Вы находитесь на странице: 1из 15

Energy Conversion and Management xxx (2017) xxx–xxx

Contents lists available at ScienceDirect

Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Carbon capture and utilization for sodium bicarbonate production

assisted by solar thermal power
D. Bonaventura a,b, R. Chacartegui a,⇑, J.M. Valverde a, J.A. Becerra a, V. Verda b
University of Seville, Spain
Politecnico di Torino, Italy

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, a novel carbon capture and utilization process is proposed. It is based on using a fraction of
Available online xxxx the captured carbon dioxide to produce sodium bicarbonate, a widely used product in the chemical and
food industries. The process couples the Dry Carbonate process for carbon dioxide capture with sodium
Keywords: bicarbonate production. Raw material is trona or sodium sesquicarbonate dehydrate, which is a relatively
CO2 capture abundant mineral composed by approximately 46% sodium carbonate and 35% sodium bicarbonate by
Coal fired power plant weight. In the process, trona is firstly converted into sodium carbonate in a fluidized bed reactor operated
at 180–200 °C and 1 bar. Heat required in the fluidized bed reactor for decomposing trona can be supplied
Dry carbonate process
by renewable sources such as low/medium temperature solar energy or biomass. A fraction of the sodium
Trona carbonate generated is recirculated for carbon dioxide capture by means of the dry carbonate process.
Sodium bicarbonate The rest is converted to sodium bicarbonate in a carbonating tower through the reaction with carbon
dioxide and water. After separation of sodium bicarbonate and other salts from water, the sodium bicar-
bonate produced is suitable for direct sale. The use of renewable sources for supplying the energy
required at the sorbent regenerator and for trona decomposition yields a near-zero carbon dioxide emis-
sions global system. As case of study, carbon dioxide capture coupled to sodium bicarbonate production
has been analysed for a 15 MWel coal fired power plant. Heat required in the carbon capture process
penalizes the global system efficiency by a 10.2%, which is reduced just to the electricity parasitic con-
sumption for solids transport and carbon dioxide compression (3%) if renewable energy sources are
integrated. From an economic perspective, the penalty in electricity consumption is fully compensated
by the new by-product sales. Taking into account the reduction of electricity sales and current prices
of trona and sodium bicarbonate a return of investment is obtained in the range between 3 and 8.7 years
with an internal rate of return over 12%. These values improve the current forecast of any other carbon
capture and storage process up to date, which suggests a high interest of the proposed conceptual inte-
gration specially for regions where trona is widely available.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction (around 35 Gt/y) largely exceed the amount of CO2 used in chem-
ical processes (200 Mt/y). However, promoting CO2 utilization
A complete replacement of fossil fuels by renewable energies is routes for the production of valuable chemicals could be a starting
not feasible in the short-term. Thus, fossil fuel power plants should point to promote the deployment of CO2 capture technologies [2].
be urgently retrofitted with CO2 capture and sequestration (CCS) According to International Energy Agency (IEA) projections, the
processes as a necessary measure to limit global warming below CCS share of cumulative emissions reduction to achieve the 2 °C
2 °C [1]. CCS would allow continuing the use of fossil fuel until a target would require about 3500 large-scale CCS projects in opera-
deeper penetration of renewable energy sources into the grid is tion by 2050. Only about 15 large-scale CCS commercial projects
attained in an orderly fashion. CO2 capture and utilization (CCU) are in operation to this date of which Boundary Dam in Canada
for commercial purposes would help mitigating capture costs that is the only coal fired power plant applying CCS in the power sector.
mainly hinder the commercial deployment of state of the art CO2 Yet, it is estimated that abandoning CCS in the power sector would
capture technologies. Current anthropogenic CO2 emissions increase the investment required over 40% in the 2 °C scenario [3].
Moreover, post-combustion capture technologies have the greatest
potential for reduction of CO2 emissions in the short term because
⇑ Corresponding author.

0196-8904/Ó 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
2 D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx

CO2 IN CO2 entering the system
Components CO2 TO STORAGE CO2 to the storage system (20 °C, 75 bar)
CARBONATING TOWER CO2 capture and NaHCO3 production CO2 + STEAM CO2 and steam (220 °C)
reactor CO2 + WATER CO2 and water(95 °C)
CARBONATOR CO2 capture reactor CRUSHED TRONA crushed trona
COAL FIRED PLANT coal fired plant for electricity production FGPLANT flue gas exits the coal fired plant
COMP1 compressor CO2 (1–10 bar) FLUE flue gas exits the carbonator
COMP2 compressor CO2 (10–25 bar) FLUID OUT chemical products exits the fluidized bed reactor
COMP3 compressor CO2 (25–75 bar) HOT STEAM super heated steam (205 °C)
COOL CO2 (20 °C) intercooler HOT TRONA hot trona (125 °C) entering the fluidized bed reactor
FLUIDIZED BED fluidized bed reactor MAKE UP sorbent MAKE up
HEATEX1 H2O-flue gas heat exchanger NA2CO3 COLD (Fig. 5) regenerated Na2CO3 (80 °C)
HEATEXCH NaHCO3-Na2CO3 Heat exchanger NA2CO3 COLD (Fig. 6) cooled Na2CO3 (40 °C)
HEATEXT Trona - Na2CO3 heat exchanger NA2CO3 HOT (Fig. 5) regenerated Na2CO3 (200 °C)
HEATEXW H2O - steam + CO2 heat exchanger NA2CO3 HOT (Fig. 6) hot Na2CO3 (220 °C)
INTERC1 CO2 (20 °C) intercooler NA2CO3 IN chemical products entering the NaHCO3 production
INTERC2 CO2 (20 °C) intercooler reactor
INTERC3 CO2 (20 °C) intercooler NAHCO3 NaHCO3 produced by the system
IP/LP intermediate pressure/low pressure NAHCO3 COLD solids exits the carbonator (60 °C)
PTC parabolic trough collector technology NAHCO3 HOT solids entering the regenerator(140 °C)
REGENARATOR sorbent regenerator WATER IN (Fig. 5) water CO2 capture reactor
SEPA1 solid-gas separator WATER IN (Fig. 6) cold water (35 °C)
SEPA2 solid-gas separator WATER OUT process water

CARBOUT final product from carbonator
CO2 CO2 recovered from the system

they can be retrofitted to existing fossil fuel power plants and are [11] presents a review about the impact of uncertainty in the sor-
also applicable to other industrial processes. bent thermo-physical properties on the design and operation of
Up to date the only post-combustion capture technology com- components and processes involved in CO2 capture.
mercially available at the necessarily large-scale of coal fired CO2 capture processes using dry solid sorbents capable of cap-
power plants is based on chemical absorption by amines dissolved turing CO2 from flue gas streams by physical adsorption show
in water. In this post-combustion capture system, the exhaust potential advantages compared with conventional CO2 capture
gases stream from the power plant is passed through an absorber systems using aqueous amine solvents [12]. Thus, a variety of
column where it comes into contact with the liquid amine flowing promising adsorbents such as activated carbonaceous materials,
downwards, which allows CO2 to be chemically absorbed by the microporous/mesoporous silica or zeolites, carbonates, and poly-
amine. The CO2 rich amine solvent is then pumped to a regenera- meric resins have been proposed in the recent literature [12]. As
tor, where heat is supplied to reverse the chemical reaction and a common feature, these solid sorbents require very small amounts
release relatively pure CO2 for its compression, transport and stor- of heat for regeneration although their capture capacity is gener-
age while the CO2 lean liquid amine is pumped back into the absor- ally low. Ref. [13] proposes the use of power plant’s waste heat
ber to be reused [4]. Although temperatures for CO2 desorption are for CO2 capture by nanomaterials porperly designed to overcome
not high (130 °C) sorbent regeneration in this process requires a the competitive adsorption of CO2 and H2O.
relatively high amount of energy to heat the large volume of water The Calcium-Looping process is a promising 2nd generation
where amines are dissolved. Thus, the energy required per ton of post-combustion process validated at the pilot level (1–2 MWth)
CO2 captured is about 3.3 GJ/tonCO2 for an advanced that uses Calcium Oxide (CaO) derived from cheap (10 €/ton)
monoethanolamines (MEA) system whereas 3.9 GJ/tonCO2 are and abundant natural limestone to capture CO2 from flue gas.
required for a typical aqueous MEA system [5]. On the other hand, The process is based on the reversible carbonation/calcination
post-combustion capture by MEA suffers from other serious issues chemical reaction at high temperatures [14]:
related to toxicity, corrosion and degradation [6]. Furthermore,
amines have a relatively high cost (>1000 €/ton), which is a major kJ
CaOðsÞ þ CO2ðgÞ ¡CaCO3ðsÞ DH298K ¼ 178 ð1Þ
problem taking into account the large scale of commercial CCS mol
applications [7]. Carbonation proceeds at a satisfactory fast rate at temperatures
Thus, there is a need to develop novel post-combustion capture in the range 625–680 °C while the reverse calcination reaction
processes using cheap, widely available and non-toxic materials at should be carried out at 900–950 °C under high CO2 partial pres-
reduced cost and energy penalty. In this line, novel amine-based sure [14]. The dry sorbent is repeatedly cycled between two reac-
solid sorbents based on direct steam stripping desorption have tors. In one reactor (carbonator) carbonation of CaO particles
shown an improved performance [8]. In Ref. [9] an organic solvent serves to capture CO2 from the flue gas. The carbonated particles
was added to a CO2 rich, aqueous ammonia/CO2 solution under are then circulated into another reactor (calciner) where sorbent
room temperature and pressure conditions. The sorbent was regeneration takes place by calcination. To close the cycle, the
regenerated by using low-temperature heat, with a reduced ther- regenerated CaO particles are returned back into the carbonator,
mal energy requirement. In Ref. [10] novel absorbents were stud- leaving a concentrated stream of CO2 in the calciner ready for com-
ied using both single and mixed amine-based absorbents. Ref. pression, transport and sequestration. However, a main drawback

