Energy Conversion and Management 48 (2007) 1313–1322

www.elsevier.com/locate/enconman

CO2 capture by hydrate crystallization – A potential solution

for gas emission of steelmaking industry
Nguyen Hong Duc, Fabien Chauvy, Jean-Michel Herri *

Centre SPIN, Ecole Nationale Supérieure des Mines de St-Etienne, URA CNRS no. 2021, 158 Cours Fauriel, 42023 Saint-Etienne Cedex 2, France

Received 10 March 2006; accepted 27 September 2006

Available online 30 November 2006

Abstract

In order to study CO2 capture from a gas mixture by hydrate crystallization, we conducted separation experiments using TBAB as an
additive, which makes the hydrate crystallization condition milder. Based on experimental results, we did flowsheeting simulations to
evaluate a realistic energetic costing and compare with other classical technologies (membranes, amines, etc.). We also estimated invest-
ment cost and production cost of the gas capture system for different kinds of blast furnaces.
 2006 Published by Elsevier Ltd.

Keywords: Hydrate; TBAB; Carbon dioxide; Gas separation; Simulation; Thermodynamic equilibrium

1. Introduction gases, volatile liquids or other small molecules can be cap-

Steel plays a crucial role, which has been at the root of
world development in the 20th century and will continue
to be in the 21st century. However, the steel making
industry needs to face the challenge of global warming
and to prepare for the post Kyoto future. The European
steel industry has to develop clean processes and reduce
its greenhouse gas emissions with a target of 50%
reduction.
Although CO2 capture is a major interest and hydrates
have been investigated in gas separation, there is only one
study on the thermodynamic hydrate equilibrium of a
CO2–N2 mixtures, which are the principal gases in gas
emissions of the steelmaking industry. Clathrates are ice
like compounds in the sense that they correspond to a
re-organization of the hydrogen links to form a solid in
which the crystallographic structure is based on H bond
links. The clathrates of water are also qualified improperly
as ‘‘porous ice’’ because the crystal structure shows that
the water molecules build a network of cavities in which
*
Corresponding author. Tel.: +33 4 77 42 02 92; fax: +33 4 77 49 96 94.
E-mail address: herri@emse.fr (J.-M. Herri).
tured. The gas hydrates can exhibit three different struc-
tures called sI, sII and sH [1]. Theoretically, we need a
high pressure to form hydrates from a CO2–N2 mixture,
whereas the pressure of gas emissions in the steelmaking
industry is low (about atmospheric pressure). So, the oper-
ative cost would be expensive if we have to compress the
gas to the necessary hydrate formation pressure. In order
to reduce the hydrate formation pressure, Kang et al. [2]
studied the hydrate phase equilibrium of CO2 and N2
using THF (tetrahydrofuran) as an additive. They found
that the equilibrium pressure of hydrates in the presence
of this additive is considerably lower than the case without
the additive.
In our study, we conduct experiments to separate CO2
from a CO2–N2 mixture by hydrate crystallization using
TBAB (tetra-n-butyl ammonium bromide C16H36NBr) to
have a suitable operating condition. From our experimen-
tal results, we determine the hydrate crystallization condi-
tion, hydrate formula and also the gas storage capacity of
hydrates for a wide range of additive concentration.
Based on thermodynamic results, a simulation is done
by a commercial flowsheeting simulator to estimate the
operative cost of a continuous CO2 capture by hydrate
system.

