EP2694187A1

EP2694187A1 - Particle of a phase change material with coating layer

Info

Publication number: EP2694187A1
Application number: EP12713227.2A
Authority: EP
Inventors: Vincent Gueret; Christian Monereau; Pluton Pullumbi
Original assignee: Air Liquide SA; LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Current assignee: Air Liquide SA; LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date: 2011-04-08
Filing date: 2012-03-13
Publication date: 2014-02-12
Also published as: US20140023853A1; FR2973806B1; CN103476479A; WO2012136912A1; FR2973806A1

Abstract

The invention relates to a PCM particle consisting of an agglomerate comprising a phase change material (PCM), and a coating layer having a different composition from that of the agglomerate.

Description

Particle of a phase change material with a coating layer

The invention relates to modifying the physical characteristics of particles of a phase change material (PCM) by coating said particles, mixing such a coated material with at least one adsorbent material, and the adsorption unit. implementing such a mixture.

The term "thermocyclic process" refers to any cyclic process in which certain stages are exothermic, ie accompanied by a release of heat, while certain other stages are endothermic, that is to say that is accompanied by a consumption of heat.

Typical examples of thermocyclic processes according to the present invention include pressure swing adsorption gas separation processes, and any method employing chemical conversion coupled with pressure swing adsorption cycles, as mentioned herein. above, to shift the balance of chemical reactions.

In the context of the present invention, the term "PSA process" designates, unless otherwise stipulated otherwise, any pressure-swing adsorption gas separation process, implementing a cyclic variation of the pressure between a high pressure, so-called adsorption pressure, and a low pressure, called regeneration pressure. Therefore, the generic name PSA process is used interchangeably to designate the following cyclic processes:

the VSA processes in which the adsorption is carried out substantially at atmospheric pressure, called "high pressure", that is to say between 1 bara and 1.6 bara (bara = absolute bar), preferably between 1.1 and 1.5 bara, and the desorption pressure, called "low pressure", is less than atmospheric pressure, typically between 30 and 800 mbar, preferably between 100 and 600 mbar.

the VPSA or MPSA processes in which the adsorption is carried out at a high pressure substantially greater than atmospheric pressure, generally between 1.6 and 8 bara, preferably between 2 and 6 bara, and the low pressure is below the pressure atmospheric, typically between 30 and 800 mbara, preferably between 100 and 600 mbara. the PSA processes in which the adsorption is carried out at a high pressure clearly above atmospheric pressure, typically between 1.6 and 50 bara, preferably between 2 and 35 bara, and the low pressure is greater than or substantially equal to the atmospheric pressure, therefore between 1 and 9 bara, preferably between 1.2 and 2.5 bara.

Subsequently, we will speak of "RPSA process" to designate very fast cycle PSA processes, generally less than one minute.

In general, a PSA process makes it possible to separate one or more gas molecules from a gaseous mixture containing them, by exploiting the difference in affinity of a given adsorbent or, where appropriate, of several adsorbents for these different molecules of gas.

The affinity of an adsorbent for a gaseous molecule depends on the structure and composition of the adsorbent, as well as the properties of the molecule, including its size, electronic structure and multipolar moments.

An adsorbent may be, for example, a zeolite, an activated carbon, an activated alumina, a silica gel, a carbon molecular sieve or not, a metallo-organic structure, one or more oxides or hydroxides of alkali or alkaline-earth metals, or a porous structure containing a substance capable of reacting reversibly with one or more gas molecules, such as amines, physical solvents, metal complexing agents, metal oxides or hydroxides, for example

Adsorption is an exothermic phenomenon, each molecule-adsorbent pair being characterized by an adsorption enthalpy (isosteric heat) or a reaction enthalpy in general. Symmetrically, the desorption is endothermic.

In addition, a PSA process is a cyclic process comprising several sequential stages of adsorption and desorption.

Consequently, certain stages of the PSA cycle are exothermic, in particular the step of adsorption of the adsorbed gas molecules on the adsorbent, while other stages are endothermic, in particular the step of regeneration or desorption of the molecules. adsorbed on the adsorbent.

The thermal effects that result from the enthalpy of adsorption or reaction enthalpy generally lead to the propagation, at each cycle, of a heat wave at the adsorption which limits the adsorption capacities and from a cold wave to desorption limiting desorption. This local cyclical phenomenon of temperature bursts has a significant impact on the separation performance of the process, such as productivity, separation efficiency and separation specific energy, as described in EP-A-1188470.

