metals

Article
Synthesis of Magnesium Carbonate via Carbonation
under High Pressure in an Autoclave
Srecko Stopic 1, *, Christian Dertmann 1 , Giuseppe Modolo 2 , Philip Kegler 2 ,
Stefan Neumeier 2 , Dario Kremer 3 , Hermann Wotruba 3 , Simon Etzold 4 , Rainer Telle 4 ,
Diego Rosani 5 , Pol Knops 6 and Bernd Friedrich 1
1 IME Process Metallurgy and Metal Recycling, RWTH Aachen University, Intzestrasse 3,
52056 Aachen, Germany; cdertmann@metallurgie.rwth-aachen.de (C.D.); bfriedrich@ime-aachen.de (B.F.)
2 Forschungszentrum Jülich GmbH, Wilhelm Johnen Strasse, 52428 Jülich, Germany;
g.modolo@fz-juelich.de (G.M.); p.kegler@fz-juelich.de (P.K.); s.neumeier@fz-juelich.de (S.N.)
3 AMR Unit of Mineral Processing, RWTH Aachen University, Lochnerstrasse 4-20, 52064 Aachen, Germany;
kremer@amr.rwth-aachen.de (D.K.); wotruba@amr.rwth-aachen.de (H.W.)
4 Department of Ceramics and Refractory Materials, GHI-Institute of Mineral Engineering, Mauerstrasse 5,
52064 Aachen, Germany; etzold@ghi.rwth-aachen.de (S.E.); Telle@ghi.rwth-aachen.de (R.T.)
5 HeidelbergCement Technology Center–Global R&D, Oberklamweg 2-4, 69181 Leimen, Germany;
Diego.Rosani@heidelbergcement.com
6 Green Minerals, Rijksstraatweg 128, NL 7391 MG Twello, The Netherlands; planbco2@gmail.com
* Correspondence: sstopic@ime-aachen.de; Tel.: +49-241-80-95-860




Received: 5 November 2018; Accepted: 23 November 2018; Published: 27 November 2018


Abstract: Magnesium carbonate powders are essential in the manufacture of basic refractories
capable of withstanding extremely high temperatures and for special types of cement and powders
used in the paper, rubber, and pharmaceutical industries. A novel synthesis route is based on CO2
absorption/sequestration by minerals. This combines the global challenge of climate change with
materials development. Carbon dioxide has the fourth highest composition in earth’s atmosphere
next to nitrogen, oxygen and argon and plays a big role in global warming due to the greenhouse
effect. Because of the significant increase of CO2 emissions, mineral carbonation is a promising
process in which carbon oxide reacts with materials with high metal oxide composition to form
chemically stable and insoluble metal carbonate. The formed carbonate has long-term stability and
does not influence the earth’s atmosphere. Therefore, it is a feasible and safe method to bind carbon
dioxide in carbonate compounds such as magnesite. The subject of this work is the carbonation
of an olivine (Mg2 SiO4 ) and synthetic magnesia sample (>97 wt% MgO) under high pressure and
temperature in an autoclave. Early experiments have studied the influence of some additives such
as sodium bicarbonate, oxalic acid and ascorbic acid, solid/liquid ratio, and particle size on the
carbonation efficiency. The obtained results for carbonation of olivine have confirmed the formation
of magnesium carbonate in the presence of additives and complete carbonation of the MgO sample
in the absence of additives.

Keywords: MgCO3 -powder; synthesis; CO2 - absorption; olivine carbonation; autoclave; thermal
decomposition; CO2 utilization

1. Introduction
The significance of the results coming from greenhouse gas (GHG) emissions to both the
atmosphere and our lives has already been urged and is nowadays well-known. Because of the
continuous increase of CO2 concentration in the atmosphere since the industrial revolution, various

Metals 2018, 8, 993; doi:10.3390/met8120993 www.mdpi.com/journal/metals

Metals 2018, 8, 993 2 of 15

techniques are proposed. Carbon capture and utilization (CCU) is considered as the most promising
technique in order to use the product in cement, transforming it into insoluble carbonate (mainly
calcite and magnesite), that is able to remain stable in a geological timeframe [1].
In order to accelerate mineral carbonation, some pretreatment processes are required (microwave
heating, grinding, sieving, separation, thermal decomposition, and chemical treatment). The main
goal of pre-treatment processes is to increase the carbonation rate and improve the process kinetics.
Typical pre-treatment methods are particle size reduction, magnetic separation and thermal treatment.
Particle size reduction incorporates various grinding methods for an increase of specific surface
area. In magnetic separation, undesired ferrous particles are separated from the rest of the feedstock.
Thermal treatment is necessary for hydrated minerals, such as serpentine that contains H2 O molecules
in the mineral structure. Pre-treatment is usually required in direct carbonation processes [2]. However,
one must consider the balance between increase of reaction rate and additional energy costs, possible
CO2 -production related to energy supply and the influence on the beneficial utilization of the final
products. The major problem of pre-treatment is its high energy input, i.e., thermal treatment should
be avoided due to the high energy demand and CO2 -emissions (depending on the energy source).
Overall, the most potentially economical pre-treatment proved to be size reduction [3]. Although there
are large resources, it is not a feasible feedstock material because of its crystallographic stability and
thus the necessary step of thermal pre-treatment.
Industrially produced by-products containing alkaline metals are also feasible for mineral
carbonation, such as numerous types of slags, scraps, red gypsum, combustion residues, fly ashes and
other forms of metal oxide materials such as red mud [4]. Unlike natural feasible materials, industrial
by-products usually do not require mining and pretreatment processes for utilization because they
already have high alkaline metal contents which are sufficient for mineral carbonation [5]. Because of
high availability in minerals and secondary materials among all of the possible materials selections,
calcium oxide and magnesium oxide are the most favorable options, as shown in Equations (1) and
(2) [6,7].
CaO(s) + CO2(g) = CaCO3(S) + 179kJ/mol (1)

