Accepted Manuscript

Study of CO2 capture by seawater and its reinforcement

Hongwei Li, Zhigang Tang, Xiao Xing, Dong Guo, Longpeng Cui, Xian-zhong Mao

PII: S0360-5442(18)31830-9

DOI: 10.1016/j.energy.2018.09.066

Reference: EGY 13760

To appear in: Energy

Received Date: 17 July 2018

Accepted Date: 08 September 2018

Please cite this article as: Hongwei Li, Zhigang Tang, Xiao Xing, Dong Guo, Longpeng Cui, Xian-
zhong Mao, Study of CO2 capture by seawater and its reinforcement, Energy (2018), doi: 10.1016/j.
energy.2018.09.066

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 ACCEPTED MANUSCRIPT

Study of CO2 capture by seawater and its reinforcement

Hongwei Li1,3, Zhigang Tang2*, Xiao Xing2, Dong Guo2, Longpeng Cui3, Xian-zhong Mao1*

1. Division of Ocean Science and Technology, Graduate School at Shenzhen, Tsinghua

University, Shenzhen, P.R. China

2. State Key Laboratory of Chemical Engineering, Department of Chemical Engineering,

Tsinghua University, Beijing, P.R. China

3. Research Institute of Petroleum Processing, SINOPEC, Beijing, P.R. China

*Corresponding authors.
E-mail address:
maoxz@sz.tsinghua.edu.cn(X.-Z. Mao),
zhg-tang@tsinghua.edu.cn (Z. Tang).
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Abstract: Numerous coal-fired power plants, cement plants and steel mills are concentrated

in coastal areas of China, and are three major CO2 emitters. Seawater may be a potential

resource to capture CO2 in coastal areas. In this study, we used seawater as a CO2 absorber to

capture CO2. An online chromatography apparatus was used to determine CO2 solubility in

seawater with different temperatures, pressures and salinities. Then, the thermodynamics and

kinetics were studied for the influences of temperature and salinity on CO2 capture in

seawater. The experimental results show that increasing temperature and salinity were

adverse to CO2 capture by seawater because of an increase in Henry’s constant from a

thermodynamics aspect. The kinetic results show that high temperature and low salinity can

increase the CO2 absorption rate. In order to improve the CO2 absorption ability of seawater

and promote CO2 fixation in carbonate precipitation, we added CaO as major components of

industrial alkaline substances to enhance the seawater absorption of CO2. CO2 solubility in

seawater with 0.4% CaO increased by 79.25%. It shows that the addition of CaO can enhance

greatly seawater capture of CO2. The seawater and its reinforcement with CaO is a potential

method to capture CO2.

Keywords: CO2 capture, seawater, thermodynamics, kinetics

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Highlights

1. CO2 solubility in seawater was measured experimentally at different temperatures and

salinities.

2. A thermodynamic model was built to simulate CO2 solubility in seawater.

3. The kinetics of CO2 absorption in seawater was studied.

4. Seawater with CaO added can enhance greatly CO2 capture.

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1. Introduction

Increasing atmospheric carbon dioxide (CO2) concentrations, mainly caused by fossil fuel

combustion, have led to concerns regarding global warming. The Paris Agreement includes

195 nations committed to ‘‘holding the increase in the global average temperature to well

below 2 °C above pre-industrial levels and to pursuing efforts to limit the temperature

increase to 1.5 °C above pre-industrial levels, recognizing that this would significantly reduce

the risks and impacts of climate change” [1]. Over two-thirds of global emissions in 2015

originated from just ten countries, with the shares of China (28%) and the United States

(15%) far surpassing those of all others [2]. China is the world’s largest CO2-emittting nation

and is facing tremendous pressure to reduce those emissions. On June 30, 2015, the Chinese

government committed to cut CO2 emissions per unit gross domestic product by 60–65% by

2030 relative to 2005 levels, and to reach peak CO2 emissions around 2030 and make strong

efforts to do so earlier [3]. CO2 emission reduction is thus critical.

CO2 capture and storage (CCS) is regarded as having great potential for reducing CO2

emissions. Many technologies and ideas have been developed for CCS [4-6]. CO2 capture

methods include chemical or physical absorption, adsorption, membranes, and cryogenic

fractionation. Absorption [7-9] is a mature application method with effective absorption and

selectivity. Chemical absorption including alcohol-amine, amino-acid salt, Benfied, and

ammonia washing methods have good absorption and high selectivity but substantial energy

consumption in solvent regeneration. Physical absorption [10-12] including Rectisol, Flour,

Selexol, and Purisol methods, have strong CO2 solubility but substantial solvent costs. CO2

capture cost accounts for two thirds of total CCS cost [13]. Therefore, it is essential to search

for new CO2 capture methods to cut that cost.

Analysis of CO2 emission source distributions shows numerous coal-fired power plants,

cement plants and steel mills as major CO2 emitters concentrated along in the coastal areas of

China [14, 15]. Therefore, we propose CO2 capture by seawater with pH of 8.0–8.2. Natural

seawater is rich in Ca2+ and Mg2+ ions, and can directly enhance carbonate precipitation to

achieve CO2 fixation and combine CO2 capture and CO2 storage to develop CCS technology.

There have been few process studies on CO2 capture by seawater. Li et al. [16] performed

experimental research into seawater capture of CO2 from flue gas by the membrane method.
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They studied flue gas flow, CO2 concentration, seawater flow and pH, and film fill rates for

mass transfer performance of the membrane contactor. The treatment capacity was small and

operation maintenance was complex, so the reliability and cost need further study. El-Naas et

al. [17] studied the impact of temperature, reaction time, and addition quantity of ammonia on

CO2 capture by concentrated seawater, combining seawater desalination with greenhouse gas

reduction. Yu et al. [18] studied a CO2 softening method in concentrated seawater resource

utilization and seawater softening, but ammonia could not be recovered in the process.