Thus, it has been shown that if the thermal beats due to the adsorption enthalpy were completely eradicated, the productivity of some current industrial PSA 02 would be improved by around 50% and the oxygen yield would be improved by 10%. . Likewise for the other types of PSA, the attenuation of the heat beats would lead to a noticeable improvement of the separation performances.

As this negative phenomenon has been identified, several solutions have already been described in an attempt to reduce or eliminate it.

Thus, it has been proposed to increase the heat capacity of the adsorbent medium by addition of inert binder, during the manufacture of the particles, by deposition of the adsorbent medium on an inert core, by addition of particles identical to the adsorbent but inert. For example, in the case of a PSA 02 process, it has already been tested to carry out the adsorption of the nitrogen contained in the air on a composite bed composed of zeolites 5 A and 3 A differentiating only by the size of their pores: only those of zeolite 5A allow nitrogen adsorption, since those of zeolite 3A are too small in size.

Furthermore, it has also been described the use of external means of heating and / or cooling to counter-balance the thermal effects of desorption or adsorption, such as the use of heat exchangers.

Thermal couplings between the adsorption phase and the regeneration phase have also been proposed, the adsorbent being placed in the successive passages of a plate exchanger, the circulation of the fluids then being organized so that the passages are alternately in phase. adsorption and desorption.

Another solution for decreasing the amplitude of thermal beats is to add a phase change material (PCM) to the adsorbent bed as described in US-A-4,971,605. In this way, the heat of adsorption and desorption, or part of this heat, is absorbed as latent heat by the MCP, at the temperature, or in the temperature range, of the phase change of the PCM. It is then possible to operate the PSA unit in a mode closer to the isotherm. In practice, phase change materials (PCMs) act as heat sinks at their phase change temperature, or on their phase change temperature range between a lower temperature and a higher phase change temperature.

In order to be able to handle them, whether in the solid or liquid state, the MPCs are in practice generally microencapsulated in a micronic solid shell, preferably based on polymers (melamine formaldehyde, acrylic, etc.).

Microencapsulated MCP, available in powder form, can not be introduced as such into an adsorbent bed because they would be driven by the gas flows flowing in the adsorber.

WO 2008/037904 discloses a PSA-type process employing a bed comprising adsorbent particles and particles of a phase change material (PCM) in the form of agglomerates with a density different from that of the adsorbent but meeting the criteria of stability of the mixture based on the ratio on the one hand densities and on the other hand diameters of the agglomerates of MCP and adsorbent particles in the composite bed.

One of the solutions that seems to be needed to improve the thermal PSA units and hence their performance, is to achieve mixtures of adsorbent and agglomerates of MCP dimension and density relatively close to avoid or limit the problems segregation.

However, a problem that arises is to provide a mixture of adsorbent particles and MCP retaining physical and especially mechanical properties compatible with their industrial use in different types of adsorbers such as for example cylindrical adsorbers vertical axis or horizontal, radial adsorbers; and for the different applications envisaged.

Indeed, in particular, to avoid problems of creation of dust, debris particles, local compaction ..., .the mixture must have sufficient characteristics in terms of crush strength, resistance to attrition , elasticity.

For the adsorbent itself, these properties are usually part of

particular specifications defining its physical characteristics. There is typically a crush resistance value, a characteristic value of the attrition resistance. The corresponding test methods are either standardized or specific to each supplier.

For example the crush resistance can be measured ball by ball or in bed. The number of balls, the preliminary sieving of the balls, their residual water content, the way to increase the applied pressure - for example the speed - must be defined in order to have reliable and repetitive measurements.

Resistance to attrition generally consists of measuring the percentage of dust mass created after having subjected a certain quantity of adsorbent to a well-defined treatment. Here again, all the parameters must be defined to obtain useful measurements.

It is not necessary here to go into the details of all the existing procedures to measure certain mechanical properties or to list the values of these properties for all the adsorbents but just to show that these mechanical properties are part of the characteristics of adsorbents and that minimum (eg crush strength) or maximum values (eg dust generation through attrition) are required to use the adsorbents effectively and safely.

