Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
  • B01D53/62—Carbon oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/81—Solid phase processes
  • B01D53/82—Solid phase processes with stationary reactants
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/28016—Particle form
  • B01J20/28019—Spherical, ellipsoidal or cylindrical
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3204—Inorganic carriers, supports or substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
  • B01J20/3244—Non-macromolecular compounds
  • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
  • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
  • B01J20/3253—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
  • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/102—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/104—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/106—Silica or silicates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/106—Silica or silicates
  • B01D2253/108—Zeolites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/20—Organic adsorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/25—Coated, impregnated or composite adsorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
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  • B01D2257/504—Carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
  • B01D2258/0283—Flue gases
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
  • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

• Reactive media comprising a porous support impregnated with an organic compound capable of forming gas clathrates, and its use for the separation and storage of CO 2
• the present invention relates to a reactive medium comprising a porous support impregnated with an organic compound capable of forming gas clathrates, processes for preparing such a medium, as well as its uses, especially in industrial gas separation processes.
• Natural gas is currently the third most widely used source of energy in the world, after oil and coal.
• the natural gas processing chain it is necessary to separate the pollutants that are present there for economic or technical reasons.
• these pollutants it is the C0 2 which is most frequently encountered and which is generally the most concentrated in the flow of gas to be treated.
• there are numerous processes for separating C0 2 in natural gas such as absorption by chemical, physical or hybrid solvents, adsorption on solid particles (adsorbents), the use of membranes and cryogenic processes, as described in particular by Rufford et al., Journal of Petroleum Science and Engineering, 2012, 94-95, 123-154. These different techniques nevertheless have the disadvantage of generating high costs.
• a gas clathrate is an inclusion complex consisting of several molecules called “host molecules” forming a molecular cage around a molecule of gas.
• the host molecules thus form an open structure with cavities or channels in which atoms or gas molecules of appropriate size are physically entrapped, encapsulated.
• the molecules trapped in these cages are called "guest-molecules”. Since the molecular network forming the cages is stabilized by weak bonds of the hydrogen bonding type, the structures thus formed are also designated by the acronym HOFs ("hydrogen-bonded organic frameworks").
• Molecules capable of driving clathrates (or HOFs) in the presence of a molecule-guest of suitable size must have particular characteristics enabling them to associate with one another by forming cavities.
• clathrates must first be able to form between them weak bonds of the "hydrogen bond" type.
• water which can form, under certain conditions, clathrates commonly called “hydrates", one of the best known being that formed with methane (methane hydrate).
• Organic host molecules constituting clathrates are also known to those skilled in the art, and have been the subject of numerous scientific works and publications.
• hydroquinone (quinone family), a well-known model compound for forming clathrates (Mak et al., Hydroquinone, Encyclopedia of supramolecular chemistry, Vol. 1, Editors JL Atwood and JW Steed, 2004, CRC Press, Talor & Francis, pages 679-686)
• hydroquinone molecules in which one or both hydroxyl groups -OH are substituted with a thiol group -SH.
• phenol derivative mention may be made in particular of mono-substituted phenols such as p-cresol, p-bromophenol, ethyl phenol, t-butyl phenol, phenyl phenol, p-fluorophenol, m-phenol and the like.
• -Fluorophenol and o-fluorophenol MacNicol et al Structure and Design of Inclusion Compounds: The Clathrate of Hydroquinone, Phenol, Dianin's Compound and Related Systems, pp. 1-45, JL Atwood, JED Davies, DD MacNicol., Inclusion Compounds, Vol. 2, 1984, Academy Press Inc., London).
• R Me for example (MacNicol et al., Structure and design of inclusion compounds: the clathrate of hydroquinone, phenol, Dianin's compound and related systems, pages 1-45 in JL Atwood, JED Davies, DD MacNicol., Inclusion compounds, Vol. 2, 1984, Academy Press Inc., London). obtained by substitution of carbons (C2) and (C4)
• R 2 H
• gas hydrates in which the host molecules are water molecules, have already been studied for the capture of C0 2 .
• the use of gas hydrates does not make it possible to obtain a high selectivity in favor of CO 2 , for example in the case when CO 2 is separated from certain gas mixtures, for example a mixture of CO 2 and CO 2. CH 4 .