There are many studies of CO2 solubility in seawater. Stewart and Munjal [19] determined

CO2 solubility in seawater by sample titrimetric analysis. Li and Tsui [20] determined CO2

solubility in water, seawater and NaCl solution using sample analysis with an infrared gas

analyzer. They found that CO2 solubility in seawater is identical to that in NaCl solution at the

same mass. Murray and Riley [21] used sample and gravity analyses to obtain CO2 solubility in

seawater with varying amounts of chlorine. The above methods applied sample analyses

outside the equilibrium system, thereby readily causing differences between samples and the

equilibrium composition. The methods also have complicated experimental procedures.

Li et al. [22] measured CO2 solubility using a gas-phase flow method at ordinary pressure.

Wang et al. [23, 24] investigated CO2 absorption by seawater via a bubbling reactor, and

analyzed liquid samples to determine CO2 solubility at ordinary pressure. These methods

cannot obtain CO2 solubility at high pressure. Therefore, we used online chromatography to

measure CO2 solubility in seawater. Equilibrium was maintained in a high-pressure autoclave

and samples were taken from the sample circulation line to ensure samples identical to the

equilibrium composition. We thereby studied the influences of temperature and salinity on

CO2 capture by seawater. Moreover, thermodynamics and kinetics were studied. To improve

the CO2 absorption ability of seawater and promote CO2 fixation in carbonate precipitation,

taking full advantage of industrial-source alkaline byproducts with abundant alkaline matter

and the Ca2+ ion, we added CaO as major components of industrial alkaline substances (such

as steel slag, cement kiln dust, and coal fly ash) into seawater to study its influence on CO2

capture by seawater.

2. Experimental description
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2.1. Materials

CO2 and N2 with volume fraction 0.9999 were supplied by BeiWen Gas in Beijing,

China. Solvents (NaCl, MgCl2, MgSO4, CaCl2, KCl, NaHCO3, NaBr, and CaO) were all

obtained from China Pharmaceutical Group Chemical Reagent Co. Ltd. at the same mass

fraction of 0.99. All components were used without further purification. We used synthetic

seawater (Table 1) in the experiments.

2.2. Apparatus and Experimental Procedures

Vapor–liquid phase equilibrium data between CO2 and seawater were determined by the

online chromatography method reported in a previous work [25]. A schematic diagram of the

experimental apparatus is shown in Fig. 1. This included an equilibrium cell, gas-phase

recirculation line and gas chromatograph (GC). The equilibrium cell was made of titanium

(TA2) with an inner volume of ~1000 ml and alarm pressure of 10.0 MPa. A stirrer that was

rotated at variable speed by an external magnet accelerated the attainment of equilibrium. The

temperature was monitored using a Pt-100 resistance thermometer with uncertainty of

±0.1 ℃, while pressure was measured using a 0.5% diffusion silicon pressure transducer with

uncertainty of ±0.02 MPa. The pH of solution in equilibrium cell was measured using a pH

meter with 0.01pH resolution. Gas in the equilibrium cell was withdrawn from the top of the

cell by a metering pump through the gas sample valve, and then was directed into the cell

from the bottom. This accomplished the full gas-phase recirculation and accelerated gas–

liquid equilibrium. Online analysis of the equilibrium composition was carried out using a GC

(GC 7800, Purui Company, Beijing, China) with uncertainty of 0.03. The GC was equipped

with a thermal conductivity detector (TCD) and a Porapak Q column, which were 2 m in

length and 3 mm in diameter, respectively. The carrier gas was hydrogen with a flow rate of

30 ml/min. The injection, TCD and GC column temperatures were 220, 200 and 180 ℃,

respectively. The current of the TCD was 100 mA.

When the pressure and temperature were constant in the equilibrium cell, the system was

considered to be at equilibrium. The CO2 pressure and pH were recorded in real time. Then,

according to the GC analyzed results, the mole fraction of CO2 in liquid phase at that pressure

and temperature could be obtained. The data calculation is also described in detail in the

literature [26].
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2.3. Thermodynamic model

CO2 dissolution behavior in seawater was divided into three steps, as shown in Fig. 2. The

CO2 in gas phase was converted into liquid phase by Henry’s law (Eq. 1). Then, dissolved

CO2 in liquid phase carries out the first dissociation forming H+ and HCO3− (Eq. 4) and

secondary dissociation forming H+ and CO32− (Eq. 5) [27-28]. Finally, CO32− and Ca2+/Mg2+

form precipitation from solution (Eqs. 2 and 3).

All ions in liquid phase follow charge conservation (Eq. 6). Then, Eq. 6 can be expressed

by a function of CO2 partial pressure (pCO2) and [H+] (or pH). When pCO2 is given, [H+] (or

pH) can be obtained by that equation. After [H+] (or pH) is known, [CO2], [HCO3−], [CO32−]

[Ca2+] and [Mg2+] in liquid phase can be determined.

During the entire process, carbon (Eq. 7), magnesium (Eq. 8) and calcium (Eq. 9) are

conserved. The total absorbed CO2 can be obtained from Eq. 7 and expressed by Eq. 10.

(1) Phase equilibrium

(a) Gas-liquid equilibrium:

pCO2
CO2  g  ƒ CO2  l  pCO2  H [CO2 ] CO2 [CO2 ]=
H  CO2 (1)
8477.711  T  T 
2

ln H  155.1699- -21.957 ln T  0.005781T  S 0.023517  0.023656  0.0047036   
T  100  100  

Where the subscript g is for gas; l is for liquid; S is the salinity of seawater; T is temperature;

and H is Henry’s constant (apparent constant) [28].

(b) Liquid-solid equilibrium:

Ca 2  CO32 ƒ CaCO3 ( s ) K s1  [Ca 2 ] Ca2 [CO32 ] CO2 , (2)

3

Mg 2  CO32 ƒ MgCO3 ( s ) K s 2  [ Mg 2 ] Mg 2 [CO32 ] CO2 , (3)

3

where the subscript s is for solid; Ks1 is the equilibrium constant of calcium carbonate; and Ks2

is the equilibrium constant of magnesium carbonate.

