Production of Precipitated Calcium Carbonate From Steel Converter Slag and Other Calcium-Containing Industrial Wastes and Residues

CHAPTER TEN
Production of Precipitated
Calcium Carbonate from Steel
Converter Slag and Other
Calcium-Containing Industrial
Wastes and Residues
Hannu-Petteri Mattila, and Ron Zevenhoven
Thermal and Flow Engineering Laboratory, Åbo Akademi University, Turku, Finland
Contents
1. Introduction 348
2. Existing PCC Manufacturing Technologies 350
2.1 Carbonation process 350
2.2 Solvay process 353
2.3 Lime-soda process 354
2.4 Calcitech process 354
2.5 Filler recycling processes 355
3. Mineral Carbonation Processes 355
4. PCC Manufacturing Technologies Based on Industrial Waste Materials 356
4.1 Oil shale ash indirect aqueous carbonation 356
4.2 Salty water carbonation 359
4.3 Ash, dust, and concrete-based processes 360
4.4 Carbonation of gypsum waste 362
5. PCC Manufacturing Based on Steel Slag Carbonation 363
5.1 Waste streams from steelmaking processes 363
5.2 Direct versus indirect aqueous carbonation of steel converter slag 365
5.3 Leaching studies on steel slags 366
5.4 Selective extraction of calcium from steel converter slag 366
5.5 Vanadium extraction from the residual slag 370
5.6 Calcium carbonate precipitation 371
5.7 Current status of the development of the Finnish steel converter slag
carbonation process 375
6. Remarks on Applicability of Various Processes in Global Scale 378
7. Conclusions 380
Acknowledgments 380
References 381
Advances in Inorganic Chemistry, Volume 66 # 2014 Elsevier Inc. 347

ISSN 0898-8838 All rights reserved.
http://dx.doi.org/10.1016/B978-0-12-420221-4.00010-X
348 Hannu-Petteri Mattila and Ron Zevenhoven
Abstract
Precipitated calcium carbonate, a widely used filler material, is nowadays mainly pro-
duced by the so-called carbonation process. Natural limestone is first calcined and then
contacted with carbon dioxide to precipitate particles of a controlled purity, size, and
morphology. In the production process, an amount of carbon dioxide equal to or larger
than what is later bound to the actual product is released.
For climate change mitigation, it would be possible to reduce carbon dioxide
emissions by capturing CO2 from flue gases, if the required calcium could be obtained
from another source than the natural rocks. Industrial alkaline by-product and waste
streams such as slags and ashes contain calcium often in a readily soluble form. Recently,
several processes have been developed to apply these materials for carbon dioxide cap-
ture, utilization, and storage, while simultaneously producing materials with market value.
Since the chemistry of calcium carbonate precipitation is relatively complex, the levels
of impurities should be maintained low in the carbonation process. In case of utilizing a
solid waste stream, this requires efficient separation of the residual waste material from
the calcium-rich solution after extracting the soluble calcium from the solids.
Aspects related to a two-step aqueous process for steel converter slag carbonation are
discussed in more detail, since a continuous laboratory-scale setup has been constructed
and is currently under further development at Finnish universities. Even though the current
issues related to product quality can be resolved, the process is still in such a small scale that
it mainly serves the demonstration purposes for mineral carbonation technologies.
Keywords: Calcium carbonate, Carbon dioxide capture and utilization, Mineral
carbonation, Steel converter slag, Waste stream utilization
1. INTRODUCTION
Calcium carbonate (CaCO3) is a substance widely used for various
purposes, for example, as a filler and pigment material not only in paper,
plastics, rubbers, paints, and inks but also in pharmaceutics, cosmetics, con-
struction materials, and asphalts and as a nutritional supplement in animal
foods (1). Besides the so-called ground calcium carbonate (GCC), which
is milled from natural limestone, precipitated calcium carbonate (PCC) is
used in applications where, for example, higher brightness or a narrow par-
ticle size distribution is required. In PCC, manufacturing these properties
can be controlled, since unlike GCC, the product is fully synthetic (2).
Figure 10.1 shows the demand distribution between the different applica-
tions in North America, paper filler being the major use of PCC. In
2011, 14 Mt of PCC was consumed worldwide, Asia being the largest
regional market. GCC consumption reached 60 Mt in 2011, since as a
cheaper, less processed product, it has a wider area of applications. The
Production of Precipitated Calcium Carbonate from Industrial Wastes and Residues 349
144; 7 %
48; 2 %
96; 4 %
144; 7 %
Paper
Plastics
144; 7 % Rubber
Paint
Adhesives/Sealants
Others
1600; 73 %
Figure 10.1 2011 PCC consumption by end use in North America in kilotons. Data from
Ref. (2).
estimated production capacity of PCC and GCC combined exceeds

100 Mt/year, of which 17 Mt is PCC production (2,3).
Carbon dioxide for PCC manufacturing is in general taken from cleaned
flue gases of industries located nearby the PCC plant, thus reducing the CO2
emissions from this specific source. However, the production of reactive cal-
cium from limestone usually generates an amount of CO2 equal to or larger than
what is chemically stored in carbonates (1). Thus, in case calcium could be
brought into a PCC manufacturing process with a smaller carbon dioxide pen-
alty, the process route would contribute to mitigating CO2 emissions and global
climate change. Carbon dioxide would be stored as a solid and stable mineral by
using the technology commonly known as mineral carbonation (4).
Applicability and process economics of several calcium-containing solid
industrial waste materials, such as steel slag (5–10), air pollution control residue
(11,12), bottom ash from municipal solid waste or refuse-derived
fuel incineration (6,12,13), oil shale ash (14), waste concrete (15–17), cement
kiln dust (CKD) (18), and brines (19,20), for mineral carbonation in general
have been studied during recent years. Examples of main elemental compo-
sition of these materials are presented in Tables 10.1 and 10.2 in Section 4.
For PCC manufacturing, however, it is essential to guarantee a high
product quality, particularly high purity, as well as a suitable particle
size and crystal morphology (30). Assuming that these properties are
not compromised, the product could be marketed as a replacement for
PCC produced with traditional methods. This would, besides reducing
industrial waste streams and CO2 emissions, also bring direct economic ben-
efits for applying new PCC manufacturing routes like Slag2PCC—see
Section 5.7 (31).
2. EXISTING PCC MANUFACTURING TECHNOLOGIES

Several methods for production of PCC have been developed and are
used nowadays. The processes differ from each other in layout and process
equipment and in the starting chemicals. This results in differences, for
example, in the production costs and in impurities that are found in the
product (2,32). The various technologies are discussed in the following
and summarized in Table 10.3.
2.1. Carbonation process

The most frequently used, most simple, and most cost-efficient production
method for PCC is the so-called carbonation process (Figure 10.2), where
limestone (calcium carbonate) is first calcined in a lime kiln at 900–1000 C.
The produced calcium oxide is then slaked with water, after which the puri-
fied waste gas from calcination containing carbon dioxide is contacted with
the solution in bubbled gas tank reactors. Then, the precipitate is screened to
remove possible unreacted calcium hydroxide, and a filter press and a dryer
are used to dewater the product. If the plant is located near the end user of
the produced carbonate, the product can also be delivered as slurry without
drying. Also, it is possible to have the calcination and carbonation reactors
on different sites, depending on the feasibility of different transportation
options.
The reactions together with the reaction heats for carbonation process
are shown as Equations (10.1)–(10.3). Carbonation reactors are typically
operated batchwise and are equipped with mechanical mixing equipment
and recirculation of the aqueous solution to produce particles of a predefined
quality (1,32,33):
heat
CaCO3 ðsÞ $ CaOðsÞ þ CO2 ðgÞ ðDH ¼ 163 kJ=mol at 1000 CÞ ð10:1Þ
CaOðsÞ þ H2 OðlÞ $ CaðOHÞ2 ðsÞ ðDH ¼ 65 kJ=mol at 20 CÞ ð10:2Þ
CaðOHÞ2 ðsÞ þ CO2 ðgÞ $ CaCO3 ðsÞ þ H2 OðlÞ
ð10:3Þ
ðDH ¼ 113 kJ=mol at 20 CÞ
Table 10.1 Main elements in various industrial waste materials excluding iron and steelmaking slags
Analysis
Material method Ca Mg Fe Al Si Na S K Mn Ba Sr Rest Refs.
Air pollution ICP–AAS % 35.0 0.8 0.1 0.2 1.0 3.8 – 0.6 – – – 58.5 (21)
control residue
Brine (average ICP mg/ 33,450 1837 434 – – 62,780 – 2350 – 917 10,041 – (19)
of five samples) L
Brown coal fly ICP % 21.2 15.4 7.8 1.3 4.3 4.8 6.0 0.4 – – – 38.8 (22)
ash
Cement kiln – % 27.2–35.7 <1.2 0.7–2.8 1.6–3.2 5.1–7.5 <1.5 1.6–7.2 2.5–10.8 – – – 32.8–61.3 (18)
dust (typical)
Estonian oil ICP % 21.5 3.0 2.0 3.4 0.2 0.9 2.4 1.7 0.4 – – 64.5 (23)
shale ash
FGD gypsum XRD/other % 23.2 – 0.1 0.2 0.3 – 17.9 0.1 – – – 58.2 (24)
Lignite fly ash ICP–AES % 12.8 3.7 5.9 7.9 24.1 4.1 – 2.3 – – – 39.2 (20)
Paper bottom XRF % 22.1 3.1 2.8 7.2 16.6 0.6 0.4 1.3 0.2 – – 45.7 (25)
ash
Phosphogypsum XRF % 31.9 0.1 – 0.1 0.2 0.9 20.1 2.3 – – 0.1 44.2 (26)
Pulverized coal SEM–EDS % 0.9 – 2.8 14.5 16.8 4.4 – 1.6 – – – 59.0 (27)
fly ash
Waste cement ICP–AES/ % 23.8 0.1 2.5 0.7 2.9 – – – – – – 71.1 (28)
XRF
Table 10.2 Chemical compositions of various iron and steelmaking slags measured by XRF analysis (29)
Slag CaO Fe SiO2 Mn MgO Al2O3 V Na2O P S K2O Ti Cr Rest
Blast furnace 34.5 0.2 31.2 – 16.2 12.7 – 0.7 – 2.6 0.5 1.3 – 0.1
Desulfurization 58.0 7.0 15.0 0.3 1.3 2.5 0.1 3.1 – 2.9 0.1 1.0 – 8.7
Steel converter 45.2 16.7 11.4 2.6 1.5 1.4 1.2 – 0.4 – – 0.6 0.2 18.8
Ladle 49.4 4.4 14.1 0.7 5.8 21.0 0.3 – – 0.2 – 0.7 – 3.4
Table 10.3 Existing technologies for PCC manufacturing