• organic clathrates in which the host molecules are organic molecules, are selective for certain gases, such as C0 2 , as shown by Lee and Yoon, The Journal of Physical Chemistry, C 201 1, 1 , 22647-22651, and Lee et al., ChemPhysChem 201 1, 12, 1 -4, in the case of an organic hydroquinone clathrate.
• the hydroquinone used in these studies is commercial solid hydroquinone milled and this type of solid packaging proves not usable in an industrial gas treatment process. Indeed, it has several disadvantages, especially because it is crystal powder, the gas / solid exchange surface is relatively low, there may be a clogging of the contactors and its use leads to the formation of fines particles.
• the formation of organic gas clathrates requires particular pressure and temperature conditions, which can vary depending on the medium in which they are formed.
• organic compound (s) in the sense of the present invention, an organic compound (s) known (s) of the state of the art, particularly of the literature, as being able to act as molecule (s) -host (s) constitutive of clathrate, that is to say capable (s) to assemble to form clathrates gas.
• organic compounds may especially be those mentioned above.
• clathrate denotes an inclusion complex consisting of one or more molecular hosts forming a molecular cage (FIG. 1A).
• gas clathrate then designates the assembly formed by a molecular cage and a molecule of gas located within the cage ( Figure 1B).
• the reaction of capture of a molecule of gas by a clathrate is qualified as “enclathration”, while the reaction of release of a molecule of gas by a gas clathrate is qualified as "declathration”.
• reactive media means a medium or system capable of reacting via a chemical reaction and / or a physical and / or physicochemical process when brought into contact with appropriate chemical compounds.
• porous support is intended to mean a solid material comprising pores and on which a given compound may be deposited.
• an organic compound capable of forming gas clathrates is deposited on the porous support. This organic compound gives the media of the invention its reactive character, at least in part, by its ability to form gas clathrates.
• the present invention therefore proposes a reactive medium comprising a porous support on which is deposited, on the surface and / or within the pores of the support, an organic compound in solid form, acting as a host molecule constituting clathrate.
• a reactive medium comprising a porous support on which is deposited, on the surface and / or within the pores of the support, an organic compound in solid form, acting as a host molecule constituting clathrate.
• the weight percentage of said organic compound deposited is 5% to 60% by weight relative to the total weight of said reactive media.
• Said organic compound may especially be chosen from hydroquinone and hydroquinone molecules in which one or both -OH groups are substituted with -SH; phenol, p-cresol, p-bromophenol, ethyl phenol, t-butyl phenol, phenyl phenol, p-fluorophenol, m-fluorophenol and o-fluorophenol; the Dianin compound and its derivatives in which the oxygen atoms are substituted with sulfur atoms; quinazolinone; urea, thiourea, selenourea,
• porous supports suitable in the context of the invention must be usable in industrial processes, especially for gas separation, and in particular, not to degrade in the temperature and / or pressure conditions implemented in these processes. They must have a high mechanical strength in order to avoid any phenomenon (attrition and fragmentation) likely to modify the size of the support.
• the porous support is selected from the group consisting of silica, alumina, activated carbon, molecular sieves and zeolites.
• the porous support is silica or alumina.
• the alumina may be beta or gamma type.
• Gamma-alumina is obtained by heating low-temperature aluminum hydroxides, also called low-temperature transition alumina; it crystallizes according to a spinel structure with defects.
• the beta-alumina is a sodium aluminate, produced based on Al 2 O 3 alumina and containing a few percent of sodium oxide (Na 2 O), with very small amounts of silica and iron oxide.
• Na 2 O sodium oxide
• the peculiarity of this structure is its two-dimensional character: the crystal is made of thin parallel layers of dense alumina separated from each other by busy planes in which the sodium ions are confined.
• the porous support comprises pores of size between 2 nm and 150 nm, preferably between 20 nm and 120 nm.
• the porous support comprises, for example, pores of 50 nm or 100 nm.
• the pore size of the porous support is such that the organic compound can be deposited in solid form inside the pores and form gas clathrates therein when the reactive medium is brought into contact with gas.
