EP1062181B1 - Procede pour secher et preparer des particules microporeuses - Google Patents

Procede pour secher et preparer des particules microporeuses Download PDF

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Publication number
EP1062181B1
EP1062181B1 EP99915573A EP99915573A EP1062181B1 EP 1062181 B1 EP1062181 B1 EP 1062181B1 EP 99915573 A EP99915573 A EP 99915573A EP 99915573 A EP99915573 A EP 99915573A EP 1062181 B1 EP1062181 B1 EP 1062181B1
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Prior art keywords
fluid
particles
drying
microporous
pressure
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EP99915573A
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German (de)
English (en)
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EP1062181A2 (fr
Inventor
Friedhelm Teich
Heiner Schelling
Herbert KÖSTER
Horst Kratzer
Wolfgang Reichert
Martin Gall
Bernd Ziegler
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BASF SE
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BASF SE
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B3/00—Drying solid materials or objects by processes involving the application of heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B7/00—Drying solid materials or objects by processes using a combination of processes not covered by a single one of groups F26B3/00 and F26B5/00

Definitions

  • the present invention relates to a method for drying microporous, Fluid containing particles and a method of making microporous, spatially crosslinked particles using this drying process.
  • hydrogels e.g. Silicic acid hydrogels caused by gel precipitation can be made from water glass under supercritical conditions too to dry microporous, spatially cross-linked silica particles.
  • the interfacial tension in the microporous, spatially crosslinked particles containing fluid completely or largely canceled with the aim of shrinking the microporous, spatially cross-linked particles Avoid to a large extent when drying, as characteristic when shrinking Properties of the microporous, spatially cross-linked particles in whole or in part get lost.
  • Such a product obtained by supercritical drying is used in Called gel airgel.
  • WO-A-95 06 617 relates to hydrophobic silica aerogels obtained by Reaction of a water glass solution with an acid at a pH of 7.5 to 11, extensive removal of ionic components from the hydrogel formed Wash with water or dilute aqueous solutions of inorganic bases under Maintaining the pH of the hydrogel in the range of 7.5 to 11, displacing the in the hydrogel contained aqueous phase by an alcohol and subsequent supercritical drying of the alkogel obtained.
  • White does not mention continuous processes for granule production and desalination.
  • White prefers one with "overlaying / soaking / drainage" for the liquid phase procedure to be described which is an intermittent Represents the loading of the solid body with liquid.
  • White considers even flow to be less economical.
  • the object of the present invention was to provide an improved More economical process for drying microporous, fluid-containing Particles as well as a improved, more economical process for the production of microporous, spatially to provide crosslinked particles using the drying process, the above-mentioned disadvantages of the prior art can be avoided.
  • the invention thus relates to a method for drying microporous fluid containing particles by reducing the interfacial tension of the fluid, preferably to 0 to 1/10, in particular to 0 to 1/20, at room temperature existing interfacial tension of the fluid by using near to supercritical Pressure of the fluid increases the temperature accordingly.
  • the process is then characterized in that one for increasing the temperature supplies the required heat convectively.
  • a device which with a pressure vessel an inner container and a pressure-bearing outer container as well as suitable measuring and Has control devices as well as pump and heat exchange devices, the inner container is intended to hold the particles to be dried, and a gap or space between the inner container and outer container is provided.
  • the area in which work is preferably carried out according to the invention can thereby be defined that the microporous particles their properties during drying not lose; this means that e.g. the apparent density of the product is not significantly increased that the thermal conductivity of the product does not increase significantly, that preferably no shrinkage of over 15%, especially no shrinkage of over 10% occurs.
  • This fact can also be described in that the Airgel must not become a xerogel (gel dried at normal pressure)
  • the interfacial tension mentioned above is determined as described in "The Properties of Gases and Liquids "by Reid, Brausnitz, Sherwood, McGraw Hill, 1977, pp. 601 ff. is described, the interfacial tension at the temperature to be tested (and pressure) with the at room temperature and atmospheric pressure below im other identical conditions are measured and compared.
  • step (b) the particles obtained from step (a) a solvent stream and / or Water flow counteracts
  • step (c) the particles countercurrent to the fluid leads and leads in step (e) the dried particles towards an inert gas stream.