Process Raw materials Products Comment
Carbonation Limestone, PCC Most common PCC production
water method, high-temperature
treatment, energy-intensive
Solvay NaCl, CaCO3 Na2CO3, CaCO3 as a by-product, gypsum
CaCl2 and NaCl impurities
Lime-soda Ca(OH)2, NaOH, Used widely for NaOH production,
Na2CO3 CaCO3 CaCO3 usually of poor quality
Calcitech Limestone/ PCC Sorbitol as a solvent, a recent patent
waste materials application
Filler recycling Paper sludge PCC Reuse of filler material
Limestone
Waste gas Clean waste gas
1 3 4
Calcium hydroxide
2
7 8
Calcium oxide 5 6
Water
10
11 9
DryPCC 13 12
1. Limestone bin 2. Lime kiln 3. Gas filter 4. Gas scrubber 5. Calcium oxide bin and slaker with cooling
6. Slaked lime tank 7. and 8. Precipitation reactors 9. Prescreen tank 10. Screening for unreacted
calcium hydroxide 11. Postscreen tank 12. Filter press and dryer 13. Gas filter.
Figure 10.2 Main production stages in carbonation process for PCC making.
Reproduced from Ref. (33).
2.2. Solvay process

As a by-product of the Solvay process, used to manufacture sodium carbon-
ate and calcium chloride from sodium chloride and calcium carbonate, also
calcium carbonate is precipitated. This occurs when the process solution
containing ammonium chloride and sodium bicarbonate is contacted with
calcium hydroxide to recover gaseous ammonia, and the saturation with
respect to bicarbonate leads to CaCO3 formation (34,35).
Compared to PCC produced with the carbonation process, the Solvay

precipitate contains other types of impurities. While the major contaminant
from carbonation is magnesium carbonate, Solvay PCC also has gypsum and
sodium chloride as minor components. This, together with the lower costs
of the carbonation process, has reduced the use of Solvay process calcium
carbonate (2).
2.3. Lime-soda process

Sodium hydroxide can be produced by reacting calcium hydroxide with
sodium carbonate. Calcium carbonate is generated as a by-product, but since
this material contains substantial amounts of impurities such as gypsum, it has
limited applications. In general, it is either used as a raw material for cement
or burned in a lime kiln to regenerate lime. Some fractions are also disposed
as waste. Research efforts have been made to increase the purity of this
PCC, as the lime-soda process is widely used for NaOH production.
Increasing the economic value of the by-product would be beneficial for
the overall process economics. It has been shown on laboratory scale that
it is possible to produce lime-soda PCC of similar quality as with the
carbonation process (2,36).
2.4. Calcitech process

A recent patent application (37,38) describes a PCC production method in
which calcium is first dissolved into an aqueous solution from a raw mate-
rial such as limestone, carbide lime, or paper sludge ash. After separation of
insoluble material, the dissolved calcium is precipitated in a tank reactor by
introducing a gaseous CO2 stream. In this process, a sorbitol solution is
used as a recyclable solvent. By controlling the amount of carbon dioxide
feed based on pH measurements, the properties of the precipitate can be
tailored. When a predefined pH value is obtained, the carbonation reaction
is interrupted by introducing a substantial amount of calcium-rich sorbitol
solution into the carbonation reactor. A combination of filter press and
washing equipment is used to separate the solids from the sorbitol solution,
which is then used for a next calcium dissolution step. According to the
patent application (37), before reuse of the solvent, the weight percentage
of sorbitol was adjusted from 26% to 29% by evaporation of the aqueous
phase. Otherwise, the recovery efficiency is not specified.
2.5. Filler recycling processes

Since large amounts of mineral fillers accumulate in process streams in
paper mills, research efforts are concentrated on recovery and recycling
of this material. Often, the sludge is dried and land-filled or incinerated,
which requires energy-intensive thermal treatment. For example, the
European Union SERECARB (selective recovery of calcium carbonate
in paper sludge) project (2008–2010) focused on separation and purifica-
tion of calcium carbonate for reuse as filler (39). Also, processes have been
developed to manufacture PCC from ash that is generated in paper
recycling (40).
3. MINERAL CARBONATION PROCESSES

During the last 10–15 years, several options to reduce anthropogenic
carbon dioxide emissions to aid climate change mitigation have been pro-
posed. Besides underground storage, requiring long-term monitoring
because of potential CO2 leakage, options such as industrial use of CO2
and storage in solid, stable carbonates have been widely studied in Refs.,
for example, (4,5,41–43). As a raw material for carbonation, both natural
minerals (44) and industrial by-products or waste materials can be
deployed. Several different waste streams, often available in large amounts,
have the advantage of containing more reactive and already-processed
material, requiring less processing compared to natural minerals. Solid
industrial wastes contain various elements that can form carbonates, such
as calcium, magnesium, iron, copper, and zinc. However, the alkaline earth
metals (Ca and Mg) are most suitable for the purpose of mineral carbon-
ation, since unlike, for example, iron, they are less valuable in other appli-
cations (45).
Conceptually, the proposed and studied methods for waste material
carbonation can be divided into a few categories. Carbonation can be a
dry or an aqueous process. Reactions can occur directly, that is, carbon-
ation can happen simultaneously with (alkaline) metal removal from the
waste, producing a mixture of the carbonate and the original material
(12,46). In some cases, this product can be used for, for example, con-
struction purposes, but is not applicable for uses that require pure carbon-
ates, such as PCC in papermaking. For pure precipitates, the alkaline
cations must prior to carbonation be selectively separated from the residual
waste material, which implies the use of an indirect carbonation route

(47). Besides various conventional solvents, also biotechnological processes
such as nitrification/denitrification or fermentation possess potential for
selective treatment of waste materials (48). However, since the indirect
route approach brings extra costs for the process in form of several reac-
tion steps operating at different process conditions, the financial benefits
from marketing a more pure product should compensate for the additional
expenses (5).
4. PCC MANUFACTURING TECHNOLOGIES BASED

ON INDUSTRIAL WASTE MATERIALS
From a point of view of PCC manufacturing, it is essential to be able
to produce a calcium-rich aqueous solution without impurities such as man-
ganese or iron (49,50). Thus, even if several different processes utilizing var-
ious industrial by-products and waste streams have been developed for
carbonate production, only a limited number of them enable manufacturing
of a pure product, as discussed in the following. In Table 10.4, a short sum-
mary of the processes is presented.
4.1. Oil shale ash indirect aqueous carbonation

In Estonia, where a significant amount (over 90%) of the national electric
power requirements is supplied by oil shale combustion, research efforts
have been made toward utilizing the oil shale ash for carbon dioxide min-
eralization. This approach could both reduce the CO2 emissions and stabi-
lize the problematic waste material, which currently is mainly land-filled and
is causing alkaline aqueous emissions (14,52).
Batch carbonation experiments of oil shale ash with 8.0% free calcium
oxide were performed with 10:1 (kg:kg) water-ash slurry. Elemental com-
position of the ash is presented in Table 10.1 (23). This gave an aqueous
solution containing calcium, sulfate, potassium, chlorine, and phosphate
ions. After filtration, the filtrate was carbonated in a separate reactor, where
the solution was mixed both by a circulation pump and by a mechanical stir-
rer. Various gas flows, carbon dioxide concentrations, and stirrer speeds
were studied (14,52).
The produced PCC consisted mainly of rhombohedral calcite crystals
with a mean particle diameter range of 4–10 mm, even though also vaterite
was precipitated in some experiments. The differences in the various mor-
phologies are more thoroughly discussed in Section 5.7. Regarding product
Table 10.4 Examples of various process alternatives for carbonation of industrial by-products and waste streams
Reactor
Process Raw material Type type Temperature Pressure Solvent Time Product
Wang et al. Artificial Direct STa (batch) 25 C Atmospheric Artificial 100 min MgCO3/CaCO3
(51) seawater one- seawater,
step NH3/NH4Cl
buffer
Liu and Brine Direct PSTb 25–100 C 1–40 bar Brine in buffer 24 h CaCO3/NaCl
Maroto- one- (batch) solutions
Valer (19) step
Huntzinger Cement kiln Direct Fixed bed Ambient Atmospheric Solid state, 3.4–12 days Carbonate mix
et al. (18) dust one- (batch) humidified gas with CKD
step
Song et al. Desulfurization One- ST (batch) Ambient Atmospheric NH4OH 120 min CaCO3/CaSO4
(24) gypsum step/ solution
two-
step
Soong et al. Fly ash þ brine One- PST (batch) 20–80 C 1.4 bar Brine 60 þ 120 min >90% CaCO3
(20) step/ (þNaOH) (two-step)
two-
step
Sun et al. Fly ash Indirect PST (batch) Ambient— Atmospheric— Acetic acid 60 þ 60 min MgCO3/CaCO3
(22) two- 80 C 10 bar solution
step
Uibu et al. Oil shale ash Indirect ST (batch) Ambient Atmospheric Water 15 þ 15 min CaCO3/CaSO4
(52) two-
step
Cárdenas- Phosphogypsum Indirect ST (batch) Ambient Atmospheric Water þ NaOH 3 h þ 15 min CaCO3 with
Escudero two- trace metals
et al. (26) step
Continued
Table 10.4 Examples of various process alternatives for carbonation of industrial by-products and waste streams—cont'd
Reactor
Process Raw material Type type Temperature Pressure Solvent Time Product
Bao et al. Steel slag Indirect ST (batch) 40–94 C Atmospheric Acetic acid 60 min c c
(10) two- solution,

