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DOI: 10.1002/cssc.201300516
Design of a Continuous Process Setup for Precipitated
Calcium Carbonate Production from Steel Converter Slag
Hannu-Petteri Mattila* and Ron Zevenhoven*[a]
A mineral carbonation process “slag2PCC” for carbon capture,
utilization, and storage is discussed. Ca is extracted from steel
slag by an ammonium salt solvent and carbonated with gas-
eous CO2 after the separation of the residual slag. The solvent
is reused after regeneration. The effects of slag properties such
as the content of free lime, fractions of Ca, Si, Fe, and V, parti-
cle size, and slag storage on the Ca extraction efficiency are
studied. Small particles with a high free-lime content and
Introduction
CO2 emissions from human activities contribute to global cli-
mate change.[1] A significant source of industrial CO2 emissions
is the iron and steel industry, in which CO2 is produced both as
a result of the high temperatures and high coke consumption
in the processes. The sector has accounted for 4–7 %[2, 3] of
global CO2 emissions (in total ~ 30 Gt)[4] during recent years.
However, several options are available for the steelmakers to
lower this value. As an example, by changing the feedstock
and increasing material recycling, Ruukki Metals in Finland was
able to avoid 0.6 Mt of CO2 emissions in 2012 compared to the
use of virgin raw materials. The total CO2 emissions of the
company were 3.8 Mt in the same year.[5]
Another method for CO2 emission reduction is so-called
carbon capture, utilization, and storage (CCUS), which actually
comprises several technologies. At the moment there is no fi-
nancial incentive to use CCUS because the CO2 emission costs
are low, at approximately 5 E per ton emitted (EUA, European
Union Allowance price).[6] The cost of CO2 capture is generally
estimated to be 20 E per ton or higher, which depends on the
chosen process.[7, 8] Also, viable end-treatment solutions for the
captured gas are often absent or excluded from the calcula-
tions, which further increases the total cost of CCUS.
With so-called mineral carbonation it would be possible to
convert gaseous CO2 to solid, stable carbonates, which can be
either used for marketable products or landfilled.[9, 10] Both nat-
ural minerals and industrial waste materials that contain ele-
ments suitable for carbonation such as Ca or Mg can be uti-
lized as raw materials for mineral carbonation processes. How-
ever, industrial waste materials provide a more readily reactive
[a] H.-P. Mattila, Prof. R. Zevenhoven
Thermal and Flow Engineering Laboratory
bo Akademi University
Piispankatu 8, FI-20500 Turku (Finland)
E-mail: hmattila@abo.fi
ron.zevenhoven@abo.fi
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
minor fractions of Si and V are the most suitable. To limit the
amount of impurities in the process, the slag-to-liquid ratio
should remain below a certain value, which depends on the
slag composition. Also, the design of a continuous test setup
(total volume ~ 75 L) is described, which enables quick process
variations needed to adapt the system to the varying slag
quality. Different precipitated calcium carbonate crystals (cal-
cite and vaterite) are generated in different parts of the setup.
source of these elements because they are often in a more
processed and active form. However, the potential availability
of the waste materials is limited compared to the amount of
CO2 released.[11]
In this paper, a mineral carbonation method suitable specifi-
cally for steelmaking industries is discussed. The concept, also
known as slag2PCC, that uses steel converter slag as a raw ma-
terial to produce precipitated calcium carbonate (PCC) to be
used as, for example, paper filler, is under development from
the level of theoretical process modeling[12] and batch experi-
ments[10, 13, 14] towards a demonstration-scale continuous pro-
cess. The most important features of the process concept are
the direct use of purified flue gases, that is, the redundancy of
a separate capture stage, as well as the possibility to operate
the system at ambient temperature and pressure, which thus
reduces the energy demand.
Current trends in PCC manufacture through various technol-
ogies are summarized in a recent overview.[15] The markets for
the PCC product are limited; in 2011 the worldwide consump-
tion was estimated at 14 Mt. Together with ground calcium
carbonate (GCC), which is of lower economic value compared
to PCC, the market increases to 74 Mt.[16, 17] Measured in Mt of
CO2 captured, if all PCC and GCC production was replaced by
the slag2PCC method, 32.5 Mt of CO2 (6.2 Mt for PCC only)
could be chemically bound to calcium carbonate product.
Of all the alkaline waste materials available, steel slags are
ideal for mineral carbonation applications because of the high
Ca content.[15, 18] Still, the amount of produced steel converter
slag forms a limitation for the process applicability, even
though alternative sources of Ca (e.g., blast furnace slag)[10]
can to some extent be utilized as well.
Notably, in the case of the USA only, even the most widely
available industrial waste materials could only account for
a few percent of USA CO2 emissions.[11] Globally, in 2012 crude
steel production was estimated to be 1.5 Gt,[19] whereas the
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amount of basic oxygen furnace