MgO(s) + CO2(g) = MgCO3(s) + 118kJ/mol (2)

Although the carbonation process is an exothermic reaction, it requires an additional heat for
better dissolution of carbon dioxide in water in order to form magnesium carbonate. The benefits
of exothermic mineral carbonation may result in a positive net energy balance, which improves the
net efficiency of a combined cycle power plant [8]. Calculating energy balances of the process is
essential for the determination of the process’ profitability which might be influenced by high energy
costs. Furthermore, the overall reduction of carbon dioxide emissions has to be considered due to
further emissions in the mineral carbonation process resulting from, e.g., transportation, grinding and
processing of by-products. Furthermore, the potential use of the formed products should also be taken
into consideration.
There are abundant calcium and magnesium rich minerals available in the earth’s crust. Although
MgO and CaO are the most abundant alkali and alkaline metal oxides, they cannot be found as binary
oxides in nature. Usually, they exist as hydroxides or silicate minerals. In a mineral carbonation
process, these can also be used as feedstock to form carbonates that are chemically stable in a
geological timeframe. Silicate minerals usually are richer in alkaline metal content such as magnesium,
sodium, and calcium. Common silicate minerals suitable for carbonation are forsterite (Mg2 SiO4 ),
antigorite (Mg3 Si2 O5 (OH)4 ) and wollastonite (CaSiO3 ) and their overall reaction conversions are given
in Equations (3) to (5).

Mg2 SiO4 (s) + 2CO2 (g) + H2 O(l) = 2MgCO3 (s) + H4 SiO4 (aq) + 89kJ/mol (3)

Mg3 Si2 O5 (OH)4 (s) + 3CO2 (g) + 2H2 O(l) = 3MgCO3 (s) + 2H4 SiO4 (aq) + 64kJ/mol (4)
Metals 2018, 8, 993 3 of 15

CaSiO3 (s) + CO2 (g) + 2H2 O(l) = CaCO3 (s) + H4 SiO4 (aq) + 90kJ/mol (5)

The aforementioned mineral carbonation using slags as reactant also have the chance to
be profitable if they are built closely to the steel production site in order to reduce production
Metals 2018, 8, x FOR PEER REVIEW 3 of 14
costs [9]. Furthermore, heat integration with the steel production plant can reduce overall energy
costs significantly
significantly [9]. Carbonation
[9]. Carbonation of different
of different types types of slags
of slags areare widelystudied,
widely studied,one one study
study by by
Georgakopoulos [4]
Georgakopoulos [4] suggests
suggeststhat
thatblended
blendedhydraulic
hydraulic cement
cement BHCBHC slagslag
hashas
the the
highest conversion
highest conversionrate
which is 68.3%.
rate which is 68.3%.
Red gypsum
Red gypsum usually
usually exists
exists in
in the
the form
form of
of calcium
calcium sulfate
sulfate dihydrate
dihydrate (CaSO
(CaSO44·2H·2H22O).
O).Typically,
Typically, red
red
gypsum has
gypsum has aa purity
purity ofof 95%
95% and
and has
has large
large resources
resources in in Malaysia
Malaysia [10].
[10]. Due
Due toto the
the large
large calcium
calcium content
content
its carbonation is also a promising CCS option, i.e., one ton of red gypsum
its carbonation is also a promising CCS option, i.e., one ton of red gypsum can stably bind 0.26can stably bind 0.26 tons
tonsof
gaseous CO
of gaseous CO . A big advantage of red gypsum as carbonation resource is no mining
2 2. A big advantage of red gypsum as carbonation resource is no mining cost is required cost is required
since it exists
since it exists in in the
the form
form ofof fine
fine powder
powder which
which favors
favors thethe carbonation
carbonation reaction.
reaction.

Figure 1. Reaction
Reaction path
path of direct forsterite carbonation in aqueous solution.

Generally, the reaction path for the indirect carbonation of forsterite in an aqueous solution can
be described by Equations (6) to (12) which which is also
also illustrated
illustrated in in Figure
Figure 11 [11,12].
[11,12]. For
Forsimplicity,
simplicity, olivine
olivine
consists only of Mg22SiO44,, namely
consists namely forsterite.
forsterite. First,
First, gaseous
gaseous carboncarbon dioxide
dioxide dissolves
dissolves inin the aqueous
solution at aa certain certainmass masstransfertransferrate rateasasininEquation
Equation (6).(6).
Simultaneously,
Simultaneously, forsterite is dissolved
forsterite in the
is dissolved in
aqueous
the aqueous solution (Equation
solution (Equation (10)). In the aqueous
(10)). solution,solution,
In the aqueous all speciesallarespecies
assumedaretoassumed
be at equilibrium:
to be at
Aqueous CO2Aqueous
equilibrium: dissociates COinto bicarbonate,
2 dissociates into which furtherwhich
bicarbonate, dissociates
further into carbonateinto
dissociates (Equations
carbonate (7)
and (8)). Self-ionization
(Equations of water is given
(7) and (8)). Self-ionization by Equation
of water is given (9).
byAqueous
Equationsilicic acid thensilicic
(9). Aqueous precipitates
acid then as
amorphous silica, which is a by-product, and lastly magnesium
precipitates as amorphous silica, which is a by-product, and lastly magnesium ions and carbonate ions and carbonate form magnesite
(Equations
form magnesite (11) and (12)). (11) and (12)).
(Equations
rCO2
COCO( 2)(g) → CO CO( 2)(aq) (6) (6)
KC1
CO2((aq)) +
+ H2 O(()l) ↔ HCO(3− (aq
)+) + H(+ (aq
) ) (7) (7)