step tributyl
phosphate
Chang et al. Steel slag Direct Slurry 25 C Atmospheric Industrial 120 min Carbonate mix
(9) one- reactor wastewater with slag
step (batch)
Eloneva Steel slag Indirect ST (batch Ambient Atmospheric Ammonium salt 120 þ 60 min >98% CaCO3
et al. (5); two- or solutions
Mattila et al. step continuous)
(31)
Sun et al. Steel slag Indirect PST (batch) 20–80 C 10–40 bar NH4Cl 120 þ 60 min 95% CaCO3
(53) two- solution
step
Jo et al. (54) Waste cement One- ST (batch) Ambient Atmospheric Water, HCl, <5 h >95% CaCO3
step/ acetic acid, (two-step)
two- NH4Cl
step solutions
Katsuyama Waste cement Indirect PST (batch) 18–80 C 3 bar Carbonic acid 120 þ 30 min >98% CaCO3
et al. (16) two- (extraction), solution
step atmospheric
(carbonate)
a
ST, stirred tank.
b
PST, pressurized stirred tank.
c
No carbonation step experiments discussed.
purity, however, the results indicate a need for further studies. The sulfate
content of the ash leachate resulted in calcium sulfate coprecipitation, and in
some experiments, levels as high as 5.9% CaSO4 levels were obtained (14).
The authors do not mention other impurities. Thus, the developed process
seems to have potential for production of PCC, product purification still
requiring additional process steps. Also, calcium content of the ashes is rel-
atively low (Table 10.1), which implies large mass flows of solid material in
carbonation processes.
4.2. Salty water carbonation

Mining wastewaters often contain noticeable amounts of inorganic salts.
These so-called brines are mainly originated from underground saline aquifers
and brought to surface via utilization of oil and gas reservoirs, being a signif-
icant waste stream of oil production. According to Liu and Maroto-Valer, an
average brine solution contains sodium, magnesium, potassium, calcium, iron,
chlorine, and in some cases also strontium and barium (Table 10.1) (19). It is
also mentioned that since more than two billion m3 of brine is brought to the
surface each year by the US petroleum industry alone, the carbonation poten-
tial is substantial (Table 10.7), even if the total concentration of alkaline earth
metals would remain below 40 g/L, as shown in Table 10.1.
Batch carbonation experiments of brines were run in a pressurized reac-
tor at ambient conditions and under elevated pressure (up to 40 bar) and
temperature (up to 100 C). The precipitates contained calcite and sodium
chloride or halite, according to XRF analysis. Thus, this process would have
potential for PCC production although halite precipitates need to be washed
from the product (19).
Wang et al. (51) carbonated seawater in the presence of an ammonia/
ammonium chloride buffer solution. Since the seawater in their experiments
contained more magnesium than calcium, the produced precipitate con-
sisted mainly of magnesium carbonate and a mixture of magnesium and cal-
cium carbonates (dolomite, CaMg(CO3)2). In the literature (60), it is
mentioned that dolomite can be used as a source for PCC, although this
requires calcination of the solid material, followed by a treatment with
a sucrose solution. Since magnesium is not soluble in this solvent, it can
be separated from the calcium that forms aqueous dissolved calcium sucrate,
which can then be further processed to PCC. However, these additional
process steps would considerably increase the complexity of PCC
production.
4.3. Ash, dust, and concrete-based processes

Several research groups have focused on carbonation of both coal fly ash and
bottom ashes from different combustion processes and lime-rich concrete
and cement wastes (12,13,15–17,41,61–64). The carbonation of CKD
has also been tested experimentally. In this case, even though the studied
material contained 24.7% Ca in total, only 5.6% was in a form that could
be carbonated (typical values presented in Table 10.1). With an annual pro-
duction of 1.5 Mt in the United States alone (2006), availability of CKD
material suitable for carbonation is substantial but small compared to some
other waste materials (Table 10.7) (56). Carbonation efficiencies higher than
70% have been reached in the experiments by introducing a humidified
CO2 flow through the material (18).
In the mentioned processes, the direct carbonation approach was
applied, meaning that the carbonate product was obtained as a mixture with
the waste material residue. Thus, these developments seem to be ill-suited
for PCC production, indicating a need of applying an indirect carbonation
process.
For example, Sun et al. (22) studied indirect carbonation of brown coal
fly ash from Australia. As can be seen from Table 10.1, the calcium content
of this fly ash is on the same level as, for example, in Estonian oil shale ash,
indicating a similar suitability for calcium carbonate production. The
researchers aimed at recycling of the process solution and reducing the pro-
cess costs, following the idea presented earlier by Kakizawa et al. (65) to use
acetic acid as a solvent. However, not only calcium was extracted from the
solid fly ash but also magnesium, iron, and aluminum were leached with the
acetic acid. When carbonated, the produced precipitate consisted of calcium
magnesium carbonate or dolomite. An increase in carbon dioxide pressure
(from atmospheric to 10 bar) was observed to favor precipitation of more
pure calcium carbonate. As discussed in more detail in Section 5, according
to Teir (7) and Eloneva (5), the recycling of acetic acid seems to cause prob-
lems in case of steel slag carbonation. This depends on the need of prohib-
itively expensive sodium hydroxide addition, which is required to increase
the alkalinity of the system. However, Sun et al. claim to have been able to
regenerate and recycle the spent acetic acid, which would be essential for
both process chemistry and economics. The details of this are not given
in the literature source (22).
Soong et al. (20) combined carbonation of brine solution and fly ash
(Table 10.1) in their studies. With a two-step process, they were able to
produce 90% pure PCC, with 9% sodium chloride coprecipitation. How-
ever, this result required addition of sodium hydroxide to increase the solu-
tion pH, which is recognized as a drawback by the authors. In the same
study, also the direct carbonation methods of fly ash in brine were
discussed, but even though the carbonation was performed successfully,
the highest calcium carbonate content obtained in the solid product was
only 53%.
Zevenhoven et al. (25) reported experimental results with paper bottom
ash (Table 10.1). Several elements were extracted from the material, but the
produced carbonate was 90–98.5 wt% pure calcium carbonate. The material
seems to be suitable for indirect aqueous carbonation, even though the pro-
cess requires large volumes of aqueous solutions due to a low solid-to-
liquid ratio.
Jo et al. (54) extracted calcium from lime, waste Portland cement, and
waste concrete by using water, hydrochloric acid, acetic acid, and ammo-
nium chloride solutions. They discovered that the ammonium chloride
solution was most effective in calcium extraction for all the tested materials,
although for the waste concrete the extraction efficiency was low compared
to other materials. For carbonation, only ammonium chloride solutions pre-
cipitated noticeable amounts of calcium carbonate, while almost no precip-
itates were found from the more acidic solutions. The product was found to
contain more than 95% of carbonates by TGA analysis, but the impurities
were not further discussed. Also, Iizuka et al. (28) performed experiments
with indirect carbonation of concrete sludge (Table 10.1) in water and con-
cluded that a maximum extraction of 45% was obtained after an experi-
ment of 100 min. The addition of seed crystals was also found to enhance
carbonate precipitation from the solution.
Katsuyama et al. (16) specifically aimed at production of high-purity cal-
cium carbonate precipitate by using waste cement with pressurized carbon
dioxide. A 98% pure PCC was generated, while the authors also proposed
further purification by reprecipitation in another step. In the indirect car-
bonation process concept, extraction occurs under high (up to 3.0 MPa)
CO2 pressure, which maintains an acidic pH and thus keeps the extracted
calcium dissolved. Precipitation occurs when the CO2 pressure is lowered
in a following reaction step, causing an increase in pH. According to esti-

mations of Katsuyama et al., production cost of the precipitate would be
highly competitive with the market price of PCC of a corresponding
quality.
Thus, indirect carbonation of cement and concrete sludge and of certain
ash types seems to have potential for PCC manufacturing, even though the
extraction efficiencies are highly dependent on the starting material compo-
sition, and the behavior of possible impurities must be followed
meticulously.
4.4. Carbonation of gypsum waste

Two industrial processes produce gypsum (hydrated calcium sulfate) as a
by-product on a substantial scale. During phosphoric acid production, more
than 40 Mt so-called phosphogypsum is annually generated in the United
States alone. This material is mainly land-filled, which results in environ-
mental concerns such as soil leaching and groundwater pollution (58).
The other major source for gypsum is flue-gas desulfurization (FGD)
(24,57), which is widely used for flue-gas cleaning. Based on data collected
by Lee et al. (57) from the years 2006–2010, the total FGD gypsum produc-
tion in the United States, EU, China, Korea, and Japan equaled to 46 Mt
annually.
Cárdenas-Escudero et al. (26) studied a method to stabilize phos-
phogypsum waste (Table 10.1) containing, for example, chromium, nickel,
vanadium, cadmium and lead, using NaOH to raise solution pH levels. They
concluded that the developed process was able to produce calcium carbon-
ate, where the heavy metals were incorporated to the calcite crystal struc-
ture, thus reducing the mobility of these harmful elements. However, this
also indicates that the product cannot be used as PCC due to the contam-
ination by these minor elements.
Song et al. (24) performed tests with desulfurization gypsum (Table 10.1)
and reported that five percent of the calcium present in gypsum had precip-
itated as pure calcite crystals. Otherwise, since a direct carbonation method
was used, a gypsum phase was still present 20 min after the start of the car-
bonation reaction. The product contained also substantial amounts of
vaterite, the purity of which was not specified. Lee et al. (57) reported similar
experiments, mentioning that the overall purity of calcium carbonate
phase exceeded 90%, with both calcite and vaterite phases present in the
precipitate.
5. PCC MANUFACTURING BASED ON STEEL SLAG