It is therefore necessary to produce PCM particles having mechanical properties at least close to those of the adsorbents so that these particles are not the weakest link in the mixture by breaking or eroding.

Note that in the context of the present invention, will be called "diameter", the equivalent diameter of the MCP particle. The "equivalent diameter" of a particle is that of the sphere having the same specific surface area, the specific surface area being the surface area relative to the volume of the particle considered.

Thus, for a rod of diameter d and length 1, an equivalent diameter De is obtained such that: De = 6. 1. d / (2d + 4-1)

For a pellet such as d = 1, the equivalent diameter is the diameter of the particle. In general, for the majority of particle geometries used of the cylindrical type, there is an equivalent diameter of between 0.75 and 1.3 times the diameter of the cylinder.

For a spheroidal ball, the equivalent diameter is directly the diameter of the ball. For a population of essentially spherical beads whose diameters have an inherent dispersion in the industrial manufacturing process, we retain a conventional definition: the equivalent diameter of a population of beads is the diameter of identical balls which for the same volume of bed would give the same total area. In fact, since the diameter distribution has been determined (that is to say that the different fractions Xi of diameter Di have been determined, with preferably greater than or equal to 5 to obtain a sufficient accuracy, for example by sieving or from image processing apparatuses), the equivalent diameter is obtained by the formula: 1 / De = Σi (Xi / Di)

For crushed adsorbents, a form in which we can in particular find some activated carbons, the particles are assimilated to spheres whose diameter distribution is determined by sieving, and then the preceding calculation formula is applied.

A solution of the invention is a particle of MCP consisting of an agglomerate comprising a phase change material (PCM) and a coating layer of a composition different from that of the agglomerate.

Also, the solution consists only in modifying the surface of the agglomerate to increase its mechanical properties, that is to say to modify the composition or the distribution of the constituents used during the formation of the particle a little before 'get the desired size. In this way the agglomerate is coated with a layer having different mechanical properties generally improving the mechanical strength of the MCP particle: crush strength, attrition and elasticity.

It appeared that this coating could also have other beneficial functions such as improving the fluid tightness of the particle that can be made non-porous, resistance to chemical attack, heat transfer ...

It should be noted that this coating process is not applicable to the adsorbent since in its case the transfer of the molecules of the fluid to the active sites of the adsorbent is predominant and any additional resistance to this transfer would be detrimental or even catastrophic. if we tended towards a tight barrier.

Coating of the MCP particles is only possible here because the adsorption functions (the adsorbent particle) have been physically separated from the heat sink function (the MCP particle). FIG. 1 represents a particle of MCP 1, according to the invention, consisting of an agglomerate of microcapsules of MCP 2 - optionally agglomerated with a binder 3- and coated with a coating layer 4.

One advantage of a coating layer is that in case of accidental release of microcapsule microcapsules of the aggregate, they are retained inside the coating layer and are not likely to be entrained. by the fluid.

At the extreme, this makes it possible to limit the quantity of binder to a minimum in order to ensure the cohesion of the agglomerate during its manufacture thus making it possible to obtain a particle which is very rich in MCP and therefore very thermally efficient. The mechanical properties, in particular resistance to attrition are then essentially due to the presence of the coating layer which in this case has a role of shell.

Depending on the case, the MCP particle according to the invention may have one or more of the following characteristics:

the thickness of the coating layer represents between 0.001 and 10% of the diameter of the particle, preferably between 0.01% and 1% of the diameter of the particle; Note that the thickness of the coating is a compromise between the amplitude of the changes in the mechanical or thermal properties that are sought and the useful volume of microcapsules MCP, that is to say in practice the amount of volume heat available during phase change. The thickness will also depend on the deposition process implemented. The nature of the deposit can be varied. It will depend mainly on the improvements that are sought;

the coating layer comprises an organic or inorganic material; An organic coating will, for example, improve resistance to attrition and elasticity while an inorganic coating will promote heat conduction and hardness.

the content of organic or inorganic material is greater than the content of organic or inorganic material of the agglomerate;

the organic material is at least one polymer; The volume percentage of the at least one polymer in the coating layer is preferably greater than 50% and can reach 100%. A fully polymer coating layer can render the MCP particle completely gas-tight, thereby making for improved performance of the adsorption unit that would use such MCP particles (by decreasing the volume of the MCP particle). gaseous in the adsorbent bed / MCP). The polymer is preferably polyurethane and / or polycarbonate. These polymers are indeed one of the basic solutions for producing the envelope and more particularly the polyurethane because of its low cost and its physical properties.