HCO− ((aq)) K↔
C2
CO23−((aq))++ H+( (aq
)) (8)
(8)
3
H O( ) KW OH −( ) + H +( ) (9)
H2 O(l) ↔ OH (aq) + H (aq) (9)
Mg SiO ( ) + 4 H ( )+ 2 Mg
rMg2 SiO
( ) + H SiO ( ) (10)
Mg2 SiO4 (s) + 4H (aq) → 4 2Mg2+ (aq) + H4 SiO4 (aq) (10)
H SiO ( r)SiO SiO ( ) + 2 H O( ) (11)
H4 SiO4 (aq) →2 SiO2 (s) + 2H2 O(l) (11)
Mg ( ) + CO ( ) r MgCO ( ) (12)
MgCO3
Mg2+ (aq) + CO23− (aq) → MgCO3 (s) (12)
The particular process is characterized by several equilibrium and non-equilibrium reactions.
The determination
The particularofprocess processisparameterscharacterized suchby asseveral
temperature, pressure
equilibrium andand pH for maximum
non-equilibrium overall
reactions.
conversion
The determination rates is of elementary.
process parameters Direct COsuch 2 sequestration at high
as temperature, pressure
pressure with
and pH olivine as a feedstock
for maximum overall
has already been performed in numerous studies at different temperatures and pressures with or
without the use of additives such as carboxylic acid, and sodium hydroxide [11,12]. It is reported that
optimal reaction conditions are in the temperature range of 150–185 °C and in the pressure range of
135–150 bar [10]. Additives are reported to have a positive influence on carbonation rate. Optimal
addition of additives are reported by Bearat et al. [13] in studies about the mechanism that limits
Metals 2018, 8, 993 4 of 15

conversion rates is elementary. Direct CO2 sequestration at high pressure with olivine as a feedstock
has already been performed in numerous studies at different temperatures and pressures with or
without the use of additives such as carboxylic acid, and sodium hydroxide [11,12]. It is reported
that optimal reaction conditions are in the temperature range of 150–185 ◦ C and in the pressure
range of 135–150 bar [10]. Additives are reported to have a positive influence on carbonation rate.
Optimal addition of additives are reported by Bearat et al. [13] in studies about the mechanism that
limits aqueous olivine carbonation reactivity under the optimum sequestration reaction conditions
observed as follows: 1 M NaCl + 0.64 M NaHCO3 , at 185 ◦ C and P (CO2 ) about 135 bar. A reaction
limiting silica-rich passivating layer forms on the feedstocks grains, slowing down carbonate formation
and raising process costs. Eikeland [14] reported that NaCl does not have significant influence on
carbonation conversion. The presented results show a conversion rate of more than 90% using a
NaHCO3 concentration of 0.5 M, without adding of NaCl. Ideally, the solid phases exist as pure phases
without growing together. In reality, different observations are made on the behavior of solid phases.
Daval et al. [15] reported about high influence of amorphous silica layer formation on the dissolution
rate of olivine at 90 ◦ C and elevated pressure of carbon dioxide. This passivating layer may either built
up from non-stoichiometric dissolution, precipitation of amorphous silica on forsterite particles or a
combination of both. In contrast to that, Oelkers et al. [16] and Hänchen [17] observed stoichiometric
dissolution and no build-up of a passivating layer except during start-up of experiments. Additionally,
magnesite may precipitate on undissolved forsterite particles leading to a surface area reduction and
therefore a reduction on forsterite dissolution rate, which was reported by Turri et al. [18]. Besides
this undesired intermixing of solids, they observed pure particles of magnesite to be predominant in
the smallest particle class, amorphous silica particles to be mainly present in the intermediate particle
class and unreacted olivine particles to be predominant in the largest particle class. This knowledge
may be of value for subsequent separation of products.
CO2 sequestration with olivine as a feedstock was performed in a rocking batch autoclave at
175 ◦ C and 100 bars in an aqueous solution and a CO2 -rich gas phase from 0.5 to 12 h. Turri showed
maintainable recovery of separate fractions of silica, carbonates and unreacted olivine. Characterization
of the recovered solids revealed that carbonates predominate in particle size range below 40 µm.
The larger, residue fraction of final product after carbonation consisted mainly of unreacted olivine,
while silica is more present in the form of very fine particles. An addition of sodium hydrogen
carbonate at 0.64 M, oxalic acid at 0.5 M and ascorbic acid at 0.01 M was successfully applied in
order to obtain maximal carbonation. The positive influence of the above-mentioned additives on the
carbonation efficiency was reported by Olajire [19]. They studied the technology of CO2 sequestration
by mineral carbonation with current status and future prospects, but the positive influence of additives
was not explained in detail.
Formation of submicron magnesite during reaction of natural forsterite in H2 O-saturated
supercritical CO2 was studied between 35 and 80 ◦ C and at pressure of 90 bars [20]. The magnesite
particles formed under below-mentioned conditions exhibited an extremely uniform submicron
grain-size and nearly identical rhombohedral morphologies at all temperatures. Then an evidence
for carbonate surface complexation during forsterite carbonation in wet supercritical carbon dioxide
was also considered. The effect of Fe on the measured rates of olivine carbonation and its role in the
formation of Si-rich surface layers, which can significantly inhibit olivine dissolution and limit the
extent of the carbonation reaction was considered by Saldi et al. [21]. A series of batch and flow-through
reactor experiments was conducted in pure water at 90 and 150 ◦ C and under a CO2 partial pressure
of 100 and 200 bar, using both a natural sample of Fe-bearing olivine and a synthetic sample of pure
forsterite. Experimental results show that Fe plays an ambivalent role in the carbonation.
The preparation of a magnesium hydroxy carbonate from magnesium hydroxide and carbon
dioxide includes the formation of a magnesium hydroxide slurry and sparging CO2 gas through it.
Various experimental conditions are evaluated in order to obtain the conditions that result in the
formation of the magnesium hydroxy carbonate [22].
Metals 2018, 8, 993 5 of 15

