabatic; its
temperature was fixed at 900 °C; full combustion of elemental sul-

where mO is the rate of oxygen transfer needed to achieve complete phur was achieved; the air flow fed to the AR was preheated from
combustion of sulphur to SO2 according to reaction (7); ROC is the 25 °C to 400 °C; an excess of 10 vol.% over stoichiometric condi-
oxygen transport capacity of the oxygen carrier material taking into tions (k = 1.1) was used; and the solid elemental sulphur (25 °C)
consideration the corresponding redox pair and fraction of metal was melted and fed into the FR at 150 °C. Finally, 1 MW of power
oxide present in the particles; and DXS is the variation in solids con- from the use of solid elemental sulphur as fuel was taken as refer-
version in the reactors. ence. This power corresponds to a sulphur stream feed of 3.37 mol/
Fig. 4(a) shows the solids circulation rate per MW of power s. It should be mentioned at this point that the heat flows con-
obtained from the use of solid elemental sulphur as fuel as a func- sumed or generated in the different units that make up the CLC
tion of the variation in solids conversion for different values of ROC. system have been given a designation between Q1 and Q5, as
The solids circulation rate profile corresponding to the Fe-based shown in Fig. 2.
oxygen carrier selected for this work (blue1 line) was calculated Fig. 4(b) illustrates the AR temperature and the thermal power
taking into consideration that ROC = 0.02 (redox pair: Fe2O3/FeAl2O4; that can be recovered from the AR as a function of the variation in
fraction of metal oxide: 20 wt.% Fe2O3 on Al2O3). In the case of the solids conversion (DXS) in the CLC unit using the Fe20cAl material
Fe20cAl material, it was observed that a variation in solids conver- as the oxygen carrier. The total amount of thermal power that can
sion in the reactors higher than 0.35 was needed in order to obtain be recovered from the heat generated in the AR (Qrecover,AR) is equal
a solids circulation rate value lower than the upper limit established to the sum of the thermal power recovered in the series of heat
by the current technology of circulating fluidized beds fixed at exchangers located inside the reactor (Q4) and the net thermal
power recovered from the hot flue gas stream of the aforemen-
1
For interpretation of colour in Figs. 2, 4 and 8, the reader is referred to the web tioned reactor (Qnet, flue gas AR). It must be taken into account that
version of this article. the thermal power recovered from the hot flue gas stream (Q5) is
F. García-Labiano et al. / Applied Energy 178 (2016) 736–745 741

30
(a)
ROC = 0.005
25

moc (kg s MW )
-1
20 ROC = 0.01
Hydrodynamic limit

-1
15 ROC(Fe20γAl) = 0.02

. 10 ROC = 0.05

5 ROC = 0.1

0
1.0 925
(b)
920
0.8 Q
Qnet,flue gas net,flue
AR
gas, AR
915
Qrecover,AR

0.6

TAR (ºC)
910
0.4 Qhe,AR
905

0.2 Q4 900

0.0 895
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

ΔXS

10 5 3.33 2 1.25 1
φ
Fig. 4. Relation between the variation in solids conversion in the CLC unit and (a) the solids circulation rate, and (b) both the thermal power extracted from the air reactor and
the temperature of the air reactor.