Table 1. XRF results of the various slag fractions.
(BOF) slag produced is approxi-
mately 126 kg per ton of steel.[20] Slag fraction Component [%]
If we assume that the CO2 cap- CaO Fe SiO2 Mn MgO Al2O3 V Na2O P S K2O Ti Cr rest
ture capacity of  0.1 kg CO2 per 2008 45.2 14.9 12.4 2.4 1.7 1.5 1.4 0.1 0.4 0.1 0.1 0.6 0.2 19.0
kg slag reported previously[21, 22] 2011 44.9 12.0 22.7 2.6 1.6 2.6 2.5 0.2 0.4 0.1 0.2 0.8 – 9.4
2011 (aged, small) 44.5 13.4 23.0 2.6 1.8 2.6 2.6 0.3 0.4 0.1 0.2 0.8 0.2 7.5
can be maintained, independent
2011 (aged, large) 42.2 17.6 22.5 2.4 1.7 2.4 2.4 0.2 0.4 0.1 0.2 0.7 0.2 7.0
of the variations in slag quality, 2012 42.4 17.7 11.9 2.1 1.4 1.5 1.3 0.1 0.3 0.1 0.1 0.7 0.3 20.2
the slag2PCC process would be 2012b 47.5 17.4 11.7 2.6 1.8 1.4 1.3 0.1 0.3 0.1 0.1 0.7 0.2 14.8
able to capture 19.1 Mt CO2 an-
nually. Thus, theoretically the
limiting factor of the discussed
technology would be the size of the PCC market, or if the
scale of the produced materials is widened, the amount of
generated slag.
In conclusion, although the amounts of CO2 handled by this
Ca-based process may never become significant for CO2 emis-
sions reduction on a global scale, for a particular steel manu-
facturer the process could still be beneficial with respect to
minimizing the amount of waste materials generated to pro-
Figure 1. The process concept.
duce a marketable product. These kinds of economic benefits
are recognized to be essential for the early implementation of
mineral carbonation technologies.[11] which are the extraction of Ca from steel converter slag and
The slag2PCC process can convert two low-value byproducts the carbonation of the dissolved Ca with gaseous CO2
or waste streams (slag and CO2) into a profitable product, (Figure 1). The governing reaction for Ca extraction is simpli-
which avoids disposal and emission costs. In the case of fied as Reaction (R1), which describes the effect of the ammo-
Ruukki Metals steel mill with an annual steel production of nium salt solvent on the dissolution of calcium oxide.
2.3 Mt in 2012,[23] this would mean, by using the same average
values for slag production as for the global estimates, approxi- CaOðsÞ þ2 NH4 XðaqÞ þH2 OðlÞ ! CaX2ðaqÞ þ2 NH4 OHðaqÞ ðR1Þ
mately 30 kt CO2 captured with BOF slag to produce 69 kt of
PCC annually. In this context, CaO represents all water-soluble Ca regard-
Currently, the research on slag2PCC has focused on the ef- less of the actual crystal form in which it is bound. As dis-
fects of input slag properties and other parameters (e.g., sol- cussed in earlier studies,[12, 13] the crystal forms from which Ca
vent concentration, slag-to-liquid ratio) on the process chemis- is most easily extracted are free calcium oxide or hydroxide
try and the resulting PCC quality. As steel converter slag con- (CaO/Ca(OH)2) and dicalcium silicate (Ca2SiO4). The crystalline
tains several elements besides Ca (Table 1), it is essential for compounds identified by XRD analysis are listed in Table 2.
product purity to ensure the efficient but also selective extrac- For the carbonation step, the main reactions can be sum-
tion of Ca only. For this purpose, different solvent concentra- marized as Reactions (R2) and (R3):
tions, different slag-to-liquid ratios, and differently processed
and stored slag fractions have been studied experimentally. 2 NH4 OHðaqÞ þCO2ðgÞ $ ðNH4 Þ2 CO3ðaqÞ þH2 OðlÞ ðR2Þ
Moreover, the experimental validation of the most suitable
ðNH4 Þ2 CO3ðaqÞ þCaX2ðaqÞ $ CaCO3ðsÞ þ2 NH4 XðaqÞ ðR3Þ
values for process variables, such as residence times of the re-
actor steps, is ongoing based on earlier modeling work.[12]
Most importantly, our research efforts concentrate on ensuring X in Reactions (R1)–(R3) represents CH3COO , NO3 , or Cl
process operability in such a way that a specified PCC particle ions, even though only ammonium chloride was utilized as
size, crystal morphology, and
purity are obtained on a continu-
ous basis by using a subpilot- Table 2. XRD results of the various slag fractions.
scale setup, which is also dis-
Slag fraction Component [%]
cussed in this paper. lime portlandite larnite srebrodolskite calcium magnesium iron silicate quartz other
(CaO) (Ca(OH)2) (Ca2SiO4) (Ca2Fe2O5) (Ca2Fe1.2Mg0.4Si0.4O5) (SiO2)

Process concept 2008 5 – 59 26 – – 10

2011[a] – – yes yes – – yes
The slag2PCC process is based 2012 12 17 – – 65 6 –
on the recirculation of an aque- 2012b 9 10 – – 38 – 43

ous ammonium salt solution as [a] No quantitative XRD analysis was performed on this material
a solvent between two stages,

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a solvent in the experiments reported here, the choice of

which was motivated by the low cost of the salt.[13] A recent
comparison of the three solvents is given in Ref. [24].
From Reactions (R1)–(R3) it can be seen that, theoretically,
the ammonium salt spent in extraction is stoichiometrically re-
generated in the carbonation step. Also in lab-scale experi-
ments, it has been possible to reuse the solvent to a large
extent.[13] For good process economics the recyclability should
be as high as possible, that is, losses from the process should
be minimized. As also known from earlier studies, important
features that lower the process equipment cost and require-
ments are the overall exothermicity of both reaction steps as
well as the operability at ambient pressure and temperature.
Figure 2. Extraction efficiencies of Ca, Na, and K from different slag fractions.
Values calculated from comparison of ICP-OES and XRF measurements of
Results and Discussion solvents and solid slag.

