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Energy Procedia 63 (2014) 8017 – 8025

GHGT-12

A CCS Mineralization Process: Investigation of the Production of

Magnesium Carbonates from Magnesium Chloride Solution
Rui Haoa *, Professor Abir Al-Tabbaab
0F

a,b
University of Cambridge, Engineering Department, Trumpington Street, Cambridge CB2 1PZ, United Kingdom

Abstract

Carbon Capture and Storage (CCS) is considered as a promising technology to remediate the severe carbon dioxide
release in the atmosphere. Mineralization in the storage process has several advantages, and its products can be used
as low carbon footprint construction materials –magnesium oxide (MgO) cement. It is thought as a good
replacement of traditional Portland Cement (PC) from both technical and environmental perspectives. In this study,
MgO was obtained by mixing pure magnesium chloride and CO2 under alkaline condition, to produce hydrated
magnesium carbonates as the intermediate product; and then calcined into the final one. This part of research
presented in the paper mainly focused on the first stage of carbonation process, and investigated the importance of
the pH effect, while other reaction parameters were fixed during the reaction. Filtrates and precipitates were then
analysed by ICP and XRD respectively, and the results showed pH>9 has good performance in precipitation, and all
the sediments formed in a short time are irrelevant to pH.
© 2014
© 2013The TheAuthors.
Authors. Published
Published by Elsevier
by Elsevier Ltd.
Ltd. This is an open access article under the CC BY-NC-ND license
Selection and peer-review under responsibility of GHGT.
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
Keywords: Carbon capture and storage Mineralization process, Low carbon footprint cement , Magnesium carbonates, pH

1. Introduction

The rapid increase of carbon dioxide and methane emitted from current energy industries is a main causing factor of
global warming, which will lead to several serious consequences including sea level rise and changes in the water
cycle and ocean circulation patterns [1]. Thus it is important to deploy a sophisticated technique to remediate this
environmental problem.

* Corresponding author. Tel.:44 1223 766683.

E-mail address: haorui928@hotmail.com

1876-6102 © 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
doi:10.1016/j.egypro.2014.11.838
8018 Rui Hao and Abir Al-Tabbaa / Energy Procedia 63 (2014) 8017 – 8025

Over a few years development, Carbon Capture and Storage (CCS) technology has been recognized as a good
alternative for CO2 reduction, as well as providing a potential high yield with a reasonable cost. The idea behind
CCS is to capture the produced CO2 when the chemical energy in fossil fuels transfers to electrical energy, and
sequester the carbon elsewhere rather than the atmosphere [2]. It includes the capture, transportation and subsequent
storage of CO2 in suitable geological and ocean sites, or storage as carbonates/bicarbonates via mineral carbonation
[3].
By comparing these storage’s methods, the geological sequestration option is a relatively well established operation
and has a competitive cost. But it also suffers from slow progress during the underground CO2 injection, limited
accessibility, and potential CO2 leakage problems [4]. Different to those, mineralization reaction is a fast and
permanent process, ensuring the safety long term environmental storage, and has adequate feedstock by comprising
calcium and magnesium ions [5]. Moreover, it is not release CO2 until pH<2, and acid rain is unlikely to below 2.5
naturally [6], hence the normal environment will not affect the magnesium carbonates dissolution. However, the cost
is still not as cheap as geological storage [7]. Even though there is an expenditure deficiency in the mineralization
process, considering its other strengthens, it is still worth to investigate and industrialize.
This research mainly investigates and optimizes its process, to apply the resulting products in cement industry,
which accounts for around 10% CO2 emission globally during traditional Portland Cement (PC) production [8]. It is
therefore a great demand to develop their sustainable alternatives. MgO cement is thought as a good substitution
from both environmental and technical point of view. It has much lower calcination temperature, higher propensity
for binding with waste, more recyclable properties, high strength and durability characteristics compared to
traditional PC [9]. The process can be achieved through MgCl2, a main component of waste brine, via the
calcination of Hydrated Magnesium Carbonates (HMCs). Other MgO utilizations include stabilizing agents in soil
and waste stabilization/solidification, fire retarding and capture techniques [10].
In the mineralization carbon sequestration process, ammonia salts not only behave as a buffer (ammonia base) in the
carbonation step, but also can be recycled back to the dissolution step (ammonia acid), which is significant
advantage compared to the strong acid and base method [11-12]. Hence this paper concentrates on the production of
hydrated magnesium carbonates (HMCs) by using ammonia, a composition of urea and waste water, as Equation 1
and 2 shown below, following on the successful work from Mignardi et al. [13] and Hassan [14], and to further
investigate the impact of variables. This involved studying the effects of temperature, solution concentrations,
stirring speed, CO2 flow rate and particularly the controlled pH on the resulting HMCs. The precipitates were then
analysed using X-Ray Diffraction (XRD) and calcined to MgO later on as Equation 3, while the remaining solution
was investigated though Inductively Coupled Plasma (ICP) at the same time.