used both to preheat the air stream fed to the AR (Q1) and to melt in the air flow was 3.37 mol/s to obtain the optimum O2/SO2 ratio
the sulphur fed into the FR (Q2). Therefore, the net thermal power needed at the converter inlet (1/1), which corresponds to twice the
is calculated by stoichiometric requirement.
The boundary of this extended energy balance is shown in Fig. 2
Q net;flue gas AR ¼ Q 5  ðQ 1 þ Q 2 Þ ð14Þ
in dashed lines. The same assumptions as the ones previously used
Some remarkable results can be deduced from Fig. 4(b). Firstly, to calculate the energy balance to the CLC system were now con-
the variation in temperature between the FR and AR is very small sidered. The selected oxygen carrier-to-fuel ratio (/) in the CLC
for the whole range of DXS values, since the maximum temperature unit was 2, which was suitable for this oxygen carrier in order to
obtained in the AR was 919 °C at DXS = 1. This means that the ther- fulfil the circulation rate criteria of a CLC unit, see Fig. 4(a).
mal integration of both reactors would be very easy to carry out. The heat flows obtained in each of the stages of the analysed
Secondly, a significant and almost constant flow of heat can be system are shown (values in red) in Fig. 2. In this case, the surplus
recovered from the heat exchangers placed inside the AR (Q4) inde- energy obtained from the waste heat recovery unit (Q5-Q1-Q2) was
pendently of the solids circulation rate in the CLC unit. The flow of enough to preheat the air flow fed to the mixer (Q6) up to the
recovered heat is 0.68 MW per MW of sulphur fed, which repre- desired temperature (240 °C). In addition, the flow of heat available
sents approximately two-thirds of the power supplied to the CLC to generate electricity by applying CLC technology to the H2SO4
system. Thirdly, the net thermal power recovered from the hot flue production process was greater than in the conventional process
gas stream of the AR (Qnet,flue gas AR) is positive and takes an approx- once the energy demands corresponding to the stages of elemental
imate value of 0.16 MW per MW of sulphur fed for the whole sulphur melting and air drying had been met.
range of DXS values. The latter result implies that the energy
Q net;CLC ¼ Q 5 þ Q 4  ðQ 1 þ Q 2 þ Q 6 Þ ¼ 0:75 MW ð15Þ
potential of the hot flue gas stream of the AR (Q5) is high enough
to meet the energy requirements to preheat the air stream fed to This statement is demonstrated by the energy balance con-
the AR (Q1) and to melt the sulphur fed into the FR (Q2), and also ducted on the conventional H2SO4 production process (see Fig. 1).
to provide a surplus of energy that could be used to meet other
Q net;conv ¼ Q 4  ðQ 1 þ Q 2 Þ ¼ 0:7 MW ð16Þ
energy demands in the H2SO4 production process.
Finally, this detailed study of the sulphur combustion process This remarkable result reveals that the H2SO4 production pro-
via CLC to produce H2SO4 was completed with an energy balance cess with sulphur combustion through CLC technology is a process
that includes the mixer from which the concentrated SO2 gas with a very high degree of exploitation of the energy potential of
stream was sent to the converter of the H2SO4 production plant. sulphur. In addition, the energy balances performed to both config-
In the mixer, the concentrated SO2 stream was blended adiabati- urations demonstrate one of the main advantages of the applica-
cally with air preheated at 240 °C. The amount of oxygen present tion of CLC technology to the production of H2SO4 previously
742 F. García-Labiano et al. / Applied Energy 178 (2016) 736–745

discussed, i.e. the flow of gases at the inlet of the converter when tions at the outlet of both reactors. A further description of this
elemental sulphur is burnt in a CLC unit is reduced by 40% com- adapted CLC facility is presented elsewhere [19,20].
pared to the case of conventional combustion (see the values in The system used to feed the elemental sulphur into the CLC pro-
green in Figs. 1 and 2). This reduction in the gas flow rate to be totype is also shown in Fig. 5. Although the feeding of sulphur is a
treated downstream would result in the corresponding capital well-known process in an H2SO4 plant at industrial scale, achieving
and operating costs being reduced by approximately 25% [5]. a constant feed of elemental sulphur in small units is not an easy
In addition, the heat and mass flows, and temperatures in the issue. The use of solid sulphur particles obtained from pelletizing,
different streams of the process (see scheme in Fig. 2) could be milling and sieving to the desired particle size was discarded con-
used as basis for the design of the heat exchangers. It must be sidering that the continuous CLC facility used in this work was not
remarked the additional advantage of being manufactured using adapted to feed solid materials. Furthermore, the pumping of liq-
standard materials because they are located at non-corrosive uid sulphur, the form in which it is currently fed into industrial
places in contrast with the high corrosive sulphurous atmosphere units, was also discarded due to the small amounts needed in this
existing in the furnace of the conventional process. CLC pilot plant. It was therefore decided that it would be fed in a
gaseous phase by saturating a flow of nitrogen in sulphur at a con-
trolled temperature. The usual procedure to carry out the combus-
3. Proof of concept
tion tests was based on by-passing the sulphur feeding system
during the initial period of heating. Once a stable operation was
Once the validity of the CLC process integrated into an H2SO4
reached in the CLC unit, the carrier gas was subsequently passed
production unit using the Fe20cAl oxygen carrier is corroborated,
through the sulphur evaporator at the temperature at which the
the corresponding proof-of-concept must be experimentally
vapour pressure increases up to 1 atmosphere (440 °C) and both
demonstrated. There was no previous experience regarding the
gases (carrier gas + gaseous sulphur) were fed in at the bottom of
feeding and burning of elemental sulphur in a CLC unit. Therefore,
the FR. These gases then passed through the distributor plate,
this work represents the first time ever that elemental sulphur has
which was manufactured in Kanthal APM, a material resistant to
been burnt using an oxygen carrier as the oxygen source for
sulphur compounds.
combustion.

