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  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

• Adsorbent mixture comprising adsorbent particles and particles of phase-change material
• the invention relates to an adsorbent mixture consisting on the one hand of particles of a phase change material (PCM) and on the other hand of adsorbent particles, a mixture for use in a thermocyclic separation process. adsorption.
• PCM phase change material
• adsorbent mixture means any mixture of an adsorbent material and an additive material shaped or not and in variable proportions.
• thermocyclic process is any cyclic process in which certain stages are exothermic, that is to say accompanied by a release of heat, while certain other stages are endothermic, that is to say accompanied by a consumption of heat.
• phase change materials act as heat sinks at their phase change temperature.
• Typical examples of thermocyclic processes for which the invention can be beneficially implemented include processes having a relatively reduced cycle time for which heat transfer between the adsorbent bed and the MCP agglomerates must be carried out. only a fraction of this cycle time.
• PSA Pressure swing adsorption
• MPSA Mated Pressure Swing Adsorption
• the pressure swing adsorption separation processes are based on the physical adsorption phenomenon and make it possible to separate or purify gases by pressure cycling the gas to be treated through one or more adsorbent beds, such as a bed of zeolite or coal. active, activated alumina, silica gel, molecular sieve or the like.
• adsorbent beds such as a bed of zeolite or coal. active, activated alumina, silica gel, molecular sieve or the like.
• 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:
• 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 atmospheric pressure typically between 30 and 800 mbara, preferably between 100 and 600 mbara.
• PSA processes in which the adsorption is carried out at a high pressure substantially 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 pressure atmospheric, therefore between 1 and 9 bara, preferably between 1.2 and 2.5 bara.
• the RPSA (Rapid PSA) processes designate very fast cycle PSA processes, generally less than one minute.
• 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-based or non-carbon molecular sieve, a metallo-organic structure, an alkali or alkaline-earth metal oxides or hydroxides, or a porous structure containing a substance capable of reacting reversibly with a or a plurality of gas molecules, such as amines, physical solvents, metal complexing agents, metal oxides or hydroxides for example.
• the thermal effects resulting from the adsorption enthalpy or the reaction enthalpy generally lead to the propagation, at each cycle, of a heat wave at the adsorption which limits the capacitances of adsorption and a desorption cold wave limiting desorption.
• a particular case covered in the context of the present patent is the storage / removal of gas in a reactor or adsorber containing at least partly one or more adsorbents.
• thermo-cyclic process using an adsorbent material with release of heat during storage (pressure increase) and release of cold during destocking (pressure decrease)
• a solution for decreasing the amplitude of the thermal beats is to add a phase change material (PCM) to the adsorbent bed as described in US-A-4,971,605.
• PCM phase change material
• the heat of adsorption and desorption, or a part of this heat is adsorbed 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.
• a hydrocarbon or a mixture of hydrocarbons can be advantageously used.
• the hydrocarbon contained in the ball absorbs heat and stores it.
• the hydrocarbon contained in the ball restores the latent heat stored by changing the liquid phase to the solid.
• the temperature remains approximately constant (according to the composition of the wax) and allows the temperature to be regulated at levels well determined by the nature of the hydrocarbon (or hydrocarbons when it comes to mixture) and in particular the length of the chain and the number of carbon atoms.
• phase change material For reasons of heat transfer through the phase change material itself, it should generally be in the form of small particles, generally less than 100 microns. Subsequently, we speak of micro particle or micro capsule to designate this basic particle.
• micro encapsulated MCPs can not be introduced as such into an adsorbent bed because it would be difficult to control the distribution. In addition, they would be driven by the flow of gas flowing in the adsorber. It is therefore necessary to previously produce “agglomerates”.
• agglomerate hereinafter is understood to mean a solid of dimension greater than 0.1 mm which may take various forms, in particular a form of ball, pellet, crushed cheese obtained by crushing and sieving blocks of larger dimensions, or wafer obtained by cutting previously compacted leaves, or others.
