PROCEEDINGS OF ECOS 2012 - THE 25TH INTERNATIONAL CONFERENCE ON

EFFICIENCY, COST, OPTIMIZATION, SIMULATION AND ENVIRONMENTAL IMPACT OF ENERGY SYSTEMS

JUNE 26-29, 2012, PERUGIA, ITALY

CAPTURE OF CARBON DIOXIDE USING GAS

HYDRATE TECHNOLOGY
Beatrice Castellania, Mirko Filipponib, Sara Rinaldia and Federico Rossib
a
CRB Biomass Research Center, University of Perugia, Perugia, Italy, castellani@ipassnet.it
b
CIRIAF, University of Perugia, Perugia, Italy, filipponi.unipg@ciriaf.it CA

Abstract:
According to IPCC Fourth Report, carbon dioxide emissions from the combustion of fossil fuels have been
identified as the major contributor to global warming and climate change. To reduce these environmental
concerns, there is a considerable R&D effort in all technical fields to capture carbon dioxide and
subsequently lower the emissions.
One of the new approaches for capturing carbon dioxide is based on gas hydrate crystallization. Gas
hydrates have a large capacity for the storage of gases which also resemble an attractive method for gas
filtration.
Gas hydrates are crystalline solids, in which low molecular weight guest molecules are trapped inside cages
of hydrogen-bonded water molecules. These crystals are stable under high pressures and low temperatures.
The basis of the separation is the selective partition of the target component between the hydrate phase and
the gaseous phase. It is expected that carbon dioxide is preferentially encaged into the hydrate crystal phase
compared to the other components.
In the present paper, after a comparison of gas hydrates with existing capture technologies, a novel
apparatus for gas hydrate production is illustrated and results of a first set of experimental applications of the
reactor for CO2 hydrate formation and separation are presented. Results are a basis for setting up a
procedure for CO2 separation and capture.

Keywords:
Carbon dioxide capture, Gas hydrate, Gas separation, Promoters, Water spraying.

1. Introduction

Carbon capture and sequestration (or storage) - known as CCS - has attracted interest as a measure
for mitigating global climate change because large amounts of carbon dioxide emitted from fossil
fuel use are potentially available to be captured and stored or prevented from reaching the
atmosphere.
A variety of capture processes have been developed for removing or isolating carbon dioxide from a
gaseous stream. These processes include absorption, adsorption, membrane separation, cryogenic
fractionation [1-3].
After separation, the captured carbon dioxide must be definitely stored: methods under study
include storage in depleted oil reserves, salt formations, terrestrial ecosystems and geological
formations or direct injection into the deep ocean [4]. To be considered viable, a storage method
must provide stable and long-term storage, be environmentally safe and cost-effective.
One of the biggest issues is the high energy consumption for CO2 separation. It has been estimated
that, the cost of separation and disposal of CO2 from existing coal-fired, air-blown boilers would
increase the cost of electricity by about 75% [5]. The cost of CO2 separation may reduce the power
generation efficiency from 38 to 26% [6].
Therefore, the major research interest is in the development of new less energy intensive processes.
Several works on estimation of energy consumption for CCS processes are available in literature. In
every CCS process, separation of CO2 from a flue gas mixture and its compression are the largest
contributors to the cost [2,6,7].
Aaron and Tsouris [8] reviewed in detail all processes available for recovery of CO2 from a flue gas
mixture including some which are still at the laboratory stage and concluded that the absorption
with monoethaolamine (MEA) is the best method. However the regeneration of the solvent makes
the absorption process energy-intensive.
The need to reduce costs motivates further research into the subject. One of the novel separation
techniques for subsequent storage or utilization of CO2 is through gas hydrate formation [8].
Hydrate technology for gas separation seems to be cheaper in case of a CO2 rich source gas and gas
separation by hydrate technology will be competitive in application fields where the inlet gas has a
high pressure such as the oil and gas industry [9].
Gas hydrates are crystalline solids, in which low molecular weight guest molecules are trapped
inside cages of hydrogen-bonded water molecules.
The three most commonly occurring hydrate structures are Structure I (sI), Structure II (sII) and
Structure H (sH), all with individual crystal structures (see Fig.1). The three structures are formed
by five different water cavities, the 512, 51262, 51264, 51268 and the 435663 [10]. In its pure form, the
unit cell of the sI hydrate contains two 512 and six 51262 cavities while a unit cell of the sII hydrate
contains sixteen 512 and eight 51264 cavities. Both of these unit cell lattice structures belong to the
cubic type. The sH hydrate structure is more complex and contains three 512, two 435663 and one
51268 cavities [10]. This hydrate structure forms a hexagonal unit cell.