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx 3

of this process is the progressive deactivation of the CaO particles standard equipment and materials of construction; (iv) more
mainly due to marked sintering in the high temperature calcina- stable and cheaper sorbent than amines.
tion stage, which requires a large make-up of fresh limestone thus Reaction (2) is also at the basis of the Solvay process to produce
increasing the energy penalty of the process taking into account sodium bicarbonate (NaHCO3 also known as baking soda) through
the high temperatures at which it must be carried out to enhance the reaction of calcium carbonate, sodium chloride, ammonia, and
the reaction kinetics. carbon dioxide in water. In this process (Solvay), the initial reaction
Concerning the penalty imposed by the capture system, Ref. of CO2 with an aqueous solution of sodium hydroxide (NaOH) to
[15] examines potential design routes for the capture, transport produce sodium carbonate (Na2CO3) is:
and storage of CO2 in UK coal-fired power stations Around 90% of
CO2 þ 2NaOH ! Na2 CO3 þ H2 O ð3Þ
operational carbon emissions could be captured with an energy
penalty between 14 and 30% and rises by 27–142% of electricity Further addition of CO2 yields NaHCO3 through reaction (2),
cost [16]. However, CO2 capture system integration, with an ade- which at sufficiently high concentration precipitates out of the
quate heat and work integration would result in significant energy solution. Sodium hydroxide (NaOH) is mainly produced from elec-
savings [17]. The CO2 capture installation requires large amounts trolysis (2NaCl(aq) + 2H2O(l) ? H2(g) + Cl2(g) + 2NaOH(aq),
of heat for solvent regeneration in appropriate quantity and qual- DH298K = 422 kJ/mol) [27]. This involves a certain amount of waste
ity, a cooling system to discharge waste heat and additional power energy to produce NaHCO3. NaHCO3 can be also produced com-
to drive CO2 compressor and auxiliary equipment (pump, fans). In mercially using the Na2CO3 obtained from trona, a naturally occur-
[18] the steam for Carbon Capture and Utilization (CCU) is ring mineral, which is dissolved in water and treated with CO2 [28].
extracted from IP/LP crossover pipe showing the high impact of This process avoids the use of electrolysis for NaOH production, but
the design IP/LP crossover pressure on the power unit efficiency. a small amount of energy is still required for trona dissociation
Integration with solar could by a driving factor to favor CO2 cap- (133.9 kJ/mol).
ture implementation at the commercial scale. Ref. [19] studies flex- In this manuscript a novel CCU concept is introduced, which
ible operation of solvent-based capture for three types of plants combines the production of NaHCO3 with the dry carbonation pro-
obtaining the highest revenue to electricity ratio in the case where cess for CO2 capture and sorbent regeneration is assisted by renew-
solar repowering was used for power boosting. Ref. [20] analyses able energy sources (solar thermal power or biomass). The
the use of solar energy to provide the energy of the capture system. structure of the manuscript is the following. First, the current state
A CaL based capture system assisted by solar energy is assessed in of the art technology for sodium bicarbonate production from
[20] for reducing the global system efficiency penalty. trona decomposition is described. Then the concept of CO2 capture
Following this line, CCS feasibility could be fostered by integra- and sodium bicarbonate production for CO2 fixation in a valuable
tion of the capture system with other processes and valuable chemical product is described. Na2CO3, CO2 and H2O are obtained
chemicals. Ref. [21] suggests a method for combining CCS and bio- from trona decomposition. These three components, together with
fuel production using CO2 as a feedstock. [22]. A significant part of a relevant fraction of CO2 from the capture system are used for
the cost for CCS is related to the compression of the captured CO2, sodium bicarbonate production. The integration scheme is applied
however the conditions for CCU can reduce the parasitic energy to a small 15 MWel coal power plant or, equivalently, to a fraction
consumption. Ref. [23] addresses the critical technologies in CO2 of the flue gas from a bigger size plant.
capture, transport, utilization and storage and proposes technical The novel concept of this manuscript consists of the synergistic
priorities by evaluating critical indexes such as the objective con- combination of the dry carbonate process with sodium bicarbonate
tribution rate and technical maturity. production starting from a raw natural material such as trona. This
Among the carbon capture technologies in a research and devel- study shows that the penalty imposed by the capture system can
opment (R&D) phase [24], one of the most promising CO2 capture be mitigated from the production of a valuable material such as
processes is the dry carbonate process, which uses sodium carbon- sodium bicarbonate with an economic return. The results obtained
ate (Na2CO3), also known as soda ash, as sorbent to separate CO2 in this preliminary analysis demonstrate the environmental and
from others flue gases producing sodium bicarbonate (NaHCO3). economic interest of the proposed concept
The process is based on the reversible chemical reaction [25]:

kJ 2. Trona mineral
Na2 CO3ðsÞ þ CO2ðgÞ þ H2 OðgÞ ¡2NaHCO3 DH ¼ 129:1 ð2Þ
Trona consists mainly of sesquicarbonate sodium (systematic
Equal molar quantities of CO2 and H2O are produced during sor-
name is trisodium hydrogendicarbonate) having the chemical
bent regeneration, and pure CO2 suitable for use or sequestration is
available after condensation of the H2O. In contrast with the
Calcium-Looping process, the carbonation reaction in the dry car- Na2 CO3  NaHCO3  2H2 O ð4Þ
bonate process takes place efficiently at relatively low tempera-
As specified in Table 1, natural trona is composed of approxi-
tures (60–70 °C), which is below the typical stack flue gas
mately 46% Na2CO3 and 35% NaHCO3 being relatively abundant
temperature. At these temperatures, the capture efficiency can be
in nature and widely distributed around the world [29]. Among
as large as 90%. Moreover, the required sorbent regeneration tem-
other places it is found in Wyoming [30,31], Tanzania [32], Namib
perature is not high (120–200 °C) allowing the use of medium tem-
perature heat sources. Na2CO3 is an abundant and relatively cheap
(100 €/ton) natural mineral lacking serious problems of degrada- Table 1
tion, toxicity or corrosiveness at the working temperatures of the Natural trona composition [38].
process [26]. Component Wt%
The research triangle institute (RTI) has designed and con-
Na2CO3 46.53
structed a Dry Carbonate based prototype unit showing a number NaHCO3 34.82
of potential advantages over MEA systems such as [26]: (i) lower Na2SO4 0.568
total regeneration energy requirement; (ii) less energy require- Insolubles 2.98
ment also to operate due to lower pressure drop; (iii) Modest tem- Hydration water 14.92
Others 0.182
peratures of operation and noncorrosive reactants allowing

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
4 D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx

[33], Turkey [34], and China [35]. Calcination and dehydration of tower and transferred to another centrifuge, where the excess
raw trona in industrial processes are applied for different purposes solution (filtrate) is filtered out. The crystals are then washed in
[36]: to eliminate carbonate for reducing acid consumption if an a bicarbonate solution, forming a cake-like substance ready for
acidic treatment is to be applied, to decrease the weight of the drying. The filtrate removed from the centrifuge is recycled to
material for reducing transportation costs in the case that it the rotary dissolver, where it is used to saturate more intermediate
involves hydration in large quantities, or as a necessary step in a soda ash crystals. The washed filter cake is then dried on either a
chemical process such as the production of Na2CO3, which is the continuous belt conveyor or in a vertical tube drier [44].
main focus of the current manuscript. Trona decomposition and Na2CO3 carbonation involve several
In the production of Na2CO3 from trona, the monohydrate pro- reactions. Dissociation reactions of trona and NaHCO3 are:
cess is the most commonly used method [36]. The first step of this
2ðNa2 CO3  NaHCO3  2H2 OÞðsÞ ¡3Na2 CO3ðsÞ þ CO2ðgÞ
method is thermal decomposition of the mineral, which yields
Na2CO3 via the following reaction [37]: þ 5 H2 OðgÞ ¡3Naþ þ CO 
3 þ HCO3 þ 2H2 O ð7Þ

2ðNa2 CO3  NaHCO3  2H2 OÞðsÞ ! 3Na2 CO3ðsÞ þ CO2ðgÞ þ 5 H2 OðgÞ

NaHCO3 ¡Naþ þ HCO3 ð8Þ
In the process, a number of other salts can be also formed such
as sodium carbonate decahydrate (Na2CO310H2O), sodium car-
DH298K ¼ 133:9 bonate heptahydrate (Na2CO310H2O), sodium carbonate monohy-
drate (Na2CO310H2O) and Wegsheider’s salt (Na2CO33NaHCO3).
Trona-phase equilibrium diagrams for low and high tempera- Thus, other possible reactions are:
ture regions have been analysed in detail in [39]. Trona is stable
at temperatures up to 57 °C under dry conditions. Intermediate
Na2 CO3  10H2 O¡2Naþ þ CO3 þ 10 H2 O ð9Þ
salts such as wegschiderite (Na2CO33NaHCO3) and sodium mono-
hydrate (Na2CO3H2O) are produced between 57 °C and 160 °C Na2 CO3  7H2 O¡2Naþ þ CO3 þ 7H2 O ð10Þ
[40]. Above 160 °C, trona decomposes into Na2CO3 and NaHCO3.
NaHCO3 decomposes to Na2CO3, H2O and CO2 in the temperature Na2 CO3  H2 O¡2Naþ þ CO3 þ H2 O ð11Þ
range of 100–200 °C [41]. Reaction kinetics is fast at 200 °C [42]:
Na2 CO3  3NaHCO3 ¡5Naþ þ CO 
3 þ 3HCO3 ð12Þ
2NaHCO3 ! Na2 CO3 þ H2 O þ CO2 ð6Þ
Thus, the final decomposition of trona generates Na2CO3, CO2 2ðNa2 CO3  NaHCO3  2H2 OÞ¡3Naþ þ CO 
3 þ HCO3 þ 2H2 O ð13Þ
and H2O.
NaHCO3 ¡Naþ þ HCO3 ð14Þ
3. Sodium bicarbonate production To model the dependence of the equilibrium constants (Ks) for
the dissociation reactions of the different salts involved in NaHCO3
The novel concept presented in this manuscript combines CO2 production a polynomial equation has been used:
capture and production of NaHCO3 at low temperature using for
both processes natural trona as raw material. CO2 capture is real- ln K s ¼ A þ þ C lnðTÞ þ D T ð15Þ
ized via the reaction expressed by Eq. (2). This section briefly
reviews NaHCO3 production from raw trona as currently applied which provides a good fit to experimental curves shown in [39]
in industry and the reactions involved that will be used in this (R2 > 0.99). Best fittings parameters are given in Table 2.
work. For example, at 200 °C, it is Ks > 1 for the NaHCO3 dissociation
In the NaHCO3 production process, crushed raw trona is fed into reaction and hence the reaction is shifted to dissociation while
a vertical hollow tubular vessel with a perforated bottom that sep- for Na2CO3 dissociation it is Ks < 1 indicating that Na2CO3 dissoci-
arates an upper fluidizing chamber from a lower plenum chamber. ation is not thermodynamically favored at this temperature.
A gas stream is introduced into the plenum chamber through the Equilibrium between carbonate and bicarbonate ions in the aque-
perforated bottom to fluidize crushed trona. Part of the charge ous solution determines the stable solid phase in a saturated solu-
remains in suspension while the decomposition gases such as tion and the corresponding solubility concentrations of carbonate
H2O and CO2 are redirected to the carbonator for NaHCO3 produc- and bicarbonate. This equilibrium is strongly affected by the CO2
tion. The fluidized bed reactor acts both as a calciner for the partial pressure. At T < 80 °C (KsNaHCO3 < 1) and ambient CO2 partial
crushed trona and as a separator to remove fine particles of pressure, solid bicarbonate (nahcolite) is the thermodynamically
crushed trona from the coarse portion of the charge remaining in stable solid [45]. Equilibrium between the dissolved bicarbonate
fluid suspension in the fluidized bed reactor. Thus, fine particles and dissolved carbonate establishes itself by sorption of CO2.
of crushed trona become entrained in the effluent gas and exit
the fluidized bed before they become calcined. The thermal energy 4. Integration of sodium bicarbonate production and carbon
required to achieve the conversion of crude trona to Na2CO3 is sup- dioxide capture
plied by heating the fluidizing gas or by placing heating means
within or around the bed in order to attain a temperature of In this section a novel concept of integration of the NaHCO3 pro-
125–225 °C [43]. The intermediate Na2CO3 solution evolves by cen- duction process above described and the dry carbonate CO2 cap-
trifuge to separate the crystals. They are then dissolved in a soda ture process is presented. The integration is originally conceived
ash solution in a rotary dissolver, to obtain a saturated solution. for its application in a coal fired power plant (CFPP), which is retro-
The saturated solution is filtered to remove non-soluble materials fitted with the dry carbonate process using Na2CO3 for CO2 capture,
and is pumped through a feed tank to the top of a carbonating although it can be used in other industrial applications with CO2
tower. Purified CO2 is introduced into the bottom of the tower emissions. The flow diagram of this integration is shown in
and held under pressure. As the saturated sodium solution moves Fig. 1. Part of the Na2CO3 produced by trona calcination is used
through the tower, it cools down and reacts with CO2 to form as sorbent make-up in the CO2 capture process while a
NaHCO3 crystals. These crystals are collected at the bottom of the fraction of the CO2 released from sorbent regeneration, together

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx 5

Table 2
Best fitting parameters used in the model for the equilibrium constant Ks (Eq. (15)) of the reactions involved in NaHCO3 production from raw trona.

Reactions A B C D

CO2 þ 2H2 O¡H3 O þ HCO

231.47 12092.7 36.78 0
3 þ H2 O¡H3 O þ CO3
 216.05 1243.7 35.48 0
NaHCO3 ¡Naþ þ HCO 3
63.26 1308.41 13.48 0.034
Na2 CO3 ¡2Naþ þ CO 3
548.32 18070.74 94.75 0.165
Na2 CO3  H2 O¡2Naþ þ CO 3 þ H2 O
281.77 9970.6 44.56 0.0221
Na2 CO3  7H2 O¡2Naþ þ CO 3 þ 7H2 O
484.91 18935 80.12 0.114
Na2 CO3  10H2 O¡2Naþ þ CO 3 þ 10 H2 O
1165.01 37.81 200.08 0.335
2ðNa2 CO3  NaHCO3  2H2 OÞ¡3Naþ þ CO 3 þ HCO
3 þ 2H2 O
277.24 14523.8 41.0 0.0085
Na2 CO3  3NaHCO3 ¡5Naþ þ CO 3 þ 3HCO3
 1209.46 29113.05 213.72 0.363

Fig. 1. Flow diagram of the research triangle institute (RTI) dry carbonate process for CO2 capture coupled to NaHCO3 production using raw trona and assisted by medium
temperature solar thermal power.

