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PROCEEDINGS OF ECOS 2012 - THE 25 TH 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 Castellani a , Mirko Filipponi b , Sara Rinaldi a and Federico Rossi b

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 CO 2 separation. It has been estimated that, the cost of separation and disposal of CO 2 from existing coal-fired, air-blown boilers would increase the cost of electricity by about 75% [5]. The cost of CO 2 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 CO 2 from a flue gas mixture and its compression are the largest contributors to the cost [2,6,7].

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Aaron and Tsouris [8] reviewed in detail all processes available for recovery of CO 2 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 CO 2 is through gas hydrate formation [8]. Hydrate technology for gas separation seems to be cheaper in case of a CO 2 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 5 12 , 5 12 6 2 , 5 12 6 4 , 5 12 6 8 and the 4 3 5 6 6 3 [10]. In its pure form, the

unit cell of the sI hydrate contains two 5 12 and six 5 12 6 2 cavities while a unit cell of the sII hydrate

contains sixteen 5 12 and eight 5 12 6 4 cavities. Both of these unit cell lattice structures belong to the cubic type. The sH hydrate structure is more complex and contains three 5 12 , two 4 3 5 6 6 3 and one

5 12 6 8 cavities [10]. This hydrate structure forms a hexagonal unit cell.

[10]. This hydrate structure forms a hexagonal unit cell. Fig. 1. Hydrate structures. A given hydrate

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 CO 2 separation method but also in marine sequestration applications, where the replacement of CO 2 in marine methane hydrate fields is carried out. Results

of this process will be sequestration of CO 2 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 CO 2 is separated from N 2 and O 2 ; with synthesis gas from integrated coal gasification power plants,

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in which CO 2 is separated from H 2 , but also in biogas upgrading processes, in which CO 2 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 CO 2 is preferentially encaged into the hydrate crystal phase compared to the other components. For instance, the equilibrium pressure of N 2 hydrate is three times greater than that of CO 2 . This difference allows to separate CO 2 from treated flue gas, that is a CO 2 -N 2 mixture [12]. Flue gas from power plants usually contains from 15% to 20% mol. of CO 2 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 CO 2 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 CO 2 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 CO 2 hydrate formation are presented and discussed. Experiments on formation of hydrates from pure CO 2 are

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preparatory to further applications, such as biogas upgrading and CO 2 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).

up to 120 bar and provided with a safety valve (Fig. 2). Fig. 2. Schematic diagram

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

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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.

The installation of the apparatus is shown in Fig. 3. Fig. 3. Installation of the experimental

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.

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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:

P V = Z n R T

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 CO 2 and in Nm 3 /m 3 , can be determined, since hydrate density is known.

In the calculation of hydrate storage capacity, the contribute of CO 2 solubility in water was also

taken into account.

(1)

3. Results and discussion

A first set of experimental runs were carried out for CO 2 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.

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8 32 7 30 6 28 5 26 4 24 3 22 2 20 Internal
8
32
7
30
6
28
5
26
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
Temperature ( ° C)
Pressure (bar)

Time (min)

Fig. 4. Pressure and temperature profile with elapsing time for CO 2 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 29 28 no promotor SDS 300 ppm 27 THF 1%wt 26 1
32
31
30
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
Pressure (bar)

Time (min)

Fig. 5. Pressure profiles with elapsing time for CO 2 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.

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Hydrate storage capacity was measured in CO 2 wt% (weight percentage) and in Nm 3 /m 3 (Nm 3 of gas entrapped in 1 m 3 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 CO 2 hydrate formation.

Run

T initial,

°C

Promotor

Water spraying

time, min

CO 2 Wt%

Storage capacity Nm 3 /m 3

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 shows the picture of the hydrates formed in Run 2. Fig. 6. Carbon dioxide

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].

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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 CO 2 hydrate formation are presented. Improvements on reactor design allowed to overcome issues relating to thermal effects and mass transfer barriers, resulting in a rapid CO 2 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 Nm 3 /m 3 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 CO 2 hydrate formation are preparatory to investigation on other applications of industrial interest. In particular, our research activities will focus on CO 2 separation from gas mixture, especially in case of biogas upgrading, and CO 2 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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