0196-8904/$ - see front matter  2006 Published by Elsevier Ltd.

doi:10.1016/j.enconman.2006.09.024
1314 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322

Nomenclature

A area M molar weight

bhp brake horsepower M&S Marshall and Swift equipment cost index
D diameter x mole fraction
Fc correction factor y mass fraction
H height qL density of liquid
m mass
m0 mass of gas bottle

2. Experimental apparatus and techniques 2.3. Experimental apparatus

2.1. Chemical reactants
Carbon dioxide (CO2) and nitrogen (N2) are delivered by
Air Liquide with a certified purity higher than 99.95 vol%.
Ordinary tap water is used. TBAB at ambient pressure and
temperature is a white crystalline solid. It is delivered by
V3-Chimie with a purity of 97% wt. It can be dissolved
in water in every proportion.
A tracer (LiNO3) is added to water in low proportion. It
is an ionic substance tracer which is not incorporated into
the hydrate structure. With the tracer, we are able to deter-
mine the quantity of the liquid phase by measuring the tra-
cer concentration in the liquid phase. So, the tracer must
fulfil some conditions:
• It must be in low concentration so that it does not mod-
ify the refractive index of the liquid solution.
• It must be in low concentration so that it does not mod-
ify the hydrate equilibrium.
• It must be analysed using a conventional technique.
2.2. Gas preparation
CO2 + N2 mixture. The mixture is prepared from two
bottles of pure CO2 and pure N2. After being vacuumed
(0.3 mmHg), another bottle is weighed (m0) and filled with
CO2 (m0 þ mCO2 ) and then with N2 (m0 þ mCO2 þ mN2 ). The
mole fraction of CO2 in the mixture is eventually calculated
as
mCO2 =M CO2
xCO2 ¼
mCO2 =M CO2 þ mN2 =M N2
where M denotes the molar weight.
Water–TBAB mixture. The density qL of this solution
was experimentally measured and interpolated by Darbo-
uret et al. [3]:
qL ðkg=m3 Þ ¼ 999:9 þ 113:29y
where y denotes the mass fraction of TBAB in the
solution.
The experimental set up is a classical batch reactor. The
cell is a pyrex cylinder that is filled with a mixture of water,
TBAB and tracer. The cell is 0.2 m in height, 0.003 m thick
and 0.1075 m in diameter. It is located in a stainless steel
autoclave in which the pressure can be raised to 10 MPa.
The autoclave is surrounded by a cooling jacket. Ethanol
is circulated from a cryostatic temperature controller (tem-
perature controlled within 0.02 K). Two sapphire windows
(0.1 m in height, 0.015 m in width), mounted on both sides
of the reactor, make observation possible. A four vertical
blade turbine impeller ensures stirring of the suspension
during crystallization. The speed rate can be varied from
0 to 600 rpm (Fig. 1).
Temperature is monitored by a Pt100 probe in the bulk.
Pressure is measured by means of pressure transducers
(range: 0–10 MPa). The pressure uncertainty is estimated
to be within 0.4% of full scale. Temperature and pressure
measurements are displayed or controlled by the West
instrument (model 8010 and 6100). The data acquisition
unit is also connected to a personal computer through
two cards, National Instruments (PCI –6023E and
Lab1200).
2.4. Analytical measurement
Gas composition. The composition of the gas phase is
determined thanks to a gas chromatograph (VARIAN
model CP-3800 GC) equipped with a thermal conductivity
detector (TCD) and two analytical columns (PoraBOND Q
and Molsieve 5A). Gas sampling is performed by way of a
ROLSITM instrument, a static analytic apparatus taking
ð1Þ advantage of an electromagnetic capillary sampler devel-
oped in the Cenerg/TEP laboratory of Paris School of
Mines. This tool collects a controlled volume of gas (some
lm3), which is directly injected in the loop of the gas chro-
matography. Peak integrations are done on a computer
through software developed by Varian (Galaxie version
1.6).
ð2Þ
Liquid composition. A classical valve is used to take a
1 ml sample for determination of the TBAB concentration
by refractive index measurement. The other part of the
 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322 1315

Fig. 1. Experimental apparatus.