(2) Chemical equilibrium:

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[ H  ][ HCO3 ] pCO2 K a1
CO2  l   H 2O ƒ H   HCO3 K a1  [ HCO3 ]=
[CO2 ] H [H  ]
12092.1
ln K a1  235.482   36.7816 ln T  A1 gS 0.5 +B1 gS  C1 gS 1.5  D1 gS 2  ln 1  0.001005gS 
T (4)
1
A1  228.39774  9714.36839g  34.485796gln T
T
1
B1  54.20871  2310.48919g  8.19516gln T
T
1
C1  3.969101  170.22169g  0.603627gln T
T
D1  0.00258768

Here, Ka1 is the first ionization constant of carbonic acid (apparent constant) [28].
[ H  ][CO32 ] pCO2 K a1K a 2
HCO3 ƒ H   CO32 Ka 2  [CO32 ]=
[ HCO3 ] H [ H  ]2
12431.7
ln K a 2  220.067   35.4819 ln T  A2 gS 0.5 +B2 gS  C2 gS 1.5  D2 gS 2  ln 1  0.001005gS 
T (5)
1
A2  167.69908  6551.35253g  25.928788gln T
T
1
B2  39.75854  1566.13883g  6.171951gln T
T
1
C2  2.892532  116.270079g  0.45788501gln T
T
D2  0.0061342

Here, Ka2 is the second ionization constant of carbonic acid (apparent constant) [28].

(3) Charge conservation:

[H  ]  [ Na  ]  [ K  ]  2[ Mg 2 ]+2[Ca 2 ]=[OH  ]+[ HCO3 ]+2[CO32 ]  [Cl  ]  [ Br  ]  2[ SO4 2 ] (6)
(4) Mass conservation
Conservation of carbon:

[CO2 ]0  [CO2 ] f  [CO2 ]  [ HCO3 ]  [CO32 ]  [ MgCO3 ]  [CaCO3 ] (7)

Conservation of magnesium:

[ Mg 2 ]0 [ Mg 2 ] f  [ MgCO3 ] (8)

Conservation of calcium:

[Ca 2 ]0 [Ca 2 ] f  [CaCO3 ] (9)

Here, 0 denotes the initial concentration and f the final concentration.

(5) CO2 solubility:

cT  [CO2 ] f  [CO2 ]0   H 2CO3   [ HCO3 ]  [CO32 ]  CaCO3    MgCO3  (10)

2.4. Kinetic study

Based on the online chromatography apparatus, the stirred tank method was used to
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measure the CO2 absorption rate by seawater. That rate can be expressed by Eq. 11.
Vn (11)
KG  p  p*  
aVt

where p is CO2 partial pressure, Pa; p* is the CO2 pressure in equilibrium with the liquid,

Pa; KG is the mass transfer coefficient of the gas phase; a is the gas–liquid interfacial area, m2;

Δn is the change of CO2 in gas phase, mol; Δt is the change time during the process, min.

The CO2 pressure in gas phase (p in Eq. 12) can be obtained by experiment. The CO2

pressure in equilibrium with the liquid (p* in Eq.11) can be obtained by pH from

experimentation and Eq. 7. The change of CO2 can be obtained by the gas equation of state.

Therefore, KGa is given by Eq. 12 (from Eq. 11).

pt
V   dp (12)
p0
KG a  t
RT  [ p(t )  p (t )]dt
*
0

3. Results and discussion

3.1. Influence of temperature on CO2 capture by seawater

The online chromatography method was executed to determine CO2 solubility in seawater

at 15, 20 and 25 °C, as shown in Fig. 3. It is seen that CO2 solubility increases with increasing

pressure and decreasing temperature. For example, at pressure 0.3 MPa, CO2 solubility in

seawater increased on average by 14.73% when temperature decreased by 5℃. At

temperature 25 °C, CO2 solubility in seawater increased by 91.66%, 47.82%, 32.35% and

24.44% when pressure increased in 0.1MPa steps from 0.1MPa to 0.5MPa, respectively.

The rate of increase of CO2 solubility decreased as pressure increased. Decreasing of

temperature and increasing of pressure favor CO2 capture by seawater and pressure increasing

is more effective than temperature decreasing.

The thermodynamic model was used to calculate CO2 solubility in seawater. The results

are shown in Table 2 and Fig. 3. The average error between experimental and calculated data

is 1.69%. The calculated data agree well with the experimental data and so the model can

predict the solubility of CO2 in seawater.

From Table 2, with increasing pressure at the same temperature, CO2 physical dissolution

([H2CO3]) in seawater increases by Henry’s law, [HCO3−] remains unchanged because

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seawater contains a certain concentration of HCO3− (0.00246 mol/L), and [CO32−] decreases

because of [H+] increase with CO2 absorption by seawater and inhibition via Eq. 5. [CO2] (or

[H2CO3]) are the dominant forms of CO2 in seawater, accounting for 93%. [HCO3−] is second

and [CO32−] the least. CO2 physical dissolution plays the dominant role causing CO2 total

solubility in seawater to increase with pressure.

Temperature influences CO2 capture in seawater by changing Henry’s constant and the

dissociation constant of carbonic acid. With increasing temperature, Henry’s constant

increases (Eq. 1) and less CO2 dissolves. Because [CO2] (or [H2CO3]) is the dominant forms

of CO2 (Table 3), CO2 solubility in seawater decreases with increasing temperature.

In the process of CO2 capture by seawater, p gradually declines and p* calculated by pH

and Eq. 6 gradually increases until the two variables are equal and the system reaches

equilibrium. The influence of p and pH on KGa in CO2 capture of seawater at different

temperatures is shown in Fig. 4. It is found that KGa decreases with decreasing p and pH.

With p decrease, the mass transfer force of gas–liquid weakens, so KGa decreases. A pH

decrease means an increase of CO2 in solution, which also reduces the mass transfer force of

gas–liquid and causes KGa to decrease with the decrease of pH. Table 3 shows that KGa

increases with temperature and that rising temperature can promote the CO2 absorption rate

by seawater.