with the fraction of CO2 derived from trona dissociation pressure, which poses a technological challenge for CO2 capture
(0.5 molCO2/moltrona), is utilized to produce in the carbonating For the 15 MWel generated in the pulverized coal-fired (PC) power
tower NaHCO3 suitable for sale. As Fig. 1 shows H2O is used in plant used in this study, the exhaust gases flow rate is 830 m3 per
the calciner for trona decomposition and carbonation of the flue minute with a CO2 concentration between 10% and 15% in volume
gas stream. H2O is generated in the carbonating tower during [46]. Assuming standard performance of equipment, the pulverized
NaHCO3 production and in the NaHCO3 regenerator. An optimized coal-fired boiler combusts 6.1 tons per hour (tph) of coal and gen-
integration would recirculate these hot water streams between erates 44.7 MWth (HHV). The boiler output provides 39.7 MWth,
these systems, regenerator to carbonator in the CCS system, and which yields a boiler efficiency of 88.6%. Since the present work
from the carbonating tower to the calciner in the NaHCO3 produc- is focused on the postcombustion system analysis and given the
tion system. Calcination of trona and sorbent regeneration are complexity and proprietary nature of power plant steam turbine
assisted by medium temperature heat, which could be available cycles, a general 42% thermal to electric steam cycle efficiency is
from renewable sources such as solar thermal or biomass. If these assumed [47], which leads to 16.67 MWel generated. In addition,
renewable sources are used, the global system (power plant plus a 10% in-house power plant electricity is consumed resulting in a
capture of CO2, part of which is stored and the rest used for net electrical generation of 15 MWel delivered to the grid.
NaHCO3 production) becomes a near zero CO2 emissions system. The relatively small size of the reference CFPP (15 MWel) has
Fig. 2 illustrates a Sankey diagram where the different routes been chosen with the purpose of storing the captured CO2 in tanks
followed by the CO2 are detailed. of reasonable volume to be ready for utilization. This size can be
As Fig. 2 shows an amount of about 35% of CO2 produced by the representative of small coal power plants or for dealing with a frac-
CFPP is employed for NaHCO3 production while the rest is sent to tion of the exhaust gases of bigger plants. Main data for a plant of
the compression system and could be stored or eventually utilized this reference CFPP are shown in Table 3. Composition of the flue
for others purposes. gas from the plant used for the analysis is detailed in Table 4.
The use of the dry carbonate process in a CFPP for CO2 capture is
described in [26]. An optimized integration with solar thermal
5. Reference power plant energy is schematized in Fig. 3. Alternatively, the heat source could
be either biomass or coal. Overall, the dry carbonate process yields
This section describes the main characteristics of the CFPP used a CO2 removal efficiency of 92% (assuming a fixed value for Na2CO3
in this work as reference case. CFPP flue gases are characterized by conversion to NaHCO3 of X = 0.75) and utilizes 43 ton/h of Na2CO3
a dilute concentration of CO2 at large volumetric flow and ambient as CO2 sorbent to remove 12.5 t/h of CO2 in a continuous cycle. A

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
6 D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx

Fig. 2. Sankey diagram of CO2 routes in the overall process.

Table 3 heat exchanger (HEATEX1) between the flue gas leaving the power
Power consumption for the reference CFPP [46]. coal plant and the flow exiting the carbonator is used for cooling
Item Magnitude Unit the flue gas. Another heat exchanger (HEATEXCH) is interposed
Coal consumption 6.1 t/h
between the incoming and the outgoing flow in the regenerator.
Air in 69.2 t/h Both heat exchangers serve to increase significantly the total effi-
Gross power introduced 44.7 MWth ciency of the plant. They allow to reduce the heat required for sor-
Net power introduced 39.7 MWth bent regeneration by about 10% with a thermal flow exchanged of
Net power produced 15 MWel
1.45 MWth (0.8 MWth + 0.65 MWth). This makes possible working
Net efficiency 33.5 %
with different operating conditions in the regenerator (200 °C in
the best case scenario and 140 °C with solar radiation support).
With this configuration the heat requirement, in the case the work-
Table 4
Flue gas flow composition from the reference CFPP [46]. ing condition in the regenerator are set equal to T = 200 °C and
p = 1,01 bar, is about 11.4 MWth (the theoretical value for the heat
Coal flue gas component Mole flow (kmol/h) Mass flow (t/h)
required using DH ¼ 129:09 mol
at T = 298 K is 10.25 MWth).
N2 1715.42 52.97
The Na2CO3 make-up flow rate is 0.3 ton/h, the heat required for
CO2 308.56 13.60
H2O 147.19 2.94 Na2CO3 regeneration is around 11.4 MWth and the power con-
O2 78.18 2.76 sumption for CO2 compression and solid conveying is 1.58 MWel
CO 14.07 0.39 (Table 5). Power demand for solid separation in two stages cen-
NO 13.54 0.45
trifugation can be estimated as 0.3 MWel by taking as reference
SO2 3.75 0.26

Fig. 3. Integration of the RTI dry carbonate process into a CFPP for CO2 capture [48].

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx 7

Table 5 and 1 bar using solar thermal power as heat source. A schematic
Power consumption for a 15 MWel CFPP with integrated RTI dry carbonate process for layout of the process is shown in Fig. 4. For the temperatures
CO2 capture.
needed in this application, medium temperature parabolic troughs
Power production Power consumption collectors coupled with a thermal energy storage system (i.e. with
CFFP 15 MWel 44.7 MWth pressurized water tanks), are suitable to provide the necessary
Regenerator 11.4 MWth energy input.
COMP 1.33 MWel As seen in Fig. 4, the stream of trona (CRUSHED TRONA), ini-
Wsolid 0.25 MWel
Centrifugation 0.3 MWel
tially at 25 °C and 1 bar, passes, before entering the fluidized bed
Net Power 13.12 MWel reactor, through a solid–solid heat exchanger (HEATEXT) where it
Total heat requirement 56.1 MWth exchanges heat with the effluent Na2CO3 stream from the fluidized
bed reactor (Na2CO3 HOT), which raises trona temperature up to
127 °C. Another heat exchanger (HEATEXW) transfers heat from
a high efficiency centrifuge used as salt separator. Thus, the total the gases and water vapor stream (CO2 + STEAM) exiting the flu-
efficiency of the CFPP retrofitted with the dry carbonate process idized bed reactor to the water stream (WATER IN) entering the
drops from 33.5% to 24% due to the penalty in power and addi- fluidized bed, which raises up its temperature to 205 °C. The total
tional heat required. If medium temperature solar thermal energy heat recovered by means of these heat exchangers amounts is 1.85
is used as energy input for sorbent regeneration, and taking thus MWth as detailed in Table 6. Flow rates of the streams entering and
into account only the penalty in power consumption, the economic exiting the fluidized bed reactor are summarized in Table 7.
efficiency, defined in basis of the operation costs including fuel, The heat required in the fludized bed reactor for decomposing
decreases just to about 30%. 19.2 t/h of trona is 5.1 MWth at 220° (the theoretical value to
To achieve a near zero CO2 emissions global system, renewable decompose 85 kmol/h of trona at T = 25 °C is 3.15 MWth from the
energy must be used for heating the calciner, either solar or bio- reaction enthalpy DH298K ¼ 133:9 mol kJ
[28]. Such amount of heat,
mass. In the case of solar, and to take into account its discontinu- which can be provided by medium temperature solar thermal
ous availability, different options for heat storage can be power, warrants the production of 13.55 t/h of Na2CO3 (Na2CO3
considered such as: (i) heat storage using tanks with pressurized COLD in Fig. 4) plus 1.85 ton/h of CO2 and 4 t/h of water
water/steam. For instance a thermal storage of about 3 h of steam (CO2 + STEAM) of which 300 kg/h are used as makeup in the dry
can be obtained with the support of three tanks of 350 m3; (ii) mol- carbonate process for CO2 capture (MAKE UP) while the rest is sent
ten salts tanks; (iii) synthetic oils; (iv) a combination with a bio- to a carbonating tower (Na2CO3 IN) to produce sodium bicarbonate
mass boiler for supporting heat requirements of the post- (NAHCO3) using a 3.75 t/h stream of pure CO2 from the carbon cap-
combustion system. ture system (CO2 IN) and the CO2 and water streams released from
Regarding the required CO2 storage volume, a total flow rate of the fluidized bed reactor (CO2 + STEAM). From the Na2CO3 carbon-
68,000 m3/h in the carbonator must be processed. Assuming a res- ation reaction (Eq. (2)) it turns out that 20.75 t/h of NaHCO3 are
idence time of 15 s, a total storage volume of 270 m3 would be suf- produced at a total flow rate of about 9.5 m3/h. In this way, a com-
ficient for the carbonator working at low pressure. This can be mercial chemical product is produced using captured CO2 from the
achieved in practice using a CO2 storage tank of 6 m in diameter power plant with a higher economic value than the raw mineral.
and 10 m high, which is affordable with current technologies. For
greater power a sequence of standardized tanks could be used.
7. Overall system efficiency
6. Sodium carbonate and sodium bicarbonate production from
trona The CFPP efficiency is reduced due to the heat needed for the
production of NaHCO3, albeit an economic revenue is obtained.
This section analyses production of Na2CO3 and NaHCO3 from Considering the 5.1 MWth needed in the fluidized bed reactor,
trona decomposition in a fluidized bed reactor working at 220 °C the total heat requirement is 61.2 MWth (Table 8).