the coating layer comprises solid particles of thermal conductivity greater than 0.5 W / m / K; the coating layer preferably comprises in volume between 0 and 50% of solid particles, more preferably between 0 and 15% of solid particles;

the coating layer comprises at least 0.5% of polymer and is impervious;

the inorganic material is a metal compound, a metal or a metal alloy; Nitrides, oxides or carbides, or metal alloys as well as pure metals can be used. A ferro magnetic character different from that of the adsorbent particles may allow magnetic separation of the particles of MCP and adsorbent.

the phase change material content of the coating layer is lower than the content of phase change material of the agglomerate;

the coating layer comprises graphite rods.

the phase-change material is chosen from paraffins, fatty acids, nitrogen compounds, oxygenated compounds, phenyls and hydrated salts or a mixture of these compounds.

Note that unless otherwise stipulated, when we mention diameter of a population of particles (agglomerates of MCP, adsorbent), we mean "mean equivalent diameter".

The thickness of the coating layer varies naturally locally for a given particle but also from particle to particle.

By thickness of the layer is meant average thickness that can be measured from a sample of particles open in their middle. Figure 8 shows a sample of 4 half-balls corresponding to a sample of 4 random particles.

The ratio can be defined as the average of the 8 EP thicknesses measured along the AA axis on the average of the 4 diameters D measured along the same axis.

If we want to define this ratio more precisely, we can use a larger number of particles (say 25).

In practice, to define the average thickness of the protective layer, the diameter of a sample of uncoated agglomerates and the diameter of a second sample of the same population (same manufacture) coated. By difference of the diameters, it is easy to go back to the thickness of the coating.

It should be noted that the heat absorption capacity of a PCM increases as its latent heat increases. Generally, MCPs are exploited for their solid-liquid phase change.

To be able to handle them, whether they are in the solid or liquid state, the MCPs are in practice generally microencapsulated in a micronic solid shell, preferably based on polymers (melamine formaldehyde, acrylic, etc.).

Since paraffins, in particular, are relatively easy to encapsulate, they are generally MCPs of choice over hydrated salts, even though paraffins have a latent heat that is generally lower than those of hydrated salts.

In addition, paraffins have other advantages such as reversal of phase change, chemical stability, defined phase change temperature or defined lower and higher phase change temperatures (i.e. there is no hysteresis effect), low cost, limited toxicity and wide choice of phase change temperatures depending on the number of carbon atoms and the structure of the molecule.

The microencapsulated paraffinic PCMs are in the form of a powder, each micro capsule constituting this powder being between 50 nm and 100 μm in diameter, preferably between 0.2 and 50 μm in diameter. Each micro capsule has a thermal conductivity of the order of 0.1 to 0.2 W / m / K, depending on whether the paraffin is in the solid or liquid state inside the microcapsule.

In the context of the invention, these microcapsules are agglomerated. By agglomerate of micro-capsules is meant a solid of dimension greater than 0.1 mm manufactured according to one of the known techniques of powder agglomeration (granulation, extrusion, atomization, fluidized bed, etc.) and which may take various forms. , in particular a form of ball, extruded, pellet, cracked obtained by crushing and sieving blocks of higher dimensions, or wafer obtained by cutting previously compacted leaves, or other.

The agglomerate of microcapsules of MCP is formed by a wet-granulation process in a fluidized bed (spray coating) or by an extrusion process followed optionally by shaping in a fluidized bed granulation process.

The method of wet granulation in a fluidized bed (spray coating) consists in the progressive coating of the micro-capsules by spraying a suspension containing these PCMs, according to the technique known as spray-coating, on the agglomerates being formed and advantageously simultaneously dried. The particles are kept in suspension in a stream of hot air while the coating suspension composed of a solvent (preferably water, MCP whose concentration in said suspension varies between 10% and 50% by weight as well as binders and if necessary surfactants) is sprayed. The passage several times in the coating cycle makes it possible to uniformly cover the surface of the particles. The temperature and the air flow, as well as the flow rate and the spray pressure are chosen so as to form a homogeneous layer and to prevent the formation of scales. In this way, a population of spheroidal particles of essentially identical diameter is obtained.