MgCl2.6H2O(aq) + 2NH4OH(aq) + 2CO2(g) => Mg(HCO3 )2(aq) + 2NH4Cl(aq) + 6H2O(l) (1)

Mg(HCO3)2(aq) + NH4OH(aq) + 2H2O(l)=> MgCO3.3H2O(s) +NH4HCO3(aq) (2)
MgCO3.3H2O(s)=>MgO(s)+CO2(g)+3H2O(s) (3)

The carbonation process (Eqn 1 &2) can occur under ambient conditions, whereas the calcinations part (Eqn 3)
requires a high temperature operation in a furnace. In a well-controlled process, both the by-products produced in
Eqns 2 &3, the NH4+ in NH4HCO3 and the CO2 respectively, can be recycled back to assist the first one, thus
avoiding further environmental pollution.

2. Methodology

All the materials were used as received from suppliers without further purification, based on their chemical process
including MgCl2*6H2O, NH3*H2O and CO2. The aqueous MgCl2*6H2O solution was prepared by dissolving
stoichiometric amounts in deionized water, and purity level 25% NH4OH (aq) and 99.5% CO2 (g) were also used in
the experiment. The photograph of the apparatus is presented in Figure 1. As shown, MgCl2*6H2O was transferred
to a beaker and then mixed with titration NH4OH and sparging CO2. A hot plate was operated for stirring speed and
 Rui Hao and Abir Al-Tabbaa / Energy Procedia 63 (2014) 8017 – 8025 8019

temperature.

CO2 pH & thermometer

MgCl2 solution
Pump

Ammonia
Hot plate

Figure 1: A photograph of the apparatus setting up

In this experiment, the pH was maintained at a constant value through a controlled pump, and other six parameters
were fixed as Table 1. Firstly, CO2 and ammonia were added to the MgCl2 solution for 10min; temperature, pH and
time were recorded during the experiment. After that, another 20min was operated under a controlled pH level.
Precipitates obtained during these processes were then filtrated accordingly. This process is termed as “carbonation
studies”, in accordance with the analysed results below. Obtained liquid after the filtration step was monitored at
ambient temperature and pressure over a period of 1-3 days as a long time pH test. In order to study continuing
chemical process over time, samples were collected from filtrates at the same time as the long-time pH test, at a
certain interval over 1-3 days, and acidified using HNO3 (70%) to prevent further reaction. All experiments were
duplicated to ensure its reliability.

Table 1: Parameters in experiment

Solution Initial Mg2+ concen CO2 flux rate Stirring speed Temp Pressure
Vol to solution
100ml 6g/l=0.25mol/l 250cm3/min 150rpm Room temp, around Atmospheric
20oC
The pH variables were 8, 8.5, 8.75, 9, 9.25, 9.5, 10, 10.3* (max); ±0.1.

The composition of the HMCs was determined using X-Ray Diffraction (XRD), conducted on a Siemens D500
diffractrometer at 40kV and 40mA. Machine was operated from 5o to 60o, where most of interest compounds
existing, 2ș values at a rate of 0.05o per step and with a 1s per step counting time. Meanwhile, the amount of
unreacted magnesium ions in solution, used as a measure of reaction efficiency, was determined using a Perkin
Elmer 7000 Inductively Coupled Plasma (ICP) optical emission spectrophotometer.
8020 Rui Hao and Abir Al-Tabbaa / Energy Procedia 63 (2014) 8017 – 8025

3. Results and Discussion

3.1. Carbonation studies

Carbonation studies particularly aim to explore the variations during the first 30min reaction, and its resulting
weight of precipitates. Due to the fixed pH property with the desired precipitates requirement in the reaction, only
temperatures were recorded during then (Figure 2).
pH=8
pH=8.5 pH=8
a b pH=8.5
26 pH=8.75
pH=9 26 pH=8.75
25 pH=9.25 pH=9
pH=9.5 25 pH=9.25
24 pH=9.5
pH=10
pH=10.3 24 pH=10
23 pH=10.3
Temp (oC)

23

Temp (oC)
22

22
21

20 21

19 20

18 19
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (min) Time (min)

Figure 2: Temperature vs time profiles in the two duplicated experiments over 30min