  • microporous, fluid-containing particles which are suitable for drying according to the invention are not subject to any particular restrictions per se. All particles, solids, structures or granules are suitable which are at least partially, preferably entirely, microporous and contain a fluid in the pores. Suitable particles are, for example, gels which consist of inorganic or organic materials or of polymer material, for example of inorganic oxides or hydroxides such as boron or silica, oxides or hydroxides of the metals titanium, molybdenum, tungsten, iron or tin, aluminum oxide or organic gels such as agar-agar , Gelatin or albumin. The process according to the invention is particularly suitable for drying silica gels.
  • Gels can be used which contain compounds with a critical temperature lower than 350 ° C. or mixtures or mixtures thereof, preferably water and / or liquid organic compounds, as a fluid.
  • Suitable as fluid include all compounds that will be mentioned later in the description of the drying fluids.
  • Particularly suitable fluids are water, C 1 -C 6 -alkanols or mixtures thereof, methanol, ethanol, n- and isopropanol being preferred. Most preferred is isopropanol.
  • hydrogels and alkogels The method according to the invention is used most frequently in the drying of silica gels which contain water, the abovementioned liquid organic compounds or mixtures thereof as a fluid.
  • the particle diameters range from 1 to 15 mm, in particular 2 to 6 mm.
  • the particles contain macro, meso and / or Micropores.
  • the microporous particles to be dried can have any shape own, e.g. Pearls (balls) or angular shapes.
  • the drying process according to the invention is also suitable for drying microporous, fluid-containing Particles or structures that have a certain regular arrangement of building blocks can have.
  • Suitable particles are also present structures crystallized from thermally degradable templates, nanostructures, their regular arrangement is self organized or nanocomposites as well their precursors or clathrates.
  • it can be the microporous particles also around a microporous cover layer provided with a certain doping act on a non-porous support.
  • Aerogels are formed after drying. Do not contain the particles to be dried for drying suitable fluid according to the invention, this can be before drying be replaced by a suitable fluid or a more suitable fluid.
  • some microporous particles can be dried using water as the fluid become.
  • a water-miscible one Drying fluid e.g. on Alcohol
  • you can change the water contained in the hydrogel against a fluid more suitable for drying e.g. an alcohol, whole or partially out.
  • Exchange and drying can also be done at the same time become.
  • the convective heat supply according to the method according to the invention can be seen in different ways and is not subject to any particular restriction.
  • Convection medium or current are suitable for all substances that are not decomposed in the can be brought to a supercritical state. These are preferably opposite the particles to be dried are inert.
  • the convection current from one Certain temperature substances are also added to the structure to be dried chemically modify, impregnate or e.g. Remove traces of water. A Modification may be desirable if, e.g. the interfacial tension can be reduced.
  • drying is used for drying as a convection stream or drying medium, the critical data of which are not too high in order to avoid a greater outlay on equipment.
  • Suitable drying fluids are ammonia, sulfur dioxide, nitrogen dioxide, sulfur hexafluoride; Alkanes such as propane, butane, pentane, hexane and cyclohexane; Alkenes such as C 1 -C 7 -n-, iso-, neo-, secondary or tertiary alkenes, for example ethene or propene; Alkanols such as methanol, ethanol or n- or isopropanol or butanols; Ethers such as dimethyl, diethyl ether or tetrahydrofuran; Aldehydes such as formaldehyde or acetaldehyde; Ketones such as acetone; Esters such as the methyl, ethyl, n- or i-
  • C 1 -C 6 -alkanols ethers, ketones, aldehydes, alkanes, alkenes, esters or amines are preferred. Most preferred are C 1 -C 3 alkanols, especially isopropanol.
  • halogenated hydrocarbons are also possible, but these will be avoided for reasons of material selection and environmental protection requirements. Media with high critical temperatures or high pressures, such as water, will also be attempted to be avoided.
  • supercritical carbon dioxide is also suitable as the drying fluid. Because of its favorable critical temperature of 31 ° C, this is particularly suitable for thermally sensitive substances.