3.2. Influence of salinity on CO2 capture by seawater

CO2 solubility in seawater with different salinities (25, 35, 55, and 65) was determined, as

shown in Fig. 5. It was found that CO2 solubility decreases with increasing salinity. For

example, at temperature 25 °C and pressure 0.3 MPa, CO2 solubility in seawater increased on

average by 3.60% when salinity decreased by 10.

Then, the thermodynamic model was used to calculate CO2 solubility in seawater with

variable salinity. The results are shown by Table 4 and Fig. 5. The average error between

experimental and calculated data is 1.95%. The calculated data agree well with the

experimental data and so the model can predict the solubility of CO2 in seawater.

With increasing salinity, Henry’s constant increases (Eq. 1) and CO2 solubility in seawater

decreases. Moreover, there is more HCO3− in seawater with increasing salinity and this can

inhibit Eq. 4 and further absorption of CO2. Therefore, CO2 solubility in seawater decreases
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with increasing salinity.

During CO2 capture by seawater with variable salinity, KGa was as shown in Table 5. It is

seen that KGa decreased with increasing salinity and that increasing salinity was adverse to

the CO2 absorption rate by seawater.

3.3. Influence of CaO on CO2 capture by seawater

Tables 2 and 4 reveal that the concentrations of Ca2+ and Mg2+ and of CO32− in seawater

were beyond the precipitation conditions of CaCO3 (Ksp = 4.95 × 10−9) and MgCO3 (Ksp = 1.15

× 10−5). Seawater itself has no ability to form carbonate deposits, even if we increase the

pressure and enhance [CO32−] in seawater. To improve the CO2 absorption ability of seawater

and CO2 fixation in carbonate precipitation, we added CaO as the main component of

industrial alkaline sources to seawater and used this to capture CO2.

CO2 solubility in seawater with 0.4% CaO was determined as shown in Fig. 6. It is seen

that this solubility was greater than with seawater alone and CaO could enhance seawater

capture of CO2. For example, at temperature 25 °C and pressure 0.3 MPa, CO2 solubility in

seawater with 0.4% CaO increased by 79.25% over that of seawater. Compared with the

influence of temperature (14.73%) and salinity (3.60%), CO2 solubility in seawater increased

greatly with adding CaO.

Fig. 6 indicates that the p–x line of CO2 capture in seawater can pass through the origin,

but that of CO2 capture in seawater with CaO cannot. There is alkaline matter with strong

CO2 absorption ability. As is known, the chemical absorption rate is greater than that of

physical absorption. At first, chemical absorption is more important, causing the p–x line to

be offset from the origin.

The thermodynamic model was used to calculate CO2 solubility in seawater with CaO.

The results are given in Table 6 and Fig. 6. With CaO, the average error between

experimental and calculated data is 1.95%. The calculated data agree well with the

experimental data and thus the model can predict the solubility of CO2 in seawater with CaO.

From Table 6, [Ca2+] × [OH−]2 is beyond the precipitation conditions of Ca(OH)2 (Ksp =

7.88 × 10−6). Therefore, CaO is dissoluble in seawater, enhancing solution alkalinity,

promoting carbonic acid ionization, increasing [HCO3−] and [CO32−], and augmenting the

concentration of Ca2+. Then, the concentrations of CO32− and Ca2+ attain the precipitation
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conditions of CaCO3 and form calcium carbonate precipitation from the seawater solution.

With increasing pressure, CO2 increasingly dissolves in seawater and pH in that seawater

declines. Then, calcium carbonate precipitation undergoes the following reaction (Eq. 14) and

dissolves again into solution. Therefore, with increasing pressure, the concentration of Ca2+

increases and the CaCO3 quantity decreases. This process also consumes CO2 and promotes

CO2 capture.
CaCO3  H 2O  CO2 ƒ Ca 2  2 HCO3 (14)

3.4. Potential application

The solubility of CaO in seawater and the rate constant of CaO-CO2 reaction are

comparatively low compared with chemical or physical solvents. However, for CO2 capture

by seawater and its reinforcement with CaO, the whole process of CO2 absorption is that CO2

enters the seawater to produce carbonate ion, and calcium oxide enters into the seawater to

produce calcium hydroxide. The calcium ion in the solution is combined with the carbonate

ion to produce calcium carbonate. The whole process is controlled by the solubility product of

calcium carbonate, not the solubility of calcium oxide, as long as it guarantees calcium ions in

the solution. This is enough to produce precipitation with carbonate ions, and the solubility

product of calcium hydroxide is much larger than that of calcium carbonate. Therefore the

seawater and its reinforcement with CaO is a potential method to capture CO2 in coastal areas.

Numerous coal-fired power plants, cement plants and steel mills are concentrated in

coastal areas of China, and are three major CO2 emitters, producing more than 92% of CO2

emission [14, 15]. Seawater is a potential resource to capture this CO2. There are few process

studies on CO2 capture by seawater. Seawater flue gas desulfurization is a good example to

study seawater decarbonization.

There are many studies and engineering applications for SO2 capture by seawater. Chen

and Zhou [29] described SO2 capture by seawater at the Zhangzhou Power Plant, China. Yang
[30] studied seawater desulfurization and its engineering application. Oikawa et al. [31]

examined the value and performance results of seawater flue gas desulfurization. Tokumura et

al. [32] described a process of seawater flue gas desulfurization, including experimental

investigation, dynamic modeling, and simulation. Liu et al. [33] investigated key parameters of

seawater flue gas desulfurization through industrial experiments. We can learn from research
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into seawater flue gas desulfurization to study seawater decarburization (Fig. 7). Feed gas

enters the bottom of an absorber while the absorbent (seawater) is pumped from an absorbent

storage tank to the top of the absorber. CO2 is separated from the gas by countercurrent

contact with seawater to produce calcium carbonate or magnesium carbonate precipitation

and reduce pH. Seawater from the bottom of the absorber enters the separator for liquid–solid

separation, and the solid can be used as raw material in industries such as cement. The

seawater after absorption of CO2 has low pH and the industrial alkaline sources are strongly

alkaline. Therefore, industrial alkaline sources are added into the separator for seawater

quality recoverability to reach the discharge standard (pH > 6.5). Ions of industrial alkaline

sources (such as Ca2+, Mg2+) can be added to seawater, with little effect on the ocean

environment because seawater contains many ions.