liquid sample is used to measure the tracer concentration in
a DIONEX ionic chromatograph.
2.5. Experimental procedure
The hydrate is crystallized from a mixture of gas (CO2
and/or N2), water, TBAB and tracer. At the beginning,
the reactor and its loading lines are vacuumed. The cell is
first loaded with its CO2–N2 gas mixture to reach its oper-
ative pressure (16 bar in Fig. 2). The gas supply from the
reference tank is closed. The reactor is cooled to a temper-
ature low enough to form CO2–N2–TBAB hydrates but
high enough to avoid formation of pure TBAB hydrate.
We observe a first temperature increase due to the gas com-
pression, and then, the temperature decreases to reach the
operative temperature (Phase 1). As the system reaches a
constant temperature and a constant pressure, 600 ml of
liquid mixture of water + TBAB + tracer is injected by
using a HPLC pump. A temperature increase and a pres-
sure increase are simultaneously observed due to the
‘‘high’’ temperature of the liquid mixture and due to gas
compression. Then, the pressure drops due to gas dissolu-
tion (Phase 2). After 4 h, we observe a sudden temperature
increase (Phase 3) that characterizes the end of the nucle-
ation delay and the beginning of the crystallization. During
phase 3, crystallization consumes the gas and generates
heat. After a while, the crystallization stops, and the tem-
perature slightly returns to the operative condition.

Fig. 2. Evolution of pressure and temperature during experiment.

1316 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322

Determination of thermodynamic equilibrium condition. Table 1

Once the hydrate crystallization finishes, the system is Equilibrium pressure of CO2 hydrate with and without TBAB
slowly heated at a rate of 1.5 K/h. During phase 4 and 6, % TBAB (mol) T (K) P (bar) P (without TBAB) (bar)
the temperature and pressure increases without hydrate 0.29 279.3 2.73 35
dissociation. The pressure increases in consequence of the 282 6.4 36.9
gas solubility change and thermal gas expansion. Phase 5 284 8.4 143.6
corresponds to the hydrate dissociation equilibrium curve, 0.61 286.1 10.7 270
which is of main interest for determination of the hydrate 286.2 11.2 372
equilibrium curve.
Determination of gas phase and hydrate phase composi- 3.6 290.9 33.2 1220
tion at equilibrium. During hydrate dissociation, we con-
9.4 284 8.15 143.6
duct measurements of the gas phase and liquid phase 285 9.86 243
compositions. Before withdrawing a gas sample to analyze
by gas chromatography, we evacuate the capillary tube
between the reactor and the gas sampler, while the liquid Table 2
phase composition is determined thanks to the DIONEX Equilibrium pressure of N2 hydrate with and without TBAB
ionic chromatography and the refractive index detector. % TBAB (mol) T (K) P (bar) P (without TBAB) (bar)
We assume that the presence of TBAB does not have a con-
0.29 279.3 6.64 303
siderable effect on the solubility of CO2 and N2 in the liquid 279.84 10.85 330
phase [4].
0.61 284 29 500
3. Experimental results and discussion

3.1. Effect of additive TBAB on simple gas hydrates
We tested many solutions with different TBAB concen-
trations (molar): 0.29%, 0.61%, 3.6% and 9.4%. The new
equilibrium pressures of CO2 hydrate are shown in Fig. 3
and compared to the case without additive in Table 1.
The new equilibrium pressures of N2 hydrate are shown
in Table 2. From the experimental results, we can conclude
that TBAB is a good candidate. It decreases the hydrate
crystallization pressure by a factor from 10 to 50 for both
CO2 and N2 simple hydrates. For example, CO2 hydrates
can be formed at 2.73 bar and 279.3 K in the presence of
TBAB (while it is 35 bar at the same temperature without
TBAB).
We can also note that the equilibrium pressure of N2
hydrate is three times greater than that of CO2. This differ-
ence may be considered very promising to separate CO2
from a CO2–N2 mixture. Another remark concerns the
40
30
Pressure, bars
effect of the initial TBAB concentration on the equilibrium
pressure modification. In Fig. 3, the equilibrium pressures
of CO2 hydrate in the two cases (initial TBAB concentra-
tion of 9.4% and 0.29%) are quite the same at the same
temperature. We also make this remark when we compare
the experimental points with 0.29%, 0.61% and 9.4%
TBAB. So, the TBAB concentration of the initial liquid
solution does not have a significant effect on the hydrate
crystallization pressure.
3.2. Effect of additive TBAB on mixed gas hydrates
In our experiments, a solution of 0.29% molar of TBAB
is used to decrease the equilibrium pressure of mixed
hydrate CO2–N2. The three phases H–L–V equilibrium of
the TBAB–CO2–N2–water system are determined at differ-
ent gas loading compositions. The mixed hydrates are
formed over the wide temperature and pressure ranges of
282–295 K and 5–44 bar depending on gas composition.
The measured equilibrium data are shown in Table 3. In
Table 3, the equilibrium pressure of the mixed hydrates is
quite low for a CO2 poor gas mixture (CO2 maximum =
23.4%) in comparison to bibliographic data (without addi-