  • drying fluid In general, the selection of drying fluid depends on various points. If you want to set "close” critical conditions, this determines, among other things thermal stability of the particles to be dried or the end product the selection of the drying fluid and thus also limits the critical temperature of the Drying fluid. In addition, a possible fluid recovery, the toxicological harmlessness, the miscibility with the fluid in the to drying particles, product properties and safety data at the Selection of drying fluid play a role. There is also the option of Drying fluid to add a component that contains functional groups to the implemented, absorbed or adsorbed the surface of the particles to be dried become. This means that a uniform coating can be Coating or impregnation of the particles to be dried can be achieved. A modified application of the drying fluid is e.g.
  • drying fluid e.g. to be able to dry acidic hydrogels without that isopropanol decomposes.
  • methanol as the drying fluid, the addition causes of ammonia, that an undesirable amount of ether is not formed.
  • methanol used as the drying fluid for isopropanol or isobutanol Hydrophobization of a silica gel can be added.
  • suitable chemical or physical modification of the particles to be dried Components added before or when the critical temperature of the fluid is reached become.
  • drying fluid with that in the particles to be dried contained fluid at least under the conditions present during drying is miscible.
  • the same is advantageously used as the drying fluid like fluid contained in the microporous particles. Examples of among the Drying conditions are completely miscible fluids / drying fluids Mixture of water with higher alcohols or aromatics.
  • the convection current can top the bed of the particles to be dried below, from bottom to top or from an axial distributor to the outside or flow through in reverse.
  • the mechanical stability, the elasticity, the grain size distribution and the mean grain diameter of the particles determine the type of Flow through the bed. Any fine-particle material that may form carried or separated in the fluid circuit.
  • the filling can be at a Inflow from below can be fluidized in whole or in part.
  • the convection current can be circulated using a temperature-resistant pump, or in a straight-forward mode, only "fresh" drying fluid is heated to temperature brought.
  • the drying is carried out in this way performed that you first depressurize the convection medium in the drying room and then the particles to be dried, which are preferably heated are flushed in without pressure. Then the pressure in the drying room is on the desired value in the vicinity of the critical point. Then the Convection medium preferably set a graft flow. Then will the temperature rises to near the critical point. After reaching the near critical to supercritical conditions of the fluid is relaxed, causing the Particles are "dried". The convection medium can be circulated become.
  • the interfacial tension of the contained in the pores of the particles to be dried Fluids can also be reduced by adding surface-active substances or a previous modification of the microporous, fluid-containing Particles by e.g. Silanization, organic esterification or etherification or at Silica gels by siloxanization of vicinal silane mono / di / triols of the inner and outer surface.
  • the invention relates to a method for manufacturing of microporous, spatially cross-linked particles through those defined above Levels (a) to (e).
  • microporous particles containing pore liquid can be carried out according to Processes known to the person skilled in the art take place continuously.
  • a washing step for the particles obtained in step (a) can take place if undesirable components, such as unreacted starting material or impurities in the Educts to be removed.
  • a desalination step (b) of the microporous, pore liquid or Particles containing solvent can be before, after or simultaneously with the Wash or be provided alone (without washing) if the particles contain unwanted salts. If such a step is used, it will carried out continuously by the particles obtained from step (a) or particles obtained after washing as a moving bed a stream of water contrary results.
  • a suitable ratio or a suitable setting of the material flows of particles to be dried and water or solvents for the production and maintenance of the moving bed can be done by a specialist within the scope of the usual practice Attempts to be determined.
  • This setting depends, among other things. from the height of the moving bed, the internal mass transfer in the particles to be dried and the vortex point, i.e. on the density and grain size or grain size distribution of the microporous, too drying particles.
  • the water flow or solvent flow becomes preferably set so that there is no fluidization in the moving bed and thus too no unwanted segregation comes.
  • the backmixing on the water side or solvent side is lowest when you are at a water or solvent flow rate near the loosening point of the moving bed is working. All are suitable as entry and exit devices for the particles to be dried Types of pumps that are suitable for conveying granular material, whereby modified concrete pumps have proven particularly successful.