Common industrial-source alkaline byproducts include coal fly ash (FA) from coal

combustion [34], steel slag (SS) including electric arc furnace (EAF) dust from the iron and

steel industry [35-39], waste concrete [35, 40] and cement kiln dust (CKD) from the cement

industry [40-42], municipal waste incinerator (MSWI) ash from waste incineration [43-45],

asbestos mine tailings from asbestos mining [34], and bauxite residue from the aluminum

industry [46]. Although the morphology and composition of different industrial alkalinity

sources vary, these byproducts generally contain substantial amounts of reactive metal oxides

(primarily calcium oxide or CaO). CKD, FA, and SS are the more common industrial-based

alkalinity sources, and the typical CaO fraction is 30–50% by weight. Coal-fired power

plants, cement plants and steel mills are three major CO2 emitters that are concentrated in the

coastal areas of China [14, 15]. The above materials are cheap and available near strong point

sources of CO2, and tend to react relatively quickly with CO2 because of their chemical

instability.

4. Conclusions

The online chromatography method was carried out to determine CO2 solubility in

seawater. CO2 solubility increased with increasing pressure and decreasing temperature. The

thermodynamic model had an average error of 1.69% relative to the experimental results,

showing that temperature influences CO2 capture in seawater by changing Henry’s constant
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and the dissociation constant of carbonic acid. The kinetic studies showed that KGa increased

with increasing temperature and that the increase in temperature can promote the CO2

absorption rate by seawater.

CO2 solubility in seawater with variable salinity (25, 35, 55, and 65) was determined,

showing that this solubility decreases with increasing salinity. The thermodynamic model had

an average error of 1.95% relative to the experimental results. This showed that with

increasing salinity, Henry’s constant increased and CO2 solubility in seawater decreased. The

kinetic studies showed that KGa decreased with increasing salinity and that the increase of

salinity was adverse to the CO2 absorption rate by seawater.

CaO as the main component of industrial alkaline substances was added into seawater to

capture CO2. This promoted CaCO3 precipitation generation and caused a CO2 solubility

greater than that of seawater, thereby promoting CO2 capture by seawater. CO2 solubility in

seawater with 0.4% CaO increased by 79.25% over that in seawater at 25℃ and 0.3MPa.

Compared with the influence of temperature (14.73%) and salinity (3.60%), CO2 solubility in

seawater increased greatly with adding CaO. Data calculated via the thermodynamic model

compared favorably with the experimental data. CaO can enhance seawater capture of CO2.

Industrial alkaline substances with high percentages of CaO, including steel slag, cement

kiln dust, and coal fly ash, are concentrated in coastal areas and can be used into seawater to

enhance CO2 capture with low cost. Further studies are wanted on the performance of

seawater absorbing CO2, when steel slag rich in CaO or other alkaline substances are added.

Acknowledgements

This study was supported by the National Key Technology Support Program of China (No.

2015BAC04B00) and Shenzhen Science and Technology Plan project of China

(JCYJ20160608165926763).
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References:
[1] Rogelj J, den Elzen M, Hohne N, et al. Paris Agreement climate proposals need a boost to keep
warming well below 2 degrees C. Nature 2016; 534: 631-9
[2] International Energy Agency(IEA). CO2 emissions from fuel combustion: highlights.2014.
[3] UNFCCC, China’s intended nationally determined contribution: enhanced actions on climate
change. 2015.
[4] Boot-Handford M, Abanades J, Anthony E, et al. Carbon capture and storage update. Energy
Environ Sci 2014; 7: 130-189
[5] Li B, Duan Y, Luebke D, et al. Advances in CO2 capture technology: A patent review. Appl Energy
2013; 102: 1439-1447
[6] Yan J. Carbon Capture and Storage (CCS). Appl Energy 2015; 148: A1-A6
[7] Yu C-H. A Review of CO2 Capture by Absorption and Adsorption. Aerosol Air Qual Res 2012;
12(5): 745-769.
[8] Koronaki I P, Prentza L, Papaefthimiou V D. Parametric analysis using AMP and MEA as aqueous
solvents for CO2 absorption. Appl Therm Eng 2017; 110: 126-135
[9] Hu Y, Ahn H. Process integration of a Calcium-looping process with a natural gas combined cycle
power plant for CO2 capture and its improvement by exhaust gas recirculation. Appl Energy
2017; 187: 480-488
[10] Park S, Lee S, Lee J, et al. The quantitative evaluation of two-stage pre-combustion CO2 capture
processes using the physical solvents with various design parameters. Energy, 2015, 81: 47-55
[11] Chen W, Chen S, Hung C. Carbon dioxide capture by single droplet using Selexol, Rectisol and
water as absorbents: A theoretical approach. Appl Energy 2013; 111: 731-741
[12] Urech J, Tock L, Harkin T, et al. An assessment of different solvent-based capture technologies
within an IGCC–CCS power plant. Energy 2014; 64: 268-276
[13] Freund P. Making deep reductions in CO2 emissions from coal-fired power plant using capture
and storage of CO2. Proc Inst Mech Eng , Part A 2003; 217: 1-7
[14] Li X, Wei N, Liu Y, et al. CO2 point emission and geological storage capacity in China. Energy
Procedia 2009; 1: 2793-2800
[15] Dahowski R, Li X, Davidson C, et al. Regional Opportunities for Carbon Dioxide Capture and
Storage in China: A Comprehensive CO2 Storage Cost Curve and Analysis of the Potential for
Large Scale Carbon Dioxide Capture and Storage in the People’s Republic of China; United
States, 2009-12-01, 2009.
[16] Li X, Guo C, Liu G, et al. Experimental study on CO2 removal from a gas stream by membrane
with seawater. Membr Sci Technol 2012; 92-96
[17] El-Naas M, Al-Marzouqi A, Chaalal O. A combined approach for the management of desalination
reject brine and capture of CO2. Desalination 2010; 251: 70-74
[18] Yu H, Gao X, Su B, et al. A New Method to Remove the Calcium and Magnesium from the Sea
Water with CO2[C]//Advanced Materials Research. Trans Tech Publications, 2012, 361: 990-995.
[19] Stewart P, Munjal P. Solubility of carbon dioxide in pure water, synthetic sea water, and synthetic
sea water concentrates at-5. deg. to 25. deg. and 10-to 45-atm. J Chem Eng Data 1970; 15: 67-71
[20] Li Y, Tsui T. The solubility of CO2 in water and sea water. J Geophys Res 1971; 76: 4203-4207
[21] Murray C, Riley J. The solubility of gases in distilled water and sea water—IV. Carbon dioxide.
Deep-Sea Res Oceanogr Abstr 1971;18: 533-541
 ACCEPTED MANUSCRIPT