• the porous support is in the form of porous particles, in particular of average size between 20 ⁇ and 5 mm, preferably between 40 ⁇ and 700 ⁇ for a fluidized bed process and between 1 mm and 5 mm for bed operations. fixed or moving bed.
• beads of porous material for example silica beads, are used.
• the choice of the size of the porous particles generally depends on the desired use and therefore varies according to the stage of the industrial process in which it is desired to implement the reactive media. Nevertheless, the performance of gas capture is often improved as the particle size decreases. Porous particles of small size, for example 45 ⁇ to 500 ⁇ , will therefore preferably be chosen.
• the porous support has a specific surface area of 30 m 2 / g to 1000 m 2 / g.
• the gas / solid exchange surface is considerably increased.
• the specific surface area increases, the amount of organic compound deposited increases and the number of capture sites of the gas molecules, ie the organic clathrates, increases, thus leading to a better capture efficiency.
• the mass percentage of solid deposition is from 5% to 60%, advantageously from 10% to 30% by weight relative to the total weight of said reactive media.
• the mass percentage of solid deposition can be determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques.
• the thickness of this deposit typically depends on the average pore diameter of the porous support. This deposit must be thick enough so that gas clathrates can be formed and thin enough to prevent the pores from clogging, which would reduce the access of gas molecules to clathrates. In the particular case where the pores would be completely filled with solid deposit, the gas molecules would have access only to the pore entry surface. Access to clathrates would then be possible by progressive diffusion of the gas into the clogged pores, which would make the clathration reaction extremely slow and unusable in an industrial process.
• the porous support comprises a solid deposit of an organic compound capable of forming gas clathrates.
• the organic compound is selected from the group consisting of hydroquinone and its derivatives, phenol and its derivatives, the compound of Dianin and its derivatives, quinazolinone and urea and its derivatives. derivatives.
• the organic compound is hydroquinone and phenol.
• said organic compound is hydroquinone.
• This forms clathrates that are selective for certain gases, notably C0 2 .
• gases notably C0 2 .
• the present invention also relates to a process for preparing a reactive medium according to the invention comprising the following steps:
• Step a) consists in impregnating the porous support with a solution comprising the organic compound, thus leading to the production of a porous support impregnated with the organic compound in liquid form.
• Step b) then consists of drying the impregnated porous support in order to obtain a solid deposit of the organic compound at the surface and within the pores of the support.
• the drying step b) is for example carried out in an oven.
• the porous support for example silica beads
• the porous support is immersed in a solution comprising the organic compound and then dried in an oven in order to obtain a thin layer of solid deposit lining the pores of the porous support.
• Steps a) and b) of the process as defined above can be carried out in several separate devices (liquid-phase impregnation) or in a single device.
• the liquid-phase impregnation process may further comprise a step of filtering the porous support between the impregnating step a) and the drying step b).
• This filtration step makes it possible to eliminate the excess solution comprising the organic compound in the porous support, allowing, after drying, obtaining a thin layer of solid deposition of the organic compound on the porous support.
• the solvent of the solution comprising the organic compound which may be described as "impregnating solution” is a solvent in which the organic compound is stable and soluble.
• concentration of the organic compound in the impregnating solution and therefore the amount of organic compound that can be deposited on the porous support generally depends on the nature of the solvent.
• the organic compound is hydroquinone used in the form of saturated hydroquinone alcoholic solution.
• Alcohol solution denotes a solution in which the solvent is an alcohol, especially ethanol.
• the present invention also relates to a reagent medium obtainable by the method described above.
• the present invention also relates to the use of the reagent medium according to the invention for the capture of C0 2 .
• the present invention relates to a process for separating C0 2 in a gas mixture comprising C0 2 and at least one gas different from C0 2 ; in said method, a capture of the CO 2 is carried out by cleavage by means of a reactive medium according to the invention.
• the process according to the invention may be discontinuous, semi-continuous or continuous.
• Capturing C0 2 by cleavage in the reactive medium according to the invention has the advantage of being reversible. Indeed, if we proceed to declathration of the gas under vacuum to release the clathrate gas, these clathrates can again capture C0 2 , and this manner identical to the previous capture reaction. In particular, the CO 2 capture reaction is reproducible in terms of reaction rate and amount of captured gas.