3.3. Testing conditions


3.1. Oxygen carrier
A total of 14 h of continuous operation with elemental sulphur
The Fe-based oxygen carrier was prepared at ICB-CSIC by the as fuel was carried out at the ICB-CSIC-g1 facility. Loads of 140 g of
incipient impregnation method using c-Al2O3 as support. A sulphur powder with 100% of purity were used as fuel in all tests. It
detailed description of the preparation method can be found else- must be remarked that these tests were performed with the same
where [24]. The iron oxide content (Fe2O3) present in the oxygen batch of Fe-based oxygen carrier particles previously used for sour
carrier particles was 20.4 wt.%. As previously mentioned, this gas (20 h) and acid gas (18 h) combustion tests with very high H2S
material was designated as Fe20cAl. The main properties of the concentrations, up to 20 vol.% [19,20]. In all tests, the temperature
fresh oxygen carrier particles are shown in Table 1. in the FR and AR was fixed at 900 °C. This temperature was
selected because the Fe20cAl oxygen carrier had previously pre-
3.2. Description of the ICB-CSIC-g1 facility sented a good reactivity with gaseous fuels at this condition [25].

A schematic diagram of the ICB-CSIC-g1 facility (500 Wth) used 3.4. Sulphur combustion tests
to burn elemental sulphur is shown in Fig. 5. It was composed of
two interconnected fluidized bed reactors, a riser for solid trans- Fig. 6 shows the gas product distribution obtained in FR and AR
port, a solid valve to control the solids circulation rate, a loop seal outlet streams during some of the tests of sulphur combustion.
and a cyclone. The FR (1) and AR (3) consisted of two bubbling This figure also illustrates the temperature evolution in the sulphur
fluidized-beds (0.05 m i.d.) with a bed height of 0.1 m. The AR furnace once a stable operation was reached at the ICB-CSIC-g1
was followed by a riser (4) of 0.02 m in diameter and 1 m in height. facility in terms of solids circulation and temperature. Initially,
This unit was previously used for the combustion of different the temperature in the sulphur furnace was set at 300 °C. It should
sulphur-containing fuels, including sour gas and acid gases be recalled that there was no previous experience regarding the
[19,20]. Therefore, it was adapted for a safe operation when high feeding of sulphur into small CLC units, and moderate conditions
H2S and/or SO2 concentrations were considered. Specific analysers were preferred during the first trial. Smooth operation of the CLC
for sulphur compounds were located downstream from the FR and unit was achieved during this and subsequent tests, and no opera-
AR, respectively. Two non-dispersive infrared (NDIR) analysers tional problems, such as agglomeration or defluidization, were ever
(Siemens Ultramat U22) were used to measure the SO2 concentra- encountered. The maximum SO2 concentration measured in the FR
was 5 vol.%, whereas the SO2 concentration detected in the AR was
negligible throughout the test. The low concentration of SO2
Table 1
detected in the FR outlet stream implied that the reduction degree
Main physicochemical properties of fresh particles of the Fe20cAl material.
of the oxygen carrier particles in this reactor was also low and, con-
Units Fresh particles sequently, the O2 concentration measured in the AR barely chan-
Fe2O3 content wt.%a 20.4 ged during the time of operation.
Oxygen transport capacity, ROC % 2.0 In view of the promising results obtained during this test, and
Particle size lm 200–400
with the objective of increasing the concentration of SO2 detected
Bulk density kg m3 3900
Porosity % 50.5
in the FR, the temperature in the sulphur furnace was increased up
Specific surface area BET m2 g1 39.1 to 440 °C for the subsequent tests. In this case, the concentration of
Crushing strength N 1.5 SO2 detected at the FR outlet greatly increased, reaching values of
Attrition index, AJI % 4.7 up to 18 vol.%. In this sense, nearly pure SO2 streams would be
Crystalline phases, XRD Fe2O3, a-Al2O3
expected in an industrial H2SO4 unit pumping pure liquid sulphur
a
Determined by TGA. into the CLC system as fuel. The presence of a higher amount of SO2
F. García-Labiano et al. / Applied Energy 178 (2016) 736–745 743

stack

Cupboard
8 Gas analysis
O2, SO2
8 stack
11
5

6 9

4
Gas analysis
7 SO2
8 stack

Secondary 10
Air
1 1.- Fuel reactor
9
2.- Loop seal
2
3.- Air reactor
4.- Riser
Sulphur feeding 5.- Cyclone
By-pass
system 6.- Diverting solids valve
3
7.- Solids valve
10 ΔP 8.- Filters
9.- Na2CO3 scrubbers
Sulphur
10.- Furnaces
11.- SO2, H2S detectors
N2
Air N2 10