• a first solution leads to an intimate mixture of the adsorbent - in the form of powder or crystals - and micro particles of MCP and to agglomerate the mixture.
• Products obtained by dry pressing are generally too fragile for industrial use. Agglomeration in liquid or wet phase poses the problem of activation of the active phase of the agglomerate.
• the required temperature level is generally above 200 ° C, often in the range of 300 to 450 ° C. These temperature levels are not compatible with the mechanical strength of MCPs.
• a second solution consists in making agglomerates solely of MCP, in the form of a structure that is easy to handle and to introduce into an adsorber.
• the processes for manufacturing agglomerates according to the simplest state of the art do not make it possible to obtain agglomerates with sufficient mechanical and / or thermal properties to be used effectively. in thermocyclic processes.
• a third way consists in integrating the MCP microparticles into a preexisting solid structure such as a "honeycomb" honeycomb structure or a foam, a lattice, a grid, for example by bonding to the walls.
• a preexisting solid structure such as a "honeycomb" honeycomb structure or a foam, a lattice, a grid, for example by bonding to the walls.
• Such materials that can be made in the laboratory can not be used today in large-scale industrial units (with a volume greater than 1 m 3 and more generally greater than 10 m 3 ) not only for reasons of manufacture or cost but also for condition of increasing the overall porosity of the adsorbent bed and the dead volume associated with the spaces that are not accessible to the agglomerates of adsorbents (often in the form of beads, rods or crushed particles).
• a problem that arises is to provide an improved adsorbent mixture meeting the criteria of stability of the mixtures, making it possible to increase the exchange surface and more generally to improve the kinetics, while not increasing the pressure drop. composite bed, and respecting the speed of attrition.
• a solution of the present invention is an adsorbent mixture comprising:
• PCM phase change material
• the two dimensional parameters can be generally considered equal and are easy to measure by simple means such as sieving.
• the section is generally cylindrical, one can imagine dies of any shape for example equilateral triangle, trilobed, ellipse ... but as a priori rarer as rectangular with a side significantly different from the other.
• these shapes can be modified with blunt angles. At the ends, there may also be changes in shape.
• Dm is obviously equal to the average diameter of the cylinder. This diameter will be very close to the diameter of the die, with the variations that can undergo the extruded out of the die (elongation or swelling of a few%).
• the most common dies correspond to cylinders whose diameters are of the order of 5mm, 3mm, 2mm, 1.5mm, 1mm, 0.75mm; These dimensions are 10/15% close to the fact of basic use of metric or Anglo-Saxon dimensions (3/16 ", 1/8", 1/16 "etc. ..) and small changes between diameter of the die and diameter of the extruded.
• the second characteristic dimension is the average length of the extrusion.
• RF has a value greater than 1, generally greater than 2. This type of value (> 2 for example) indicates that the particle is anisotropic, with a dimension greater than the others. These are usually elongated particles.
• characteristic particle sizes within the scope of this invention are determined simply: by sieving for approximately isotropic particles (beads, crushed, etc.); by direct measurements and calculation of the equivalent diameter for the elongated particles.
• the adsorbent mixture according to the invention may have one or more of the following characteristics:
• the adsorbent is in the form of rods of diameters selected from the following group: 5 mm, 3 mm, 2 mm, 1.5 mm and 1 mm
• the particles of MCP are in the form of rods of diameters selected from the following group 3 mm, 2 mm, 1.5 mm, 1 mm and 0.75 mm
• the MCP particles have a shape chosen between the regular cylinder, the cylinders with the rounded ends and the ellipsoidal shapes, and the shape obtained by extrusion followed or not by a spheronization step;
• the ratio of the densities of the MCP particles and the adsorbent particles is less than or equal to 2;
• the MCP particles have a density of 300 to 1000 kg / m 3 , preferably of the order of 500 to 750 kg / m 3 ;
• the particles of MCP are derived from a manufacturing process implementing an extrusion step.