Effects of differences in slag properties

The effects of variations in slag production and storage pro-
cesses on the extraction step conversion efficiencies were stud-
ied by nine experiments, each with a different slag sample.
The tested slags were obtained from Ruukki Metals Oy Raahe
steelworks in Finland, and consisted of three chemically differ-
ent materials. Slag labeled 2008 contained both free lime and
dicalcium silicate, 2011 slag had no free lime, but high Si and V
contents, and slag 2012 had high amounts of free calcium
oxide and hydroxide.[13, 24] Detailed compositions and mineralo-
gies for each material are given in Tables 1 and 2. Data for slag
2012b are also given, although it was not used until later for
tests with the continuous process setup.
The slag fractions also differed in particle size both before Figure 3. Extraction efficiencies of V and Mg from different slag fractions.
and after milling, that is, the fractions named large in Table 3 Values calculated from comparison of ICP-OES and XRF measurements of
consisted originally of larger (> 300 mm) particles than frac- solvents and solid slag.
tions labeled small (10–50 mm). Both of these fractions were
milled to 75–125 and 125–250 mm particles that were used in in fresh slag prior to experiments. As mentioned above, not all
extraction tests. The fractions named aged were stored out- Ca in slag is present in a reactive form, but because the overall
doors for approximately 16 months to study the effect of degree of Ca conversion is of high interest, all the efficiency
chemical changes caused by, for example, leaching with rain- calculations in this paper are made according to this method.
water as described in Refs. [25, 26]. In addition to the elements shown in Figures 2 and 3, only
The extraction efficiencies, shown in Figures 2 and 3 for vari- small amounts of Si were measured in the solutions as extrac-
ous elements, are calculated by comparing the concentrations tion conversions less than 1.0 %. The slag fractions with a high
in liquid samples after extraction to the total amount present amount of free lime or calcium hydroxide were able to release

Table 3. Mass losses and experimental parameters in the experiments with different slag fractions.

Entry Slag fraction Slag amount [g] Weight loss Volume NH4Cl molarity Solid-to-liquid T[a] Particle size Reaction time
initial final [%] [L] [mol L1] [g L1] [8C] [mm] [min]
1 2008 25.0 18.9 24.4 0.25 2 < 250 60
2 2011 50.0 46.3 7.5 125–250 60
3 50.0 46.5 7.0 125–250 68
2011 (aged)
4 50.0 44.5 11.1 75–125 67
5 50.0 45.7 8.6 100 ambient 125–250 66
2011 (aged, small) 0.5 1
6 50.0 44.9 10.3 75–125 78
7 50.0 43.5 12.9 125–250 66
2011 (aged, large)
8 50.0 44.5 11.0 75–125 86
9 2012 49.5 36.3 26.7 125–250 85

[a] Ambient temperature in these experiments varied between 20 and 25 8C.

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more Ca than those that contained Ca in a more bound form, was also assessed with these experiments. Slag 2012 (Tables 1
as expected.[10, 25] Also, the smaller the slag particles used in and 2) with a high content of free calcium oxide was used in
the experiments, the better the extraction. However, the origi- these tests because it was expected to release large amounts
nal particle size before milling did not have a significant effect. of Ca in pure water.
Storage outdoors decreased the extraction efficiencies slightly, The measured concentrations are presented together with
but no significant differences were observed, in accordance concentrations calculated from the measured final pH values
with the literature.[27] As the slag used in the outdoor storage by stoichiometric solubility limitations in Table 5. The solubility
experiments contained no free lime, the tests only studied the
ageing behavior of dicalcium silicate, and the results could
have been different for a more lime-rich slag. Table 5. Ca extraction efficiencies [mol L1 and %], measured with Ca-se-
In addition to Ca, K and Na were also extracted efficiently lective ISE (ELIT 8041, NICO 2000 Ltd.) and calculated from stoichiometry.
(up to 30 %) from the slag, but because the amounts of these Entry [Ca2+] [mmol L1] Ca pH
elements present in the fresh slag are small, only 0.2–0.5 % in measured predicted difference extracted % of fresh end
total, the concentrations remained low in the aqueous solu- 1 0.39 0.36 0.03 0.2 13.0
tions. Up to 3 % V and 0.1–1.4 % Mg were extracted (Figure 3). 2 0.44 0.40 0.04 0.2 13.0
As expected, more V was released from the high-V-content 3 1.26 1.10 0.16 0.6 12.8
slag 2011 than from slags 2008 and 2012. The extraction yield 4 7.08 43.80 36.72[a] 3.8 12.0