Fig. 5. Scheme of the ICB-CSIC-g1 facility including the system to feed in elemental sulphur.

Temperature of sulphur furnace, TS (ºC)


25 500
Fuel Reactor
TS
SO2 concentration (vol.%)

20 400

15 300
SO2

10 200

5 100

0 0
0 Air
1 Reactor
2 3 4 5 6 7 8
SO2 concentration (vppm)

Time (h)
O2 concentration (vol.%)

20 80
O2
15 60

10 40

5 20

SO2
0 0
0 1 2 3 4 5 6 7 8 12 13 14 15 16 17 18

Time (h)

Fig. 6. Gas composition at the outlet stream from fuel and air reactors corresponding to the first sulphur combustion tests carried out with the Fe20cAl material at the ICB-
CSIC-g1 facility.
744 F. García-Labiano et al. / Applied Energy 178 (2016) 736–745

at the FR outlet led to an appreciable variation in the O2 concentra- tion of iron sulphides in the oxygen carrier particles. To determine
tion at the AR outlet as a result of a higher degree of oxygen carrier the presence of sulphur in the Fe20cAl material, samples extracted
particle regeneration. This test was repeated again and similar from the CLC system at different times of operation were analysed
results were obtained. Finally, it should be pointed out that SO2 in a Thermo Flash 1112 elemental analyser. Sulphur was never
was not detected in the AR during the combustion test, which detected in any of the samples, which agrees with the thermody-
seemed to indicate that no iron sulphides were formed during sul- namic data since the oxygen carrier-to-fuel ratios used in the CLC
phur combustion in the FR. unit during the experimental campaign were always higher than
A total sulphur mass balance was performed at the end of the 1. The absence of sulphur in the oxygen carrier particles was also
different tests. These balances closed at values of about 80%, which corroborated by SEM-EDX techniques. By way of example, Fig. 7
can be considered as a satisfactory result considering the experi- illustrates an SEM image of the cross-section of a used oxygen car-
mental errors derived from the difficulty of operating with solid rier particle, and SEM-EDX analysis revealed a negligible amount of
sulphur in a small-scale CLC system and during the analysis. In fact, sulphur inside.
to avoid condensation problems in the sampling lines connected to Finally, analysis was conducted to verify whether the use of ele-
the analysers and analyser failure, two impingers at 10 °C were mental sulphur as fuel affected the reactivity of the Fe20cAl mate-
located downstream from the FR. During the experimentation, a rial. Reactivity tests were performed in a thermogravimetric
white mist was observed in the impingers and in the condenser analyser, CI Electronics type, described elsewhere [26]. The reduc-
fridge located before the analysers. However, the amount of sul- tion and oxidation reactivity of the oxygen carrier particles was
phur collected at these places was negligible. determined by means of performing standard reactivity tests on
In addition, a deep characterization was made of used oxygen CLC technology. These tests were carried out at 950 °C using
carrier particles extracted from the FR and AR in order to discard methane (CH4) and air as reducing and oxidising agents, respec-
the possibility that the deviations found were caused by the forma- tively. Fig. 8 shows the reduction and oxidation conversion vs time
curves for a sample extracted from the CLC unit at the end of the
experimental campaign using elemental sulphur as fuel (red lines).
These curves were compared to the corresponding ones obtained
both for the fresh material (blue lines) and for the samples
extracted from the CLC plant after the sour gas and acid gas tests
(green lines). The results confirmed that the Fe20cAl oxygen car-
rier maintained its high reactivity during the 14 h of continuous
operation with addition of elemental sulphur.
Based on the excellent results above obtained during the proof
of concept of the process it can be concluded that this sulphur-
resistant material could be selected as a promising oxygen carrier
to be used in a sulphuric acid plant via CLC using elemental sulphur
as raw material.