Our paper deals with the formation of magnesium carbonate using an Italian olivine (35.57 wt%
MgO) and a synthetic reference material, mainly consisting of magnesia (97.56 wt% MgO) with special
attention on the influence of the additives and different solid/liquid ratio. After carbonation, the
settled solid fraction contained mainly carbonation products, which was studied by structure and
composition analysis (X-Ray Diffraction XRD) and reactivity (Thermogravimetric analysis TGA and
Differential Scanning Calorimetry DSC). The water solution was analyzed by Inductively Coupled
Plasma Optical Emission Spectroscopy ICP-OES in order to determine the concentration of nickel, iron,
magnesium and cobalt.

Metals 2018, 8, x FORSection

2. Experimental PEER REVIEW 5 of 14

The samples
The samples used
used were
were Italian
Italian olivine (Figure 2a)
olivine (Figure 2a) and
and aa high-grade
high-grade synthetic
synthetic dead
dead burned
burned
magnesia (Figure 2b). From its chemical composition apart from the chromite
magnesia (Figure 2b). From its chemical composition apart from the chromite present at approx. 0.45 present at approx.
0.45 wt%
wt% and and
otherother
inertinert minerals
minerals at trace
at trace levels,
levels, the the olivine
olivine waswas considered
considered as aasmixed
a mixed Mg-Ni
Mg-Ni andand
Fe
Fe silicate.
silicate.
The olivine
The olivine has
hasbeen
beendelivered
deliveredwithwitha particle
a particlesizesize
of below 200 200
of below the used
µm,µm, magnesia
the used has a has
magnesia grain
a
size between 10 and 30 mm. Particle Size Distribution PSD Analysis was performed
grain size between 10 and 30 mm. Particle Size Distribution PSD Analysis was performed used used Mastersizer
Hydro 2000G
Mastersizer (Malvern
Hydro 2000GPANalytical GmbH, Kassel,
(Malvern PANalytical Germany)
GmbH, Kassel, Germany)
The carbonation tests were planned for the three
The carbonation tests were planned for the three different different particle sizesize
particle fractions <20<20
fractions 20–63
µm,µm, µm
20–63
and 100–200 µm in order to evaluate the optimal process parameters and the use
µm and 100–200 µm in order to evaluate the optimal process parameters and the use of additives. of additives.

(a) (b)
(a) Photos
Figure 2. (a) Photos of Italian Olivine; (b) Reference material after grinding.

The olivine
The olivine with
with d 90 ==100
d90 100µm (90%below
µm(90% below100
100microns)
microns) as
as itit is
is presented
presented in
in the
the sieve
sieve analysis
analysis in
in
Figure 33 has
Figure has been
been sieved
sieved wet
wet to
to produce
produce the
the three
three grain
grain size
size fractions.
fractions. The The magnesia
magnesia sample
sample has
has been
been
crushed and milled in a lab-scale jaw crusher and has also been sieved wet into the
crushed and milled in a lab-scale jaw crusher and has also been sieved wet into the required grainrequired grain
size fractions.
size fractions.

100
Cumulative Passing

80
60
(%)

40
20
0
0.00 0.01 Particle Size (mm) 0.10

Figure 3. Sieve Analysis (Particle Size Distribution PSD) of olivine <200 µm.

The chemical composition of olivine and magnesia was analyzed by X-ray fluorescence XRF
using Device PW2404 (Malvern Panalytical B.V., Eindhoven, Netherlands), such is presented in Table
1.

Table 1. Chemical composition of the investigated olivine and magnesia in wt%.

 Figure 2. (a) Photos of Italian Olivine; (b) Reference material after grinding.

The olivine with d90 = 100 µm (90% below 100 microns) as it is presented in the sieve analysis in
Figure 3 has been sieved wet to produce the three grain size fractions. The magnesia sample has been
crushed
Metals 2018,and milled in a lab-scale jaw crusher and has also been sieved wet into the required 6grain
8, 993 of 15
size fractions.