of V was higher from smaller particles, but for Mg the results
were the opposite; more Mg was extracted from the larger
(125–250 mm) particles. Nonetheless, the accumulation of the
minor elements in the process solutions must be accurately
followed.
Most of the experimental pH values leveled off at approxi-
mately the same value (9.3–9.5). All the 2011 slag experiments
with the smaller particle size (75–125 mm), as well as one of
the 125–250 mm tests (different mixing compared to other
125–250 mm tests) and the 2008 slag experiment showed this
behavior. The 2012 slag resulted in a higher final pH (10.2),
which is understandable based on the high CaO/Ca(OH)2 con-
tent. However, 2011 slag with larger particle sizes (125–
250 mm) yielded pH values of 8.7–9.0.
Thus, two main reasons for different end pH values can be
identified based on these experiments; the content of free cal-
cium oxide/hydroxide and the particle size of the input slag in
the experiments. Particle size effects can to some extent be
compensated for with enhanced mixing. The ageing history
and the size of the original slag particles before milling did not
affect the pH values significantly.
[a] Not enough reactive Ca available, thus equilibrium calculation was not
valid.
information was obtained from HSC Chemistry 5.11.[28] The
amounts of dissolved Ca remained small at only 0.2–3.8 % of
the total Ca available in fresh slag. This is because of the lack
of a buffer effect of ammonium salts; if the solution pH ap-
proaches 13, the Ca solubility is reduced noticeably. As
a result, Ca was first dissolved from the slag but reprecipitated
as calcium hydroxide before a sample was withdrawn for con-
centration measurements. For the PCC production process this
would be detrimental because the Ca could not be separated
efficiently from steel slag and transferred in dissolved form
from the extraction to the carbonation step. In traditional PCC
manufacture, in which calcium hydroxide is used as a Ca
source, this is not a problem because no impurities are includ-
ed in the solid material, and the unreacted calcium hydroxide
can be removed by screening as a result of the different parti-
cle sizes.[29] Actually, the rate of calcium hydroxide addition can
also be used to steer the particle morphology of the produced
PCC.[30, 31]

Effect of ammonium salts on Ca extraction

To confirm the potential and advantages of ammonium salt
solvents in the extraction of Ca from steel converter slag, an-
other series of experiments was performed with distilled water
as a solvent and by reusing the slag from the first test in the
three other tests (Table 4). Thus, the effect of slag recycling
Process conditions that promote selective and efficient Ca
extraction and the production of pure PCC
The effects of higher concentrations of ammonium salt (up to
4.9 mol L1) and higher solid-to-liquid ratios (up to 300 g L1)
on selective Ca extraction were studied with additional experi-

Table 4. Mass losses and experimental parameters in the experiments with distilled water as a solvent.

Entry Slag fraction Slag amount [g] Weight loss Volume NH4Cl molarity Solid-to-liquid T[a] Particle size Reaction time
initial final [%] [L] [mol L1] [g L1] [8C] [mm] [min]
1 2012 5.00 4.46 10.8 25.0 93
2 from previous 4.46 3.81 14.6 22.3 107
0.2 0 ambient 125–250
3 from previous 3.81 3.35 12.1 19.1 68
4 from previous 3.35 2.42 27.8 16.8 92

[a] Ambient temperature in these experiments varied between 20 and 25 8C.

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Table 6. Mass losses and experimental parameters in the experiments with varying solvent molarity and solid-to-liquid ratio (slag fraction 2008).

Entry Slag amount [g] Weight loss Volume NH4Cl molarity Solid-to-liquid T[a] Particle size Reaction time
initial final [%] [L] [mol L1] [g L1] [8C] [mm] [min]
1 15 10.3 31.3 0.75 0.5 20 30 125–250 120
2 25 18.9 24.4 1.8 100
3 50 40.4 19.3 1.8 200
4 75 60.8 19.0 1.8 300
5 25 19.8 20.9 3.5 100
6 50 40.3 19.5 0.25 3.5 200 20 < 250 60
7 75 63.2 15.8 3.5 300
8 50 41.5 17.0 4.9 200
9 25 19.0 23.9 4.9 100
10 25 21.1 15.8 4.9 100

[a] Temperature was controlled by immersing the reactor in a water bath at the specified temperature.

Figure 6. Mg extraction efficiency, % of total amount in fresh slag, as a func-

Figure 4. Ca extraction efficiency, % of total amount in fresh slag, as a func- tion of NH4Cl solvent molarity [m] and solid-to-liquid ratio [g L1].
tion of NH4Cl solvent molarity [m] and solid-to-liquid ratio [g L1].

other tests, and thus the experiment is not fully comparable

Figure 5. Si extraction efficiency, % of total amount in fresh slag, as a func-
tion of NH4Cl solvent molarity [m] and solid-to-liquid ratio [g L1].
ments. The extraction efficiencies of Ca, Si, and Mg are pre-
sented in Figures 4–6, respectively, obtained from the experi-
ments listed in Table 6.
It must be mentioned explicitly that the 20 g L1 experiment
was performed with a 125–250 mm slag size fraction, whereas
in the other experiments the < 125 mm particles were included
in the test material. Moreover, this experiment was performed
at 30 8C, whereas in all the other experiments the temperature
was 20 8C. Also the reaction time was twice as long as in the
with the other tests.
Besides the mentioned Ca, Si, and Mg, no other elements
were detected from the solutions by inductively coupled
plasma optical emission spectroscopy (ICP-OES), although, for
example, Mn precipitates were visibly present in the plastic
sample containers, especially after tests with salt concentra-
tions higher than 1.8 mol L1.[32] The extraction efficiencies are
calculated by comparing the concentrations in liquid samples
after extraction (measured by ICP-OES) to the total amount
present in fresh slag prior to the experiments (measured by X-
ray fluorescence spectroscopy; XRF).
As reported earlier,[24, 33] the increase of the solid-to-liquid
ratio from 20 to 300 g L1 reduces the extraction efficiency of
Ca from ~ 50 % to roughly 35–40 %. In those studies, the
reason for this behavior was unclear. However, if the dissolved
Si concentrations in different experiments (Figure 5) are com-
pared with the Ca levels, it can be observed that the changes
in extraction efficiencies of Ca and Si follow similar trends from
experiment to experiment.
According to Refs. [34, 35], Si can be dissolved in water in
concentrations of typically around 100 ppm, which depends
on the origin of the Si, the pH of the solution, etc. However,
both ammonium and calcium ions are used as coagulants for
Si to aid in its precipitation from solutions. Moreover, ammonia
in aqueous solutions is known to reduce the rate of Si dissolu-