[22] Li H, Shi Y, Zhan B, et al. Determination and correlation of equilibrium data for low
concentration CO2 absorbed in seawater. China Sciencepaper 2015; 2209-2215
[23] Wang W, Hu M, Zheng Y, et al. CO2 Fixation in Ca2+-/Mg2+-Rich Aqueous Solutions through
Enhanced Carbonate Precipitation. Ind Eng Chem Res 2011; 50: 8333-8339
[24] Wang W, Hu M, Ma C In Possibility for CO2 Sequestration Using Sea Water, 2010 4th
International Conference on Bioinformatics and Biomedical Engineering, 18-20 June 2010; 2010;
pp 1-4.
[25] Li H, Tang Z, He Z, et al. Performance evaluation of CO2 capture with diethyl succinate. Appl
Energy 2017; 200: 119-131
[26] Edwards T, Maurer G, Newman J, et al. Vapor-liquid equilibria in multicomponent aqueous
solutions of volatile weak electrolytes. AIChE J 1978; 24: 966-976
[27] Chen C, Britt H, Boston J, et al. Extension and application of the pitzer equation for vapor-liquid
equilibrium of aqueous electrolyte systems with molecular solutes. AIChE J 1979; 25: 820-831
[28] Zeebe R, Wolf-Gladrow D. CO2 in seawater: equilibrium, kinetics, isotopes. Gulf Professional
Publishing, 2001.
[29] Chen Y, Zou X. The transformation process of seawater desulfurization of supercritical 600MW
unit in Zhangzhou Houshi Power Plant. China Electric Power(Technology Edition) 2013; 09: 45-
47
[30] Yang Z. Seawater flue gas desulphurization technology and its engineering application in power
plant. J Power Eng 2008; 28: 612-615
[31] Oikawa K, Yongsiri C, Takeda K, et al. Seawater flue gas desulfurization: Its technical
implications and performance results. Environ Prog 2003; 22: 67-73
[32] Tokumura M, Baba M, Znad H T, et al. Neutralization of the Acidified Seawater Effluent from the
Flue Gas Desulfurization Process:  Experimental Investigation, Dynamic Modeling, and
Simulation. Ind Eng Chem Res 2006; 45: 6339-6348
[33] Liu T, Guan Y, Wang H, et al. Industrial experimental study on key parameters of seawater flue
gas desulfurization process. Electr Power 2010; 50-55
[34] Gerdemann S, O'Connor W, Dahlin D, et al. Ex Situ Aqueous Mineral Carbonation. Environ Sci
Technol 2007; 41: 2587-2593
[35] Stolaroff J, Lowry G, Keith D. Using CaO- and MgO-rich industrial waste streams for carbon
sequestration. Energy Convers Manage 2005; 46: 687-699
[36] Teir S, Eloneva S, Fogelholm C, et al. Dissolution of steelmaking slags in acetic acid for
precipitated calcium carbonate production. Energy 2007; 32: 528-539
[37] Huijgen W, Comans R. Mineral CO2 Sequestration by Steel Slag Carbonation. Environ Sci
Technol 2005; 39: 9676-9682
[38] Lekakh S, Rawlins C, Robertson D G C, et al. Kinetics of Aqueous Leaching and Carbonization of
Steelmaking Slag. Metall Mater Trans B 2008; 39: 125-134
[39] Bonenfant D, Kharoune L, Sauve´ S, et al. CO2 Sequestration Potential of Steel Slags at Ambient
Pressure and Temperature. Ind Eng Chem Res 2008; 47: 7610-7616
[40] Huntzinger D, Eatmon T. A life-cycle assessment of Portland cement manufacturing: comparing
the traditional process with alternative technologies. J Cleaner Prod 2009; 17: 668-675
[41] Huntzinger D, Gierke J, Kawatra S, et al. Carbon Dioxide Sequestration in Cement Kiln Dust
through Mineral Carbonation. Environ Sci Technol 2009; 43: 1986-1992
 ACCEPTED MANUSCRIPT

[42] Huntzinger D, Gierke J, Sutter L, et al. Mineral carbonation for carbon sequestration in cement
kiln dust from waste piles. J Hazard Mater 2009; 168: 31-37
[43] Rendek E, Ducom G, Germain P. Carbon dioxide sequestration in municipal solid waste
incinerator (MSWI) bottom ash. J Hazard Mater 2006; 128: 73-79
[44] Rendek E, Ducom G, Germain P. Influence of waste input and combustion technology on MSWI
bottom ash quality. Waste Manage 2007; 27: 1403-1407
[45] Toller S, Kärrman E, Gustafsson J P, et al. Environmental assessment of incinerator residue
utilisation. Waste Manage 2009; 29: 2071-2077
[46] Hind A, Bhargava S, Grocott S. The surface chemistry of Bayer process solids: a review. Colloids
Surf, A 1999; 146: 359-374
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Figure Legends