tive). For a mixture of 23.4% CO2, the equilibrium pressure

0.29% TBAB is 5 bar at 282 K if TBAB is used, while the equilibrium
20 0.61% TBAB pressure of a mixture richer in CO2 (48.2%) is 90 bar at
3.60% TBAB the same temperature. So, with TBAB, CO2–N2 hydrates
9.40% TBAB
10
can be stabilized at quite low pressures.

3.3. Gas distribution in gas phase and hydrate phase

0
280 282 284 286 288 290 292
We present here the distribution of gas in the two
Temperature, K phases: gas and hydrate. Tables 4 and 5 show, respectively,
Fig. 3. Equilibrium pressure of CO2 hydrate (using TBAB). the gas and hydrate compositions at 285.15 and 286.15 K.
 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322 1317

Table 3
Equilibrium temperature-pressure of mixed CO2–N2–TBAB hydrates
Gas Temperature (K) Pressure (bar) Gas Temperature (K) Pressure (bar)
15.5% CO2 287.15 50 23.4% CO2 282.25 5.5
287.55 51 283.35 9.2
287.95 52.2 285.15 12.7
289.75 53.2 286.95 19.2

19.2% CO2 286.25 36.3 21.5% CO2 285.75 31.2

286.85 37.4 286.15 31.7
287.15 37.8 286.75 32.3
287.85 38.9
293.15 44.0
295.25 44.3

Table 4 60
CO2 concentration in loading, gas phase and hydrate phase at 19.8% CO2
T = 285.15 K 37.9% CO2

V-gas/ V-hydrate
50
Pressure (bar) Loading Gas Hydrate
6.58 1 1 1
40
20.11 0.3744 0.175 0.789
20.50 0.3745 0.1743 0.7827
32.80 0.1025 0.0609 0.2749 30
44.44 0 0 0

20
7 9 11 13 15
Temperature, ˚C

Fig. 4. Gas storage capacity of mixed hydrates CO2–N2–TBAB.

The relative CO2 amount in the hydrate phase increases as
the relative CO2 amount in the loading increases. In Table
4, with a loading of 10.25% CO2, the CO2 concentration in CO2 of loading) is used to form hydrates. The gas storage
the hydrate phase appears to be about 27.49% at 285.15 K. capacity of hydrates is about 30–35 m3/m3 of hydrates.
At the same temperature, for a loading of 37.45% CO2, the
CO2 concentration in the hydrate phase is 78.9%.
The experimental results also suggest the possibility of a 4. Simulation
CO2 separation process using hydrate crystallization
because the CO2 selectivity in the hydrate phase is at least We performed simulations of CO2 capture by hydrate
four times better than in the gas phase. After being cap- crystallization using PRO II (version 7.1). It is a theoretical
tured in the hydrate, CO2 can be easily recovered simply estimation based only on the energy aspect and our exper-
by either heating or depressurization. imental results.