  • the washing step and / or desalination step are accelerated by increasing the temperature, i.e. the higher the temperature, the faster they run off. Preferably they are therefore carried out at elevated temperature, the upper limit for the Temperature etc. through the decomposition of the particles to be washed or desalinated, whose clumping / tendency to stick, dissolve in the fluid, etc. is specified.
  • the cross-mixing can also pulsate the solvent or water flow be provided.
  • bubbling in gas e.g. Air that Hiking layer to be loosened.
  • Silica gel is preferably added in step (b) Desalination of aging.
  • step (c) the pore liquid contained in the particles is partially or completely, especially 97 to 99%, replaced by a fluid.
  • suitable Fluids are those described above in describing the microporous, fluid-containing Particles described fluids. Analogous to desalination favor increased Temperatures the exchange. With regard to the suitable temperature, this therefore applies What was said above under stage (b). This also applies to the setting of the moving bed What was said above under stage (b).
  • step (c) the pore fluid in the particles first through one with the pore fluid miscible liquid, but not exchanged fluid suitable for drying becomes. In this case the liquid becomes miscible with the pore liquid then replaced by a fluid suitable for drying.
  • stage (c) there is also the possibility of material flows of different purities at different heights feed.
  • a combination of the exchange step with a Separation of fines or e.g. of adhering oil from the gelation possible and can save a separate classification step if necessary. It can also Summary of desalination in stage (b) and exchange in stage (c) in one Apparatus can be advantageous with appropriate kinetic conditions.
  • step (d) the microporous, fluid-containing particles are dried.
  • the Drying is carried out by means of convective heat, as described above for the drying process according to the invention is described.
  • step (e) the dried particles of absorptively and / or adsorptively bound gases and / or substances separated or exempted.
  • This step is carried out continuously in the moving bed in countercurrent, whereby the dried particles, preferably at reduced pressure, are directed towards an inert gas stream become.
  • Suitable inert gases are nitrogen, carbon dioxide or noble gases. Air or flue gas can also be used under certain circumstances.
  • the setting of the moving bed applies analogously to what was said above under stage (b). It there is also the possibility of adding a component to the inert gas phase which with the dried particles react or is absorbed or adsorbed.
  • the separation step can possibly by a displacement adsorption with a stronger adsorbent material can be improved.
  • the removal of the absorptive and / or adsorptively bound substances and / or gases by application alone done by vacuum.
  • Stage (e) can be followed by a continuous final assembly step, in which the microporous, spatially cross-linked particles into the desired shape brought, e.g. by grinding, sieving or mixing with for use suitable additives.
  • a continuous final assembly step in which the microporous, spatially cross-linked particles into the desired shape brought, e.g. by grinding, sieving or mixing with for use suitable additives.
  • the particles obtained to provide a hard shell e.g. by means of sintering to increase their mechanical strength increase.
  • microporous, spatially cross-linked particles obtained are same particles as those above in the invention Drying processes have been described, these particles compared to the above-mentioned are additionally freed from undesirable by-substances.
  • microporous particles obtained by means of the method according to the invention can be used in many technical fields. Among other things, they are suitable for the production of transparent or opaque thermal insulation materials (under certain circumstances as a substitute for fluorine-chlorine-hydrocarbon-containing materials). You will also find use as catalysts and catalyst supports, Adsorbent, obtained by coking microporous polymers Carbon aerogels as electrodes (e.g.
  • Membranes soaked in electrolyte in capacitive energy stores
  • Membranes Cerenkov detectors
  • super light sponges Storage / storage or as a gelling / thickening / thixotropic agent liquid fuels for space travel, as insecticides, sinterable precursors for Ceramics or high-purity light guides, piezoceramic transducers in ultrasonic transmitters, in acoustic antireflection layers, as dielectrics, as a carrier for Fluorescent dyes, as matting agents, as additives in lubricants, rubber and sealants, in composite materials and in paints and sheets.
  • a preferably used device for drying microporous fluid containing particles comprises at least one "two-shell" container Inner container and pressure-bearing outer container as well as suitable measuring and Control devices as well as pump and heat exchange devices.
  • the inner container is for holding the particles to be dried provided or determined, and there is a gap between the inner and outer containers or space provided.