Fig. 1. Hydrate structures.

A given hydrate structure is typically determined by the size and shape of the guest molecule.
Carbon dioxide is known to form structure I. Each cavity may encapsulate one - or in rare cases
more - guest molecules of proper sizes. It is the presence of the guest molecule that stabilizes the
crystalline water structure at temperatures well above the normal freezing point.
Gas hydrate technology may be used as a CO2 separation method but also in marine sequestration
applications, where the replacement of CO2 in marine methane hydrate fields is carried out. Results
of this process will be sequestration of CO2 and release of methane for energetic purposes [4].
As a separation method, gas hydrates may be used with treated flue gas from power plants in which
CO2 is separated from N2 and O2; with synthesis gas from integrated coal gasification power plants,
in which CO2 is separated from H2, but also in biogas upgrading processes, in which CO2 must be
separated from biomethane [1;9;11].
The basis of the separation is the selective partition of the target component between the hydrate
phase and the gaseous phase. It is expected that CO2 is preferentially encaged into the hydrate
crystal phase compared to the other components. For instance, the equilibrium pressure of N2
hydrate is three times greater than that of CO2. This difference allows to separate CO2 from treated
flue gas, that is a CO2-N2 mixture [12].
Flue gas from power plants usually contains from 15% to 20% mol. of CO2 and are released at
atmospheric pressure. The gas/hydrate equilibrium pressure for this kind of gas mixture is relatively
high. For example, the equilibrium pressures for a gas mixture containing CO2 at 17.61% mol. are
7.6 MPa and 11.0 MPa at 274 K and 277 K, respectively [13]. These pressures are not compatible
with the industrial reality, since the operative cost will be expensive if it is necessary to compress
the gas to the hydrate formation pressure.
In addition, evaluations of energy consumption for gas separation processes by the clathrate hydrate
formation indicate that hydrate separation process is competitive – compared to other conventional
separation processes - under lower pressure conditions, as well as in case of lower hydrate
formation heat [14].
Consequently, the main challenge is to obtain a decrease in the operating pressure. This task can be
achieved using specific compounds called promoters that allows to reach milder conditions for
hydrate formation. A suitable promoter is essential to help in reducing the hydrate formation
pressure and the energy consumption.
Conventionally, water-soluble additives are classified either as kinetic or as thermodynamic
additives. Thermodynamic additives consist of organic compounds and have the tendency to
displace the equilibrium conditions towards higher temperatures or lower pressures. Kinetic
additives consist typically of surfactant molecules and have the effect to accelerate hydrate
formation [10,12].
Several studies report a significant reduction of hydrate equilibrium pressures at a given
temperature by adding small amounts of tetrahydrofuran (THF) in the aqueous phase. Kang et al.
[13] and Linga et al. [15] found that the equilibrium pressure of hydrates in the presence of this
additive is considerably lower than the case without the additive.
Another promoter is Sodium dodecyl sulfate (SDS), which seems the best commercially available
surfactant to be used for enhancement of hydrate formation [16] and has already been investigated
in various works [17-20]. It was found that a small concentration of SDS added to the aqueous
phase drastically increases the kinetics of hydrate formation.
Recently, Liu et al. [21] and Torré et al. [22] showed that THF and SDS used in combination are
efficient additives for promoting CO2 hydrate formation.
According to previous works [23-26] a continuous production of hydrates is feasible, provided that
the technology assures an optimal contact between gas and liquid phases.
The choice of the correct gas-liquid mixing method, together with the proper promoter, is crucial
for producing hydrates in a continuous manner suitable for scale-up to industrial settings.
The apparatus described in the present work allows the use of aqueous solutions with additives for
rapid hydrate production.
In particular, the reactor was designed to maximize interfacial area between reactants. A first set of
hydrate formation experiments indicated that mass transfer barriers and thermal effects that
negatively affect conversion of reactants into hydrate are minimized, resulting in fast hydrate
production and good storage capacity [20].
In the present paper, an improved configuration of the apparatus and its application to CO2 hydrate
formation are presented and discussed. Experiments on formation of hydrates from pure CO2 are
preparatory to further applications, such as biogas upgrading and CO2 replacement in methane
hydrates.