3.4. Gas storage capacity of mixed hydrates 4.1. Simulation data

From the results concerning liquid quantity and the Inlet gas composition. To simulate continuous CO2 cap-
composition of the liquid and hydrate phases, the gas stor- ture by a hydrate system, we use data of the gas emissions
age capacity of hydrates can be calculated. Fig. 4 shows the from different kinds of blast furnaces. In gas emissions
results of experiments in which a mixture (19.8% and 37.9% from blast furnaces in the steelmaking industry, there are
three principal gases: CO, CO2 and N2. From the literature
[5], CO hydrate has a similar equilibrium condition to that
Table 5 N2 hydrate. So, in our simulation, CO is replaced by N2
CO2 concentration in loading, gas phase and hydrate phase at with an assumption that there is no significant effect on
T = 286.15 K the formation condition of the mixed hydrates CO–CO2–
Pressure (bar) Loading Gas Hydrate N2. There are four principal kinds of blast furnaces: nitro-
8.30 1 1 1 gen free blast furnace (NFBF) with shaft injection, NFBF
22.17 0.3745 0.2051 0.9266 plasma, conventional blast furnace (CBF) top gas and CBF
22.57 0.3745 0.0233 0.9182 flue gas. The data of these gases are shown in Table 6.
34.00 0.1025 0.0656 0.2851 Specifications. To meet suitable conditions for pipeline
46.81 0 0 0
transport followed by injection of CO2 into many potential
1318 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322

Table 6
Properties of inlet gas
CBF top gas CBF flue gas NFBF shaft injection NFBF plasma
Hours/year 8500 8500 8500 8500
Average flow rate (N m3/h) 663,500 457,600 595,000 288,300
Pressure (bar) 2.5 1 2.5 2.5
Temperature (C) 55 200 55 55
Composition CO2% 23 24 36 35
N2% 77 76 64 65

geologic storage reservoirs and for enhanced oil recovery
(EOR), the total content of all non-condensable gases in
CO2 rich gas must be lower than 4 vol%. This fluid must
have a temperature of 0 C and a pressure of 110 bar.
Another specification is that the CO2 slippage in N2 rich
gas must be lower than 3 mol%.
4.2. Utilities used in simulation
Power: 10 kV–50 Hz available with a price of 40 €/
MWh.
Cooling water: (40 €/1000 m3) is supplied at 20 C and
has a standard quality for rotating machines. The temper-
ature rise is not more than 10 C.
4.3. Hypotheses of simulation
• Thermal properties of TBAB solution are unknown, so
we consider that they are the same as the thermal prop-
erties of liquid water.
• Slurry can be handled up to a solid content of 30% (vol-
ume) solid.
• Efficiency of compressors, pumps and expanders is 80%.
• Maximum ratio outlet pressure/inlet pressure of a com-
pressor is 2.5 and maximum outlet temperature of a
compressor is 150 C.
• Minimum driving force of a heat exchanger is 10 C.
4.4. Description of one stage separation
Each stage of separation is composed of a compressor
for gas coming from stage (n  1) plus a heat exchanger
to cool to operative temperature, a valve for slurry coming
from stage (n + 1), a mixer and a crystallizer plus a phase
separator (gas on one side, slurry on the other).
4.5. Description of multi-stage separation
To reach the specifications, we used a six stage of CO2
crystallization (Fig. 5). Pressures of the six stages are from

Fig. 5. Flow sheeting of continuous hydrate crystallization system for ‘‘NFBF with shaft injection’’.
 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322 1319

7.5 to 50 bar. The temperature in each crystallizer is kept

constant (283 K). The solid fraction maximum of solid-
liquid mixture coming from the crystallizers is 30%, so with
our hypotheses, it is possible to circulate the fluid (in refer-
ence to our experimental work on pure TBAB hydrate slur-
ries [3]).
Before entering the hydrate crystallizer system, the inlet
gas is compressed to operational pressure. The energy of
the high pressure inlet gas is used to melt a part or all of
the hydrate particles. We can also recuperate the energy
of the final CO2 rich gas after final compression (the final
CO2 gas needs to be compressed to meet the specifications
for pipeline transport, EOR and geologic storage
(110 bar)). The final N2 rich gas coming from the top crys-
tallizer has a pressure of 50 bar. We can recuperate
mechanical energy for the compressors system by using
an expander. After passing the expander, the gas tempera-
ture is low, and it could be an cold point for cooling fluids
that are compressed before entering the crystallizers.