• the PCM particles were obtained by the fluidized bed agglomeration process and were in the form of quasi-spherical beads with a diameter ranging from 2 to 3 mm, that is to say close to the size of the adsorbent.
• the basic solution envisaged was to use MCP beads of minimum diameter with respect to the stability of the mixture, that is to say in practice of half diameter. from that of the adsorbent.
• the number of PCM beads is approximately twice the number of adsorbent beads while it was one quarter in the tested configuration.
• the comparison focused on the pressure drop and the rate of attrition between a bed composed solely of adsorbent and the composite beds.
• the rate of attrition has been defined as the velocity of the gas passing through the bed (assumed to be empty) and causing either bed disassembly or the setting in motion of a representative number of particles at the free surface or at the level of the cylindrical walls. .
• Offset of the bed corresponds to an upward movement of the free surface and a representative number of moving balls means a fraction of the order of 5% of the surface.
• the localized motions of some particles, especially if they are the smallest ones on the free surface, are noted but are not taken into account. There are indeed simple ways to limit or eliminate these movements such as adding a thin layer of adsorbant alone to the free surface.
• the acquisition system measures pressure, flow, temperature and pressure drop. The maximum acceptable pressure is 5 bar absolute.
• the gas used is nitrogen cryogenic quality.
• the adsorbent or the homogeneous adsorbent / MCP mixture is introduced via a cross-sieve system in order to obtain a dense and reproducible filling.
• Figure 2 illustrates in a general way the type of results obtained. This is the measurement of the pressure drop of a stream of pure nitrogen passing through the same volume of particulate material under the same conditions of pressure and temperature. The different curves were stopped at the speed of attrition (in practice, the observation of swelling of the bed in the majority of cases).
• Curve 1 corresponds to the adsorbent bed alone (in the form of balls, crushed or cylinders of length less than 2 times the diameter).
• the flow rate Ql corresponding to the attrition rate is such that the pressure drop compensates for the weight of the bed, which is a general observation.
• Curve 2 corresponds to a mixture of approximately 85% volume of adsorbent (identical to that corresponding to curve 1) and approximately 15% volume of PCM particles of the same shape but of approximately half size.
• size about half it is meant for example in the case of beads that the diameter of the PCM beads is half the diameter of the adsorbent beads; in the case of crushed, it is the ratio between the diameter determined by sieving as previously explained; in the case of cylinders, it is the ratio of the diameters.
• the tests here consist of carrying out PSA cycle tests with 80%> adsorbent volume and 20%> volume particles mixtures of MCP. Various sizes of MCP particles are tested while the adsorbent is still the same.
• Thermal beat means the difference between the maximum and minimum temperatures recorded on a cycle. A perfectly isothermal cycle would give a beat equal to zero.
• the mixtures with the larger particles of MCP are observed to increase, indicating that the particles of MCP no longer have sufficient efficacy. or at least, have less efficiency. This is what was observed on the industrial PSA mentioned above.
• the beats remain constant showing that MCP particles have kept in cycle time reduced their effectiveness. The productivity measures between the different tests confirm that mixtures with small MCP particles are more efficient, especially since the cycle is fast.
• MCP rods of average diameter Dm (mcp) less than the diameter of the adsorbent, for example by a factor of 1.5 to 3 and of average length DM (mcp) in the range from 2 to 8 times the average diameter Dm (mcp) are a good compromise between the different constraints.
• particles, whether adsorbent or MCP are not all the same size but their characteristics (diameter, length, thickness ..) are distributed statistically around average values;
• Figure 3 shows by way of example a few of the shapes actually observed with respect to the theoretical cylindrical shape.
• the different particles have variations around a common general form.
• the spheres are not perfect but are ellipsoidal or even patatoidal.
• the existing industrial PCMs which can be used in the context of the present invention, are in the form of microcapsules which are then agglomerated, as explained below.