CARBONATION
Besides the carbonation concepts presented in the previous section,
also solid by-products of steel manufacturing could be utilized as suitable,
calcium-rich starting materials for mineral carbonation. Indirect aqueous
carbonation of especially steel converter slag has been widely studied in Fin-
land, at both Åbo Akademi University and Aalto University (5,31,66). In
this section, aspects related to that process will be discussed in more detail.
5.1. Waste streams from steelmaking processes

In steelmaking, large amounts (300–400 kg/ton steel, steel production
worldwide 1527 Mt in 2011) (42,67) of solid alkaline by-products are
formed. These slags contain elements such as calcium, magnesium, iron,
and silicon mainly in oxide form. Since steelmaking is a batch process,
the properties of the slags vary from batch to batch.
Slags originating from different unit operations in a steel plant differ in
chemical composition and mineralogy. As shown in Figure 10.3, the main
slag types are blast furnace slag, desulfurization slag, steel converter slag, and
ladle slag. All these slags have been used in experimental work by Eloneva,
Mattila et al., and Teir et al. (5,31,66), materials supplied by Ruukki Metals
Oy in Raahe, Finland, and Ovako Koverhar, Finland. (Note that the latter
was recently closed.) In Table 10.2, the compositions of these various slags
are listed, while Table 10.5 presents the mineralogies.
Recycled
Pellets Oil (100 kg) steel
(350 kg) O2 (240 kg)
Air
Coking
plant Desulphur Basic
Coal oxygen Ladle
Blast ization Casting
(440 kg) furnace furnace
furnace
Sinter
plant
Iron ore
(740 kg)
Lime Steel slab
Desulphurization Ladle
kilns Steel (1000 kg)
slag (20 kg) slag (20 kg)
Limestone converter
Blast furnace slag (70 kg)
(210 kg)
slag (230 kg)
Figure 10.3 Unit operations in a steel plant (68).

Table 10.5 Mineralogical compositions of various iron and steelmaking slags measured by XRD analysis (29)
Slag Ca2(Al(AlSi)O7) Ca3Mg(SiO4)2 CaMgSiO4 Ca2(Mg0.5Al0.5) (Si1.5Al0.5O7) Others
Blast furnace 38 23 20 18 1
Larnite (Ca2SiO4) Lime (CaO) Brownmillerite (Ca2FeAlO5) Ca3Al0.84Fe1.16Si3O12 Others
Desulfurization 60 25 13 – 2
Steel converter 43 <10 19 – <38
Ladle 34 – – 53 13
Primary phases often present in steel converter slag have been reported to
be larnite (dicalcium silicate, Ca2SiO4) and srebrodolskite (dicalcium ferrite,
Ca2Fe2O5). These compounds never exist as pure substances; instead, they
contain various amounts of, for example, phosphorus, manganese, and mag-
nesium bound to the main matrix (31,69).
5.2. Direct versus indirect aqueous carbonation of steel

converter slag
As in case of other solid alkaline waste materials, several options for a car-
bonation process exist also for steel slags. Chang et al. (9) used steel converter
slag in a slurry reactor to bind CO2. They utilized wastewaters from metal
industries as a solvent, aiming at simultaneous reduction of the alkalinity of
the slag and of the wastewater. Calcium carbonate particles were produced,
but were mixed with the residual slag, and actually precipitated on the sur-
faces of the slag particles. Thus, the authors concluded that these carbonate
particles prevented further dissolution of reactive oxide species from the slag.
Furthermore, being a slag-carbonate mixture, the product has no application
as PCC.
To reduce the amount of impurities in carbonate precipitation, the
approach chosen by Teir (7) and Eloneva (5) was to use an indirect carbon-
ation process divided in separate extraction and carbonation steps. Schemat-
ically, the process concept is represented in Figure 10.4. The most important
feature regarding process economics, besides the efficiencies of the separate
steps, is to ensure a regeneration and reuse of the aqueous solvent that are as
complete as possible (70). A continuous use of makeup chemicals would not
be cost-efficient. More recently, a similar approach has been reported also by
Regenerated solvent
CO2
containing gas
Calcium-
rich
Slag solution Non reacted
Extraction Carbonation
gases
Residue CaCO3
Figure 10.4 Slag carbonation process depicted schematically.

Sun et al. (53) but with reaction conditions utilizing higher pressures and
temperatures compared to Teir and Eloneva.
5.3. Leaching studies on steel slags

Since different steel slags are widely used as construction materials, earlier
research has mainly concentrated on the leaching properties of the different
elements during long-term contact with aqueous solutions. This occurs when
the materials are subjected to rainwater and frost. Also, the so-called aging that
takes place when the slag is stored outdoors prior to further processing has
been simulated and followed in various experiments (69,71–74). For exam-
ple, Engström et al. (75) have reported that of synthesized slag compounds
such as calcium magnesium silicate (åkermanite), calcium aluminum silicate
(gehlenite), and dicalcium silicate, only the latter one dissolved in significant
amounts over a pH range from 4 to 10. The other compounds only dissolved
under acidic conditions. Thus, dicalcium silicate-containing slags are expected
to have a different leaching behavior and to be more unstable compared to
other compositions, which has also been observed in practice (5).
Doucet (8) compared the compositions of steel converter slags from dif-
ferent sources, and concluded that the variations between them are not sig-
nificant. He also reported that compared to other calcium-containing
wastes, slags have a higher calcium content (Tables 10.2 and 10.3) and
are thus theoretically more suitable for mineral carbonation. Standard
leaching tests of various slags were performed with ultrapure water, with nit-
ric and sulfuric acids, and with sodium hydroxide. The conclusions of this
study were that calcium and magnesium can be extracted in acidic solutions
quite efficiently but the carbonation of these dissolved components is prob-
lematic since the solutions will remain too acidic. In alkaline solutions, the
slags were found to be quite inert (8).
5.4. Selective extraction of calcium from steel converter slag

Eloneva (5) performed calcium extraction experiments with blast furnace
slag, desulfurization slag, ladle slag, and steel converter slag, as mentioned
earlier. From blast furnace slag and ladle slag at maximum, 20% of the cal-
cium was extracted with various solvents, while from desulfurization and
steel converter slags over 50% extraction was obtained. This comparison
shows the effect of the slag mineralogy on extraction of elements from
the slag material. Since steel converter slag is produced in noticeably larger
quantities than desulfurization slag, the research was concentrated on steel

converter slag only (76). Chemical compositions of the different studied steel
converter slag samples are shown in Table 10.6. As can be observed, com-
position fluctuations occur especially not only regarding the major elements
calcium, iron, and silicon but also for certain minor components such as
manganese and vanadium.
Calcium extraction efficiency of various solvents from steel slags was also
investigated by Eloneva (5). It was found that although strong acids extract
calcium efficiently, the reaction is not selective, as other metals are leached
from the slags as well. Moreover, since calcium carbonate precipitation
requires carbonate ions, present in high concentrations only at pH values
above 9 (Figure 10.5), solutions of (strong) acids were found to be too acidic
after extraction. Thus, the use of an additional base such as sodium hydrox-
ide would be required to increase the pH enough to enable efficient carbon-
ate precipitation (5). This goes against the goal of using a recyclable solvent,
and thus, it was concluded to be infeasible to use (strong) acids as leaching
agents for a carbonation process.
Bao et al. (10) studied the leaching of elements from steelmaking slag
with acetic acid as a solvent. They used an organic solvent, tributyl phos-
phate (TBP), to extract acetic acid from the aqueous phase when it is formed
by calcium acetate carbonation. It is reported that besides calcium, also mag-
nesium, iron, and aluminum were extracted from the slag. Furthermore, the
authors emphasize the fact that the TBP phase can be recovered (by distil-
lation) and reused. However, the details of the carbonation of the formed
calcium and magnesium acetate and recovery of the acetic acid are not dis-
cussed by the authors.
On the contrary, aqueous solutions of a weak acid and a weak base, such
as ammonium nitrate, chloride, and acetate, were found out to selectively
leach calcium from slags (5). This is partly due to the pH buffering nature
of these solutions, maintaining solution pH around 9–10 instead of 12–13
when using pure water. The higher solubilities of calcium nitrate, chloride,
and acetate compared to calcium hydroxide are an important benefit.
Ammonium chloride was chosen to be used as a reference case in the exper-
imental work, since it is the cheapest of the salts mentioned, it is not con-
sidered to be an explosive (such as ammonium nitrate) and does not form
vaporizing compounds such as acetic acid from ammonium acetate (76).
Ammonium chloride solvent has also earlier been utilized for calcium
extraction from steelmaking slags (53,77,78).
Table 10.6 Compositions of steel converter slag samples from 2008, 2011, and 2012 provided by Ruukki Metals Oy, Raahe, Finland, measured
by XRF analysis
Element CaO Fe SiO2 Mn MgO Al2O3 V Na2O P S K2O Ti Cr Rest
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
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
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
1.0
HCO3–
0.8
H2CO3 CO32–
Fraction
0.6
0.4
0.2
0.0
4 5 6 7 8 9 10 11 12
pH
Figure 10.5 Coexistence of various forms of dissolved carbon dioxide as a function of
solution pH (76).
After choosing an efficient solvent, different solvent molarities and solid-

to-liquid ratios of slag and the aqueous solvent were studied experimentally
to achieve as economical a process as possible. It was observed that solvent
molarities higher than 1.0 mol/L NH4Cl resulted in unwanted extraction of
elements such as iron and manganese, giving strong coloring. Concentra-
tions lower than 0.5 mol/L were both kinetically and stoichiometrically
infeasible, since the reaction time to obtain good extraction efficiencies
was increased and the amount of ammonium ions was also theoretically
too low to extract all calcium from the steel slag (5,31,76). These findings
are summarized in Figure 10.6.
As a comparison, pure water has been used as a leaching agent by, for
example, (42,79), but due to the lower solubility of calcium hydroxide, this
resulted in low calcium extraction. If water was used as a solvent, the solid-
to-liquid ratio of slag and water should be noticeably lower than for ammo-
nium salts; otherwise, the process would not effectively utilize the calcium
source.
De Windt et al. (69) stated, actually referring to the long-term leaching
not only of certain elements such as chromium and vanadium but also of
calcium and iron, that the controlling factor of metals leaching from slags
is the limited solubility of the secondary phases such as various silicates. Also,
the study concluded that the dissolution rates of brownmillerite
(Ca2FeAlO5)- and wüstite-type phases are slower than of lime and larnite
phases. Even though water was used as solvent, these results seem to be
applicable also in case of ammonium salt-enhanced leaching (31).
5.0
4.5
Ca dissolution efficiency decreases, dissolution of impurities increases
4.0
3.5
NH4Cl (mol/l)
3.0
NH4Cl in PCC product,
2.5 wash stage(s) needed
2.0
1.5
1.0 Operational area