2. Experimental apparatus

The experimental apparatus consists of a high-pressure cylindrical AISI 304 stainless steel vessel
with internal diameter of 200 mm, an internal length of 800 mm and a total internal volume of 25 l.
It has been designed for pressure values up to 120 bar and provided with a safety valve (Fig. 2).
Fig. 2. Schematic diagram of the experimental apparatus.

To remove reaction heat and to ensure a rather constant internal temperature, the reactor was
provided with copper cooling coils wrapped around the outside of its vessel wall and with an
internal heat exchanger constituted by a finned tube.
The external cooling coils were coated with a thermally insulating paste and a metallic sheet to
minimize thermal dispersion from coils to external environment. The cooling medium is ethylene
glycol – water solution supplied by an air-cooled chiller (GC-LT Eurochiller).
Two side flanges and a bottom- smaller - flange are used to seal the reactor. One side flange has
appropriate ports for access to the interior. The five ports are used for inserting 2 temperature
sensors, for gas inlet and outlet and for pressurized aqueous solution recirculation. The temperature
sensors are mineral insulated type T thermocouples (accuracy class 1) and measure the temperature
inside the vessel in the lower part and in the upper part, near spray nozzles (see Fig. 1). The gas
inlet line is equipped with a pressure sensor, that is a digital piezo-resistive manometer (Kobold -
accuracy class 0.5) and a mass flow meter (Bronkhorst Hi-Tech) to measure flow rate of gas
injected in the reactor. Gas is supplied directly by gas bottles through a pressure-reducing valve,
that provides adjustment of the pressure to the gas injection line. Gas is injected through a manifold
on which five check valves are mounted.
The bottom flange has two ports, the former is used for the initial aqueous solution uploading and
the latter is connected to a pump for recirculation. The pump flows the aqueous solution, previously
uploaded inside the reactor, to the atomizing manifold. Water is atomized by six hydraulic nozzles
mounted on the internal part of the manifold itself. Such devices for water spraying allow control of
dimensions of water droplets and water flow. The manifold is equipped with pressure gauge for the
measure of differential pressure and with a thermocouple for the measure of recirculated solution
temperature.
Voltage signals from pressure transducers and temperature sensors are collected by a software for
data acquisition on a personal computer. The installation of the apparatus is shown in Fig. 3.
Fig. 3. Installation of the experimental apparatus.

2.2. Materials

Carbon dioxide (99% purity) was supplied by Air Liquide Italia Service. Tap water was used to
prepare solutions. SDS (purity >99%) and THF (purity >99.8%) were from Sigma-Aldrich.