4.6. Cost analysis

Chemical products consumption. In gas capture by

Fig. 6. Cost distribution of each working group.
hydrate technology, there are only two chemical products:
water and TBAB. There is nearly no loss of water and
TBAB because TBAB and water exist in liquid and solid
states during the production phase. There might be a very
little loss of chemical products that is carried by gas flow.
After hydrate dissociation to capture CO2, the TBAB
and water (in liquid state) will come back to the hydrate
crystallizer to begin a new production cycle. In the litera-
ture data, there is not any change of TBAB properties in
time.
Electric consumption. In our simulation, the compressors
(for each crystallizer, for compressing the inlet gas to oper-
ational pressure and CO2 rich gas to 110 bar), the liquid
circulation pump and the cooling source of the heat
exchangers run on electricity. We suppose a COP (coeffi-
cient of performance) of 2 for all cooling machines (see
Table 7).
Consumption of cooling water. In our simulation, cooling Fig. 7. Cost distribution of compressors sub-groups for NFBF with shaft
water is used only in the case of the CBF flue gas for cool- injection.
ing the CO2 rich gas after each compressor.
The cost distribution of the working groups (pump,
cooling water, cooling fluid before each crystallizer and reached if another additive that allows the hydrates to be
compressors) for different blast furnaces is shown in Fig. 6. formed at lower pressures can be found. In order to know
We can see that the compressors cost is the highest the proportion of each compressors sub-group (compres-
(from 50% to 80%). So, a more moderate cost could be sors for inlet gas, compressors for final CO2 rich gas, com-
pressors before crystallizers), we analyze the case of the
‘‘NFBF with shaft injection’’ in Fig. 7. The electric con-
Table 7 sumption for compressing the inlet gas to operational pres-
Electric consumption for different technologies sure is about 48% of the total electric consumption of
Technology NFBF with CBF NFBF CBF all the compressors, so this sub-group takes more than
shaft injection top gas plasma flue gas 30% of the operational cost. It is an interesting point for
Electric power, MW 167 350 68 142 gas separation by hydrate technology in other field (for
Electric power, kW h/ 420 1302 362 730 example, oil industry, etc.) where the inlet gas has a high
ton CO2 captured
pressure.
1320 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322

Table 8 Table 11
Variable cost per ton of CO2 captured Value of Fp
Technology NFBF with CBF NFBF CBF Design pressure, psi Fp
shaft injection top gas plasma flue gas
Up to 150 0.00
CO2 concentration 36 23 35 24 300 0.10
of inlet gas, % 400 0.25
Cost, €/ton CO2 16.8 22.4 14.5 29.6 800 0.52
captured 1000 0.55

Finally, the energetic costing per ton of captured CO2

corresponding to the different kinds of blast furnaces is bhp is brake horsepower determined from PRO II
shown in Table 8. It is a very interesting result in compar- simulation,
ison with classical technologies like membranes, amines, Fc is a correction factor in function of design type (Table
etc. (the price is about 20–30 €/ton of captured CO2, data 9).
supplied by ULCOS project partner). The cost decreases
with the CO2 concentration of loading except for the gas
coming from the CBF because the inlet gas of this technol- 5.2. Heat exchangers cost
ogy has a lower pressure (1 bar) and a higher temperature
(200 C) than the others. So, the hydrate technology for gas The investment cost (purchased + installed cost) of a
separation is more competitive in the case of the CO2 rich heat exchanger is estimated by formula (4):
 
gas. M&S
Cost; $ ¼ 101:3A0:65 ð2:29 þ F c Þ ð4Þ
280
5. Investment cost estimation
where A is area in ft2, 200 < A < 5000
To estimate the investment cost, we use formulas pro- Fc is a correction factor in function of design type and
posed by James M. Douglas [6]. material. Fc = (Fd + Fp)Fm (Tables 10–12).