Fig. 4. Na2CO3 and NaHCO3 production from trona assisted by solar energy.

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
8 D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx

Table 6
Heat exchanged in NaHCO3 production according to Fig. 4.

MWth Tincold (°C) Touthot (°C) Tinhot (°C) Toutcold (°C)

HEATEXT 1.15 20 95 219 205
HEATEXW 0.7 20 40 219 127
Total Thermal Power 1.85

Table 7
Flow rates of streams entering and exiting the fluidized bed reactor in the NaHCO3 production according to Fig. 4.


TRONA kmol/h 83.75 0 0
WATER kmol/h 0 85 307.5
CO2 kmol/h 0 0 42.5
NaHCO3 kmol/h 1.25 0 0
Na2CO3 kmol/h 0 0 127.5
Na2CO310H2O kmol/h 1.25 0 0
Temperature °C 127 204 219
Pressure bar 1.01 1.01 1.01
Vapor fraction 0 1 0.733
Solid fraction 1 0 0.267
Mass density kg/m3 2029 0.454 1.46
Average molecular weight 224 18.015 43.81

Table 8 8. Economic analysis

Heat requirement in different components for the production of NaHCO3.

T (° C) Thermal power consumption For the economic analysis of the integrated process different
CFFP 850 44.7 MWth scenarios are defined to analyse the competitiveness of the tech-
Regenerator 200 11.4 MWth nology [49]. These scenarios are defined in terms of:
Fluidized bed reactor 220 5.1 MWel
Total heat requirement 61.2 MWth – NaHCO3 production, to take into account the variability of
demand in the market.
– Variation of trona costs, taking into account trona cost
By avoiding storage of part of the CO2 captured for half a day variability.
(considering 12 h of daylight) the total power consumption for – Variation of NaHCO3 sale prices on the market.
compression decreases to 0.879 MWel (Table 9). – Different plant installation costs. To consider uncertainty in
For the reference CFPP with integrated CO2 capture, and consid- equipment cost evolution a maximum deviation has been con-
ering a power consumption of 0.247 MWel for solids conveying sidered for the scenario. The variation range was taken as ±9% of
and 0.3 MW for centrifuge stages, the global efficiency penalty is the average installation price.
10.2 % over the baseline plant and the mean global electricity pro-
duction is decreased by 9%. It results in a net efficiency of the global Attending to these criteria three scenarios are considered:
plant of 23%: Scenario P (Pessimistic Scenario): it takes into consideration a
combination of diverse factors such as the highest penalty in elec-
tricity generation (it has been taken as the maximum error in esti-
13:123MW el  12h þ 13:574MW el  12h mating parasitic electricity losses), the highest plant installation
gNET ¼ ¼ 0:23 ð16Þ costs, the highest cost of trona, and lowest sale price of NaHCO3
56:1MW th  12h þ 61:2MW th  12h
in the market.
Scenario BE (Best Estimation Scenario): In this scenario the val-
ues derived from the simulation above described were used to
13:123MW el  12h þ 13:574MW el  12h define the efficiency of the system. It considers a capital cost of
gNET el ¼ ¼ 0:89 ð17Þ
15MW el  24h 3 M€ for the CCS technology [28]. This scenario uses current values
of trona cost and NaHCO3 sale price in the market.
If the low temperature heat required in the calciner and regen-
Scenario O (Optimistic Scenario): this optimistic scenario
erator is provided from renewables a near zero emissions system is
implies minor trona and plant installation costs.
obtained. By using solar energy for heating, the penalty on the orig-
Considering that the price of trona is in the range 80–120 $/ton
inal plant economic efficiency amounts to only 3%, which is associ-
[50] and that the sale price of NaHCO3 is around 200–240 $/ton, the
ated to the parasitic power consumption of the post-combustion
economic profit for production of NaHCO3 can be calculated as:
_ NaHCO3  ptrona  m
EP ¼ pNaHCO3  m _ trona ð18Þ
Table 9 Here EP is the economic profit derived from NaHCO3 production,
Compression power for NaHCO3 production.
pNaHCO3 and ptrona are the selling price of NaHCO3 and purchase
Component Wcomp (MWel) price of trona, respectively, and m _ trona are the NaHCO3
_ NaHCO3 and m
Compressor 1 (4.2 bar) 0.295 and trona mass flow rates, respectively. Table 10 shows the prices
Compressor 2 (17.5 bar) 0.289 calculated for the different scenarios considered.
Compressor 3 (75 bar) 0.295 The investment cost of the solar technology is in the range
Total Wcomp (from 1 to 75 bar) 0.879
2.5–3.5 M€/MWth for a parabolic trough collectors (PTC) plant with

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx 9

Table 10 the time value of money, inflation, project lifetime or operation.

Different prices for different scenarios. For this reason, it is important to evaluate internal rate of return
Units Scen. P Scen. BE Scen. O (IRR), which can be evaluated from the definition of net present
ptrona €/ton 120 100 80 value (NPV). NPV is the sum of the discounted cash flow minus
pNaHCO3 €/ton 200 220 240 the total investment cost:
DGain €/ton 80 120 160
EGAIN €/day 22,000 32,000 44,000 X
NPV ¼  ETOT ð20Þ
k¼0 ðIR þ 1Þk

thermal energy storage [51]. For a PTC solar plant integrated with where k represents the year number, N is the total number of years,
an organic Rankine cycle [52] the costs of solar field and storage and IR is the discount rate. Assuming different values of the dis-
system were estimated as 213 €/m2 and 20.1 $/kW ht respectively. count rate the NPV has been calculated for the different scenarios
The fluidized bed reactor cost can be estimated in 0.25 M€/MWth and as function of the solar thermal technology cost. Figs. 6–8 show
with an error margin of ±25% [53]. Operation & maintenance costs the NPV calculated curves as a function of the discount rate and for
are taken as 10% of the baseline cost. The costs of other compo- different solar thermal technology costs for a life plant of 20 years.
nents of the solar field are estimated as 15% of the solar capital It can be seen how consistent revenues from the sale of NaHCO3 are
expenditures. Table 11 summarizes the investment costs of the obtained for realistic values of the discount rate (IR = 0.08–0.12) in
plant for the different scenarios considered and according to differ- all the Scenarios.
ent prices of the solar thermal technology. The total investment The internal rate of return (IRR) is the discount rate at which
cost (ETOT) takes into account the cost of solar technology (ESOLAR), NPV is equal to zero or, in other words, the rate at which an invest-
the cost of the fluidized bed reactor used for trona conversion ment breaks even. It can be seen in Figs. 6 and 7 that high values of
(EFLUID), the cost of reactors for dry carbonate process (EDRY) and internal rate of return (IRR > 0.12) are obtained, while for the pes-
the cost of operation & maintenance (EO&M). simistic scenario the value of IRR = 0.12 is reached for a solar ther-
As can be seen in Table 11 the total investment costs are highly mal cost of 3 M€/MW. Considering a lifetime of the plant of
dependent on solar installation costs. Total investment of the CCU 20 years the investment would be always of interest having cur-
system varies from 15.3 M€ to 37.15 M€ and is strongly affected by rent ordinary IR values of 0.08–0.1. Moreover, considering an IR
the solar technology cost. Table 12 shows the total investment of 0.1 higher values of NPV are obtained. Also considering a solar
costs and estimated annual profit for different scenarios and differ- technology cost of 3.5 M€/MWth, it results a NPV value of
ent solar technology costs. 31.6 M€ with an investment cost of 67 M€ referred to the best esti-
Using these data, the CCU investment’s simple payback period mate scenario. These values have been obtained assuming a con-
(SPB) can be evaluated. SPB is the time for recovering the initial stant production for sale of NaHCO3. Fig. 9 shows NPV values as a
investment, which is given by: function of the produced NaHCO3 for the Best Estimate Scenario
and using a fixed discount rate value (IR = 0.1).
SPB ¼ ð19Þ As shown in Fig. 9 a minimum production of sodium bicarbon-
ate per month is needed to ensure the return of the investment
Fig. 5 shows estimated SPB values for the different scenarios as cost (NPV = 0). In the worst case, which comprises the maximum
a function of solar thermal technology investment cost and for a
constant production of 7470 ton/month of NaHCO3.
Table 12
Fig. 5 shows that relatively short SPB periods are obtained. In
Total investment costs and yearly revenue for scenarios of analysis.
the worst case (Pessimistic Scenario) the SPB period is equal to
8.7 years while in the best case it amounts to only 3 years (Opti- Total investment Scenario P Scenario BE Scenario O
mistic Scenario). These values suggest a high interest of the inte- Solar thermal cost 2.5 M€/MW 51.34 M€ 48.83 M€ 46.87 M€
gration proposed in this paper, combining the dry carbonate CO2 Solar thermal cost 3 M€/MW 60.69 M€ 57.90 M€ 55.78 M€
capture and sodium bicarbonate production using trona as raw Solar thermal cost 3.5 M€/MW 70.04 M€ 66.98 M€ 64.69 M€
Annual economic profit 8.08 M€ 11.58 M€ 15.08 M€
material where it is available. However, the SPB does not address