2.3. Procedure for hydrate formation

The reactor was designed to produce hydrates in a rapid manner, with hydrate formation times of
few minutes. Moreover the new - improved - configuration is suitable for hydrate formation both
through bubbling gas into the liquid phase and through spraying aqueous solution into the gas
phase. In this set of experiments, the reactor was used to produce carbon dioxide hydrates through
spraying aqueous solution into the gas phase according to the procedure described below.
The established amount of aqueous solution is firstly uploaded and the reactor is filled with carbon
dioxide from gas bottles until the internal pressure equals the experimental pressure and then
cooled. Gas is bubbled into the liquid phase through 5 check valves. The temperature is controlled
in order to achieve relatively uniform values inside the reactor. When the experimental conditions
are reached, aqueous solution is flowed by the recirculation pump through the nozzles.
Since the flow rate of aqueous solution through the nozzles depends on the differential pressure on
nozzles themselves, the water spraying is continued for several minutes until the established total
amount of aqueous solution is injected. During the experiment pressure and temperature data are
collected every 5 seconds.
Each experiment is carried out with a constant internal pressure. When the internal pressure
decreases because of hydrate formation, gas is injected into the reactor to re-establish the correct
pressure value.
Investigations were carried out in batch conditions. Therefore, at the end of each experiment, gas is
vented out from gas outlet port. Flange is opened both for visual observations and for taking hydrate
samples out.
In fact, several samples are taken directly out from the reactor. Hydrate storage capacity is
determined putting hydrate samples inside a custom built dissociation vessel. It is a cylindrical AISI
304 stainless steel vessel with a volume of 1.4 lt. It was designed and built to carry out the
dissociation of samples of gas hydrate formed.
After sealing the vessel, the dissociation starts and gas pressure and temperature after dissociation
are measured. To calculate number of gas moles Eq.(1) was used:

PV=ZnRT (1)

where P is the gas partial pressure in the vessel at the end of dissociation, V is the volume of gas in
the vessel, n is number of the gas moles, T is the temperature in K at the end of dissociation, R is
the universal gas constant, and Z is the compressibility factor, which can be calculated using
Benedict-Webb-Rubin equation of state.
As the number of gas moles is calculated, hydrate storage capacity, measured both in %wt of CO2
and in Nm3/m3, can be determined, since hydrate density is known.
In the calculation of hydrate storage capacity, the contribute of CO2 solubility in water was also
taken into account.

3. Results and discussion

A first set of experimental runs were carried out for CO2 hydrate production. Effects of additives,
such as THF and SDS, were tested. The amount of additives was chosen according to the optimal
ranges of concentration found in literature [15, 18, 19].
Typical profiles of internal pressure and temperature for an experimental run of 15 minutes are
shown in Fig. 3. Those profiles are for experimental run 2 in Table 1.
In particular, internal temperature is calculated as the average of the two temperature values
measured by two thermocouples in two different positions.
All experimental runs were carried out with an internal pressure of 3 MPa and with initial
temperature values of ca. 3 °C. With an experimental pressure of 3 MPa, the equilibrium
temperature of carbon dioxide hydrates is ca. 280 K [27], therefore experiments were carried out
with a not negligible subcooling as a driving force for the process.
Before starting aqueous solution recirculation and spraying, a slight decrease in pressure values was
observed and ascribed to carbon dioxide solubility. Therefore, only when constant values of
temperature and pressure were reached, recirculation started and continued for 15 minutes (runs
1,2,3 in Table 1) or 30 minutes (Runs 4,5 in Table 1).
As a result of the hydrate formation, which is an exothermic process, internal temperature increases
after ca. four minutes. Heat removal and temperature control is an issue, especially for applications
in scaled-up systems, in which constancy and uniformity of internal temperature are difficult to
achieve. With the improvements brought to the temperature control system, variations were kept
within 1 °C, as shown in the temperature profile.
Moreover, internal and external heat exchangers of the apparatus allow to achieve also relatively
uniform values of temperature inside the entire internal volume.
In Fig.4 it can be noted that internal pressure is constant for the first minute and then decreases
smoothly for 6-7 minutes. This can be ascribed to gas consumption due to hydrate formation. The
following four peaks result from gas injection for re-establishing the fixed experimental pressure.
After each peak, a rapid decrease in internal pressure, due to formation of gas hydrates, is
observable.
 8 32

7 30

6 28
Temperature (°C)

5 26

Pressure (bar)
4 24

3 22

2 20
Internal Temperature
1 18
Internal Pressure
0 16
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

Time (min)

Fig. 4. Pressure and temperature profile with elapsing time for CO2 hydrate formation in SDS 300
ppm- experimental run 2 in Table 1. Water spraying starts at t = 2 min.