5.1. Compressors cost 5.3. Reactors cost

The investment cost (purchased + installed cost) of a The investment cost (purchased + installed cost) of a
compressor is estimated by formula (3): reactor (pressure vessel) is estimated by formula (5):
   
M&S M&S
Cost; $ ¼
0:82
517:5ðbhpÞ ð2:11 þ F c Þ ð3Þ Cost; $ ¼ 101:9D1:066 H 0:082 ð2:18 þ F c Þ ð5Þ
280 280

where M&S is the Marshall and Swift equipment cost index where H is height in ft, D is diameter in ft and Fc is correc-
given by Chemical Engineering tion factor in function of pressure and material,
Fc = Fp + Fm (Tables 13 and 14).
(M&S = 1260.9 in 2005), To estimate the volume of reactors, we consider that the
filling ratio of a reactor is 70%, and the residence time is
about 1 min. So, we can know the flow rate of the liquid
Table 9 phase (water and TBAB) for 1 min from the PRO II simu-
Value of Fc
lation, and it is the volume of liquid in a reactor. From this
Design type Fc data, the reactor volume can be estimated.
Centrifugal, reciprocating, 1.00 The ratio of height/diameter of a reactor is 2, and in case
Reciprocating, steam 1.07 the diameter is bigger than 5 m, we will use a system of 2 or
Centrifugal, turbine 1.15
3 parallel reactors.
Reciprocating, motor 1.29
Reciprocating, gas engine 1.82
5.4. Other equipments cost

We estimate that the investment cost of other equip-

Table 10 ments (expanders, pumps, valves) is about 10% of the total
Value of Fd investment cost of the three groups (compressors, heat
Design type Fd exchangers and reactors).
Kettle, reboiler 1.35 Summary. The investment costs of a gas capture system
Floating head 1.00 for the four kinds of blast furnaces are shown in Table 15.
U-tube 0.85 The rate of exchange between the US dollar and € is con-
Fixed-tube sheet 0.80
sidered 1:1. The same as the energetic cost estimation, the
 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322 1321

Table 12
Value of Fm
Shell and tube material, Fm
A, ft2 CS/CS CS/Brass CS/MO CS/SS SS/SS CS/Monet Monet/Monet CS/Ti Ti/Ti
1000–5000 1.00 1.30 2.15 2.81 3.75 3.10 4.25 8.95 13.05

Table 13
Value of Fp
P, psi Up to 50 100 200 300 400 500 600 700 800 900 1000
Fp 1.00 1.05 1.15 1.20 1.35 1.45 1.60 1.80 1.90 2.30 2.50

Table 14 7. Technology evaluation

Value of Fm
Shell material CS SS Monet Titanium Robustness. The presence of CO2 in water will make an
Fm, clad 1.00 2.25 3.89 4.25 acid liquid solution, but a very small CO2 quantity in water
Fm, solid 1.00 3.67 6.34 7.89 (about 1–2% molar) is not enough to make the liquid solu-
tion sensitive to steel.
compressors group is the most expensive: It takes at least Flexibility. The hydrate production process can work
83% of the total investment cost. with a large range of loading compositions. The operation
principles of hydrate crystallization are essentially based on
6. Production cost thermodynamic aspects. With a different gas composition,
the two parameters that will be controlled are temperature
Maintenance and repair. The yearly cost for maintenance and pressure.
and repair is 3% of the total investment cost. Feasibility. According to Marit Mork and Gudmunds-
Amortization.We consider that our equipments will be son [7], Iwasaki et al. [8], Hideo Tajima et al. [9] and Dwain
amortized after 15 years. So, the amortization is 7%. F. Spencer [10], it is possible to crystallize hydrates contin-
Summary. The production cost of a CO2 capture system uously, but until now, in the open literature, there is no
based on hydrate technology is summarized in Table 16. study of CO2–N2 mixtures. The essential point of this tech-
The preliminary cost shows the process to be viable with nology is a gas–liquid mixing type that gives an optimal
the cost of 22 and 40 € for a ton of captured CO2 corre- contact between the gas and liquid. Current research is
sponding to NFBF (with shaft injection and plasma) and underway to determine the mixing type and kinetics of
conventional BF (top gas and flue gas) respectively. hydrate crystallization.