100

Cumulative Passing
80

(%)60
40
20
0
0.00 0.01 Particle Size (mm) 0.10

Figure 3.
Figure 3. Sieve Analysis (Particle
(Particle Size
Size Distribution
Distribution PSD)
PSD) of
of olivine
olivine <200
<200 µm.
µm.

The
The chemical
chemicalcomposition
compositionofof
olivine andand
olivine magnesia waswas
magnesia analyzed by X-ray
analyzed fluorescence
by X-ray XRF using
fluorescence XRF
Device PW2404
using Device (Malvern
PW2404 Panalytical
(Malvern B.V., Eindhoven,
Panalytical Netherlands),
B.V., Eindhoven, such issuch
Netherlands), presented in Table
is presented 1.
in Table
1.
Table 1. Chemical composition of the investigated olivine and magnesia in wt%.
Table 1. Chemical composition of the investigated olivine and magnesia in wt%.
Components Olivine Magnesia
Components
SiO2 Olivine
46.43 Magnesia
0.32
Al2 O
SiO 23 2.55
46.43 0.200.32
Fe2 O3 10.88 0.58
Al2O3 2.55 0.20
TiO2 0.11 0.05
FeCaO
2O3 10.88
2.16 0.750.58
TiO
MgO 2 0.11
35.57 97.560.05
K2 O
CaO 0.39
2.16 0.020.75
Na2 O
MgO 0.17
35.57 0.1097.56
MnO 0.17 0.24
Cr2 O3 0.45 0.00
P2 O5 0.00 0.00
ZrO2 0.02 0.03
SO3 0.00 0.00
BaO 0.00 0.00
ZnO 0.08 0.08
NiO 0.89 0.09
Co3 O4 0.08 0.00
CuO 0.06 0.00
Total 100.00 100.00

The planned experiments are shown in Table 2.

Table 2. Experimental plan (T = 175 ◦ C, pCO2 : 117 bar, 300 rpm, 4 h).

S/L Concentration of Additives

Exp. No Fraction Size (µm) Material
(g/mL H2 O) in Water, (mol/L)
10/150
1 100–200 No Olivine, Italy (35.57 wt% MgO)
(0.066)
10/150
2 <20 No Olivine, Italy (35.57 wt% MgO)
(0.066)
0.64 NaHCO3
30/150
3 20–63 0.06 H2 C2 O4 Olivine, Italy (35.57 wt% MgO)
(0.2)
0.003 C6 H8 O6,
30/150
4 20–63 No Synthetic magnesia (97.56 wt% MgO)
(0.2)

Carbonation tests have been carried out in the 250 mL autoclave from Parr Instrument Company
(Moline, IL, USA), USA as shown in Figure 4 at 175 ◦ C and 117 bars with pure grade CO2 . An amount
ranging from 10 to 30 g olivine has been added to 150 mL solution in different experiments.
 (0.2)
0.003 C6H8O6,
30/150
4 20–63 No Synthetic magnesia (97.56 wt% MgO)
(0.2)

MetalsCarbonation
2018, 8, 993 tests have been carried out in the 250 mL autoclave from Parr Instrument Company
7 of 15
(Moline, IL, USA), USA as shown in Figure 4 at 175 °C and 117 bars with pure grade CO2. An amount
ranging from 10 to 30 g olivine has been added to 150 mL solution in different experiments. After
After reaction,
reaction, the liquid
the liquid had veryhadlow
very low contents
contents of metalofcations,
metal cations,
thereforetherefore characterization
characterization of the
of the reaction
reaction products was restricted to the solid phase by TGA/DSC using Instrument
products was restricted to the solid phase by TGA/DSC using Instrument STA 449F3 with Proteus STA 449F3 with
Proteus
SoftwareSoftware
(NETZSCH,(NETZSCH, Selb, Germany)
Selb, Germany) and XRD-Analysis
and XRD-Analysis usingD8
using Bruker Bruker D8 Advance
Advance with
with LynxEye
LynxEye detector (Bruker AXS, Karlsruhe, Germany ). X-ray powder diffraction
detector (Bruker AXS, Karlsruhe, Germany). X-ray powder diffraction patterns were collected on a patterns were
collected
Bruker-AXSon aD4Bruker-AXS D4 Endeavor diffractometer
Endeavor diffractometer in Bragg–Brentano
in Bragg–Brentano geometry,
geometry, equipped equipped
with a copperwith a
tube
copper tube and
and a primary a primary
nickel nickel filterCu
filter providing providing Cu Kα1,2
Kα1,2 radiation (λ radiation
= 1.54187 (λ
Å).= 1.54187 Å).

Figure 4. Parr Autoclave with maximum pressure of 200 bar and maximum
maximum temperature
temperature of 250 ◦°C.
of 250 C.

3. Results and Discussion

The characterization of products was performed using TGA, DSC, XRD and ICP-OES analysis
(SPECTRO ARCOS, SPECTRO Analytical Instruments GmbH, Kleve, Germany) in order to confirm
the formation of MgCO3. Additionally, the influence of additives on carbonation was discussed.

3.1. Product Characterization–XRD Analysis of Product after Carbonation

To evaluate the overall capability of the carbonation process, an experiment was performed on a
synthetic reference material (>97 wt% MgO) considering the present mineralogical phases detected via
XRD before and after the carbonation (Figures 5 and 6).
3.1. Product Characterization–XRD Analysis of Product after Carbonation
To evaluate the overall capability of the carbonation process, an experiment was performed on
a synthetic reference material (>97 wt% MgO) considering the present mineralogical phases detected
Metals 2018, 8, 993 8 of 15
via XRD before and after the carbonation (Figures 5 and 6).