• Phase change materials or PCM in themselves may be organic, such as paraffins, fatty acids, nitrogen compounds, oxygenated compounds (alcohol or acids), phenyls and silicones, or inorganic compounds, such as salts hydrated and metal alloys. They are generally micro-encapsulated in a micronic solid shell, preferably based on polymers (melamine formaldehyde, acrylic, etc.).
• paraffins 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.
• paraffins have other advantages such as phase change reversibility, chemical stability, phase change temperature, or phase change temperature range defined (no hysteresis effect), a low cost, limited toxicity and wide range of phase change temperatures available depending on the number of carbon atoms and the structure of the molecule.
• the micro encapsulated paraffinic PCMs are in the form of a powder, each microcapsule constituting this powder being between 50 nm and 100 ⁇ m in diameter, preferably between 0.2 and 50 ⁇ m in diameter.
• the MCP can not be used as such because, because of their small size, they would be irretrievably driven by the circulating fluid, that is to say say the gas to be treated.
• this binder if it is necessary in obtaining the agglomerates, is at least as conductive of the heat as the MCP in the liquid state so as not to substantially limit the heat exchange.
• this binder may be a clay (bentonite, attapulgite, Kao Imite, etc.) or a cement-type hydraulic binder or a polymer, preferably melting at a low temperature (below 120 ° C.), or still an adhesive or a resin, optionally an adhesive or a resin with improved thermal conductivity, that is to say containing for example metals (Fe) or graphite, or simple fibers or powders improving the performance of the whole (carbon fibers, metal powders ).
• the use in the manufacturing process of an extrusion step which comprises the passage of a paste comprising the micro-particles of PCM through an extruder makes it possible to control in a fairly precise manner the RF agglomerates obtained and the parameters defined in patent application WO 2008/037904 (average diameter, density) to obtain a homogeneous and stable mixture of particles of MCP and adsorbent (ie for example a density ratio of less than 3 and a diameter ratio of less than 2).
• extrudates composed mainly of MCP are obtained mainly in the form of rods made via an agglomeration process using at least one extrusion step such as that described in US Pat. No. 7,575,804 B2 (Basf, Lang-Wittkowski et al., 2009). and PCT WO 02/055280 A1 (Rubitherm GMBH, 2002) although other forms are possible.
• microparticles are spheroidal in shape and have a mean diameter of between 1 and 25 microns;
• extrudates are recovered in the general form of rods and have a mean diameter of between 0.1 and 10 mm, preferably between 0.3 and 5 mm;
• an extrusion pressure of less than 10 MPa is used, preferably of between 5 MPa and 8 MPa, more preferably less than 5 MPa;
• the paste comprising the MCP particles remains at a temperature below 100 ° C., preferably below 80 ° C. during the extrusion step;
• said method comprises, downstream of the extrusion step, a step of drying the extrudates recovered at the end of the extrusion step;
• said method comprises, upstream or simultaneously with the drying step, a spheronization step of the extrudates recovered at the end of the extrusion step;
• the final agglomerate will preferably be in spheroidal form with a mean diameter of between 0.1 mm and 10 mm, preferably between 0.3 and 5 mm;
• said method comprises, upstream or simultaneously with the drying step, a step of coating the extrudates recovered at the end of the extrusion step;
• the coating step is such that the thickness of the coating formed around the extrudates is between 0.001 and 10% of the diameter of the agglomerate recovered at the end of the process;
• the spheronization, drying and coating steps are preferably carried out in a fluidized bed.
• the binder is chosen from cellulosic polymers, vinyl acrylic copolymers, carboxyvinyl polymers, water glass (sodium silicate, more precisely sodium metasilicate), polyethylene glycol 4000, polyvinyl acetate; the binder is preferably chosen from hydroxypropyl cellulose (HPC) and / or carboxymethyl cellulose-sodium (CMC-Na).
• the dough may also include solid additives. These additives can be organic and / or inorganic. It may be a material of thermal conductivity greater than 1 W / m / K, capable of increasing the thermal conductivity of the agglomerate, preferably a metal compound or graphite in the form of powder or filaments.