(a) First set of experiments; (b) Second set of experiments

These two temperatures profiles illustrated a similar tendency: temperature increased by 3-6oC sharply during the
first 10min when reactants infused in; then declined back gradually in the later 20min. This is due to the molecular
motion in microscopic manifestation, hence this phenomenon can be inferred by the more hastened molecules
movements during reactants additions than its independent reaction, triggering higher collision chances among the
molecules, thus to generate more energy in the first part. Moreover, temperature increased to some extent as an
overall, to validate its exothermal characteristic.
In the internal evaluation, higher pH tended to activate higher temperature. Similar to explanations above, it is
owing to more hydroxide ions (reactants) providing higher collisions probabilities among particles, so as to produce
more amount of energy. The only exclusion in graph is pH=10.3 in Figure 3b, this might be attributed to the long-
time placed of ammonia in a transparent glass, making its decomposition to some extent, also another important
reason was from under estimation of ammonia using, which caused supply shortage at nearly the end of reactants
addition time, 7 min.
Weight of precipitates can also reflect the total first 30min reaction from another aspect, Figure 3 was calculated by
average two duplicated experiments, and error bar was drawn by standard derivation function. It can be seen that no
precipitate was formed at pH=8 after 30min, while highest amount appeared at pH=9 and pH=9.25, with both
acquired 1.9 sediments, as well as showing the best magnesium sequestration ability at related values. pH=8.75 and
pH=9.5 also obtained some HMCs to some extent, with 1.3g and 0.8g respectively. In contrast, pH=10 and above
 Rui Hao and Abir Al-Tabbaa / Energy Procedia 63 (2014) 8017 – 8025 8021

had the smallest amount in this series. Consequently, in a short retention time, pH range from 8.5 to 9.5 is
recommended, although best performances emerge at 9 and 9.25.

pH=9.25
2.5

pH=9
2.0
pH=8.75
pH=9.5
1.5
Weight (g)

1.0
pH=8.5

0.5
pH=10
pH=8 pH=10.3

0.0

8.0 8.5 9.0 9.5 10.0 10.5

pH

Figure 3: Weight of precipitates after 30min reaction

Two representative precipitates photos obtained from pH=8.75 and pH=10 after 30min reaction were taken, to
record the products morphology from the macro-scope point of view (Figure 4 &5). It is found out that lower pH
was likely to produce finer aggregated particles (Figure 4) compared with higher one, which acquired more sheet-
like dispersive crystals (Figure 5). The reason of it is attributed to the lower pH value restriction on the nucleation
rate of HMCs formation, due to the dominance of bicarbonates; so the nuclei tend to aggregate together into larger
particles. However, with the ascended pH value, the nucleation rate gradually increases, thus to be able to crystallize
into small particles independently.

Figure 4: Precipitates obtained from pH=8.75 after 30min reaction

8022 Rui Hao and Abir Al-Tabbaa / Energy Procedia 63 (2014) 8017 – 8025

Figure 5: Precipitates obtained from pH=10 after 30min reaction

3.2. Long-time pH test

In the long time pH test, two measurements were carried out, one was monitored through three days, selecting 0.5h
(after 30min reaction), 4.5h, 20h, 42.5h and 70h as testing times, while the other one was a two days one, followed
the same procedures with first four testing points. Starting pH (time=0) was set up as a standard. Figure 6 displays
that pH> 9 could keep a constant pH range (standard value ± 0.1) over three days, due to its high buffering capacity
from exceeded ammonia or formed ammonia carbonates when pumping CO2 in it. However, pHİ9 had a 0.2-0.5
decrease slowly, starting from 2h, over a long time reaction. This is estimated that the molecules, which provided
the steady pH capacity, were just about to be used in the precipitates formation, leading to the scarcity of hydroxide
ions in solution.
pH=8 pH=8
a
pH=8.5
pH=8.75 b 10.5 pH=8.5
pH=8.75
pH=9 pH=9
pH=9.25 pH=9.25
10.0
10 pH=9.5 pH=9.5
pH=10 pH=10
pH=10.3 pH=10.3
9.5

9.0
pH
pH

8.5

8.0
8

7.5
-10 0 10 20 30 40 50 60 70 80 0 10 20 30 40 50
Time (h) Time (h)

Figure 6: pH vs time profile in the two duplicated experiments

(a) First set of experiments pH over 3 days test; (b) Second set of experiments pH over 2 days test
 Rui Hao and Abir Al-Tabbaa / Energy Procedia 63 (2014) 8017 – 8025 8023