4. Conclusions

This work proposes a new H2SO4 production process that inte-


grates the use of elemental sulphur as fuel in a CLC process to
obtain streams with high SO2 concentrations. The energy balance
a.u.

referred to the sulphuric acid production via CLC ended up being


Fe a process with a very high degree of exploitation of the energy
potential of the sulphur. In fact, this process offers several advan-
S tages with respect to the state of the art of the current technology
for H2SO4 production.
0 50 100 150 200 250
dp (μm)
– The higher SO2 concentration obtained after combustion signif-
Fig. 7. SEM-EDX image of the cross-section of a used oxygen carrier particle at the icantly reduces the capital and operational costs of the whole
ICB-CSIC-g1 facility during the combustion tests with elemental sulphur. H2SO4 plant.

1.0 1.0

0.8 Reduction 0.8 Oxidation


conversion

conversion

0.6 0.6

0.4 0.4

Fresh
0.2 0.2
After acid gas & sour gas tests
After elemental sulphur tests
0.0 0.0
0 50 100 150 200 250 300 0 10 20 30 40 50 60

Time (s) Time (s)

Fig. 8. Reduction and oxidation reactivity of the Fe20cAl oxygen carrier after the combustion tests with elemental sulphur. Reducing gas composition: 15 vol.% CH4, 20 vol.%
H2O and N2 to balance. Oxidising gas composition: pure air. T = 950 °C.
F. García-Labiano et al. / Applied Energy 178 (2016) 736–745 745