Table 11
Total investment cost: NaHCO3 production + solar thermal.

Units Scen. P Scen. BE Scen. O

Solar thermal 2.5 M€/MW
ESOLAR (FLUID+DECARB) M€ 42.5 41.25 40.5
EDRY M€ 4 3 2
EFLUID M€ 1.9 1.5 1.15
EO&M M€ 4.84 4.58 4.37
ETOT M€ 51.34 48.83 46.87
Solar thermal 3 M€/MW
ESOLAR (FLUID+DECARB) M€ 51 49.5 48.6
EDRY M€ 4 3 2
EFLUID M€ 1.9 1.5 1.15
EO&M M€ 5.69 5.4 5.18
ETOT M€ 60.69 57.9 55.78
Solar thermal 3.5 M€/MW
ESOLAR (FLUID+DECARB) M€ 59.5 57.75 56.7
EDRY M€ 4 3 2
EFLUID M€ 1.9 1.5 1.15
EO&M M€ 6.54 6.23 5.98
ETOT M€ 70.04 66.98 64.68

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
10 D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx


Simple Pay Back Period

2 .5 3 3 .5
Solar Thermal Cost [M€/MW]
Fig. 5. SPB as a function of solar thermal technology costs for the different scenarios analysed.


65.00 SOLAR COST = 2500 €/KW
NPV(20 YEARS) [M€]

SOLAR COST = 3000 €/KW

55.00 SOLAR COST = 3500 €/KW




0.075 0.08 0.085 0.09 0.095 0.1 0.105 0.11 0.115 0.12 0.125
Fig. 6. Best Estimate Scenario: NPV in 20 years as function of internal rate value and solar thermal technology costs.


100.00 SOLAR COST = 2500 €/KW
NPV(20 YEARS) [M€]

SOLAR COST = 3000 €/KW

SOLAR COST = 3500 €/KW




0.075 0.08 0.085 0.09 0.095 0.1 0.105 0.11 0.115 0.12 0.125

Fig. 7. Optimistic Scenario: NPV in 20 years as function of internal rate value and solar thermal technology costs.

cost of solar thermal technology, at least 5080 ton/month (68%) of result in additional cost savings that would increase the interest
sodium bicarbonate must be produced to cover the investment of the investment. Table 13 summarizes the data used for calculat-
with a discount rate of IR = 0.1. On the other extreme, for the best ing the costs according to the different scenarios for a total amount
case (a minimum cost of solar thermal technology), a production of of 108.9 kton/year avoided CO2 emissions using the dry carbona-
3585 ton/month would be needed. tion system.
The carbon tax is assumed as constant during the next years in
the worst scenario (Scenario P) while is supposed that it will
8.1. Carbon taxes increase in the future years for the optimistic scenario (Scenario
O). Average values of carbon tax are taken into account for the
The previous analysis does not include any benefit in terms of analysis. The gain from avoided CO2 emission is given by:
taxes due to avoided CO2 emissions. However, this technology
would dramatically reduce emissions of the plant, which would ECO2;AVOIDED ¼ ðtonCO2;ref  tonCO2;CCS Þ  cCO2 ð21Þ

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx 11


25.00 SOLAR COST = 2500 €/KW

NPV(20 YEARS) [M€]
SOLAR COST = 3000 €/KW
20.00 SOLAR COST = 3500 €/KW




0.075 0.08 0.085 0.09 0.095 0.1 0.105 0.11 0.115 0.12 0.125

Fig. 8. Pessimistic Scenario: NPV in 20 years as function of internal rate value and solar thermal technology costs.


NPV (20 YEARS) [M€]





50 60 70 80 90 100
Sodium Bicarbonate Producon Level (%)
Fig. 9. NPV in 20 years as function of NaHCO3 production and solar technology costs for a fixed discount rate IR = 0.1.

Table 13
CO2 emission data for different scenarios.

Reference plant Dry carbonate (P) Dry carbonate (BE) Dry carbonate (O)
Power (MWel) 15 15 15 15
CCS power consumption (MWel) 2.5 1.6 1.5
Regenerator heat requirement (MWth) 11.9 11.4 11.1
Net power (MWel) 15 12.5 13.35 13.5
CO2 emissions (tons/hr) 13.5 1.07 1.07 1.07
CO2 emissions (kmol/h) 308 24.32 24.32 24.32
CO2 avoided emissions (kton/year) 108.9 108.9 108.9
CO2 emissions (tons/MW hel) 0.9 0.085 0.08 0.079

where cCO2 is the carbon tax expressed in €/tonCO2. The economic Table 14
benefits derived from CO2 avoided emissions under the different Revenues due to CO2 emission reduction for different scenarios (20 years).
carbon tax scenarios are shown in Table 14. Scenario P Scenario BE Scenario O
Figs. 10–12 show the economic impact due to CO2 avoided
Carbon tax 10 €/tonCO2 18 €/tonCO2 25 €/tonCO2
emission for different scenarios and different values of IR. Yearly economic gain 1.09 M€/year 1.96 M€/year 2.72 M€/year
Under carbon taxes scenarios the NPV of the CCU investment IR = 0.08 10.89 M€ 19.60 M€ 29.00 M€
can be recalculated adding cost savings due to carbon taxes. IR = 0.1 8.72 M€ 15.70 M€ 23.18 M€
IR = 0.12 7.71 M€ 13.88 M€ 20.33 M€
Results, considering a production level of 7470 ton/month, are
shown in Table 15, where only in the worst case (Pessimistic Sce-
nario, maximum cost of solar thermal technology and IR = 0.12)
NPV negative values are obtained. Considering the Best Estimate market and taking into account a variable production (from 50%
Scenario, with a mean cost of solar technology (3 M€/MW), and to 100%). A fixed IR = 0.1 is considered in these analyses.
IR 0.1, the NPV goes up to 56.4 M€ in 20 years. Figs. 13–15 illustrate a map of CCU investment profitability as
function of sodium bicarbonate price and demand (linked to pro-
duction). In this sense, production capacity depends on solar
8.2. Sodium bicarbonate prices energy input. For periods without solar resource availability ther-
mal storage can be used to assure CO2 capture and sodium bicar-
In Figs. 13–15 NPV data are plotted for different investment bonate production. The use of biomass would maintain the near
costs as a function of the sale price of NaHCO3 and trona in the zero emissions condition and could support capture when the

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
12 D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx

Best Esmate - Carbon Tax = 18 €/tonCO2



5 ir=0,1
0 5 10 15 20
Fig. 10. Best Estimated Scenario: Economic Gain due to CO2 avoided emissions.


30 Opmisc - Carbon Tax = 25 €/tonCO2




5 ir=0,08

0 5 10 15 20
Fig. 11. Optimistic Scenario: Economic Gain due to CO2 avoided emissions.

Pessimisc - Carbon Tax = 10 €/tonCO2

4 ir=0,12
2 ir=0,08

0 5 10 15 20
Fig. 12. Pessimistic Scenario: Economic Gain due to CO2 avoided emissions.

Table 15
NPV(20 years) values including savings from CO2 emission reduction.