  • the inner container can have any shape a rotationally symmetrical shape is preferred, e.g. a cylinder with conical Spout or a ball so that the gap can be rotationally symmetrical.
  • the inner container can be above and / or below be conical. It can be made from any material that comes with the drying temperature to be set still have the required strength. Stainless steel, boiler plate or glass fiber reinforced plastic Am are preferred stainless steel is most preferred.
  • the inner container is preferably thin-walled, the inner container is preferably designed for pressures of less than 6 bar.
  • the outer container consists of materials that have the compressive strength required for drying have. Fine comb steel or heat-resistant steel is preferred.
  • the gap or The space between the inner and outer container provides thermal insulation. It is conveniently with an inert gas, preferably a bad one thermally conductive gas, such as nitrogen or krypton. To improve the Insulation can also be filled with insulation material (e.g. rock or glass wool) become.
  • the figure describes a device with inner and outer container and suitable measuring and control devices and pumps and heat exchangers, which is particularly suitable for carrying out the drying process according to the invention.
  • the actual dryer consists of the thin-walled inner container 1 and the pressure-bearing outer container 2.
  • the method according to the invention is carried out as follows. First, the inner container 1 is filled with drying fluid via line 3. The particles to be dried are then flushed in from the storage container 4 via line 5 at the top of the dryer with drying fluid. The dryer is closed and the pressure in it is increased to near to supercritical conditions. The pump 6 then presses the drying fluid heated in the heat exchanger 7 into the particle bed from below.
  • a differential pressure control is preferably used between the inner container 1 and the outer container 2, since the inner container 1 is to be constructed as thinly as possible.
  • This differential pressure control operates as follows: increases the level in the storage vessel 10, because the drying fluid circuit a positive pressure is present and drying fluid flow to the storage vessel 10 via the cooler 11, is a level sensor 12 by means of a N 2 -Splitrange control 13 the pressure of the N 2 pads in the gap formed between the inner and outer container increased.
  • the N 2 split-range control 13 will correspondingly reduce the pressure of the N 2 cushion in the gap.
  • a small cleaning fluid flow 14 is fed to the standing container 10 via a flow control.
  • This flow of material may also take on the task, inter alia, of reducing the level of components which are formed and are disruptive by supplying fresh fluid.
  • an overflow valve between the inner and outer container (not shown) preferably protects the inner container 1.
  • the pressure drop between the foot and head of the particle bed should be limited. If corresponding regulations fail, the inner container 1 is protected from destruction by a further overflow valve in a dryer bypass (not shown).
  • the invention offers the advantages that considerable amounts of energy can be saved because the outer container in the drying process only a small temperature change subject.
  • the temperature change stress on the flanges and other parts of the apparatus largely reduced compared to known methods from the state of the art.
  • To load the dryer only the Inner container, e.g. by evaporative cooling. By eliminating heating and The cooling time of the outer container significantly shortens the batch time.
  • silica hydrogels have been used manufactured. At least 95% by volume of it had a pearl diameter from 2 to 12 mm. Coarse material was submerged in water Harp sieve separated. Next, the silica hydrogels were added before Desalination undergoes continuous electricity classification.
  • each desalination moving bed there was one moving from top to bottom Flow of approx. 510 l / h classified hydrogel from the previous stage (approx. 150 of the 5101 a gap of approx. 2450 l / h flows from below into the gap volume) sent to meet. After about 30 hours at the latest, the patient had become stationary set in the moving bed. The conductivity of the samples taken at the different Locations taken along the bed showed no changes. in the Overflow was measured a conductivity of more than 1 milli-Siemens / cm. The Water in the gap volume of the desalinated hydrogel had a conductivity of 40 Micro-Siemens / cm on what a sodium content of about 1 wt .-% in the gel equivalent.
  • the liquid exchange step was 11m high and 500mm wide Moving bed carried out, which was similar to that for desalination was used.
  • the alcohol was supplied above the rotary valve by means of a distributor.
  • the water / alcohol mixture could pass through slotted screens expire. At low flow speeds and with tendencies to stick Gels were able to improve cross-mixing in bed with static mixers.