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tion.[23] In the current process, all of the mentioned compounds
are present, partly also in high concentrations. Thus, it seems
clear that if both Ca and Si concentrations in the slurry are in-
creased by using high solid-to-liquid ratios, Ca dissolution is
hindered because of the limited solubility of Si. This reduces
the Ca yield of the extraction step. An increase of the pH coun-
teracts this phenomenon by enhancing Si dissolution.[35]
The effect of the ammonium salt concentration is not equal-
ly clear, although, as seen in Figures 4–6, at high concentra-
tions the extraction efficiencies are slightly decreased com-
pared to lower ammonium salt concentrations. As a result of
these effects, the observed experimental Si concentrations
remain between 3–15 ppm, which is low compared to the liter-
ature value of 100 ppm for pure water.
It can be concluded that depending on the content of Si-
bound Ca in slag, solid-to-liquid ratios in the extraction step
should not significantly exceed 100 g L1 because higher
values result in a rapid decrease of the Ca extraction efficiency
(Figure 4). The fraction of free lime (CaO) is an essential param-
eter to choose the best solid-to-liquid ratio for efficient Ca ex-
traction because the dissolution of CaO is not affected by the
Si concentration in the solution. If the slag contains only small
amounts of free lime, the solid-to-liquid ratio should be pref-
erably as low as 20 g L1. This will require larger process equip-
ment[24] and becomes subject to the cost optimization of the
overall process.
Moreover, even though it is beneficial to have ammonium
salts present in solution to aid Ca dissolution as discussed in
the previous section, too high concentrations should also be
avoided as these result in the adverse extraction of impurities
as seen, for example, in the case of Mg (Figure 6). As reported
earlier, product purity also suffers from ammonium salt precipi-
tation that occurs at salt concentrations above 1.8 mol L1[32]
because PCC should not contain, for example, any compounds
of ammonia or chlorine.
These observations are summarized in Figure 7, and the
most beneficial area of process operation from the point of
view of selective Ca extraction is indicated by the double
Figure 7. Observed limitations for selective Ca extraction with ammonium
chloride solvent, the experiments listed in Table 6 are marked with circles.
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arrow in the bottom left of the graph. However, too low sol-
vent concentrations result in slow kinetics,[12] again not benefi-
cial for the overall process. The stoichiometric limit in Figure 7
is calculated for a slag that contains 45 % CaO, of which 50 % is
in a reactive form.
The Ca extraction efficiencies in all the experiments dis-
cussed are plotted against a combination of the identified sig-
nificant variables (z) in Figure 8. z [mm g L1] is calculated from
Figure 8. Ca extraction efficiency, % of total amount in fresh slag, as a func-
tion of the parameter z. Triangles show experiments with substoichiometric
ammonium concentrations.
the slag properties according to Equation (1), in which mslag is
the solid-to-liquid ratio of the slag and ammonium salt solvent
(g L1), d̄slag is the arithmetic mean diameter of the slag parti-
cles [mm] (Tables 3, 4, and 6), and fSi, fV, fFe, and fCa are mass
fractions of Si, V, Fe, and Ca in fresh slag based on XRF meas-
urements, respectively (Table 1). As the reactivity of other Ca
compounds is lower than that of free lime, an additional pa-
rameter group is included to adapt Equation (1) for slags with
various fractions of bound Ca. This group consists of the sum
of an empirical constant 0.5 and the cubic root of free Ca frac-
tion, fCa, free, calculated according to Equation (2) based on XRD
analysis (Table 2).
Interestingly, the ammonium salt concentration does not
seem to affect the Ca extraction efficiency directly. However, as
mentioned in earlier studies,[12] the kinetic rates of extraction
reactions are affected by the solvent concentration. Triangles
represent the experiments in which the used solvent concen-
tration is below the expected stoichiometric calcium concen-
tration in Figure 8, which are thus not comparable with the
other experiments in which Ca extraction did not meet this
limitation. The range of validity and applicability of Equa-
tion (1) need to be followed up as a part of our future work.
mslag  dslag  fSi  fV  fFe
z¼ pffiffiffiffiffiffiffiffiffiffiffi ð1Þ
fCa ð0:5 þ 3 fCa;free Þ
fCaO þ fCaðOHÞ2
fCa;free ¼ ð2Þ
fCa;total;XRD
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Figure 9. Process scheme and picture of the constructed demonstration setup.
Continuous process setup
Based on the observations summarized in previous sections, it
was considered essential to ensure that the process can be run
in a continuous reactor system to reduce repeated operational
changes and to be able to rapidly adapt the process to chang-
ing input slag quality. At the same time, the produced PCC
amounts should be large enough to guarantee a constant and
good product quality, in terms of product purity as well as
crystal properties. For these purposes a subpilot-scale continu-
ous reactor setup was constructed, the detailed process
scheme of which is shown in Figure 9.
Extractor design
The extraction reactor (on the left in Figure 9) consists of a cy-