Not enough solvent for all reactive calcium
0.5
Slow kinetics
0.0
0 50 100 150 200 250 300
Slag (g/L)
Figure 10.6 Observed limitations for selective calcium extraction with ammonium chlo-
ride solvent. Circles represent the performed experiments.
5.5. Vanadium extraction from the residual slag

Since steel converter slag contains valuable metals such as vanadium, the
price of which is currently on the level of 9800 !/ton (80), being high com-
pared to, for example, the value of steel (300 !/ton (81)), it would be ben-
eficial to separate also these high-value elements from the converter slag.
Actually, the slags form a major source for world’s vanadium already (74),
but the processes are mainly focused on acid-enhanced leaching of vanadium
directly from fresh converter slag. If the slag is utilized for mineral carbon-
ation, the mineralogy will change, resulting in different extraction rates. This
has been shown by, for example, van Zomeren et al. (73), who directly car-
bonated steel converter slag and concluded that although the alkalinity of the
solids was reduced, vanadium was leached easier than from fresh slag.
In conclusion, although carbonation can solve an environmental prob-
lem caused by high alkalinity of the slag, it can also enhance the leaching of
elements that were stable under alkaline conditions (73,82). Thus, it seems
reasonable to aim at developing a process in which the alkalinity of the slags
is used for mineral carbonation, while the residual slag is processed further to
separate the valuable elements. Naturally, revenues from the products should
compensate for the processing and waste treatment costs.
5.6. Calcium carbonate precipitation

The precipitation of calcium carbonate is an intricate process, which is
affected not only by numerous factors such as flow rate and bubble size of
the carbon dioxide gas feed but also by pH, temperature, and presence of
additives (83). Thus, it has been widely studied for obtaining a better under-
standing of crystallization technologies in general. The complexity arises
from the fact that calcium carbonate has three different stable or metastable
polymorphs or crystal shapes, calcite, aragonite, and vaterite, respectively,
for the precipitate. Besides the stable polymorphs, also other hydrated forms
of calcium carbonate are known, but these exist only as intermediates or
under nonatmospheric conditions (84). The needle-shaped aragonite is
formed at high temperatures (above 50 C), while spherical vaterite and
cube-formed or star-shaped calcite are formed at lower temperatures
(85,86). Vaterite is a semistable crystal form and will in aqueous solutions
be transformed either to calcite or to aragonite depending on the solution
temperature (84). Three examples of the calcium carbonate particles pro-
duced during laboratory-scale experiments of indirect two-step aqueous car-
bonation of steel converter slags are shown in Figures 10.7–10.9. Figure 10.7
depicts scalenohedral, star-shaped calcite; Figure 10.8 depicts rhombohe-
dral, cubical calcite, while Figure 10.9 is of spherical vaterite particles.
Figure 10.7 Scalenohedral calcite crystals, scale bar 2 mm.

Figure 10.8 Rhombohedral calcite crystals, scale bar 10 mm.
Figure 10.9 Spherical vaterite particles, scale bar 10 mm.

For instance, in papermaking, the crystal shape is an important factor

while estimating the suitability of PCC product as filler, calcite form being
the most favorable one. Another crucial factor is the particle size and size
distribution, preferably, for example, 90% <2 mm. These properties enable
good retention of the filler in paper sheets, as well as good optical properties
for the paper. Moreover, the product should have a high whiteness
according to the ISO (International Organization for Standardization) mea-
surement method, which requires high purity of the precipitate. As an
example, certain elements such as manganese and iron can lead to dis-
coloring already in low concentrations. Also, other types of impurities such
as gypsum (calcium sulfate) should be avoided, since they can react with
other chemicals present in paper production, resulting in unwanted effects
such as poor printability (87,88).
Besides the commonly used batchwise or semicontinuous (continuous
with respect to gas and batchwise with respect to aqueous solution) precip-
itation in a stirred tank discussed in Section 2, developments for the carbon-
ation process have been proposed by several research groups.
Bang et al. (89,90) used a so-called micro bubble generator for introduc-
ing carbon dioxide into the reactor system. This consists of a nozzle system
through which both the gaseous and the aqueous phases are pumped, instead
of a traditional frit where only gas is introduced through a porous structure
into the bulk liquid. As a result of the new gas-contacting device, the reac-
tion time required for carbonating a certain amount of calcium was reduced
by up to 50%, while also, the particle size was reduced and the specific sur-
face area increased, compared to the frit reactor under similar conditions.
However, the detailed design of this bubble generator is not presented in
the source literature.
Varma et al. (91) studied the effect of dispersion agents to synthesize
nanocrystals of calcite and concluded that citric acid is promoting the selec-
tivity toward calcite over vaterite and aragonite. They also tested two reactor
types, a standard bubble column and a rotating reactor, although the effect of
the reactor type on the particle properties was not thoroughly analyzed. In
Ref. (92), it is described how ultrasonic agitation and supercritical CO2 have
been combined in a laboratory-scale reactor to enhance the reaction rates.
However, some damage to the crystals was observed due to the ultrasonic
fluctuations, even though the crystals were mainly of the typical cubical cal-
cite morphology. Santos et al. (93) successfully enhanced formation of ara-
gonite over calcite by applying ultrasound together with, for example,
addition of magnesium. Supercritical, liquid, and pressurized carbon dioxide
was experimentally tested in calcium carbonate precipitation by Domingo

et al. (94). They concluded that the formation of rhombohedral and
scalenohedral calcite crystals could be controlled by the phase (gaseous, liq-
uid, or supercritical) of the introduced CO2: at higher pressures, the rhom-
bohedral form was favored over other crystal structures.
Besides ultrasound, other approaches to reduce the concentration gradi-
ents and thus generate a more even distribution of substances in the aqueous
solutions have been, for example, the use of the so-called Couette–Taylor
reactor. There, a small, rotating horizontal cylinder is placed inside a station-
ary one, and the process solution is contained in the space between these two
cylinders. This has been found to generate a uniform shape distribution of
smaller particles than in a traditional tank reactor. It is also one of the few
reported experiments with a continuous setup (49).
Ukrainczyk et al. (50) reported that in highly supersaturated solutions and
at low temperatures, a submicrometric precipitate was generated, while the
rate of calcium feed in the beginning of carbonation reaction also affected
the particle properties. Besides the total degree of super saturation, also
the mass ratio of calcium and carbon dioxide or more accurately carbonate
ions in the process solutions had according to Han et al. (95,96) an effect on
the morphology of the formed precipitate. When low initial calcium ion
concentrations were used, vaterite was coprecipitated with calcite, while
at higher concentrations, only calcite was found. For carbon dioxide, the
effect was opposite, that is, the more CO2 per a time unit was introduced
into the reactor, the more vaterite was precipitated.
Regarding PCC production from industrial by-products and waste
materials, an essential factor is the effect of various impurities in the process
solutions. In the literature, both changes in the particle morphology and in
reaction rates as a result of the presence of impurities have been analyzed.
Substances such as magnesium, nickel, iron, and cobalt have been found
to favor aragonite formation, while manganese and lead enhanced calcite
precipitation. Sodium, potassium, and ammonium ions can give lattice
inclusions, thus decreasing product purity (49). Magnesium, iron, and man-
ganese can substitute calcium ions in the crystal structure, since they have a
smaller ionic radius than calcium (97). Sulfate ions in high concentrations
have been found to stabilize vaterite compared to calcite (98). Regarding
ammonia, it is known that carbon dioxide absorption rate is increased com-
pared to pure water solutions, thus enabling a faster precipitation reaction
(99,100). At higher concentrations, the precipitation rate has been reported
to decrease, seemingly due to the formation of carbamate ions (31).
Magnesium also reduces the transformation rate of vaterite to calcite by

inhibiting the crystal growth (101).
Additional compounds can be used to control the properties of the pre-
cipitate as well. For example, Niedermayr et al. concluded that magnesium
concentration in combination with polyaspartic acid and control of carbon
dioxide addition rate can be used to steer the polymorphism of calcium car-
bonate (102). Other processes including the use of additives have been stud-
ied by, for example, Li et al. (103,104), who combined a bacterial carbonic
anhydrase enzyme in calcium chloride solution and pH control by absorp-
tion of gaseous ammonia and carbon dioxide. Thus, in this process, all the
main features already present in steel slag aqueous carbonation as developed
by Eloneva (5) and Teir (7) and coworkers are combined. The role of the
enzyme was to change the carbonate/bicarbonate ratio to favor carbonate
ions, thus enhancing the reaction rate. It was found that the precipitate qual-
ity changed in a similar manner than described earlier for solutions without
additives, although the presence of carbonic anhydrase resulted in more
irregular and porous crystal surfaces.
Nebel and Epple (101) chose not to use the most common calcium car-
bonate precipitation method, gas–liquid carbonation. Instead, they success-
fully prepared all the stable polymorphs in a continuous liquid–liquid system
of calcium chloride and alkali carbonates. Only minor impurities were
detected in the products (101). The industrial-scale applicability remains
as an open question, since unlike gaseous carbon dioxide, alkali carbonate
solutions are not widely available on large scale.
5.7. Current status of the development of the Finnish steel