• the reactive medium according to the invention is therefore reusable once regenerated by declathration of the gas.
• the present invention also relates to the use of the reactive medium according to the invention for the separation of CO 2 in a gas mixture comprising CO 2 and at least one gas other than CO 2 .
• the reactive medium according to the invention can be used to separate the
• the separation is particularly effective when it is a reactive medium comprising hydroquinone because the gas capture reaction by hydroquinone clathrates is much more selective for C0 2 than for CH 4 or H 2 (Lee et al., ChemPhysChem 201 1, 12, 1-4).
• the present invention also relates to the use of the reactive medium according to the invention for the treatment of natural gas, pre-combustion synthesis gas or post-combustion flue gas.
• pre-combustion synthesis gas treatment is meant the treatment of fuels, such as oil and coal, upstream of their combustion. This treatment consists of separating C0 2 from a C0 2 / H 2 mixture called "synthesis gas”.
• post-combustion flue gas treatment is meant the treatment of off-gases after the combustion in the air of fuels such as oil and coal.
• This treatment consists of separating C0 2 from a CO 2 / N 2 mixture, which may contain a small proportion of so-called “annex” gases such as oxygen, carbon monoxide (CO), sulfur oxides (SO x ) or nitrogen oxides (NO x ).
• annex gases such as oxygen, carbon monoxide (CO), sulfur oxides (SO x ) or nitrogen oxides (NO x ).
• the present invention also relates to the various uses described above in a discontinuous, semi-continuous or continuous industrial process.
• the process can be carried out by means of an installation comprising a reactor or column, having isolation valves, means for pressurizing this reactor as well as pressure regulating means as per FIG. example a pressure reducer or an automatic valve, a pressure control device such as a sensor or a pressure gauge, a heating and cooling means such as a jacket or an internal heat exchanger, a device for measuring the quantity of gas entering the reactor such as a flow meter, a device for recording and monitoring the reactor to check the temperature and pressure over time.
• the reactive medium is first loaded into the reactor, then is brought into contact with the gas to be treated under the appropriate conditions of temperature and pressure so that the organic molecules deposited in the reactive medium form clathrates with the gas present in the reactor. .
• the reactive media may undergo a conditioning or regeneration step prior to the reaction, for example with a heating step or a vacuum.
• the reactive media implemented in the form of reactive particles can be immobile, or moving in the reactor (rotary basket for example).
• the cleavage reaction occurring within the medium changes the gas composition initially introduced. Once the reaction is complete, the gas still present is purged by one of the reactor valves and the operating conditions of the reactor are modified in such a way that the gas clathrate is no longer stable and can release the gas, for example by increasing the temperature reactor or reducing its pressure.
• the gas thus recovered has a composition different from the initial gas, for example it has a higher CO 2 content than the initial gas.
• Another variant of operation consists in transporting the reaction medium after reaction in another apparatus, called reactor or dissociation column, to perform the gas release phase. This batch process is shown schematically in Figure 4.
• the process is most often carried out by means of several discontinuous separators operating either in a fixed bed or in a fluidized bed, at least one of which is in regeneration while the others are operating in reaction.
• the fixed bed is a reactor or a column containing a fixed layer of reactive particles, arranged in bulk, through which the gas can circulate, while inside a fluidized bed, the particles are set in motion with the flow of gas entering the reactor.
• the fixed bed or fluidized bed reactor has the same elements as for discontinuous operation, with, in addition, a gas inlet and outlet device.
• the particles have a narrow particle size but their average size can vary between 40 microns and 5 millimeters depending on operations.
• FIG. 6 represents an operation of a multi-stage fluidized bed in which the gas to be treated passes successively through several beds of fluidized particles.
• a complete unit comprises two sections: one of capture and one of regeneration with solid recycling.
• Gas-solid contact occurs either in moving beds or in multi-stage fluidized beds with solid recirculation between the stages ( Figure 8).
• the present invention also relates to the use of the reactive medium according to the invention for the storage of gases, such as CH 4 , CO 2 or H 2 .
• the present invention also relates to a method for treating natural gas, precombustion synthesis gas or post-combustion flue gas, comprising the CO 2 separation method according to the invention.