lindrical Perspex tube (height 650 mm, width 240 mm, total
volume 29.4 L), inside which a mechanical pitched blade
paddle stirrer with two paddles (width 150 mm, distance be-
tween paddles 260 mm, distance from bottom to lower paddle
30 mm) is placed. The stirrer works according to the radial flow
principle, that is, the slurry in the reactor is directed towards
the walls at the paddle height. This was verified with a test ex-
periment by using inert glass beads of size fraction 125–
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212 mm and a density of ~ 2600 g L1,[36] which are similar to
the actual reactive slag particles.
The mixing efficiency was estimated by calculating the theo-
retical solids concentration in the reactor and measuring the
actual solids concentration in the reactor outflow. The mea-
surement was performed by pumping slurry from the reactor
and filtering, drying, and weighing the solid particles in
a known volume. At the height of the outlet in the reactor
(80 mm from the reactor bottom), the particle concentration
was observed to be 120 g L1, whereas the calculated value
was 100 g L1. Thus, as also confirmed visually, the reactor
volume was not uniformly utilized, and a lower particle con-
centration was maintained at approximately 100 mm (550 mm/
650 mm  100 g L1/120 g L1) below the reactor lid. To prevent
vortex formation on the liquid surface, however, this stirrer
configuration was considered to be satisfactory. To reduce the
tendency for the complete rotation of the reactor contents,
three baffles of 20 mm width were attached to the reactor
walls at 1208 intervals. Also, a 7 mm gap was left between the
reactor wall and the baffles to prevent particle accumulation
behind the baffles. The design mainly followed the guidelines
for a standard geometry-agitated tank,[37] modified by practical
limitations set by, for example, material availability.
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Power dissipation e [kW; Eq. (3)] in mixing can be estimated
in a similar manner as for lab-scale experiments presented in
earlier work.[38] Po is the power number, 1 is the slurry density
[kg m3], n is the frequency of rotation of the mixer [s1], and
d is the diameter of the mixer [m].
Po  1  n3  d 5 ð3Þ
e¼
1000
The power number is estimated from the Reynolds number
of mixing, which is obtained according to Equation (4), in
which hmixture is the viscosity of the slag and ammonium salt so-
lution mixture of 1.102 mPa s.[38]
1  n  d2
Rev ¼ ð4Þ
hmixture
Together with 1 = 1074 kg m3, and with experimental values
n = 5.8 s1 and d = 0.15 m, Rev = 127 184. In other words, the
mixing situation is clearly turbulent, and the volumetric dis-
charge rate from one paddle becomes roughly 10 L s1.[37] The
power number in a vessel without baffles for a turbine stirrer
is then estimated to 1.4 without baffles, and 0.98  1.4 = 1.38
with three baffles.[37] Moreover, the configuration of dual pitch-
ed paddles lowers this value by a factor of 0.7  1.38  0.96,
which results finally in an energy dissipation of 15 W or
0.456 W kgsolution1 for the extraction reactor with 1.0 mol L1
NH4Cl solution and a 100 g L1 slag-to-liquid ratio.[37] These are
the highest concentration levels under which the process will
be operated based on information presented in the previous
sections. The obtained energy dissipation is of a similar order
of magnitude as estimated earlier for lab-scale (1 L) experi-
ments (0.369 W kgsolution1), in which the difference originates
from a larger impeller diameter compared to the reactor
diameter.
Carbonator design
The carbonation reactor (on the right in Figure 9) is a Perspex
tube identical to the extraction reactor. At a height of 5 cm
from the reactor bottom, a porous polyethylene sheet (SPC
PE3530)[39] of 3.0  0.10 mm thickness and a mean pore size of
39 mm is installed. CO2 gas is introduced into the reactor
through the porous sheet from a gas bottle of 99.9996 % CO2
(Oy Aga Ab). The gas line is equipped with both a manometer
and a flow meter (Kytçl LH-4CR-HR). The distance between
the mechanical stirrer and the reactor bottom is 70 mm in-
stead of 30 mm as in the extraction reactor because of the gas
inlet. Besides the mixing provided by the gas flow and the me-
chanical stirring, a circulation pump capable of pumping
1.5 L min1 is installed in the reactor, with the intake at the top
and the outlet at the bottom, which generates a co-current
flow with respect to gas flow and ensures the presence of PCC
seed crystals in the reactor (except at the start of the reaction).
By default, the unreacted gas is vented from the system, but
the vent can also be closed to provide an overpressure of ap-
proximately 0.015 bar.
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
The initial gas bubble diameter (db, i) in a bubble column can
be estimated from Equation (5),[40] in which s is the surface
tension of the liquid phase (73 mN m1[41]), d0 is the orifice di-
ameter of the gas distributor (mean diameter 39 mm), g is the
gravitational acceleration (9.81 m s2), and 1l and 1g are the
densities of liquid and gaseous phases, respectively (1015 and
2 kg m3).
" #1
3
6  s  d0
db;i ¼   ð5Þ
g 1l  1g
On introduction of the numerical values, an initial bubble
size of approximately 1.2 mm is obtained under near atmos-
pheric pressures and ambient temperature. With Stokes’ law
[Eq. (6)] and the viscosity of water hl = 1.003 mPa s, this yields
the initial bubble rise speed of approximately 0.79 m s1.
 