IR Solar cost(M€/MW) Scenario P Scenario BE Scenario O

0.08 2.5 38.93 84.51 130.24
3 29.58 75.44 121.33
3.5 19.87 66.34 112.41
0.1 2.5 26.22 65.50 104.73
3 16.87 56.43 95.82
3.5 7.6 47.33 86.90
0.12 2.5 16.77 51.58 86.14
3 7.42 42.51 77.23
3.5 2.29 33.41 68.31

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx 13

Revenues due to different price market for NaHCO3 and Trona- IR=0.1
- 100% Producon

NPV (20 YEARS) [M€]




CNaHCO3=220€/ton - CTrona = 100€/ton

CNaHCO3=200€/ton - CTrona = 120€/ton
CNaHCO3=250€/ton - CTrona = 80€/ton
15 20 25 30 35 40 45 50 55 60

Fig. 13. NPV in 20 years as function of investment costs and NaHCO3 price with 100% of NaHCO3 total production.

Revenues due to different price market for NaHCO3 and Trona -
IR=0.1 - 75% Producon
NPV (20 YEARS) [M€]

CNaHCO3=220€/ton - CTrona = 100€/ton
CNaHCO3=200€/ton - CTrona = 120€/ton
60 CNaHCO3=250€/ton - CTrona = 80€/ton



15 20 25 30 35 40 45 50 55 60
Fig. 14. NPV in 20 years as function of investment costs and NaHCO3 price with 75% of NaHCO3 total production.

Revenues due to different price market for NaHCO3 and Trona -
NPV (20 YEARS) [M€]

50 IR=0.1 - 50% Producon

40 CNaHCO3=220€/ton - CTrona = 100€/ton
CNaHCO3=200€/ton - CTrona = 120€/ton
30 CNaHCO3=250€/ton - CTrona = 80€/ton


15 20 25 30 35 40 45 50 55 60

Fig. 15. NPV in 20 years as function of investment costs and NaHCO3 price with 50% of NaHCO3 total production.

stored thermal energy is not able to deal with it. Another impor- scale although the local sale impact could be significant. Indepen-
tant factor to consider is how NaHCO3 demand could vary on the dently of sodium bicarbonate sale, the CC system results in a per-
market. For example, if the demand raises constantly, production manent CO2 fixing in the sodium bicarbonate and its integration
could be maintained at the maximum capacity but it must be kept with renewables (solar, biomass) drives to a near CO2 emissions
in mind that a massive introduction of the concept proposed in this technology. In addition, CO2 avoided emission reduction has an
paper necessarily would affect to the sodium bicarbonate produc- economic return if carbon taxes are applied.
tion price by reducing it. In any case this is not pretended to be a
global solution but one for locations with trona availability. From 9. Conclusions
an economic perspective, the market is expected to grow at 4%
per year in the next few years and will reach 4.2 million tons by In this work a novel Carbon Capture and Utilization concept is
2018 driven mainly by the Asia region and China in particular. presented based on the integration of a CO2 post-combustion sys-
The European market is expected to grow by a 2% per year [54]. tem using the dry carbonate process assisted by renewables for
A plant of 15 MWel could produce about 40 kton of NaHCO3. Thus, sodium bicarbonate production. Results suggest a potentially high
such production would have a relatively low impact at the global interest of the integration. Main aspects of the concept are:

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
14 D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx

 Sodium bicarbonate is produced for sale and for make-up in the [12] Samanta A, Zhao A, Shimizu GKH, Sarkar P, Gupta R. Post-combustion CO2
capture using solid sorbents: a review. Ind Eng Chem Res 2012;51:1438–63.
dry carbonate CO2 capture process.
 An abundant, non-toxic and cheap raw material (trona) is used. [13] Joos L, Lejaeghere K, Huck JM, Van Speybroeck V, Smit B. Carbon capture
 When coupled with renewables for heating, biomass or medium turned upside down: high-temperature adsorption & low-temperature
temperature solar thermal, technology to regenerate the sor- desorption (HALD). Energy Environ Sci 2015;8:2480–91. http://dx.doi.org/
bent and calcination of trona, the global system results in a near [14] Fennell PS, Davidson JF, Dennis JS, Hayhurst AN. Regeneration of sintered
to zero CO2 emissions technology with a reduced penalty in limestone sorbents for the sequestration of CO2 from combustion and other
power generation. systems. J Energy Inst 2007;80:116–9. http://dx.doi.org/10.1179/
 NaHCO3 production could allow permanent CO2 storage. [15] Hammond GP, Spargo J. The prospects for coal-fired power plants with carbon
 As concept application it has been applied to the flue gases capture and storage: a UK perspective. Energy Convers Manag
stream equivalent to a small coal power plant of 15 MW, or 2014;86:476–89. http://dx.doi.org/10.1016/j.enconman.2014.05.030.
[16] Hammond GP, Akwe SSO, Williams S. Techno-economic appraisal of fossil-
for a fraction of flue gases of a bigger coal power plant. fuelled power generation systems with carbon dioxide capture and storage.
 Energy analysis show a minor penalty in power consumption Energy 2011;36:975–84. http://dx.doi.org/10.1016/j.energy.2010.12.012.
(<3%). [17] Fu C, Gundersen T. Heat and work integration: fundamental insights and
applications to carbon dioxide capture processes. Energy Convers Manag
 According to the economic analysis with different Scenarios the 2016;121:36–48. http://dx.doi.org/10.1016/j.enconman.2016.04.108.
Simple Pay Back time (SPB) for the integrated solution has very [18] Ste˛pczyńska-Drygas K, Łukowicz H, Dykas S. Calculation of an advanced ultra-
short periods (8.7 years in the worst case and 3 years in the best supercritical power unit with CO2 capture installation. Energy Convers Manag
2013;74:201–8. http://dx.doi.org/10.1016/j.enconman.2013.04.045.
case) remarking the interest of the concept.
[19] Qadir A, Sharma M, Parvareh F, Khalilpour R, Abbas A. Flexible dynamic
 The preliminary study shows an interesting potential for operation of solar-integrated power plant with solvent based post-combustion
advancing in this technology in further studies (kinetics, sor- carbon capture (PCC) process. Energy Convers Manag 2015;97:7–19. http://dx.
bent deactivation, optimization of integration, equipment doi.org/10.1016/j.enconman.2015.02.074.
[20] Zhai R, Li C, Qi J, Yang Y. Thermodynamic analysis of CO2 capture by calcium
design, byproducts usage, etc.). looping process driven by coal and concentrated solar power. Energy Convers
 When heat supply is based on solar, the proposed technology Manag 2016;117:251–63. http://dx.doi.org/10.1016/j.enconman.2016.03.022.
requires heat storage or support from other sources as biomass [21] Rahman FA, Aziz MMA, Saidur R, Bakar WAWA, Hainin M, Putrajaya R, et al.
Pollution to solution: capture and sequestration of carbon dioxide (CO2) and
to work continuously. Various storage technologies (phase its utilization as a renewable energy source for a sustainable future. Renew
change liquid, thermal oils, molten salt) are already available Sustain Energy Rev 2017;71:112–26. http://dx.doi.org/10.1016/j.
on the market. A detailed study on the relative volumes of accu- rser.2017.01.011.
[22] Joos L, Huck JM, Van Speybroeck V, Smit B. Cutting the cost of carbon capture:
mulation and on the exploitation of renewable sources is a case for carbon capture and utilization. Faraday Discuss 2016;192:391–414.
required yet to define in the best way the effective feasibility http://dx.doi.org/10.1039/C6FD00031B.
of this system. [23] Zhang X, Fan J-L, Wei Y-M. Technology roadmap study on carbon capture,
utilization and storage in China. Energy Policy 2013;59:536–50. http://dx.doi.
[24] Meisen A, Shuai X. Research and development issues in CO2 capture. Energy
Convers Manag 1997;38:S37–42. http://dx.doi.org/10.1016/S0196-8904(96)
Acknowledgements 00242-7.
[25] Swaddle TW, Thomas W. Inorganic chemistry: an industrial and
This work was supported by the Spanish Government Agency environmental perspective. Academic Press; 1997.
[26] Nelson TO, Coleman LJI, Green DA, Gupta RP. The dry carbonate process:
Ministerio de Economia y Competitividad and FEDER Funds carbon dioxide recovery from power plant flue gas. Energy Procedia
(CTQ2014- 52763-C2-2-R and MAT2013-41233-R). 2009;1:1305–11. http://dx.doi.org/10.1016/j.egypro.2009.01.171.
[27] Intratec Solutions. Chlorine Production from Sodium Chloride - Cost Analysis -
Chlorine E11A - Intratec Solutions - Google Libros; 2016.
References [28] Nelson TO, Coleman LJI, Green DA, Gupta RP. The dry carbonate process:
Carbon dioxide recovery from power plant flue gas. Energy Procedia 2009; 1:
1305–11. http://dx.doi.org/10.1016/j.egypro.2009.01.171.
[1] Abanades JC, Rubin ES, Anthony EJ. Sorbent cost and performance in CO2
[29] Cho KJ, Keener TC, Khang S-J. A study on the conversion of trona to sodium
capture systems. Ind Eng Chem Res 2004:3462–6. http://dx.doi.org/10.1021/
bicarbonate. Powder Technol 2008;184:58–63. http://dx.doi.org/10.1016/j.
[2] Aresta M, Dibenedetto A, Angelini A. The changing paradigm in CO2 utilization.
[30] Wyoming Mining Association. Wyoming Mining Association: Trona Mining n.
J CO2 Util 2013;3–4:65–73. http://dx.doi.org/10.1016/j.jcou.2013.08.00.
d. <http://www.wyomingmining.org/minerals/trona/> [accessed December 1,
[3] IEA. Carbon Capture and Storage Technologies 2016. <http://www.iea.
org/topics/ccs/> [accessed December 1, 2016].
[31] Harris RE. Fifty years of Wyoming trona mining 1997:177–82.
[4] Zhang X, Singh B, He X, Gundersen T, Deng L, Zhang S. Post-combustion carbon
[32] Manega PC, Bieda S. Modern sediments of Lake Natron, Tanzania. Sci Geol -
capture technologies: energetic analysis and life cycle assessment. Int J Greenh
Bull 1987;40:83–95.
Gas Control 2014;27:289–98. http://dx.doi.org/10.1016/j.ijggc.2014.06.016.
[33] Eckardt FD, Drake N, Goudie AS, White K, Viles H. The role of playas in
[5] Zhang W, Liu H, Sun Y, Cakstins J, Sun C, Snape CE. Parametric study on the
pedogenic gypsum crust formation in the Central Namib Desert: a theoretical
regeneration heat requirement of an amine-based solid adsorbent process for
model. Earth Surf Process Landforms 2001;26:1177–93. http://dx.doi.org/
post-combustion carbon capture. Appl Energy 2016;168:394–405. http://dx.
[34] Helvaci C. The Beypazari trona deposit, Ankara Province, Turkey. Proc First Int
[6] Booth A, Silva E Da, Brakstad O. Environmental impacts of amines and their
Soda Ash; 1998.
degradation products: current status and knowledge gaps. 1st Post Combust
[35] Zhang Y. Geology of the Wucheng trona deposit in Henan, China - Google
Capture 2011.
Académico. In: Sixth Int Symp Salt; 1985. p. 67–73.
[7] Bailey RT, McDonald MM. CO2 capture and use for EOR in Western Canada. 1.
[36] Ekmekyapar A, Ersßahan H, Yapıcı S. Nonisothermal decomposition kinetics of
General overview. Energy Convers Manag 1993;34:1145–50. http://dx.doi.org/
trona. Ind Eng Chem Res 1996;35:258–62. http://dx.doi.org/10.1021/
[8] Fujiki J, Chowdhury FA, Yamada H, Yogo K. Highly efficient post-combustion
[37] Berg RL, Vanderzee CE. Enthalpies of dilution of sodium carbonate and sodium
CO2 capture by low-temperature steam-aided vacuum swing adsorption using
hydrogen carbonate solutions, and the standard enthalpies of ionization of
a novel polyamine-based solid sorbent. Chem Eng J 2017;307:273–82. http://
aqueous carbonic acid, at 298.15 K. J Chem Thermodyn 1978;10:1049–75.
[9] Novek EJ, Shaulsky E, Fishman ZS, Pfefferle LD, Elimelech M. Low-temperature
[38] Vanderzee E. J Chem Thermodyn 1982;14:219–38. http://dx.doi.org/10.1016/
carbon capture using aqueous ammonia and organic solvents. Environ Sci
Technol Lett 2016;3:291–6. http://dx.doi.org/10.1021/acs.estlett.6b00253.
[39] Haynes HW. Thermodynamic solution model for trona brines. AIChE J
[10] Ma’mun S, Svendsen HF, Hoff KA, Juliussen O. Selection of new absorbents for
2003;49:1883–94. http://dx.doi.org/10.1002/aic.690490724.
carbon dioxide capture. Energy Convers Manag 2007;48:251–8. http://dx.doi.
[40] Gärtner RS, Witkamp GJ. Wet calcining of trona (sodium sesquicarbonate) and
bicarbonate in a mixed solvent. J Cryst Growth 2002;237–239:2199–204.
[11] Tan Y, Nookuea W, Li H, Thorin E, Yan J. Property impacts on Carbon Capture
and Storage (CCS) processes: a review. Energy Convers Manag
2016;118:204–22. http://dx.doi.org/10.1016/j.enconman.2016.03.079.