Metals 2018, 8, x FOR PEER REVIEW 8 of 14

Figure 5. XRD analysis of reference material.
Figure 5. XRD analysis of reference material.

Figure 6. XRD analysis of reference sample after carbonation process.

Figure 6. XRD analysis of reference sample after carbonation process.
The results prove the formation of magnesite (MgCO3 ) out of periclase (MgO) in the absence
Theadditives.
of any results proveBoththe formation
XRD of show
patterns magnesite (MgCO3)of
the existence outa of periclase
single (MgO)
phase, whichin underlines
the absencethe
of
any additives.
capability Both
of both theXRD patterns
reference show
material thetheexistence
and of aprocess.
carbonation single phase, which
In the next stepunderlines the
of the present
capability of both the reference material and the carbonation process. In the next step of
study, the carbonation process was applied to an Italian olivine sample as an exemplary natural raw the present
study, theaiming
material carbonation process was
at a comparable applied
MgCO to an Italian olivine sample as an exemplary natural raw
3 formation as observed utilizing a synthetic reference material.
material aiming at a comparable MgCO 3 formation as observed utilizing a synthetic reference
XRD analysis of the initial olivine sample confirms the presence of forsterite, enstatite, clinoenstatite,
material. XRD analysis of the initial olivine sample confirms the presence of forsterite, enstatite,
clinoenstatite, lizardite, spinel and tremolite, based on hydroxide and silicate of magnesium, calcium
and iron (Figure 7).
Metals 2018, 8, 993 9 of 15

lizardite, spinel and tremolite, based on hydroxide and silicate of magnesium, calcium and iron
(Figure
Metals 7).8, x FOR PEER REVIEW
2018, 9 of 14

Figure 7. XRD analysis of initial olivine sample.

Figure 7. XRD analysis of initial olivine sample.
Unfortunately, the chosen parameters (investigated fraction of 100–200 µm, solid/liquid ratio of
0.066 at 175 ◦ C and the
Unfortunately, 117chosen parameters
bar) did (investigated
not contribute fraction of
to the formation of100–200 µm,assolid/liquid
magnesite analyzed by ratio of
XRD.
0.066 at 175 °C and 117 bar) did not contribute to the formation of magnesite as analyzed
Applying the same experimental conditions on an olivine sample ground to a particle size below by XRD.
Applying
20 µm didthenotsame
yieldexperimental
any magnesiteconditions
formationon as an olivine
well. sample
However, groundby
followed tothe
a particle
additionsize below 20,
of NaHCO 3
µm did not yield any magnesite formation as well. However, followed by the addition of
H2 C2 O4 and C6 H8 O6 the formation of MgCO3 can be proved via XRD (Figure 8) when using a fractionNaHCO 3,

H 2C2O4 and C6H8O6 the formation of MgCO3 can be proved via XRD (Figure 8) when using a fraction
size of 20–63 µm.
size of 20–63 µm.

Figure 8. XRD analysis of olivine sample after carbonation.

 Unfortunately, the chosen parameters (investigated fraction of 100–200 µm, solid/liquid ratio of
0.066 at 175 °C and 117 bar) did not contribute to the formation of magnesite as analyzed by XRD.
Applying the same experimental conditions on an olivine sample ground to a particle size below 20
µm did not yield any magnesite formation as well. However, followed by the addition of NaHCO3,
H2C2O4 and C6H8O6 the formation of MgCO3 can be proved via XRD (Figure 8) when using a fraction
Metals 2018, 8, 993 10 of 15
size of 20–63 µm.

Figure 8. XRD analysis of olivine sample after carbonation.

Figure 8. XRD analysis of olivine sample after carbonation.
3.2. Analysis of Water Solution after Carbonation of an Olivine
The ICP-OES analysis of water solution after carbonation, as shown in Table 3 confirms very small
dissolution of valuable elements such as cobalt. The most dominant species are magnesium and silicon
in the order of magnitude of mg/L what corresponds to few percent of leaching efficiency. The pH
value confirmed that the solution is a neutral medium.

Table 3. Chemical analysis of Si, Mg, Fe, Ni, Cr, and Al in solution (mg/L) after carbonation.

Exp. No. Si Mg Fe Ni Cr Co Al
2 (pH-6.7) 166 229 0.11 0.73 <1 <1 <1
3 (pH-7.3) 195 705 67 10 <1 <1 <1
4 (pH-2.32) <1 211 <1 <1 <1 <1 <1

3.3. Carbonation Extent

Thermogravimetric analysis measurements were performed in order to establish the carbonation
effect. The calculated carbonation was about 45% in the presence of additives, as shown in Figure 9.
3.3. Carbonation Extent
Thermogravimetric analysis measurements were performed in order to establish the
carbonation effect. The calculated carbonation was about 45% in the presence of additives, as shown
Metals 2018, 8, 993 11 of 15
in Figure 9.

Temperature (°C)
Figure
Figure9.9.TGA/DSC
TGA/DSCAnalysis
Analysisinin
Exp. 3 in
Exp. thethe
3 in presence ofof
presence additives.
additives.