– The heat recovery equipment is set in non-corrosive locations, [6] Adánez J, Abad A, García-Labiano F, Gayán P, de Diego LF. Progress in chemical-
looping combustion and reforming technologies. Prog Energy Combust Sci
in contrast with the high sulphurous atmosphere existing in
2012;38:215–82.
the furnace of the conventional process, allowing the use of [7] Lyngfelt A. Chemical looping combustion of solids fuels – status of
standard materials and reducing manufacturing costs. development. Appl Energy 2014;113:1869–73.
– Lower production of nitrogen oxides since the temperature in [8] Lyngfelt A, Epple B, Adánez J, Yan J, editors. The 3rd international conference
on chemical looping 2014. Appl Energy, vol. 157. p. 285–7.
the air reactor, 900 °C, is much lower than that existing in [9] de Diego LF, Serrano A, García-Labiano F, García-Díez E, Abad A, Gayán P, et al.
the furnace in the conventional process, 1100 °C. Bioethanol combustion with CO2 capture in a 1 kWth chemical looping
– The air drying tower required in the conventional process is combustion prototype: suitability of the oxygen carrier. Chem Eng J
2016;283:1405–13.
now avoided. [10] Moldenhauer P, Rydén M, Mattisson T, Younes M, Lyngfelt A. The use of
– Increased electricity production. ilmenite as oxygen carrier with kerosene in a 300 W CLC laboratory reactor
with continuous circulation. Appl Energy 2014;113:1846–54.
[11] Moldenhauer P, Rydén M, Mattisson T, Hoteit A, Jamal A, Lyngfelt A. Chemical-
The excellent results obtained during the combustion tests car- looping combustion with fuel oil in a 10 kW pilot plant. Energy Fuels
ried out at the ICB-CSIC-g1 facility with the Fe20cAl material using 2014;28:5978–87.
elemental sulphur as fuel validated the corresponding proof of con- [12] Mirek P. A simplified methodology for scaling hydrodynamic data from Lagisza
460 MWe supercritical CFB boiler. Chem Proc Eng 2011;32:245–53.
cept. The CLC unit presented stable operation without any sign of [13] Abad A, Adánez J, Gayán P, de Diego LF, García-Labiano F, Sprachmann G.
particle agglomeration or deactivation by sulphides formation. Conceptual design of a 100 MWth CLC unit for solid fuel combustion. Appl
Complete combustion of elemental sulphur to SO2 was achieved Energy 2015;157:462–74.
[14] Lyngfelt A, Leckner B. A 1000 MWth boiler for chemical-looping combustion of
during 14 h of continuous operation at 900 °C. This represents
solid fuels – discussion of design and costs. Appl Energy 2015;157:475–87.
the first time ever that elemental sulphur has been burnt using [15] García-Labiano F, de Diego LF, Gayán P, Adánez J, Abad A, Dueso C. Effect of fuel
an oxygen carrier as the oxygen source for combustion. gas composition in chemical-looping combustion with Ni-based oxygen
Considering all the results obtained in this work, it can be con- carriers. 1. Fate of sulphur. Ind Eng Chem Res 2009;48:2499–508.
[16] Cabello A, Abad A, Gayán P, de Diego LF, García-Labiano F, Adánez A. Effect of
cluded that the production of H2SO4 via Chemical Looping Com- operating conditions and H2S presence on the performance of
bustion is a feasible technology which can provide a series of CaMg0.1Mn0.9O3d perovskite material in chemical looping combustion (CLC).
relevant techno-economic benefits in comparison with the current Energy Fuels 2014;28:1262–74.
[17] Ksepko E, Siriwardane RV, Tian H, Simonyi T, Sciazko M. Effect of H2S on
industrial production process. chemical looping combustion of coal-derived synthesis gas over Fe-Mn oxides
supported on sepiolite, ZrO2, and Al2O3. Energy Fuels 2012;26:2461–72.
[18] Cabello A, Dueso C, García-Labiano F, Gayán P, Abad A, de Diego LF, et al.
Acknowledgements Performance of a highly reactive impregnated Fe2O3/Al2O3 oxygen carrier with
CH4 and H2S in a 500 Wth CLC unit. Fuel 2014;121:117–25.
This work has been financed by Shell Global Solutions Interna- [19] de Diego LF, García-Labiano F, Gayán P, Abad A, Cabello A, Adánez J, et al.
Performance of Cu- and Fe-based oxygen carrier in a 500 Wth CLC unit for sour
tional B.V. within the framework of the PT22648 agreement signed gas combustion with high H2S content. Int J Greenhouse Gas Contr
between Shell Global Solutions International B.V. and Instituto de 2014;28:168–79.
Carboquímica – Consejo Superior de Investigaciones Científicas [20] García-Labiano F, de Diego LF, Gayán P, Abad A, Cabello A, Adánez J, et al.
Energy exploitation of acid gas with high H2S content by means of a chemical
(ICB –CSIC). looping combustion system. Appl Energy 2014;136:242–9.
[21] Jerndal E, Mattisson T, Lyngfelt A. Thermal analysis of chemical-looping
combustion. Chem Eng React Des 2006;84:795–806.
References [22] HSC Chemistry 6.1. Chemical reaction and equilibrium software with
thermochemical database and simulation module. Pori (Finland): Oututec
[1] Chenier PJ. Survey of industrial chemistry. New York: John Wiley & Sons; 1987. Research Oy.; 2008.
p. 45–57. [23] Abad A, Adánez J, García-Labiano F, de Diego LF, Gayán P, Celaya J. Mapping of
[2] King M, Moats M, Davenport WG. Sulfuric acid manufacture: analysis, control the range of operational conditions for Cu-, Fe-, and Ni-based oxygen carriers
and optimization. 2nd ed. Amsterdam: Elsevier; 2013. in chemical-looping combustion. Chem Eng Sci 2007;62:533–49.
[3] Ashar NH, Golwalkar KR. A practical guide to the manufacture of sulfuric acid, [24] Gayán P, Pans MA, Ortiz M, Abad A, de Diego LF, García-Labiano F, et al. Testing
oleums, and sulfonating agents. Switzerland: Springer International of a highly reactive impregnated Fe2O3/Al2O3 oxygen carrier for a SR-CLC
Publishing; 2013. system in a continuous CLC unit. Fuel Process Technol 2012;96:37–47.
[4] Apodaca LE. US Geological Survey 2012 minerals yearbook. Sulfur <http:// [25] Cabello A, Abad A, García-Labiano F, Gayán P, de Diego LF, Adánez J. Kinetic
minerals.usgs.gov/minerals/pubs/commodity/sulfur/myb1-2012-sulfu.pdf>. determination of a highly reactive impregnated Fe2O3/Al2O3 oxygen carrier for
[5] Hermann M. Sulfuric acid and sulfur trioxide. In: Elvers B, Hawkins S, William use in gas-fueled chemical looping combustion. Chem Eng J 2014;258:265–80.
R, editors. Ullmann’s encyclopedia of industrial chemistry, vol. A25. Weinheim, [26] Adánez J, de Diego LF, García-Labiano F, Gayán P, Abad A. Selection of oxygen
Germany: VCH; 1994. p. 635–700. carriers for chemical-looping combustion. Energy Fuels 2004;23:371–7.