Fig. 1. Schematic of online chromatography apparatus

Fig. 2. CO2 dissolution behavior in seawater

Fig. 3. CO2 solubility in seawater at different temperatures

Fig. 4. Influence of p and pH on KGa for CO2 capture in seawater at different temperatures

（Number denotes the change trend of KGa vs p and KGa vs pH in the obtained process of

every equilibrium point.）

Fig. 5. CO2 solubility in seawater at different salinities

Fig. 6. CO2 solubility in seawater with CaO (T = 25 °C)

Fig. 7. Schematic diagram of CO2 capture by seawater

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Table 1 Composition of synthetic seawater [24]

Concentration
Component
g/kg g/L

NaCl 26.518 27.133

MgCl2 2.447 2.504
MgSO4 3.305 3.382
CaCl2 1.141 1.167
KCl 0.725 0.742
NaHCO3 0.202 0.207
NaBr 0.083 0.085
Total salts 34.421 35.220
H 2O 965.579 964.780
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Table 2 Calculated thermodynamic results of CO2 solubility in seawater at different

temperatures
p/MPa xCO2-exp [H2CO3] [HCO3−] [CO32−] [H+] [Ca2+]*[CO32−] [Mg2+]*[CO32−] xCO2-cal AAD/%

15°C
0.10 0.000739 0.0384 0.0025 1.13 × 10−7 1.64 × 10−5 1.18 × 10−9 6.12 × 10−9 0.000755 2.19
0.22 0.001615 0.0846 0.0025 5.20 × 10−8 3.58 × 10−5 5.47 × 10−10 2.83 × 10−9 0.001608 0.46
0.34 0.002503 0.1307 0.0025 3.42 × 10−8 5.50 × 10−5 3.59 × 10−10 1.86 × 10−9 0.002456 1.88
20°C
0.11 0.000728 0.0365 0.0025 1.31 × 10−7 1.74 × 10−5 1.38 × 10−9 7.11 × 10−9 0.000720 0.99
0.18 0.001094 0.0598 0.0025 8.06 × 10 −8 2.83 × 10−5 8.48 × 10−10 4.38 × 10−9 0.001150 5.12
0.23 0.001462 0.0764 0.0025 6.35 × 10 −8 3.60 × 10−5 6.68 × 10−10 3.45 × 10−9 0.001456 0.36
0.32 0.001956 0.1063 0.0025 4.61 × 10 −8 4.98 × 10−5 4.85 × 10−10 2.51 × 10−9 0.002007 2.61
0.40 0.002459 0.1328 0.0025 3.73 × 10 −8 6.20 × 10−5 3.92 × 10−10 2.03 × 10−9 0.002495 1.47
0.50 0.003094 0.166 0.0025 3.02 × 10−8 7.70 × 10−5 3.17 × 10−10 1.64 × 10−9 0.003105 0.35
0.58 0.003604 0.1926 0.0025 2.63 × 10−8 8.90 × 10−5 2.76 × 10−10 1.43 × 10−9 0.003594 0.28
25°C
0.12 0.000717 0.0348 0.0025 1.51 × 10−7 1.84 × 10−5 1.58 × 10−9 8.18 × 10−9 0.000689 3.85
0.22 0.001200 0.0638 0.0025 8.31 × 10 −8 3.35 × 10−5 8.74 × 10−10 4.52 × 10−9 0.001224 2.03
0.33 0.001809 0.0957 0.0025 5.61 × 10 −8 4.99 × 10−5 5.90 × 10−10 3.05 × 10−9 0.001812 0.18
0.41 0.002303 0.1189 0.0025 4.56 × 10 −8 6.17 × 10−5 4.80 × 10−10 2.48 × 10−9 0.002239 2.76
0.52 0.002803 0.1508 0.0025 3.64 × 10 −8 7.77 × 10−5 3.83 × 10−10 1.98 × 10−9 0.002826 0.81

(The concentration of ions is molarity, mol/L)

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Table 3 Calculated results of KGa in CO2 capture by seawater at different temperatures

pH p/MPa KGa/mol·min−1·Pa−1 pH p/MPa KGa/mol·min−1·Pa−1 pH p/MPa KGa/mol·min−1·Pa−1

T = 15 °C T = 20 °C T = 25 °C
3.80 0.11 0.01355 3.87 0.11 0.01603 3.98 0.08 0.01805
3.71 0.22 0.01539 3.71 0.23 0.01788 3.64 0.35 0.01648
3.59 0.40 0.01487 3.58 0.45 0.02156
3.49 0.58 0.01981 3.53 0.58 0.02228
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Table 4 Calculated thermodynamic results of CO2 solubility in seawater with different

salinities (T = 25 °C)
p/MPa xCO2-exp [H2CO3] [HCO3−] [CO32−] [H+] [Ca2+]*[CO32−] [Mg2+]*[CO32−] xCO2-cal AAD/%

Salinity = 25

0.12 0.000719 0.0367 0.0018 6.12 × 10−8 2.47 × 10−5 4.59 × 10−10 2.38 × 10−9 0.000706 1.78

0.25 0.001446 0.0765 0.0018 3.02 × 10 −8 5.06 × 10 −5 2.27 × 10 −10 1.17E−09 0.001434 0.79

0.38 0.002184 0.1162 0.0018 2.04 × 10 −8 7.59 × 10 −5 1.54 × 10 −10 7.94 × 10 −10 0.002160 1.08

0.51 0.002929 0.1560 0.0019 1.56 × 10−8 1.01 × 10−4 1.17 × 10−10 6.07 × 10−10 0.002888 1.38

Salinity = 35

0.12 0.000717 0.0348 0.0025 1.51 × 10−7 1.84 × 10−5 1.58 × 10−9 8.18 × 10−9 0.000689 3.85

0.22 0.001200 0.0638 0.0025 8.31 × 10−8 3.35 × 10−5 8.74 × 10−10 4.52 × 10−9 0.001224 2.03