Thetotal
The totalanalysis
analysisofofthermal
thermaldecomposition
decompositionofofformed
formed(Mg,Fe)CO
(Mg,Fe)CO 3 is
3 is shownininTable
shown Table4.4.

ThermalDecomposition
Table4.4.Thermal
Table Decompositionofofsamples
samplesbefore
beforecarbonation
carbonationand
andafter
aftercarbonation.
carbonation.

Interval
Interval Before Carbonation
Before Carbonation After Carbonation
After Carbonation
Interval [◦ C] [°C]
Interval Loss of weight [%]
Loss of weight [%] Peak area [J/g]
Peak area [J/g]Loss of weight [%] Peak area
Loss of weight [%] [J/g]area [J/g]
Peak
25–125
25–125 0.17
0.17 1.05 1.05 6.38 6.38
125–385
125–385 0.22
0.22 0.93 0.93 No peak No peak
385–470
385–470 0.08
0.08 no no peak
peak 1.77 1.77 8.36 8.36
470–595
470–595 0.32
0.32 8.69 8.69 137 137
595–660
595–660 0.29
0.29 0.75 0.75 7.73 7.73
660–725
660–725 0.44
0.44 4.40
4.40 0.62 0.62 4.10 4.10
725–1000 0.20 No peak 0.36 No peak
25–1000 1.7 15.2

As shown in Table 4, the total weight loss for an initial sample of the Italian olivine in the interval
between 25 and 1000 ◦ C amounts 1.7%, what is the amount of bound water in the used sample.
The total weight loss for the initial olivine material in the interval between 25 and 470 ◦ C amounts
0.47% in comparison to 3.75% for this sample after carbonation. In difference for the sample without
carbonation, in the temperature interval between 470 ◦ C and 595 ◦ C, the weight loss amounts 8.69%,
with a thermal effect of 137 J/g, what confirms that this temperature range is most important for
thermal decomposition of (Mg,Fe)CO3 . Above 775 ◦ C the change of weight is not significant, and
thermal decomposition of sample is minimal, what means that the thermal decomposition is finished.
In contrast to this experiment in the presence of additives in Exp. 3 with loss of weight of 15.2%, the
overall weight losses of experiment 1 is very small (few percent) what confirms a low carbonation
degree (as confirmed with XRD analysis in Figure 6). The weight loss for experiment 2 is about
3.5% (red line at Figure 10) which confirms very small carbonation rate in the absence of additives in
comparison to the experiments with additives.
 thermal decomposition of sample is minimal, what means that the thermal decomposition is finished.
In contrast to this experiment in the presence of additives in Exp. 3 with loss of weight of 15.2%, the
overall weight losses of experiment 1 is very small (few percent) what confirms a low carbonation
degree (as confirmed with XRD analysis in Figure 6). The weight loss for experiment 2 is about 3.5%
(red line at Figure 10) which confirms very small carbonation rate in the absence of additives in
Metals 2018, 8, 993 12 of 15
comparison to the experiments with additives.

Temperature, °C
Figure
Figure 10.10.TGA
TGAand
andDSC
DSCAnalysis
Analysisin
in the
the experiments
experiments 11and
and22(TGA
(TGAand
andDSC
DSCforfor
experiment 1- green
experiment 1- green
color;
color; TGA
TGA andDSC
and DSCfor
forexperiment
experiment2-2-red
red color).
color).

Thispositive
This positiveeffect
effectmay
maybebe due
due to
to “reaction-driven
"reaction-driven cracking"
cracking”ininthe
thepresence
presenceof ofNaHCO
NaHCO 3,
3,
formationofofetch
formation etchpits,
pits,and/or
and/or other
other processes
processes thatthat continually
continuallyrenew
renewthe
thereactive surface
reactive area
surface of of
area
MgMg 2SiO4.
2 SiO4 .
NaHCO
NaHCO 3 (aq)→
3 (aq) →Na
+
Na+++H
+
CO332−2−
H+ + CO (13) (13)
AnAn additionofofoxalic
addition oxalicacid
acidleads
leads to
to formation
formation of
of Mg-ions
Mg-ionsininsolution,
solution,which
whichreact with
react carbonate
with carbonate
ions forming magnesium carbonate.
ions forming magnesium carbonate.
Mg2SiO4 + 2 H2C2O4 → 2Mg2+ + C2O42− + H4SiO4 (14)
Mg2 SiO4 + 2 H2 C2 O4 → 2Mg2+ + C2 O4 2− + H4 SiO4 (14)
Mg2+ + CO32− → MgCO3 (s) (15)
Mg2+ + CO3 2−
The two analyses of thermal decomposition
→ MgCO3 (s) carbonation of magnesia (97 wt%)(15)
of products after
confirmed
The twototal decomposition
analyses of thermalofdecomposition
the produced MgCO 3.
of products after carbonation of magnesia (97 wt%)
confirmed total decomposition
Metals 2018, 8, x FOR PEER REVIEW
of the produced MgCO 3 . 12 of 14

Temperature (°C)
Figure11.
Figure 11. TGA
TGA and
and DSC
DSCAnalysis
Analysisof of
formed product
formed afterafter
product carbonation of synthetic
carbonation magnesia
of synthetic (20
magnesia
(20 ◦ C/min,
°C/min, nitrogen, Exp.Exp.
nitrogen, 4). 4).