In Fig. 5 pressure profiles for runs 1, 2, 3 in Table 1 are reported. These three runs help to determine
the effects of two different promoters (SDS and THF). It is evident that in absence of promoter,
pressure decreases, due to gas capture in the hydrate structure, are not observable. On the other
hand, in presence of promotor, pressure starts decreasing after 4-5 minutes, with an induction time
shorter than those observed in other experiments described in literature, as already proved in our
previous applications [20].

32

31

30
Pressure (bar)

29

28
no promotor
SDS 300 ppm
27
THF 1%wt

26
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Time (min)
Fig. 5. Pressure profiles with elapsing time for CO2 hydrate formation with and without
promotors- experimental runs 1-2-3 in Table 1. Water spraying starts at t = 1 min.
Several samples were taken directly from the reactor. Hydrate storage capacity was determined
putting hydrate samples inside a custom-built dissociation vessel, as described in section 2.3.
Hydrate storage capacity was measured in CO2wt% (weight percentage) and in Nm3/m3 (Nm3 of gas
entrapped in 1 m3 of hydrates), since these two parameters represent, in a macroscopic and
engineering approach, the capability of hydrates to entrap gases in their structure.
Results of experimental applications are reported in Table 1. Initial temperature is calculated as the
mean value of those measured in the lower and upper part of the reactor, before starting
recirculation and spraying.
Table 1. Results of experimental applications for CO2 hydrate formation.
Run T initial, Promotor Water spraying CO2 Wt% Storage
°C time, min capacity
Nm3/m3
1 1.7 - 15 1.3 6.4
2 3.0 SDS 300 15 8.0 47.4
ppm
3 2.2 THF 1%wt 15 5.3 30.9
4 4.0 SDS 300 30 9.2 62.3
ppm
5 3.8 THF 1%wt 30 7.5 44.6

For comparison, a first experiment without additives was carried out (Run1). Results show that in
this case gas content is very small and the effect of gas solubility is not negligible.
Both SDS and THF promote formation of gas hydrates with a short reaction time, suitable for
industrial in-continuo applications (Run 2-3). Fig. 6 shows the picture of the hydrates formed in
Run 2.

Fig. 6. Carbon dioxide hydrates on the internal heat exchanger.

Gas storage increased of 15%, in case of SDS, and 41%, in case of THF, if the spraying time was
doubled (Run 4-5).
Gas storage capacity values are consistent with or rather greater - in case of SDS - than that
observed by other authors [9].
4. Conclusions
In the present paper, a novel apparatus for gas hydrate production is illustrated and results of a first
set of experimental applications of the reactor for CO2 hydrate formation are presented.
Improvements on reactor design allowed to overcome issues relating to thermal effects and mass
transfer barriers, resulting in a rapid CO2 hydrate formation with reaction times of even 15 minutes
with additive promotion.
Carbon dioxide hydrate formation was carried out in mild operating conditions, such as pressure
values of 30 bar and temperature of 2-3 °C. The maximum value of storage capacity was 62.3
Nm3/m3 in presence of SDS with a reaction time of 30 minutes. Gas storage capacity values are
consistent with or rather greater - in case of SDS - than that observed by other authors.
Results on CO2 hydrate formation are preparatory to investigation on other applications of industrial
interest. In particular, our research activities will focus on CO2 separation from gas mixture,
especially in case of biogas upgrading, and CO2 replacement in methane hydrates.

Acknowledgments
The authors would like to thank Consorzio IPASS Scarl, Italy for providing laboratory personnel
and materials.

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