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Creating innovative composite materials to enhance the
kinetics of CO 2 capture by hydroquinone clathrates
Romuald Coupan, Frédéric Plantier, Jean-Philippe Torré, Christophe
Dicharry, Pascale Senechal, Fabrice Guerton, Peter Moonen, Abdel Khoukh,
Sid Ahmed Kessas, Mehrdji Hemati
To cite this version:
Romuald Coupan, Frédéric Plantier, Jean-Philippe Torré, Christophe Dicharry, Pascale Senechal, et
al.. Creating innovative composite materials to enhance the kinetics of CO 2 capture by hydroquinone
clathrates. Chemical Engineering Journal, Elsevier, 2017, 325, pp.35-48. �10.1016/j.cej.2017.05.038�.
�hal-02065960�
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This is an author’s version published in: http://oatao.univ-toulouse.fr/21530
To cite this version:
Coupan, Romuald and Plantier, Frédéric and Torré, Jean-Philippe
and Dicharry,
Christophe and Sénéchal, Pascale and Guerton, Fabrice and Moonen, Peter and Khoukh,
Abdel and Kessas, Sid Ahmed
and Hemati, Mehrdji
Creating innovative composite
materials to enhance the kinetics of CO 2 capture by hydroquinone clathrates. (2017)
Chemical Engineering Journal, 325. 35-48. ISSN 1385-8947
Official URL: https://doi.org/10.1016/j.cej.2017.05.038
with a low molecular weight, such as carbon dioxide (CO2),
methane (CH4) and nitrogen (N2), can be trapped as guest mole
cules in a clathrate structure. A variety of host molecules, such as water, phenol and hydroquinone (HQ), have been studied in recent years and are described in literature[2]. Scientists have been fasci nated by gas clathrates for more than a century, but these solid compounds are now the focus of even greater attention owing to their possible practical applications such as CO2 capture and
sequestration. This new interest arises from their capacity to store large quantities of gases, more or less selectively depending on the clathrates considered and the gas mixture used.
To begin with, the most studied clathrate compounds are ‘‘gas hydrates”[3], which generally form at high pressure (a few MPa) and low temperature (a few K above 273 K) with water and gas. For the past 15 years or more, they have been the focus of many studies [4], which included adding chemical promoters or using different multiphase contactors[5 7]to overcome the many criti cal limitations that prevent hydrate based gas separation pro cesses from being deployed, from pilot to industrial scale. However, the use of gas hydrates to separate CO2from gas mix
tures such as CO2/CH4and CO2/N2is still hindered by the following
main obstacles: (i) the overall cost of the process is not competitive compared to others such as reactive absorption[8], except when the raw gas is already pressurized (as the gas compression costs are prohibitive in most cases); (ii) the difficulties in handling, con tacting and transporting a multiphase mixture composed of at least three phases that have to coexist (water or water/oil mixture, gases and solids) for the reaction to take place; (iii) the necessity to maintain a relatively low temperature in the apparatus for the gas hydrates to form (generally slightly above 273 K); and (iv) the low rate of hydrate formation and insufficient selectivity of gas hydrates toward CO2 in certain gas mixtures, particularly CO2/
CH4[9,10].
Secondly, HQ is a solid hydroxy aromatic compound recently identified in literature as a potential innovative clathrate candidate for gas storage and separation[11 13]. Interestingly, for different gas mixtures such as CO2/N2, CO2/H2 and CO2/CH4 [14,15], the
enclathration reaction with HQ seems to be highly selective to CO2. The thermodynamic pressure temperature conditions (i.e.
the clathrate phase equilibria) in which some HQ clathrates form and dissociate are mentioned in literature[16 19]and the equilib rium data and detailed characterization of CO2HQ clathrates were
recently published[20 21]. But although HQ clathrates seem very interesting for practical applications such as CO2 separation by
direct gas/solid reaction (i.e. without using any solvent), the gas clathrate formation kinetics need to be improved before these compounds can be used on an industrial scale. Previous studies involving tests carried out using powdered HQ have already attempted to do so [14,15,22]. But very fine HQ particles would be difficult to handle in an industrial gas solid contactor (such as a fixed bed reactor) for several reasons: (i) the gas circulating through the HQ powder causes a significant pressure drop that in some cases could be excessive, (ii) the very fine particles can be blown into the process equipment, and (iii) operators must apply stringent safety measures when handling large quantities of a fine pulverulent material such as HQ during loading and unloading of the reactor. Indeed, reactivity is limited by the contact area between the gas and the solid HQ, and depends on the specific area of the reactive medium used. Consequently, in an attempt to enhance the gas solid enclathration reaction, we developed a com posite material made of porous particles impregnated with HQ that can be used as a reactive medium in a clathrate based gas separa tion process.