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042
D. Bonaventura et al. / Energy Conversion and Management xxx (2017) xxx–xxx 15

[41] Heda PK, Dollimore D, Alexander KS, Chen D, Law E, Bicknell P. A method of [48] Bonaventura D, Chacartegui R, Valverde JM, Becerra JA. Dry carbonate process
assessing solid state reactivity illustrated by thermal decomposition for CO2 capture, SDEWES.SEE2016.0073. 2nd SDEWES SEE Conference, Piran;
experiments on sodium bicarbonate. Thermochim Acta 1995;255:255–72. 2016.
http://dx.doi.org/10.1016/0040-6031(94)02154-G. [49] Carlos Abanades J, Grasa G, Alonso M, Rodriguez N, Anthony EJ, Romeo LM.
[42] Otsubo Y, Yamaguchi K. Thermochemical properties and reaction processes of Cost structure of a postcombustion CO2 capture system using CaO; 2007.
alkali carbonate-ferric oxide systems as investigated by means of differential http://dx.doi.org/10.1021/ES070099A.
thermal method. Nippon Kagaku Zasshi 1961;82:557–60. [50] FMC Soda Ash Plant, Wyoming - Chemicals Technology, n.d. http://
[43] Jared Sanford Sproul ER. US 3869538 A Process for producing sodium www.chemicals-technology.com/projects/sodaash/ (accessed December 1,
carbonate from trona. US3869538 A; 1973. 2016).
[44] How baking soda is made - material, manufacture, making, history, used, [51] Renewable Energy Agency I. Solar Heat for Industrial Processes Technology
processing, structure, product n.d. <http://www.madehow.com/Volume-1/ Brief 2015.
Baking-Soda.html> [accessed February 23, 2017]. [52] Chacartegui R, Vigna L, Becerra JA, Verda V. Analysis of two heat storage
[45] Gärtner RS, Witkamp G-J. Mixed solvent reactive recrystallization of trona integrations for an Organic Rankine Cycle Parabolic trough solar power plant.
(sodium sesqui-carbonate) into soda (sodium carbonate anhydrate). Energy Convers Manag 2016;125:353–67. http://dx.doi.org/10.1016/j.
Hydrometallurgy 2007;88:75–91. http://dx.doi.org/10.1016/j. enconman.2016.03.067.
hydromet.2007.03.006. [53] Guo Z, Wang Q, Fang M, Luo Z, Cen K. Thermodynamic and economic analysis
[46] Ciferno JP, Fout TE, Jones AP, Murphy JT. Capturing carbon from existing coal- of polygeneration system integrating atmospheric pressure coal pyrolysis
fired power plants. Chem Eng Prog 2009;105:33–41. technology with circulating fluidized bed power plant. Appl Energy
[47] Romeo LM, Abanades JC, Escosa JM, Paño J, Giménez A, Sánchez-Biezma A, 2014;113:1301–14. http://dx.doi.org/10.1016/j.apenergy.2013.08.086.
et al. Oxyfuel carbonation/calcination cycle for low cost CO2 capture in [54] Market Pubblisher. Global Sodium Bicarbonate Industry Market Research
existing power plants. Energy Convers Manag 2008;49:2809–14. http://dx.doi. 2016:2016.

Please cite this article in press as: Bonaventura D et al. Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power.
Energy Convers Manage (2017), http://dx.doi.org/10.1016/j.enconman.2017.03.042