3.3. Reaction Kinetic studies

ICP was employed in this section to quantify its remained magnesium ions in solution, so as to obtain its magnesium
sequestration efficiency indirectly and appropriate yield information. Given that this was a general tendency
exploration, only several occasions were decided in this series of tests. Error analysis was pursued by duplicated two
days results, choosing 0.5h (after 30min reaction), 4.5h, 20h, and 42.5h. According to this average value,
sequestrated magnesium percentage over times was also calculated, starting magnesium concentration set up at 6g/l.
Figure 7 depict that the majority of reactions finished within first days, reaching nearly a stable level later on.
Obvious to see, there was almost no reaction at pH=8, while higher pH could enhance the precipitations, that is
exceeded hydroxide ions could promote the carbonates formation. Especially when pHı10 (pH=10 & pH=10.3),
approximate after 20h, remained magnesium ions in solution was less than 0.1g (Figure 7), with sequestration
efficiency higher than 99% (Figure 8). However, they had a slower initial rate than 9<pH<10 (pH=9.25 & pH=9.5),
which achieved less than 1g magnesium ions after 4.5h (Figure 7), with corresponded sequestration efficiency >85%
(Figure 8). These two values were finally reached <0.4g/l Mg2+ concentration left in solution and >92%
sequestration performance after 20h respectively.
In the first 30min, 8.5<pH<10 (pH=8.75, 9, 9.25, 9.5) all could capture Mg2+ more than 50%, namely less than 3g/l
Mg2+, which was higher than pHı10 (pH=10 & pH=10.3) 3.5 g/l. This good magnesium removal ability accords to
high yield of precipitates, which is also coped with weight of precipitates, first 30min result is well matched with its
mass of sediments.
pH=8
pH=8.5
7
pH=8.75
pH=9
6 pH=9.25
pH=9.5
5 pH=10
pH=10.3
Mg2+ concen (g/l)

0 10 20 30 40 50
Time (h)

Figure 7: Unreacted Mg2+ concentration over 2 days’ time with error analysis
8024 Rui Hao and Abir Al-Tabbaa / Energy Procedia 63 (2014) 8017 – 8025

pH=8
pH=8.5
pH=8.75
100 pH=9
pH=9.25
pH=9.5
80 pH=10

Sequestrated Mg2+ (%)

pH=10.3

60

40

20

0 10 20 30 40 50
Time (h)

Figure 8: Sequestrated Mg2+ percentage over 2 days’ time

3.4. Precipitates analysis

The precipitates from the 30min reactions were analysed through XRD, to identify their components. Prior to this
operation, two duplicated products were fully mixed correspondingly. Some of the samples were negligible or
insufficient during batch reaction, such as pH=8 and pH=10.3 (max) respectively. Figure 9 indicates that only
nesquehonite (MgCO3 *3H2O) formed in the 30min reaction, irrespective to pH values, with a high purity level in
terms of its solitary presence.

pH=8.5
pH=8.75
18000 N
pH=9
16000 pH=9.25
N pH=9.5
14000 pH=10
N
Intensity (a.u.)

N
12000 N N N N
N N
N
N N N N NN N N N
10000

8000

6000

4000

2000

0 10 20 30 40 50 60
2 Theta (degrees)

Figure 9: XRD diffractograms of precipitates in the first 30min reaction

 Rui Hao and Abir Al-Tabbaa / Energy Procedia 63 (2014) 8017 – 8025 8025

4. Conclusion and Future Work

The global warming in terms of excess CO2 emissions is a series environmental problem gradually, and CCS
research started to development under this circumstance. Mineralization process among this technology possesses a
number of advantages in the long term, and resulting products can be applied in the cement industry, as a good
replacement of traditional PC, which is a high carbon footprint process.
This paper has investigated the magnesium carbonates production under a controlled pH level, with pure magnesium
chloride, ammonia and CO2 addition. Results to date has illustrated that the carbonation process is an exothermal
one, and higher pH tends to generate more heat due to more reactants addition providing higher particles collision
chances. pH>9 has good performance in precipitation, but higher pH range, which can assist the reaction, is strongly
recommended, such as pH•10, where Mg2+ sequestration efficiency can achieve >99.9%, as well as to keep a
constant pH level over a long time, although the deficiency is that they tend to have a slower reaction rate initially.
Majority of production finished within a day and high purity nesquehonite was formed after 30min reaction.
Further work will concentrate on second stage of total reaction, calcination process into final desired MgO product,
by operating various temperatures and times, as well as their obtained MgO reactivity.

Acknowledgements:
This work was carried out in the Geotechnical and Environmental Research Group, Department of Engineering at
the University of Cambridge, with partially funding from Professor Abir Al-Tabbaa. This conference attendance is
sponsored by Fitzwilliam Travel Fund, Ford of Great Britain Trust Fund and Cambridge Philosophy Society Travel
Fund. It also acknowledges that advice received from Dr. Stuart Scott and other colleagues.

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