converter slag carbonation process
Based on developments of, for example, Teir (7), Eloneva (5), and Mattila
(31,76) and coworkers, and using the principal process schema (also referred
to as “Slag2PCC”) presented in Figure 10.4 as a starting point, a continuous
process setup for production of PCC from steel converter slag has been
designed, built, and taken into use. The choice of a continuous process is
primarily dictated by the varying quality and composition of the steel con-
verter slag feed material, as discussed in Sections 5.1 and 5.4. The setup is
schematically represented in Figure 10.10, and a photograph is given as
Figure 10.11.
On the left side in Figure 10.10, the extraction unit is depicted, where
slag is continuously fed in and removed after calcium extraction. The vol-
ume of 30 L is mixed by a mechanical stirrer. Also, pH and temperature
R
pH
TR
R
pH
PI PI
TR
Residue
Pi
PI PI
PCC fines
PCC
Slag
pHR pHR
TR TR
Residue
CO2
Figure 10.10 A reactor setup for production of PCC from steel converter slag according
to an indirect carbonation principle.
Figure 10.11 Photograph of the laboratory reactor setup for a continuous “slag2PCC”
process.
inside the reactor are recorded during the experiments. The reacted, residual
slag is removed from the aqueous solution with a combination of filters, a
settler tank and a so-called inclined settler, the principle of which is more
closely described by Davis and Gecol (105). Based on earlier small-scale
experiments (31,76), a base case for the process conditions has been chosen,
from which variations are then possible based on new observations. In this
base case, 1.0 mol/L ammonium chloride solution and a 100 g/L slag-to-
liquid ratio are used, and the reactor system is operated under atmospheric
pressure and temperature.
The carbonation unit is shown on the right in Figure 10.10. The
calcium-rich and solid-free aqueous phase is divided into two reactor vessels.
In the actual carbonation reactor, gaseous carbon dioxide is introduced
through a porous sheet and thus bubbled through the calcium-containing
solution (total volume 30 L). The pH and temperature of this reactor
are also measured and recorded continuously and can be adjusted by chang-
ing both the CO2 flow rate and the aqueous stream flow rate. Precipitation is
mainly expected to occur in this vessel.
The second part of the calcium-rich stream from the extractor is fed to a
second settler tube, where it is combined with calcium-poor and carbonate-
rich stream from the carbonator while removing PCC by settling. The rea-
son for this setup is to adjust the pH and calcium content of the recycled
ammonium chloride solution in such a way that an amount of carbonate/
bicarbonate ions and dissolved CO2 that is as small as possible enters the
extraction reactor. In earlier work, the carbonation has been observed to
continue in the extraction reactor, which has led to reduction of the pure
carbonate yield, with valuable product partly mixed with unreacted and
spent slag material.
The main challenges of the technology are currently in ensuring the
desired particle size, particle size distribution, crystal shape, and purity
of the produced precipitates so that the commercial applicability of the
product will not be compromised. Factors related to particle and crystal
properties are strongly affected by residence times under different pH
conditions and at different concentration levels of calcium and carbon
species and require further experimental work to obtain the most valuable
product.
If elements other than calcium are extracted from the slag, there is a pos-
sibility for accumulation of these elements in the process solution, which,
however, has not been observed to be a problem (76). This is principally
due to the different solubilities of the various minerals, as discussed in
Section 5.5 earlier, which leads to a selective extraction of calcium and sil-
icon, of which silicon is predominantly reprecipitated with the slag.
On the contrary, both the residual slag and the PCC product have been
found to contain some chlorine, originating from the ammonium chloride
solvent and thus indicating losses of the valuable solvent components. This
involves the need of additional washing steps for the solid streams compared
to the process equipment shown in Figure 10.10.
6. REMARKS ON APPLICABILITY OF VARIOUS

PROCESSES IN GLOBAL SCALE
The estimated anthropogenic carbon dioxide emissions from fossil
fuel use and cement manufacturing in 2011 reached a level of 34.8 Gt/year
(55). To compare with, the estimated capacities of the discussed carbonation
methods with the specified waste material sources are presented in
Table 10.7. With the assumption that only the calcium present in the mate-
rials is completely carbonated, while other elements such as magnesium
remain inert, none of the solid waste streams would be sufficient to capture
global CO2 emissions of even 1 day/year. It must be observed that the pres-
ented numbers are calculated only for specific geographic locations, while
the global waste amounts are larger. Nonetheless, as concluded also by Kelly
et al. (106), from energy efficiency point of view, the carbonation of indus-
trial wastes seems currently to be more attractive than carbonation of natural
minerals or industrial products.
Still, as a natural resource, seawater possesses a larger capacity than the
other studied materials, for thousands of years with the current CO2 emis-
sion rates (Table 10.7), even in the theoretical case that it would be isolated
from the surroundings. Since this will not occur and more mineral matter is
continuously dissolved in seawater, the resource cannot be accurately quan-
tified. However, the carbonation potential is huge compared to the indus-
trially processed waste materials, even though sustainable utilization of this
potential remains as a challenge.
On the other hand, since the global PCC production capacity is cur-
rently 17 Mt/year, as mentioned in Section 1, this market would be
flooded quickly in case the new production methods would be applied into
practice in global scale. Even though GCC is more a low-value product, the
generated carbonates could also be used as replacements for this material,
thus increasing the global market size with 60 Mt/year (GCC consump-
tion in 2011) (2).
Table 10.7 Estimated theoretical capacities of carbonation of some waste materials discussed in Sections 4 and 5
Ca Material Max amount of Max amount of Part of annual CO2
Mineral source content availability CO2 captureda CaCO3 produced emissionsb
Brinec 3.3% 2.3 109 m3/a 85.1 Mt/a 193.6 Mt/a 2.5 103
Cement kiln 24.7% 1.5 Mt/a 0.4 Mt/a 0.9 Mt/a 1.1 105
dustd
Fly ashe 21.2% 1.3 Mt/a 0.3 Mt/a 0.7 Mt/a 8.7 106
FGD gypsumf 23.2% 45.9 Mt/a 11.7 Mt/a 26.6 Mt/a 3.4 104
Oil shale ashg 21.5% 5 Mt/a 1.2 Mt/a 2.7 Mt/a 3.4 105
Phosphogypsumh 31.9% 40 Mt/a 14.0 Mt/a 31.9 Mt/a 9.2 104
Steel slagi 30% 1.6 Mt/a 0.5 Mt/a 1.1 Mt/a 1.5 105
Seawaterj 400 ppm 1.3 109 km3 5.9 1014 ton 1.3 1015 ton 16,900
a
Assuming that only calcium is carbonated, even if the material would contain other elements that could be carbonated.
b
Calculated with the annual emission rate of 2011, 34.8 Gt/a (55).
c
Production in the United States and the United Kingdom (19).
d
Production in the United States (2006) (56).
e
Victorian brown coal fly ash from Latrobe Valley, Victoria, Australia (22).
f
Production in the United States, EU, China, Korea, and Japan (57).
g
Production in Estonia (23).
h
Production in the United States (58).
i
Finnish steelmaking slag, year 2008, Table 10.6 (5).
j
It is assumed in calculations that no additional calcium is dissolved to sea during the carbonation. The estimates for the total volume of seawater and average calcium
concentration are obtained from Refs. (51) and (59).
These mineral carbonation concepts have been mainly focusing on pro-