Another method well suited to the agglomeration of microcapsules MCP is extrusion agglomeration. Extrusion is a (thermo) mechanical manufacturing / agglomeration process by which the powdery material is compressed (mixed or not with appropriate binders) and forced through a die having the section of agglomerated objects to be obtained. Extrusion is applied in various branches of industry, with materials such as metals, plastics, rubbers, composite materials, adsorbents, clay for the manufacture of cellular bricks, pasta.

It is these particles obtained by these two processes or other processes allowing the agglomeration of microcapsules MCP MCP-particle-agglomerates which are then coated with a final layer improving their physical properties. This coating can be achieved:

either by a liquid (or wet) process in which the components of said coating are provided in the form of a solution, emulsion or dispersion containing the solvent (preferably water) as well as the compounds necessary for the formation of the coating obtainable by polymerization or copolymerization or crosslinking by one or more of the following: increasing temperature, increasing concentration, generating free radicals or surface chemical reaction; We speak of a process by dipping, spraying, coating ...

or by a so-called dry method or the components of said coating are provided in the form of molecules in the gas phase, such as, for example, PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition) processes.

The processes where the coating is carried out by the wet process can be carried out

or in a fluidized bed (the deposition of the thin layer is carried out by atomization and by drying a solution on the surface of each particle MCP)

- Or by a chemical deposition process such as galvanic coatings.

The processes in which the coating is carried out by the dry route are generally carried out either in a fluidized bed, under vacuum, or in a rotary chamber for moving particles or extrusions MCP.

In the case of wet coatings, in particular in a fluidized bed, the nature of the solution used to make this final coating will depend on the property or properties that it is desired to improve as well as on the nature of the agglomerate of MCP. which serves as a support.

The main compound of this solution may be an aqueous dispersion of polymers chosen from the following classes of polymers:

An aqueous polyurethane dispersion (DPU), which comprises an aqueous medium with dispersed acrylic polyurethane particles, comprising a reaction product obtained by the polymerization of a pre-emulsion formed from hydrophobic monomers. polymerizable ethylenically unsaturated, of a crosslinking monomer, and of an active prepolymer of hydrogenated acrylic polyurethane, which is a reaction product obtained by the reaction of a polyol, an ethylenically unsaturated polymerizable monomer containing at least one group hydroxyl and optionally a carboxylic acid group, and a polyisocyanate. Aqueous dispersions of polyurethane (PUD), either as a single component or combined with other polymers, are increasingly used in the field of coatings (paints, coatings, inks, varnishes, etc.), particularly because of legislative pressures for the reduction of VOC emissions (Compound Organic Volatile), but also because they have excellent properties, difficult to obtain with other polymers.

The main advantages of PUDs are a wide variety in macro molecular composition and therefore a wide range of performance characteristics; good physical properties (elasticity, elongation at break ...), good resistance to shocks and abrasion; minimum temperatures of film formation and low glass transition, which has the consequence of being able to reduce the rate of coalescence and the possible addition of plasticizers; It can also be noted a good compatibility with pigments, even metallic; good adhesion to metals and plastics; good compatibility with other polymers, in particular acrylic polymers.

PUD are essentially high molecular weight linear polyurethanes / ureas stabilized in water into spherical particles with a diameter of less than 1 μιη. The dispersibility of polyurethane in water is facilitated by the presence of ionic functions within the polymer chains. The viscosity of the PUD is quite low (50 to 500 mPa.s), and it is sometimes necessary to add a thickener in order to obtain the desired rheological properties during the step of injection into the fluidized bed of MCP during the formation of film coating each particle MCP.

The dry matter content can vary from 30% for rigid products to 50% for flexible products, even 60% for textile coatings. Flexible polymers are generally solvent-free, whereas rigid polymers contain polar, water-miscible cosolvents (such as tetrahydrofuran, dimethyl formamide, or N-methyl pyrrolidone) to help coalesce the particles. The final products (polymers derived from dispersions) can combine flexible polymers, extremely flexible (used in textiles), rigid polymers, resistant to abrasion and shock, used in the design of varnish to protect wood, metal or plastics. In our case one of the desired properties was the improvement of the mechanical strength of the MCP particles. The choice of the PUDs was done to maximize this property. In addition, the residual isocyanate groups being rapidly consumed in the aqueous medium, the PUDs are much less dangerous than their solvent-based equivalents. Finally, unlike other polymers in aqueous dispersion used in printing applications, the products obtained from the PUD do not redissolve after drying in an aqueous or alkaline medium. An aqueous dispersion of a polymer of the group of thermosetting resins consisting of resins based on phenol, urea, melamine, xylene, diallylphthalate, epoxy, aniline, furan, polyurethane.