• the dough may also comprise solid additives having magnetic Ferro properties enabling a magnetization separation of MCP agglomerates from the adsorbent particles with which these agglomerates of MCP would be mixed.
• the ferromagnetic materials in particular iron powder
• the additives are of maximum size (diameter or length) of between 1 and 100 microns, preferably between 10 and 50 microns.
• the agglomerate will contain, by weight, between 50 and 99% of microcapsules of MCP.
• the MCP microparticles represent from 50 to 99.5% by weight of the dried final particle, the solid additive from 0 to 50% by weight and the binder less than 5% by weight.
• resistance to attrition, crush resistance ... should not be the weak point of the mixture.
• the attrition resistance should not be less than a factor of 2 to that of the adsorbent used together. It is the same for the resistance to crushing.
• micro particles must be preserved during the manufacturing process. Said micro particles must as explained above be able to withstand the pressure necessary for extrusion, the temperature reached in the die. They must also be insoluble in the solution containing the binder which must also give the mixture a consistency and sufficient plasticity.
• MCPs with a number of dimensional, mechanical strength, temperature, and surface characteristics.
• the retained MCPs are in the form of microbeads coated with a waterproof, water-insoluble (hydrophobic) shell-forming polymer.
• Said microencapsulation is generally obtained by phase inversion of an emulsion according to methods known to those skilled in the art.
• the shell should preferably keep more than 50% of its measured mechanical properties at ambient temperature up to a temperature of 80 or even 100 ° C
• the selected phase change material which depends on the application for which the PCMs are intended, is a mixture of linear saturated hydrocarbons with the number of carbon atoms varying between 14 and 24.
• the estimated crush strength is greater than a few MPa, which placed this product in the range of potential extrusion pressures.
• PCM PCM-based product
• BASF's Micronal® product A commercial example of PCM corresponding to this description is BASF's Micronal® product.
• a paste of rheological characteristic permitting extrusion was obtained by using a solution consisting of a solvent, a binder and, depending on the respective contents of the latter, a thickening type additive and / or a surfactant.
• the "binder” will be selected from cellulosic polymers (cellulose-based polymers), in particular hydroxypropyl cellulose (HPC) or carboxymethyl cellulose-sodium (CMC-Na), vinyl acrilic co-polymers (vinyl acrilic co polymer), carboxyvinyl polymers (CLPs), water glass, PEG 4000, PVA.
• cellulosic polymers cellulose-based polymers
• HPC hydroxypropyl cellulose
• CMC-Na carboxymethyl cellulose-sodium
• vinyl acrilic co-polymers vinyl acrilic co polymer
• CLPs carboxyvinyl polymers
• water glass PEG 4000, PVA.
• the solvent is preferably pure water but it is not necessary to totally demineralize it.
• An emulsion of polyvinyl acetate latex as an additive facilitates extrusion in certain cases by improving the rheology of the solution (viscosity, plasticity ).
• the content of the binder in the solvent solution may range generally from 1 to 50% by weight, more particularly from 1 to 20% by weight, depending on the products used.
• the present invention also relates to an adsorber comprising at least one adsorbent bed composed of an adsorbent mixture according to the invention and an adsorption unit comprising at least one such adsorber.
• the adsorption unit may be a PSA H2, a PSA CO2, a PSA 02, a PSA N2, a PSA CH4, a PSA Helium. .. (PSA "constituent X" is a PSA whose object is to produce or extract gas from said constituent.)
• 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 the PSA processes and more particularly in a nonlimiting manner, in addition to the PSA H2, O2, N2, CO and C02, the syngas fractionating PSA in at least two fractions, the PSA on natural gas intended for remove nitrogen, and PSAs used to split hydrocarbon mixtures.
• the invention can be implemented, moreover, in a method:
• PSA Ar makes it possible to produce oxygen with a purity greater than 93%>, by preferentially adsorbing either argon or oxygen, present in a flow rich in 02 resulting for example from a PSA 02.
• PSAs Ar generally use a carbon molecular sieve or a 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;

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