1l  1g g  db2
vffi ð6Þ
18h
For the gas distributor design, it is important to estimate
the bubble size under steady-state conditions in the upper
part of the reactor, not only at the feed point. Approximations
for the Sauter mean bubble diameter dsm [m] distant from the
gas inlet and gas hold-up H [m3 gas m3 total] in the reaction
vessel can be obtained by iteration with Equations (7) and
(8).[37] In addition to the parameters already introduced, Vl is
liquid volume [m3] and us is the superficial gas velocity calcu-
lated from the inlet gas flow by assuming an even gas distribu-
tion over the total reactor area [m s1].
 
s0:6
dsm ¼ 4:15  103 H1=2 0:4 0:2 þ 0:9  10
3
ð7Þ
ðe=Vl Þ 1l
 1   1
us  hl  H 2 ðe=Vl Þ0:4 10:2
l us  hl 2
H ¼ 4:24 þ0:916
gð1l  1g Þ*dsm2 s 0:6
gð1l  1g Þ*dsm
2
ð8Þ
From Equations (3) and (4) with 1 = 1031 kg m3, hmixture =
1.038 MPa s, n = 0.8 s1, d = 0.15 m, and Po = 0.93 (corrected
for a CO2 gas flow of 475 mL min1 according to Ref. [37]), the
power dissipation in the carbonation reactor is estimated as
e = 0.04 W. Together with Vl = 29 L, us = 0.18 mm s1, and hl =
1.003 mPa s, Equations (7) and (8) yield a mean bubble diame-
ter of 2.7 mm (rise speed 4.0 m s1) and a gas hold-up of 1 
104 m3 m3. Based on the experimental observations, these re-
sults seem reasonable.
These values should be considered as approximations be-
cause several simplifications are made in the calculations, for
example, the effect of the circulation pump is not included in
the power dissipation, and the effects of chemical reactions
and the precipitation of solid carbonates are excluded from
the formulas used here. Also, even if high electrolyte concen-
tration is known to reduce bubble coalescence,[42] only
changes in surface tension and viscosity are included, which
thus yields a higher value for dsm than with a lower coales-
ChemSusChem 2014, 7, 903 – 913 910
CHEMSUSCHEM
FULL PAPERS
cence rate. In the calculation of slurry densities and viscosities,
the highest measured value for the solid content (~ 40 g L1
PCC in batch experiments) is used because this yields the larg-
est power consumption.
Nevertheless, it can be concluded that the designed gas dis-
tributor can provide the system with smaller bubbles (1.2 mm)
than that maintained in the reactor under the operational con-
ditions. Thus, the mass transfer rate between the gas and
liquid cannot be increased by, for example, further reduction
of the pore size in the distributor sheet.
Process control equipment and principles
To control the flow rates in the process, five to seven peristaltic
pumps are used, as shown in Figure 9. These pumps provide
an adjustable flow up to 1.5 L min1. Also, the bypass stream is
realized with a three-way valve, which enables a variable frac-
tion of the extractor outflow to be fed directly to the PCC
settler.
The temperature and pH of the process solution are contin-
uously monitored and recorded from four different locations;
on top of both the extraction and carbonation reactors as well
as on top of the inclined settlers. As a data logging system, an
ELIT 9808 eight-channel recorder is used. The temperature and
pH in the extraction reactor can be controlled by changing the
feed rate of fresh slag. For the carbonation reactor, the most
straightforward control method is to change the CO2 gas flow
rate.
Also, because the system is designed for a recirculating sol-
vent, it is of importance to follow and adjust the quality of sol-
vent that is returned to the extraction reactor. This is per-
formed according to principles discussed in earlier work;[38]
a bypass stream is taken from the slag settler to the PCC set-
tler to precipitate as much as possible of the carbonate and bi-
carbonate ions present in the solution and thus prevent them
from entering the extraction reactor. This inhibits carbonate
precipitation on slag particles in the higher pH solution of the
extraction reactor, which would reduce the Ca extraction effi-
ciency and thus the efficiency of the entire process.
Handling of solid matter
Slag is fed to the extraction reactor in small batches at
a known rate based on the calculated outflow of solids from
the reactor, the target of which is a near-constant solid-to-
liquid ratio in the reactor. As both the residual slag as well as
the produced PCC must be removed from the process streams
continuously, the separation equipment consists of two in-
clined settlers,[36, 43] one for each solid, combined with more tra-
ditional barrier filters. Based on promising results with separa-
tion efficiencies of 99 % on a mass basis during earlier studies
with similar equipment,[36] Perspex tubes with an inner diame-
ter of 10 cm have been installed as settlers. For slag separation
the tube length is 50 cm and for PCC 110 cm.
As shown in Figure 9, additional filter units are placed after
both settlers. These filters (HOH Pure 1 mm/5“, BWT Separtec
Oy) are used to ensure that no small slag particles enter the
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
carbonation reactor, in which they would reduce the purity of
the produced PCC, and similarly that no PCC particles enter
the extraction reactor, in which the valuable product would
get mixed with slag particles and leave the system with the re-
sidual slag stream. Two filter units are used to collect the pro-
duced PCC from the underflow of the inclined settler after the
carbonation reactor. These filters are installed in parallel to
give the possibility to clean one filter while the other is in use.
All the filter units are equipped with a manometer to follow
the pressure drop over the filter element during operation.
Each filter unit can be separated from the system with two
valves. Residual slag is collected from the extraction reactor to
a separate 10 L vessel, from which it can be removed during
operation, if necessary.
Experimental results from the continuous setup