An aqueous dispersion of a polymer of the group of the following resins of i. polystyrene, polymethyl methacrylate, cellulose acetate, polyamide, polyester, polyacrylonitrile, polycarbonate, polyphenyleneoxide, polyketone, polysulphone, polyphenylenesulphide;

An aqueous dispersion of the group of thermoplastic elastomers consisting of styrene-type elastomers such as styrene-butadiene-styrene block copolymers or styrene-isoprene-styrene block copolymers or their hydrogenated form, elastomers of PVC, urethane or polyester type; polyamide, thermoplastic elastomers of polybutadiene type such as resins 1, 2-polybutadiene or trans-1,4-polybutadiene; chlorinated polyethylene;

An aqueous dispersion of a polymer of the group of water-soluble polymers consisting of cellulosic polymers, polyelectrolytes, ionic polymers, acrylate polymers, acrylic acid polymers, gum arabic, poly (vinyl pyrrolidone) poly (vinyl-alcohol), poly (acrylic acid), poly (methacrylic acid), sodium polyacrylate, polyacrylamide, polyethylene oxide, polyethylene glycol, polyethyleneformamide, polyhydroxyether, polyvinyloxidazinone, methylcellulose ethyl cellulose, carboxymethyl cellulose, ethyl (hydroxyethyl) cellulose, sodium polyacrylate, copolymers thereof, and mixtures thereof.

It may also be a solution of oligomers of polymer crosslinking solvent. This approach represents a disadvantage related to the generation of large amounts of VOCs (organo volatile compounds) requiring a post treatment dedicated to the fluidized bed outlet flows.

On the other hand, the formation of the coating can be accelerated by photo-crosslinking in situ during the formation of the coating in the fluidized bed. The UV radiation-enhanced crosslinking is a UV-initiated polymerization reaction which converts, in a fraction of a second, a coated liquid film applied to a substrate into a three-dimensional solid polymeric material. The typical formulation of a photo-crosslinkable resin contains three basic ingredients: a photoinitiator, a monomer and an oligomer, the latter two being provided with reactive chemical functions. Photocrosslinking under UV is a technique that uses UV light to start the crosslinking a liquid formulation (or a powder) and obtain a dry, solid and well-crosslinked coating. The use of UV crosslinkable coatings in a fluidized bed is one of the techniques which makes it possible to obtain excellent coatings of MCP particles having high performance for a relatively thin layer. Crosslinking is the formation of one or more three-dimensional networks, either chemically or physically. The crosslinked structures are most often prepared from linear or branched prepolymers of low molecular weight (resulting from partial polymerization), crosslinked under the effect of heat in the presence of a catalyst / hardener.

Light curing offers particularly interesting advantages over conventional thermal processes:

the polymerization is almost instantaneous, the passage from the molecule to the polymer material taking place in a few tenths of a second under intense irradiation; it requires, therefore, only a small energy expenditure;

- Crosslinking occurs only in spatially well defined areas, those that are exposed to light radiation, which allows for high resolution relief images;

the reaction can be triggered at a precise moment even inside the fluidized bed and stopped at any time, thanks to a temporal control of the irradiation;

the intensity of the light source is adjustable over a very wide range, which makes it possible to control the priming speed;

by acting on the wavelength of the light radiation and / or on the photoinitiator concentration, it is possible to adjust the penetration depth of the light and therefore the thickness of the polymer layer formed, which may vary from a few micrometers several millimeters;

the photoinitiated polymerizations are usually carried out at room temperature, with resins not containing a solvent, which reduces the emission of polluting vapors;

the polymeric substances produced by this process have technical characteristics which compare very favorably with those of the film polymerization products or by the use of aqueous dispersions and the characteristics obtained show good resistance to solvents and abrasion, excellent surface, very high degree of conversion, no smell. Different crosslinking mechanisms are possible for the initiation of the polymerization. The crosslinking mechanism by radical initiation is particularly suitable for methacrylate acrylates, poly-fumarates unsaturated polyesters, polyvinyls, polycarbonates, vinyl ethers and urethanes. The cationic initiation crosslinking mechanism is suitable for aliphatic cyclo epoxies, carbohydrate ethers as well as epoxy / oxetane systems and vinyl ethers.