0.33 0.001809 0.0957 0.0025 5.61 × 10−8 4.99 × 10−5 5.90 × 10−10 3.05 × 10−9 0.001812 0.18

0.41 0.002303 0.1189 0.0025 4.56 × 10 −8 6.17 × 10 −5 4.80 × 10 −10 2.48 × 10 −9 0.002239 2.76

0.52 0.002803 0.1508 0.0025 3.64 × 10 −8 7.77 × 10 −5 3.83 × 10 −10 1.98 × 10 −9 0.002826 0.81

Salinity = 55

0.12 0.000717 0.0314 0.0039 4.96 × 10−7 9.59 × 10−6 8.20 × 10−9 4.24 × 10−8 0.000662 7.74

0.25 0.001322 0.0654 0.0039 2.40 × 10 −7 1.99 × 10 −5 3.96 × 10 −9 2.05 × 10 −8 0.001298 1.80

0.43 0.002185 0.1125 0.0039 1.40 × 10−7 3.41 × 10−5 2.32 × 10−9 1.20 × 10−8 0.002179 0.28

0.56 0.002813 0.1466 0.0039 1.08 × 10−7 4.43 × 10−5 1.79 × 10−9 9.26 × 10−9 0.002815 0.06

Salinity = 65

0.08 0.000476 0.0199 0.0046 1.01 × 10−6 4.01 × 10−6 1.97 × 10−8 1.02 × 10−7 0.000463 2.69

0.24 0.001200 0.0596 0.0046 3.38 × 10−7 1.20 × 10−5 6.60 × 10−9 3.41 × 10−8 0.001212 0.99

0.38 0.001876 0.0944 0.0046 2.14 × 10 −7 1.90 × 10 −5 4.18 × 10 −9 2.16 × 10 −8 0.001868 0.43

0.54 0.002624 0.1342 0.0046 1.51 × 10 −7 2.69 × 10 −5 2.95 × 10 −9 1.53 × 10 −8 0.002617 0.28

(The concentration of ions is molarity, mol/L)

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Table 5 Calculated results of KGa in CO2 capture by seawater with different salinities (T =
25 °C)

pH p/MPa KGa/mol·min−1·Pa−1 pH p/MPa KGa/mol·min−1·Pa−1

Salinity = 25 Salinity = 35
4.99 0.12 0.02488 3.98 0.08 0.01805
4.67 0.25 0.02542 3.64 0.35 0.01648
4.49 0.38 0.02136 3.58 0.45 0.02156
4.36 0.51 0.03111 3.53 0.58 0.02228

Salinity = 55 Salinity = 65
4.33 0.12 0.01758 4.57 0.08 0.01705
4.01 0.25 0.01609 4.10 0.24 0.01644
4.77 0.43 0.01372 4.75 0.54 0.01228
4.66 0.56 0.01991
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Table 6 Calculated thermodynamic results of CO2 solubility in seawater with CaO (T = 25 °C)

p/MPa xCO2-exp [H2CO3] [HCO3−] [CO32−] [Ca2+] [CaCO3] [H+] [Ca2+]*[OH−]2 [Ca2+]*[CO32−] xCO2-cal AAD/%

0.03 0.001544 0.0087 0.0022 4.77 × 10−7 0.0104 0.06965 5.16 × 10−6 3.91 × 10−20 4.96 × 10−9 0.001487 3.70

0.20 0.002389 0.0580 0.0053 4.15 × 10−7 0.0119 0.06815 1.43 × 10−5 5.84 × 10−21 4.94 × 10−9 0.002424 1.45

0.37 0.003373 0.1073 0.007 3.88 × 10−7 0.0128 0.06725 2.01 × 10−5 3.17 × 10−21 4.97 × 10−9 0.003345 0.84

0.57 0.004502 0.1653 0.0084 3.67 × 10−7 0.0135 0.06655 2.56 × 10−5 2.06 × 10−21 4.96 × 10−9 0.004422 1.79

(The concentration of ions is molarity, mol/L; [CaCO3] denotes concentration of calcium carbonate
precipitation)
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Fig. 1
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Fig. 2
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0.7
15℃-seawater-exp
0.6 20℃-seawater-exp
25℃-seawater-exp
15℃-seawater-cal
0.5
20℃-seawater-cal
25℃-seawater-cal
p/MPa 0.4

0.3

0.2

0.1

0.0
0.000 0.001 0.002 0.003 0.004
xCO2
Fig. 3
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0.08
15℃ 1

kGa/mol· min-1· Pa-1

0.07 2
0.06

0.05

0.04

0.03

0.02

0.01

0.00
0.08 0.16 0.24 6.0 5.5 5.0 4.5 4.0 3.5 3.0
p/MPa pH

0.08
1
kGa/mol· min-1· Pa-1

20℃
2
3
0.06 4

0.04

0.02

0.2 0.4 0.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2
p/MPa pH

0.08
1
25℃
kGa/mol· min-1· Pa-1

2
3
0.06
4

0.04

0.02

0.00
0.0 0.2 0.4 0.6 4.4 4.2 4.0 3.8 3.6 3.4
p/MPa pH

Fig. 4
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salinity-25-exp
0.6 salinity-35-exp
salinity-55-exp
0.5 salinity-65-exp
salinity-25-cal
salinity-35-cal
0.4
p/MPa salinity-55-cal
salinity-65-cal
0.3

0.2

0.1

0.0
0.000 0.001 0.002 0.003 0.004
xCO2

Fig. 5
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0.6 seawater-exp
0.4%CaO+seawater-exp
seawater-cal
0.5
0.4%CaO+seawater-cal

0.4

p/MPa 0.3

0.2

0.1

0.0

0.000 0.001 0.002 0.003 0.004 0.005

xCO2
Fig. 6
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Fig. 7
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Highlights

1. CO2 solubility in seawater was measured experimentally at different temperatures and

salinities.

2. A thermodynamic model was built to simulate CO2 solubility in seawater.

3. The kinetics of CO2 absorption in seawater was studied.

4. Seawater with CaO added can enhance greatly CO2 capture.