There are two procedures for impregnation: wet impregnation (abbreviated as WI below) and dry impregnation (abbreviated as DI below) in a fluidized bed. Creation of a composite material by
WI consists of a dip coating method involving several steps: impregnation, filtration and drying[23]. DI in a fluidized bed was previously developed in the Laboratoire de Génie Chimique (chemi cal engineering laboratory) of Toulouse and patented by the INPT and the CNRS in 2001[24]. Unlike WI, creation of a composite material by DI in a fluidized bed is a ‘‘one pot process” in which the stages of impregnation, filtration and drying are carried out in just one apparatus. This technique consists in spraying a solu tion containing the organic precursor onto a warm fluidized bed of porous particles chosen as the support material for the precur sor. This condensed technique was initially used for depositing metal nanoparticles on porous supports (such as silica gel, alumina and activated carbon) and has shown that in operating conditions: (i) the deposition efficiency is close to 100%, (ii) the deposit is quasi uniform, and (iii) the size of the supported metal nanoparticles is controlled by the pore diameter[25 29]. In the present work, the composite materials synthesized by the two procedures (i.e. WI and DI) are evaluated as reactive media for CO2capture. Both the
gas storage capacity of the reactive media and data on the CO2cap
ture kinetics were measured and compared to the results obtained with pure powdered HQ. All experiments were performed at 3.0 MPa and 323 K by means of a gravimetric method using a mag netic suspension balance. These experimental conditions were chosen for two main reasons: (i) CO2HQ clathrates can form under
relatively high temperature (e.g. 323 K) and pressure[20]condi tions, which could be economically very advantageous when the raw gas is already hot and pressurized, the case for example of a production gas containing CO2/CH4; (ii) CO2 HQ clathrates may
reach their maximum capacity when the formation pressure is close to 3.0 MPa[30], justifying the operating pressure chosen for these tests.
2. Experimental section 2.1. Materials
The organic precursor used in this study is HQ (purity of 99.5 mol%) provided by Acros Organics. The solvent used in WI and DI is absolute ethanol (purity greater than 99 mol%). This choice was motivated by the high solubility of HQ in this solvent (e.g. 0.2063 mol% at 308.2 K)[31]and its low boiling temperature of 351 ± 2 K (calculated mean values obtained from the NIST) that facilitates the drying step. The N2, CO2and helium (He) used for the
experiments (minimum mole fraction purity of 99.995%) are pur chased from Linde Gas SA. The porous supports used are silica par ticles provided by SiliCycle. The experiments are conducted with two types of silica particles: high grade irregular silica particles (SiliaFlashÒ, referred to as SF below) and high purity analytical grade spherical silica particles (SiliaSphereÒ, referred to as SS below) with tight particle size distribution. Information concerning native SF and SS particles is given in theSupplementary Material. 2.2. Experimental set up and methods
Prior to impregnation, a saturated solution of HQ in ethanol was prepared at 308 K based on the solubility data and a correlation proposed by Li and coworkers[31]. Before each experiment, the solid particles were dried for 24 h at 423 K in a muffle furnace (from Nabertherm).
2.2.1. Wet impregnation
WI is performed in hermetic glass vessels. An oven (model 800, from Memmert) is used to maintain the temperature at a constant value with an accuracy of ±0.5 K. A vacuum filtration system com posed of a Buchner funnel connected to a vacuum pump is used for
same way as for the global capture capacity and reaction kinetics by using this type of composite material.
Acknowledgments
We would like to acknowledge the entire work group involved in the ORCHIDS project and the Carnot Institute ISIFoR (Institute for the Sustainable engIneering of Fossil Resources). We extend our thanks to the staff of the Service Analyse et Procédés of the University of Toulouse for their help. We also wish to thank Mathieu Molinier, Victor Cabrol and Sofiane Bekhti for their tech nical assistance and the Total E&P, ‘‘Gas Solutions” department for its financial backing. We would also like to thank Total for pro viding UMS 3360 DMEX with the Zeiss Xradia Versa 510 used to carry out the tomographic acquisitions reported in this article. Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the online version, athttp://dx.doi.org/10.1016/j.cej.2017.05.038. References
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