The hardness of the surface of a coating obtained by one of these methods of wet deposition in a fluidized bed, measured by indentation techniques, may vary from 10 N / mm ² to about 1000 N / mm ^2, but is, however, generally less than 500 N / mm ² .

As described above, this coating of agglomerates of microcapsules of PCM can be done by various coating processes: in liquid or dry process: spraying, immersion, coating, contact with vapors and this in specific equipment (Of reactor type) or during transfer (moving belt, vibrating belt ...) .... but preferably this coating will be carried out in a vertical fluidized bed, continuous or discontinuous.

Even more preferentially, the coating step will be carried out in the same device as the agglomeration step of the MCP particles by modifying the moment the composition of the suspension injected into the reactor.

Indeed, when the population of agglomerates of MCP reaches the required dimensions (diameter), the injected solution is modified in order to proceed to the coating step. This modification may consist in spraying only the coating product without microcapsule MCP (or with a percentage significantly lower than in the previous step of agglomeration, ie less than 50% of the previous amount, preferably less than 10 %).

It may consist in injecting a solution comprising one or more constituents of those used previously.

The present invention also relates to a mixture of MCP particles according to the invention and adsorbent particles.

Figure 2 shows a particle of MCP manufactured according to this method and further comprising in the center a core, for example an iron core. The thickness of the coating layer 13 is small compared with the diameter of the particle produced. In practice, the thickness of the coating will be from a few microns to a few tens of microns for particles of diameter generally between 0.5 and 5 millimeters. The thickness to diameter ratio will range from about 5/5000 to 50 out of 500 (in microns), ie from 0.1% to 10%.

Figures 3 to 6 show enlargements of the coating zone. Figure 3 shows a coating 23 containing solid particles 22. These solid particles can be ferro-magnetic to allow separation of MCP particles / adsorbent particles by magnetization; they can be heat conducting and improve the thermal transfer of the wall towards the microcapsules 21; they may consist of fin sorts on the surface of the particle to increase the heat transfer of the fluid to the PCM. Figure 4 shows the simplest coating 32. This layer may contain a number of microcapsules MCP still free at the beginning of the coating. The coating of FIG. 4 can be fluid-tight, in particular to a gas so that the apparent porosity of the coated PCM particle can be almost zero, let us say statistically less than 5% for a bed having a large number of people.

The coating can effectively seal the agglomerate to the treated fluid in the adsorber containing the adsorbent / MCP mixture.

This can directly increase the separation performance since the presence of gas in the adsorbent bed (interstitial gas or in the macropromes of the particles) has a negative effect. This is often the case in PSA separations, for example in H2 PSAs. Figures 5.a and 5.b illustrate a very thin coating 41 whose purpose is to enhance the adhesion of microcapsules 40 to the surface and to limit attrition.

Figure 6 shows a coating 50 trapping graphite rods or filaments 52 which can penetrate the inner agglomerate of MCP 51 and / or exit outwards.

A further advantage of such thin film-coated agglomerates is that the particle because of the lesser amount of binder - or the possibility of using other types of binder - may be more elastic than the uncoated particle.

By elastic, it means here that subjected to a unidirectional pressure, the shape of the particle changes without there being destruction of the said particle. An essentially spherical particle will initially take the shape of an ellipsoid before to break. The point contact in the case of two rigid spheres will be able to extend in such a case to a substantially larger surface ...

This possibility of deforming while keeping sufficient mechanical properties can be interesting from several points of view.

The adsorbent / MCP mixture also has a greater elasticity which leads to reducing the stresses between particles and between particles and wall of the adsorber during operations.

The possibility of the coated PCM particles to deform slightly while maintaining their physical integrity also makes it possible to increase the contact surface between the adsorbent particles and the MCP particles thus improving the direct thermal transfer by adsorptive / MCP conduction. In this case, there is a "contact surface" between the adsorbent and MCP instead of the simple "point contact" between balls supposed to be rigid.