The measured changes in pH in the four vessels during the
course of the experiment are presented in Figure 10. In the ex-
tractor, the pH was maintained at approximately 9.5 after the
Figure 10. pH in the different reactors during the course of the experiment.
pumps were switched on, whereas in the carbonator, fluctua-
tions between 8.3 and 8.9 were observed, which indicates that
the system was not able to reach a steady state during the
time interval.
Samples of the carbonate product were collected both from
the carbonator and the PCC settler after 60 min of gas feed. As
expected, the crystal properties varied noticeably, which de-
pended on where the sample was taken from. In the carbona-
tor, the particles were in the form of rhombohedral calcite
(Figure 11), whereas vaterite was formed in the PCC settler
(Figure 12). In total 614 g of PCC was produced, which corre-
sponds to 15 % of the mass of the input slag amount (or 17 %
of the total Ca). In earlier batch experiments this value varied
between 5 and 30 %, which depends on the input slag quali-
ty.[13] As impurities, only Si and Cl were detected in small
amounts (< 1 wt %) by SEM and energy-dispersive X-ray spec-
troscopy (EDX).
ChemSusChem 2014, 7, 903 – 913 911
CHEMSUSCHEM
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Figure 11. Rhombohedral calcite from the carbonation reactor after 60 min
of carbonation. Scale bar 10 mm.
Figure 12. Vaterite from the PCC settler after 60 min of carbonation. Scale
bar 10 mm.
After it is shown that the process can also be run in a contin-
uous mode and that the crystal properties can be changed by
changing the process conditions, our future research will con-
centrate on the control of the PCC crystal morphology and
also product purity. It is likely that an additional washing step
must be included in the system to reduce the level of impuri-
ties, which consist primarily of chloride. Another alternative
would be to change the solvent to, for example, ammonium
nitrate.[14]
Conclusions
A CO2 utilization and storage concept “slag2PCC” is advanced
from lab-scale experiments to a larger scale. Even though the
scale in which the process could be applied into practice is rel-
atively small, at maximum approximately 20 Mt of CO2 can be
captured per year, it would still be beneficial for a steel manu-
facturer to produce a marketable product from waste materi-
als. For the overall process efficiency, it is of importance that
the input slag releases Ca to as large an extent as possible.
Two main factors that affect this behavior were observed to be
the content of free lime in the slag and the particle size to
which the slag is milled before extraction. Ammonium salt sol-
vents enhance the Ca dissolution by introducing a buffer
effect, which is absent from systems that use only pure water
as solvent. If ammonium salts are present in over-stoichiomet-
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
ric amounts with respect to the amount of Ca, a parameter
combination of the slag-to-liquid ratio, the mean diameter of
slag particles, and the fractions of Si, V, Fe, and Ca can be con-
structed and used to predict the total extraction percentage of
Ca. A continuous four-step reactor system has been built for
the process. The first test results show that the process can be
successfully run in a continuous mode to produce several
types of PCC particles in different process stages. In our future
work, the focus will be on the control of the properties and
purity of the produced PCC.
Experimental Section
A specified amount of slag was mixed with a magnetic or an over-
head stirrer at approximately 200 rpm together with an ammoni-
um chloride solution for a certain time. The temperature and pH of
the solution were recorded during the experiments. After the ex-
periments, the residual slag was separated from the solution by fil-
tration through Whatman 589/3 filter papers and dried overnight
at 105 8C. The detailed experimental conditions are listed in
Tables 3, 4, and 6. The solid concentrations were measured by XRF,
whereas the liquid samples were analyzed by using ICP-OES. In the
experiments listed in Table 4, the Ca concentration was measured
by using an ion-selective electrode (ELIT 9808).
To test the continuous setup, an experiment was conducted by
using NH4Cl (1.0 m) as a solvent with a 100 g L1 slag-to-liquid ratio
in the extractor (slag 2012b in Tables 1 and 2) and a CO2 flow of
0.5 L min1. In the start-up phase, the slag was allowed to react
with the solvent until the pH value stabilized (50 min). After that
the pumps were switched on in such a way that the residence
time for slag in extractor became 60 min. The gas feed was started
at the same time. The total amount of slag used in the experiment
was 4200 g, of which 2800 g was added at the start, and the re-
maining 1400 g was added in two batches of 700 g at 70 min and
100 min after the start of the experiment, respectively. After
130 min from the start, the gas feed was switched off, and the
system was cleaned.
Acknowledgements
This work was carried out in the Carbon Capture and Storage
Program (CCSP) research program coordinated by CLEEN Ltd.
with funding from the Finnish Funding Agency for Technology
and Innovation, Tekes. H.-P.M. also acknowledges the Graduate
School in Chemical Engineering for support for his work. The
XRD/XRF analyses were performed by Ruukki Metals Oy, ICP-OES
by Sten Lindholm at Analytical Chemistry/AU, and SEM/EDX by
Linus Silvander at Inorganic Chemistry/AU. Also, Jimmy Dahlqv-
ist, Alf Hermanson, Daniel Legendre, and Martin Slotte are ac-
knowledged of their work on the construction of the experimen-
tal setup. SPC Technologies Ltd. provided samples of their porous
plastic sheet products to be tested in the setup.
Keywords: calcium · carbon storage · environmental
chemistry · industrial chemistry · waste prevention
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