• the present invention also relates to a reactor for separating CO 2 from a mixture of gases composed of CO 2 and at least one gas different from CO 2 ; said reactor comprising:
• said enclosure comprises a reactive medium according to the invention as defined above.
• said reactor is operating in a fluidized bed. According to another embodiment, said reactor is operating in a fixed bed.
• said operating pressure is between 0 and 100 bar.
• said operating temperature is between 0 and ⁇ ⁇ ' ⁇ .
• Figure 1 shows (A) an example of a hexagonal arrangement of a type 1 organic clathrate formed by hydroquinone molecules and (B) an example of an organic gas clathrate in which the sphere represents the gas molecule;
• FIG. 2 is a graph showing the mass in grams (g) of C0 2 captured by a reactive medium according to the invention as a function of time in minutes (min) during two consecutive cycles of cleavage, the first cycle being represented by rounds and the second cycle by squares;
• FIG. 3 is a graph showing the molar composition of the gas (in mol%) as a function of time (in minutes) during two successive formations when a reactive medium according to the invention is placed in the presence of a C0 2 mixture / N 2 of initial composition equal to 49.9 mol% C0 2 .
• the circles and triangles correspond to the concentration of C0 2 in the gas during the first and second formations, respectively.
• the squares and crosses correspond to the concentration of N 2 in the gas during the first and second formations, respectively.
• Figure 4 schematically shows a batch process according to the invention.
• FIGS. 5, 6, 7 and 8 represent different types of processes according to the invention:
• Figures 9 and 10 show the Raman spectra of the reactive media respectively before and after experiment 3 of Table 4 below.
• a reactive medium according to the invention was developed by impregnating porous particles with a saturated organic alcohol solution.
• the porous support consists of silica, alumina or activated carbon.
• the impregnation was carried out by immersing the porous support in the alcoholic solution saturated with organic compound, and then the support was dried in an oven.
• Example 2 Use of a reagent medium according to the invention for the capture of C0 2 .
• Example 1 The reactive media prepared in Example 1 were tested in the presence of pure CO 2 .
• Example 3 Use of a reactive medium according to the invention for the separation of C0 2 in a CO 2 / N 2 mixture.
• the reagent medium was prepared according to the same protocol as that described in Example 1. The analyzes carried out made it possible to measure that the amount of hydroquinone present in this reactive medium was equal to 27% by weight.
• the reactor is put at a temperature of 25 ° C using its double jacket in which circulates a coolant.
• the temperature of the reactor is measured via a PT100 probe.
• the particles were then contacted with a gas containing 49.9 mole% CO 2 , charging the reactor at a pressure of 35 bar using a pressure reducer and controlling the pressure through a pressure sensor disposed on the reactor.
• the pressure and temperature are recorded over time by an acquisition system, connected to a computer, at a frequency of 1 Hz.
• FIG. 3 shows that the composition of the gas is well modified over time, with a molar fraction of CO 2 decreasing and a molar fraction of nitrogen increasing.
• the C0 2 concentration was lowered by 9.8% and 9.5% during the first and second training, respectively.
• the characterization of the formed structure can be done, for example, using vibrational spectroscopy techniques such as Raman or Infra Red spectroscopy, which makes it possible to obtain characteristic spectra of the compounds studied.
• vibrational spectroscopy techniques such as Raman or Infra Red spectroscopy
• the organic molecule in question is reorganized to form a clathrate, it results in changes in its vibration spectrum, characteristics of the formed structure, and easily identifiable.
• the gas that is trapped within the clathrate has a characteristic signature and can be easily identified.
• the characterization of the reactive medium before and after experiment # 3 of Table 4 carried out by contacting the reactive medium P2 (silica / hydroquinone) with a mixture of CO 2 / CH 4 gas at 75 mol%, can be mentioned for example. in C0 2 .
• the characterization was carried out using a JOBIN YVON Raman spectrometer, model T64000.
• Figures 9 and 10 show two Raman spectra of the reactive media. The spectrum of Figure 9 was obtained before reaction and the spectrum of Figure 10 after reaction.
• C0 2 , C0 2 / CH 4 , C0 2 / N 2 gases and gas mixtures having compositions ranging from 25% to 100% of C0 2

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• 2013
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