FIGS. 7a and 7b respectively illustrate the contacts of the quasi-point type between adsorbent 60 and MCP 61 in the case of rigid particles and the contacts involving a not insignificant surface between rigid adsorbent 62 and relatively elastic MCP 63.

The present invention therefore also relates to mixtures in any proportion of coated PCM particles and adsorbent such as activated alumina, silica gel, zeolite, MOF, adsorbent exchanged or doped, "grafted" adsorbent that is to which we add a function, such as an amino function ...

The present invention also relates to an adsorption unit comprising a fixed bed or a moving bed in which is implemented a mixture according to the invention.

Depending on the case, the adsorption unit may have one or more of the following characteristics:

the adsorption unit comprises a fixed bed and the proportion of MCP particles is substantially constant throughout the volume of the bed;

said unit is a PSA H2, a PSA CO2, a PSA 02 or a PSA N2.

Note that if the adsorption unit comprises a fixed bed, this bed may comprise one or more layers of adsorbent commonly called multi-bed in the technical language.

The invention therefore relates to the majority of PSA processes and more particularly in a nonlimiting manner, in addition to PSA H2, O2, N2, CO and CO2, the PSA fractionation of syngas in at least two fractions, PSA on natural gas to remove nitrogen, and PSA to split hydrocarbon mixtures.

The invention can be implemented, moreover, in a method:

- Argon PSA as described in particular in US-A-6,544,318, US-A-6,432,170, US-A-5,395,427 or US-A-6,527,831. The PSA Ar makes it possible to produce oxygen with a purity higher than 93%, by preferentially adsorbing either argon or oxygen, present in a flow rich in 02 resulting for example from a PSA 02. PSA Ar generally use a carbon molecular sieve or zeolite exchanged with silver (US-A-6,432,170).

PSA He which makes it possible to produce helium by preferentially adsorbing the other molecules present in the feed stream.

- Any PSA allowing the separation between an alkene and an alkane, typically PSA ethylene / ethane or propylene / propane, for example. These separations are based on a difference in adsorption kinetics of the molecules on a molecular sieve, carbon or not.

- any PSA for splitting a synthesis gas (syngas).

- any PSA to separate CH4 from N2.

Claims

claims

1. Particle of MCP constituted:

an agglomerate of microcapsules of a phase-change material (PCM) agglomerated with a binder; and

a coating layer of a composition different from that of the agglomerate.

2. Particle of MCP according to claim 1, characterized in that the thickness of the coating layer is between 0.001 and 10% of the diameter of the particle, preferably between 0.01% and P / o of the diameter of the particle.

3. Particle of MCP according to one of claims 1 or 2, characterized in that the coating layer comprises an organic or inorganic material.

4. Particle of MCP according to claim 3, characterized in that the content of organic or inorganic material is greater than the content of organic or inorganic material of the agglomerate.

5. MCP particle according to one of claims 3 or 4, characterized in that the organic material is at least one polymer.

6. Particle of MCP according to claim 5, characterized in that the coating layer comprises solid particles of thermal conductivity greater than 0.5 W / m / K.

7. Particle of MCP according to claim 5, characterized in that the coating layer comprises at least 0.5%> of polymer and is sealed.

8. MCP particle according to one of claims 3 or 4, characterized in that the inorganic material is a metal compound, a metal or a metal alloy, or a mixture of these compounds.

9. MCP particle according to one of claims 1 to 8, characterized in that the phase change material content of the coating layer is lower than the phase change material content of the agglomerate.

10. MCP particles according to one of claims 1 to 9, characterized in that the coating layer comprises graphite rods.

11. MCP particle according to one of claims 1 to 8, characterized in that the phase change material is selected from paraffins, fatty acids, nitrogen compounds, oxygenates, phenyls and hydrated salts or a mixture of these compounds.

12. Mixture of MCP particles as defined in one of claims 1 to 9 and adsorbent particles.

13. Adsorption unit comprising a fixed bed or a moving bed in which is implemented a mixture according to claim 12.

14. Adsorption unit according to claim 13, characterized in that the adsorption unit comprises a fixed bed and the proportion of PCM particles is substantially constant throughout the volume of the bed.

15. Adsorption unit according to one of claims 13 or 14, characterized in that said unit is a PSA H2, a PSA CO2, a PSA 02 or PSA N2.