duction of pure carbonates from calcium-containing industrial by-products
and waste materials. Besides this, processes using natural minerals for mineral
carbonation and techniques producing nonpure solid mixtures could be
used for CO2 sequestration. Currently, these technologies are not econom-
ically viable, mainly because of the low reactivity of the natural materials and
the low cost of carbon dioxide emissions. Thus, the discussed PCC production
methods could provide a demonstration and generate infrastructure for the
mineral carbonation concept, since the marketable product would make them
profitable. When the concept would have been proven to work also in indus-
trial scale, it would be easier to continue the development of processes capable
of handling a larger amount of the global carbon dioxide emissions.
7. CONCLUSIONS
Climate change has given rise to several technologies aiming at reduction
of the anthropogenic carbon dioxide emissions. One interesting option seems
to be the CCUS (carbon capture, utilization, and storage), an option referred to
as mineral carbonation, where CO2 would be bound together preferably with
alkaline earth metals such as calcium or magnesium. The solid product, calcium
or magnesium carbonate, would provide stable storage under natural condi-
tions, thus removing the carbon dioxide from the atmosphere.
Besides natural minerals, also industrial waste materials could be utilized
as sources of the required metals. A selective separation of calcium followed
by carbonation would enable production of commercial-grade carbonate
products such as PCC. The financial benefit gained from marketing this
product could help to overcome the economical barrier connected to
implementing novel technologies on industrial scale.
Currently, research is ongoing with materials such as steel slag, oil shale
ash, brine, and gypsum. With the need of additional developments related to
product purity and other quality requirements, promising processes have
been designed, even though on a global scale, the significance of CO2 emis-
sion reduction would be quite small, requiring also implementation of other
types of measures.
ACKNOWLEDGMENTS
The Academy of Finland Graduate School in Chemical Engineering is acknowledged for
financial support for H.-P. Mattila. Sebastian Teir, Sanni Eloneva, Arshe Said, and Inga
Grigaliūnaitė as well as other (earlier) coworkers are acknowledged for their valuable
research work in development of the Finnish steel converter slag carbonation process.
REFERENCES
1. Specialty Minerals Inc. http://www.specialtyminerals.com/ (accessed 24 January
2013).
2. Stratton, P. http://www.roskill.com/news/download-roskills-paper-on-the-north-
american-calcium-carbonate-market/at_download/attachment1 (accessed 24 January
2013).
3. Roskill Information Services. http://www.roskill.com/reports/industrial-minerals/
ground-and-precipitated-calcium-carbonate-1 (accessed 7 February 2013).
4. IPCC, IPCC Special Report on Carbon Dioxide Capture and Storage. Cambridge
University Press: New York, 2005.
5. Eloneva, S. Reduction of CO2 Emissions by Mineral Carbonation: Steelmaking Slags as Raw
Material with a Pure Calcium Carbonate End Product. Doctoral Dissertation, Aalto
University, School of Science and Technology: Espoo, Finland, 2010.
6. Chiang, Y. W.; Santos, R. M.; Monballiu, A.; Ghyselbrecht, K.; Martens, J. A.;
Mattos, M. L. T.; van Gerven, T.; Meesschaert, B. Minerals Engineering 2013, 48, 116.
7. Teir, S. Fixation of Carbon Dioxide by Producing Carbonates from Minerals and Steelmaking
Slags. Doctoral Dissertation, Helsinki University of Technology: Espoo, Finland, 2008.
8. Doucet, F. Miner. Eng. 2010, 23, 262.
9. Chang, E.-E.; Chiu, A.; Pan, S.; Chen, Y.; Tan, C.; Chiang, P. Int. J. Greenhouse Gas
Control 2013, 12, 382.
10. Bao, W.; Li, H.; Zhang, Y. Ind. Eng. Chem. Res. 2010, 49, 2055.
11. Baciocchi, R.; Carnevale, E.; Corti, A.; Costa, G.; Lombardi, L.; Olivieri, T.;
Zanchi, L.; Zingaretti, D. Biomass Bioenergy 2013, 53, 128.
12. Costa, G.; Baciocchi, R.; Polettini, A.; Pomi, R.; Hills, C. D.; Carey, P. J. Environ.
Monit. Assess. 2007, 135, 55.
13. Baciocchi, R.; Corti, A.; Costa, G.; Lombardi, L.; Zingaretti, D. Energy Procedia 2011,
4, 4985.
14. Velts, O.; Uibu, M.; Kallas, J.; Kuusik, R. J. Hazard. Mater. 2011, 195, 139.
15. Katsuyama, Y.; Iizuka, A.; Yamasaki, A.; Fujii, M.; Kumagai, K.; Yanagisawa, Y. In
Greenhouse Gas Control Technologies; Rubin, E. S.; Keith, D. W.; Gilboy, C. F.;
Wilson, M.; Morris, T.; Gale, J.; Thambimuthu, K. Eds.; Vol. 7, Elsevier Science
Ltd.: Oxford, 2005; pp. 1433–1439.
16. Katsuyama, Y.; Yamasaki, A.; Iizuka, A.; Fujii, M.; Kumagai, K.; Yanagisawa, Y. Envi-
ron. Prog. 2005, 24, 162.
17. Fernández Bertos, M.; Simons, S. J. R.; Hills, C. D.; Carey, P. J. J. Hazard. Mater. 2004,
112, 193.
18. Huntzinger, D. N.; Gierke, J. S.; Sutter, L. L.; Kawatra, S. K.; Eisele, T. C. J. Hazard.
Mater. 2009, 168, 31.
19. Liu, Q.; Maroto-Valer, M. M. Fuel Process. Technol. 2012, 98, 6.
20. Soong, Y.; Fauth, D. L.; Howard, B. H.; Jones, J. R.; Harrison, D. K.; Goodman, A. L.;
Gray, M. L.; Frommell, E. A. Energy Convers. Manag. 2006, 47, 1676.
21. Baciocchi, R.; Costa, G.; Di Bartolomeo, E.; Polettini, A.; Pomi, R. Waste Manage.
2009, 29, 2994.
22. Sun, Y.; Parikh, V.; Zhang, L. J. Hazard. Mater. 2012, 209–210, 458.
23. Velts, O.; Hautaniemi, M.; Kallas, J.; Kuusik, R. Fuel Process. Technol. 2010, 91, 486.
24. Song, K.; Jang, Y.; Kim, W.; Lee, M. G.; Shin, D.; Bang, J.; Jeon, C. W.; Chae, S. C.
Chem. Eng. J. 2012, 213, 251.
25. Zevenhoven, R.; Wiklund, A.; Fagerlund, J.; Eloneva, S.; In’t Veen, B.; Geerlings, H.;
Van Mossel, G.; Boerrigter, H. Front. Chem. Eng. China 2010, 4, 110.
26. Cárdenas-Escudero, C.; Morales-Flórez, V.; Pérez-López, R.; Santos, A.; Esquivias, L.
J. Hazard. Mater. 2011, 196, 431.
27. Reddy, K. J.; John, S.; Weber, H.; Argyle, M. D.; Bhattacharyya, P.; Taylor, D. T.;
Christensen, M.; Foulke, T.; Fahlsing, P. Energy Procedia 2011, 4, 1574.
28. Iizuka, A.; Honma, M.; Hayakawa, Y.; Yamasaki, A.; Yanagisawa, Y. Kagaku Kogaku
Ronbun. 2012, 38, 129.
29. Teir, S.; Eloneva, S.; Salminen, J.; Fogelholm, C.-J.; Revitzer, H.; Zevenhoven, R.;
Sipilä, J.; Forsman, A.-M.; Kontu, K. Reduction of CO2 emissions and utilization of slag
products by producing calcium-based products from carbonate-free slag products (Slag2PCC Plus),
Mid-term report #2, 1.7.2007–31.12.2007. 2008.
30. Mattila, H.-P.; Grigaliūnaitė, I.; Said, A.; Fogelholm, C.-J.; Zevenhoven, R. In Pro-
ceedings of ECOS 2012 – The 25th International Conference on Efficiency, Cost, Optimiza-
tion, Simulation and Environmental Impact of Energy Systems; Desideri, U.; Manfrida, G.;
Sciubba, E. Eds.; Vol. 2, 2012; pp. 19–28.
31. Mattila, H.-P.; Grigaliūnaitė, I.; Zevenhoven, R. Chem. Eng. J. 2012, 192, 77.
32. SpecialChem S. A. http://www.specialchem4polymers.com/tc/precipitated-calcium-
carbonate/index.aspx?id¼3604 (accessed 25 January 2013).
33. Hosokawa Alpine AG. http://www.alpinehosokawa.com/engl/02powder/exampl/
minerals/pcc/pcc.htm (accessed 25 January 2013).
34. Steinhauser, G. J. Clean. Prod. 2008, 16, 833.
35. Darling, D. http://www.daviddarling.info/encyclopedia/S/Solvay_process.html
(accessed 30 January 2013).
36. Islam, M. S.; Quader, A. K. M. A. Chem. Eng. Res. Bull. 2008, 12, 1.
37. Jensen, C.; Markwardt, I. United States Patent US2012/0189515A1, 2012.
38. Calcitech Ltd. http://www.calcitech.com/s/Technology.asp?ReportID¼394496
(accessed 29 January 2013).
39. SUSPRISE. http://www.susprise.net/index.php?link¼147 (accessed 29 January 2013).
40. Minerals Technologies Inc. http://www.mineralstech.com/corporate-responsibility/
environmental-health-and-safety-ehs/environmental-benefits-of-mtis-business/benefits-
of-envirofil/ (accessed 29 January 2013).
41. Baciocchi, R.; Costa, G.; Polettini, A.; Pomi, R.; Prigiobbe, V. Energy Procedia 2009, 1,
4851.
42. Fält, M. Calcium Carbonation Studies with Ammonium Nitrate. M.Sc. Thesis, Åbo
Akademi University: Turku, Finland, 2009.
43. Teir, S.; Tsupari, E.; Koljonen, T.; Pikkarainen, T.; Kujanpää, L.; Arasto, A.;
Tourunen, A.; Kärki, J.; Nieminen, M.; Aatos, S. VTT Research Notes 2503: Carbon
dioxide capture and storage (CCS) (VTT Tiedotteita: Hiilidioksidin talteenotto ja varastointi
(CCS)). VTT Technical Research Centre of Finland: Helsinki, 2009.
44. Chen, Z.-Y.; O’Connor, W. K.; Gerdemann, S. J. Environ. Prog. 2006, 25, 161.
45. Pan, S.; Chang, E.-E.; Chiang, P. Aerosol. Air Quality Res. 2012, 12, 770.
46. Bobicki, E. R.; Liu, Q.; Xu, Z.; Zeng, H. Prog. Energy Combust. Sci. 2012, 38, 302.
47. Zevenhoven, R.; Fagerlund, J. In Carbon Dioxide as Chemical Feedstock; Aresta, M. Ed.;
Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2010; pp. 353–379.
48. Salek, S. S.; Kleerebezem, R.; Jonkers, H. M.; Witkamp, G.; van Loosdrecht, M. C. M.
Trends Biotechnol. 2013, 31, 139.
49. Jung, W.; Hoon Kang, S.; Kim, K.; Kim, W.; Kyun Choi, C. J. Cryst. Growth 2010,
312, 3331.
50. Ukrainczyk, M.; Kontrec, J.; Babić-Ivančić, V.; Brečević, L.; Kralj, D. Powder Technol.
2007, 171, 192.
51. Wang, W.; Hu, M.; Zheng, Y.; Wang, P.; Ma, C. Ind. Eng. Chem. Res. 2011, 50, 8333.
52. Uibu, M. Abatement of CO2 Emissions in Estonian Oil Shale-Based Power Production. Doc-
toral Dissertation, Tallinn University of Technology: Tallinn, Estonia, 2008.
53. Sun, Y.; Yao, M.; Zhang, J.; Yang, G. Chem. Eng. J. 2011, 173, 437.
54. Jo, H.; Jo, H. Y.; Jang, Y. N. Environ. Technol. 2012, 33, 1391.
55. Carbon Dioxide Information Analysis Center, OakRidge National Laboratory. http://
cdiac.ornl.gov/trends/emis/meth_reg.html (accessed 18 February 2013).
56. Adaska, W. S.; Taubert, D. H. In IEEE/PCA 50th Cement Industry Technical Conference,
Miami, FL, USA, 2008.
57. Lee, M. G.; Jang, Y. N.; Ryu, K. W.; Kim, W.; Bang, J. Energy 2012, 47, 370.
58. U.S. Environmental Protection Agency. http://www.epa.gov/radiation/neshaps/
subpartr/about.html (accessed 11 March 2013).
59. Elert, G., Ed. http://hypertextbook.com/facts/2001/SyedQadri.shtml (accessed
19 February 2013).
60. Mantilaka, M. M. M. G. P. G.; Karunaratne, D. G. G. P.; Rajapakse, R. M. G.;
Pitawala, H. M. T. G. A. Powder Technol. 2013, 235, 628.
61. Nyambura, M. G.; Mugera, G. W.; Felicia, P. L.; Gathura, N. P. J. Environ. Manage.
2011, 92, 655.
62. Mayoral, M. C.; Andrés, J. M.; Gimeno, M. P. Fuel 2013, 106, 448.
63. Jo, H. Y.; Kim, J. H.; Lee, Y. J.; Lee, M.; Choh, S. Chem. Eng. J. 2012, 183, 77.
64. Uliasz-Boche nczyk, A.; Mokrzycki, E.; Piotrowski, Z.; Pomykała, R. Energy Procedia
2009, 1, 4873.
65. Kakizawa, M.; Yamasaki, A.; Yanagisawa, Y. Energy 2001, 26, 341.
66. Teir, S.; Eloneva, S.; Revitzer, H.; Zevenhoven, R.; Salminen, J.; Fogelholm, C.-J.;
Pöyliö, E. Finnish Patent Application FI 20080005524, 2008.
67. World Steel Association. http://www.worldsteel.org/media-centre/press-releases/
2012/2011-world-crude-steel-production.html (accessed 8 February 2013).
68. Eloneva, S.; Teir, S.; Salminen, J.; Fogelholm, C.-J.; Zevenhoven, R. Ind. Eng. Chem.
Res. 2008, 47, 7104.
69. De Windt, L.; Chaurand, P.; Rose, J. Waste Manage. 2011, 31, 225.
70. Eloneva, S.; Mannisto, P.; Said, A.; Fogelholm, C.-J.; Zevenhoven, R. Greenhouse
Gases: Sci. Technol. 2011, 1, 305.
71. Diener, S.; Andreas, L.; Herrmann, I.; Ecke, H.; Lagerkvist, A. Waste Manage. 2010,
30, 132.
72. Galan, I.; Andrade, C.; Mora, P.; Sanjuan, M. A. Environ. Sci. Technol. 2010, 44, 3181.
73. van Zomeren, A.; van der Laan, S. R.; Kobesen, H. B. A.; Huijgen, W. J. J.;
Comans, R. N. Waste Manage. 2011, 31, 2236.
74. Aarabi-Karasgani, M.; Rashchi, F.; Mostoufi, N.; Vahidi, E. Hydrometallurgy 2010, 102,
14.
75. Engström, F.; Adolfsson, D.; Samuelsson, C.; Sandström, Å.; Björkman, B. Miner. Eng.
2013, 41, 46.
76. Mattila, H.-P. Experimental Studies and Process Modeling of Aqueous Two-Stage Steel Slag
Carbonation. M.Sc. Thesis, Åbo Akademi University: Turku, Finland, 2009.
77. Kodama, S.; Nishimoto, T.; Yamamoto, N.; Yogo, K.; Yamada, K. Energy 2008, 33,
776.
78. Yogo, K.; Teng, Y.; Yashima, T.; Yamada, K. In Greenhouse Gas Control Technologies;
Rubin, E. S.; Keith, D. W.; Gilboy, C. F.; Wilson, M.; Morris, T.; Gale, J.;
Thambimuthu, K. Eds.; Vol. 7, Elsevier Science Ltd.: Oxford, 2005; pp. 2427–2430
79. Xu, A.; Zhang, H.; Yang, Y.; Cui, J.; He, D.; Tian, N. J. Iron Steel Res. Int. 2012,
19, 34.
80. Mineralprices.com; http://www.mineralprices.com/ (accessed 6 February 2013).
81. Stena Recycling Oy. http://stenarecycling.fi/Stena-Recycling-Oy/Keskinoteeraukset/
(accessed 6 February 2013).
82. Eloneva, S.; Puheloinen, E.; Kanerva, J.; Ekroos, A.; Zevenhoven, R.;
Fogelholm, C.-J. J. Clean. Prod. 2010, 18, 1833.
83. Feng, B.; Yong, A. K.; An, H. Mat. Sci. Eng. A 2007, 445–446, 170.
84. Nehrke, G. Calcite Precipitation from Aqueous Solution: Transformation from Vaterite and
Role of Solution Stoichiometry. Doctoral Dissertation, Faculteit Geowetenschappen,
Universiteit Utrecht: Utrecht, The Netherlands, 2007.
85. Ogino, T.; Suzuki, T.; Sawada, K. Geochim. Cosmochim. Acta 1987, 51, 2757.
86. Kawano, J.; Shimobayashi, N.; Miyake, A.; Kitamura, M. J. Phys. Condens. Matter
2009, 21, 1.
87. Naydowski, C.; Hess, P.; Strauch, D.; Kuhlmann, R.; Rohleder, J. In: Calcium
Carbonate—From the Cretaceous Period into the 21st Century; Tegethoff, F. W.;
Rohleder, J.; Kroker, E. Eds.; Birkhäuser Verlag: Basel, 2001; pp. 197–312.
88. Lehtinen, E. Ed.; Pigment Coating and Surface Sizing of Paper; Papermaking Science and
Technology; Vol. 11; Gummerus Printing Oy: Jyväskylä, Finland, 2000.
89. Bang, J.; Jang, Y. N.; Kim, W.; Song, K. S.; Jeon, C. W.; Chae, S. C.; Lee, S.; Park, S.;
Lee, M. G. Chem. Eng. J. 2011, 174, 413.
90. Bang, J.; Jang, Y. N.; Kim, W.; Song, K. S.; Jeon, C. W.; Chae, S. C.; Lee, S.; Park, S.;
Lee, M. G. Chem. Eng. J. 2012, 198–199, 254.
91. Varma, S.; Chen, P.; Unnikrishnan, G. Mater. Chem. Phys. 2011, 126, 232.
92. López-Periago, A. M.; Pacciani, R.; Garcı́a-González, C.; Vega, L. F.; Domingo, C.
J. Supercrit. Fluids 2010, 52, 298.
93. Santos, R. M.; Ceulemans, P.; van Gerven, T. Chem. Eng. Res. Des. 2012, 90, 715.
94. Domingo, C.; Garcı́a-Carmona, J.; Loste, E.; Fanovich, A.; Fraile, J.; Gómez-
Morales, J. J. Cryst. Growth 2004, 271, 268.
95. Han, Y. S.; Hadiko, G.; Fuji, M.; Takahashi, M. J. Cryst. Growth 2005, 276, 541.
96. Han, Y. S.; Hadiko, G.; Fuji, M.; Takahashi, M. J. Mater. Sci. 2006, 41, 4663–4667.
97. Rimstidt, J. D.; Balog, A.; Webb, J. Geochim. Cosmochim. Acta 1998, 62, 1851.
98. Fernández-Dı́az, L.; Fernández-González, Á.; Prieto, M. Geochim. Cosmochim. Acta
2010, 74, 6064.
99. Qin, F.; Wang, S.; Hartono, A.; Svendsen, H. F.; Chen, C. Int. J. Greenhouse Gas Con-
trol 2010, 4, 729.
100. Derks, P. W. J.; Versteeg, G. F. Energy Procedia 2009, 1, 1139.
101. Nebel, H.; Epple, M. Z. Anorg. Allg. Chem. 2008, 634, 1439.
102. Niedermayr, A.; Köhler, S. J.; Dietzel, M. Chem. Geol. 2013, 340, 105.
103. Li, W.; Chen, W.; Zhou, P.; Zhu, S.; Yu, L. Chem. Eng. J. 2013, 218, 65.
104. Li, W.; Chen, W.; Zhou, P.; Cao, L.; Yu, L. Colloids Surf. B Biointerfaces 2013, 102,
281.
105. Davis, R. H.; Gecol, H. Int. J. Multiphase Flow 1995, 22, 563.
106. Kelly, K. E.; Silcox, G. D.; Sarofim, A. F.; Pershing, D. W. Int. J. Greenhouse Gas
Control 2011, 5, 1587.