Table 15
Investment cost for CO2 capture system
Technology NFBF with shaft injection CBF top gas NFBF plasma CBF flue gas
k€ % k€ % k€ % k€ %
Compressors 163,691 83.6 328,018 85.6 90,466 84.6 154,868 83.0
Heat exchangers 4631 2.4 5366 1.4 1930 1.8 5565 3.0
Reactors 9663 4.9 14,933 3.9 4832 4.5 9258 5.0
Other equipments 17,799 9.1 34,832 9.1 9723 9.1 16,969 9.1
Total installed equipments 195,784 383,149 106,951 186,660

Table 16
Production cost of CO2 capture system
Technology NFBF with shaft injection CBF top gas NFBF plasma CBF flue gas
Investment cost, k€ 197,000 385,000 108,000 186,000
Variable cost/tCO2 captured 16.8 22.4 14.5 29.6
Maintenance/investment cost ratio 3% 3% 3% 3%
Maintenance, k€/yr 5910 11,550 3240 5580
Amortisation (15 years linear) 7% 7% 7% 7%
Total CO2 captured, Mt/yr 3.4 2.3 1.6 1.7
Total cost CO2 captured, €/t 22.6 39.1 21.2 40.8
1322 N.H. Duc et al. / Energy Conversion and Management 48 (2007) 1313–1322
8. Conclusions and perspectives
(1) Thermodynamic equilibrium of CO2–N2 hydrates has
been investigated by using TBAB as an additive. The
experimental results show that the presence of TBAB
decreases considerably the formation pressure of
simple hydrates (CO2 or N2) and mixed hydrates
(CO2–N2). Other interesting points are that the CO2
selectivity in the hydrate phase is at least four times
higher than in the gas phase, and the gas storage
capacity of mixed hydrates CO2–N2–TBAB is about
35 vol of gas per volume of hydrate.
(2) Simulation of a continuous CO2 capture unit is done
by PRO II. To meet conditions suitable for pipeline
transport followed by injection of CO2 into many
potential geologic storage reservoirs and for
enhanced oil recovery and clean N2 rich gas, we need
a multi-stage crystallization with a pressure from 7.5
to 50 bar at 283 K. From an energetic cost estima-
tion, we see that the hydrate technology for gas sep-
aration is cheaper in the case of a CO2 rich source
gas.
(3) The preliminary costing shows the process is viable
with a production cost of 22 and 40 € for a ton of
captured CO2 corresponding to NFBF (with shaft
injection and plasma) and conventional BF (top gas
and flue gas), respectively.
(4) It is possible to crystallize hydrates continuously
according to the literature. Current research is under-
way to determine the mixing type and kinetics of
hydrate crystallization because the essential point of
this technology is the contact between the gas phase
and liquid phase.
(5) It is possible to have a lower energetic cost if we use a
system of air refrigerant to cool the fluid after the
compressors or to melt hydrate particles (at 10 C).
Another positive point is that we used a COP of heat
exchangers of 2, while this coefficient can be higher in
reality.
(6) Gas separation by hydrate technology will be more
competitive in application fields where the inlet gas
has a high pressure such as the oil and gas industry.
Acknowledgement
This study benefits by the financial support of European
project ULCOS (Ultra Low CO2 Steelmaking).
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