As shown at Figure 11, the weight loss of 52.34 % (TGA-red line) and 52.22 (TGA-blue line) with
maximal DSC effect (1281 J/g; blue area) at Tmax = 699.8 °C confirm the formation of magnesium
carbonate, what was compared with theoretical value, according to the Equation (16):

MgCO ( ) → + CO ( ) (16)
Metals 2018, 8, 993 Temperature (°C) 13 of 15

Figure 11. TGA and DSC Analysis of formed product after carbonation of synthetic magnesia (20
As shown
°C/min, at Figure
nitrogen, Exp.11,
4). the weight loss of 52.34 % (TGA-red line) and 52.22 (TGA-blue line) with
maximal DSC effect (1281 J/g; blue area) at Tmax = 699.8 ◦ C confirm the formation of magnesium
As shown
carbonate, whatatwas
Figure 11, the weight
compared loss of 52.34
with theoretical % (TGA-red
value, accordingline) and
to the 52.22 (TGA-blue
Equation (16): line) with
maximal DSC effect (1281 J/g; blue area) at Tmax = 699.8 °C confirm the formation of magnesium
T
carbonate, what was compared with theoretical
MgCO 3 (s) →value,
MgO according
+ CO2 (aq)to the Equation (16): (16)

where: M (Mg) = 24.30 g/mol; M MgCO (MgCO ( 3)) →

= 84.30+g/mol,
CO ( M ) (MgO)= 40.30 g/mol, M (CO (16)
2) =
44.0 g/mol.
where: M (Mg) = 24.30 g/mol; M (MgCO3) = 84.30 g/mol, M (MgO)= 40.30 g/mol, M (CO2) = 44.0 g/mol.
Using aa ratio
Using ratio between
between molar
molar mass
mass of
of magnesium carbonate and
magnesium carbonate and magnesium
magnesium oxide,
oxide, theoretical
theoretical
calculated loss
calculated loss of
of carbon
carbon dioxide
dioxide amounts
amounts 52.55%,
52.55%, what
what isis in
in good
good accordance
accordance with
with an
an experimental
experimental
determined weight loss. Finally, it confirms the completed carbonation of synthetic magnesia
determined weight loss. Finally, it confirms the completed carbonation of synthetic magnesia under under
the chosen
the chosen parameters
parameters andand formation
formation ofof magnesium
magnesium carbonate,
carbonate, which
which particle
particle size
size distribution
distribution was
was
shown at Figure
shown at Figure 12.12.

Figure 12. Particle

Particle size distribution of MgCO33 after
after carbonation
carbonation of
of synthetic
synthetic magnesia.
magnesia.

The measured
The measuredvalues
valuesofofproduced
produced magnesium
magnesium carbonate
carbonate d50 and
d50 and d84 amount
d84 amount 15.066 15.066 and
and 37.066
37.066
µm, µm, respectively.
respectively.

4. Conclusion
4. Conclusion
Synthesis of magnesium carbonate was studied via carbonation of olivine using different size
fractions (under 20 µm, between 20 and 63 µm, and between 100 and 200 µm) with different
solid/liquid ratios of 1:15 and 1:5; at 175 ◦ C and pressure of CO2 (117 bar) in an autoclave in the
presence and in the absence of additives. The characterization of products using XRD, TGA, PSD
and DSC analysis has confirmed the formation of MgCO3 . In contrast to carbonation of olivine in
the absence of additives the formation of magnesium carbonate is possible at high pressure and
temperature with olivine (35.57% MgO) from Italy in the presence of sodium hydrogen carbonate,
oxalic acid, and ascorbic acid at 175 ◦ C, 117 bar in 4 h (Exp. 3). The maximum carbonation (more than
95%) was obtained at the same conditions for synthetic magnesia (97.56 wt% MgO) in the absence
of additives. In order to validate the first results in 0.25 L autoclave, new scale up experiments will
be performed in 1.0 and 10.0 L autoclaves. Especially, the influence of rotating speed, pH-values
and different initial secondary materials such as slag and red mud shall be analyzed in our future
work. The analysis of the obtained solution after carbonation revealed very small content of cobalt and
chromium, but it will be also considered in our future work in the presence of pH buffering agents in
order to increase an extraction efficiency. Especially, a life-cycle-assessment of the carbonation process
in the presence of additives will be performed in our future work.
Metals 2018, 8, 993 14 of 15

Author Contributions: S.S. conceptualized and managed the research, and co-wrote the paper. D.K. performed
the preparation of the olivine materials (grinding, sieving) and co-wrote the paper. H.W. co- wrote the paper. S.N.
has performed experiments in an autoclave. P.K. has performed of XRD and TGA-analysis of initial sample and
obtained products. G.M. helped in discussion of TGA and XRD-analysis. C.D. analyzed the data and co-wrote
the paper. S.E. supervised the XRF- and XRD-analyses and co-wrote the paper with R.T., P.K. conceptualized the
research and provided industrial advice. D.R. managed the laboratory facilities for TGA and DSC analysis in
Heidelberg Cement Technology Center. B.F. supervised the personnel, provided funding and co-wrote the paper.
Acknowledgments: We would like to thank the BMBF (Federal Ministry of Education and Research) in Berlin for
the financial support for the CO2MIN Project (No. 033RCO14B) in period from 01.06.2017 to 31.05.2020. For a
continuous support and cooperation we would like to thank Andreas Bremen, AVT and Hesam Ostovari, LTT,
RWTH Aachen University.
Conflicts of Interest: The authors declare no conflict of interest.

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