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CHAPTER TEN

Advances in Inorganic Chemistry, Volume 66 # 2014 Elsevier Inc. 347

estimated production capacity of PCC and GCC combined exceeds

2. EXISTING PCC MANUFACTURING TECHNOLOGIES

2.1. Carbonation process

Table 10.3 Existing technologies for PCC manufacturing

2.2. Solvay process

Compared to PCC produced with the carbonation process, the Solvay

2.3. Lime-soda process

2.4. Calcitech process

2.5. Filler recycling processes

3. MINERAL CARBONATION PROCESSES

waste material, which implies the use of an indirect carbonation route

4. PCC MANUFACTURING TECHNOLOGIES BASED

4.1. Oil shale ash indirect aqueous carbonation

(10) two- solution,

4.2. Salty water carbonation

4.3. Ash, dust, and concrete-based processes

in a following reaction step, causing an increase in pH. According to esti-

4.4. Carbonation of gypsum waste

5. PCC MANUFACTURING BASED ON STEEL SLAG

5.1. Waste streams from steelmaking processes

Figure 10.3 Unit operations in a steel plant (68).

5.2. Direct versus indirect aqueous carbonation of steel

Figure 10.4 Slag carbonation process depicted schematically.

5.3. Leaching studies on steel slags

5.4. Selective extraction of calcium from steel converter slag

quantities than desulfurization slag, the research was concentrated on steel

After choosing an efficient solvent, different solvent molarities and solid-

1.0 Operational area

5.5. Vanadium extraction from the residual slag

5.6. Calcium carbonate precipitation

Figure 10.7 Scalenohedral calcite crystals, scale bar 2 mm.

Figure 10.8 Rhombohedral calcite crystals, scale bar 10 mm.

Figure 10.9 Spherical vaterite particles, scale bar 10 mm.

For instance, in papermaking, the crystal shape is an important factor

was experimentally tested in calcium carbonate precipitation by Domingo

Magnesium also reduces the transformation rate of vaterite to calcite by

5.7. Current status of the development of the Finnish steel

6. REMARKS ON APPLICABILITY OF VARIOUS

These mineral carbonation concepts have been mainly focusing on pro-

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