  • the desalted hydrogel stream from stage (b) of about 1000 l / h was a Isopropanol flow of about 1400 l / h sent. After 10 hours at the latest had become stationary in the moving bed. The densities of the samples from the various sampling points along the bed showed no change more. The residual water content in the gel, which was derived at the foot of the moving bed, was less than 1% by weight. The specific isopropanol demand volume ratio was so 1.4: 1.
  • the apparatus used corresponded schematically to the device shown in the figure.
  • the equipment used consisted of a 100 bar pressure-resistant outer container made of heat-resistant steel, stainless steel-plated inside, and a 400 mm wide inner container made of stainless steel.
  • the outer container was 8 m high, cylindrical, and had an outer diameter of 600 mm and a wall thickness of 50 mm.
  • the inner container had a wall thickness of 4 mm and tapered at the top and bottom.
  • the usable volume was 1 m 3 .
  • the nitrogen-filled annular gap between the inner and outer container was 50 mm wide in the cylindrical area.
  • the inner container communicated with the drying fluid circuit, which housed the pressure maintenance, circuit pump and heat exchanger.
  • a trunk protruded into the head of the inner container, which had the Alkogel feed line in the center and the screen surface on the outside of the cylinder for fluid / solid separation.
  • the pressure-bearing part of the dryer was heated to 300 ° C with 100 bar steam.
  • the inner container was boiled by adding isopropanol.
  • Alkogel was flushed in with isopropanol which was circulated.
  • the temperature of the alkogel hardly increased during this charging process.
  • the annular gap and inner container were brought to 60 bar pressure.
  • the pump was switched on and drying fluid was first fed in at low speed, for example 1 m 3 per hour at a density above 0.7 kg / l.
  • the bed of the alkogel was flowed from below.
  • the heat exchanger was heated.
  • the speed of the pump could be increased with decreasing density of the drying fluid.
  • the temperature at the top of the dryer could also be used as a reference variable. 70% of the isopropanol could be forced out of the circuit when cold. The supercritical temperature at the top of the bed was reached after 50 minutes. It was relaxed without affecting the two-phase area.
  • a 3 m 3 silo was used to remove / separate the sorbed gases / substances.
  • the airgel was pneumatically transferred to the silo.
  • the silo was then evacuated and a weak stream of nitrogen was allowed to flow through the bed at about 30 mbar pressure. This stream of nitrogen exchanged the gas atmosphere in the silo ten times per hour. As a result, the partial pressure of desorbed alcohol was kept low, the desorption accelerated and completed.
  • the residence time was more than 30 minutes in order to also remove sorbed gases / substances from the Knudsen pores of the airgel. If it was desired or necessary to cool down, the silo was operated at normal pressure and worked with N 2 in a circular mode over a washer.
  • the continuous assembly step was carried out by grinding and mixing of dopants in a pin mill.
  • the airgel granules obtained showed a grain size of up to 12 mm, only 2% by volume of the granules having a grain size of less than 2 mm.
  • the average thermal conductivity ⁇ 10 of the 2-3 mm fraction of the granulate was better than 18 mW / (m ⁇ K) according to DIN 52616, for the powder it was 16 mW / (mK).
  • the transparency of the 2-3 mm fraction was 60% at 1 cm layer thickness.
  • the bulk density according to ISO 3944 was 70 to 130 g / l.
  • the airgel was water-repellent and floated on water.
  • the headspace (the gas phase above the bed) of the airgel did not become explosive at 100 ° C and only explosive at 160 ° C after one hour.

Claims (11)

  1. Procédé de séchage de particules microporeuses contenant un fluide par diminution de la tension de surface du fluide, de préférence de 0 à 1/10, en particulier de 0 à 1/20, de la tension de surface existante à température ambiante du fluide, dans lequel on augmente la température significativement à pression du fluide proche ou au-delà du seuil critique, caractérisé en ce que l'on amène de façon convective la chaleur nécessaire à l'augmentation de température.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on sèche comme particules contenant un fluide des gels qui contiennent de l'eau, des C1-C6-alcanoles ou des mélanges des deux comme fluide.
  3. Procédé selon les revendications 1 ou 2, caractérisé en ce que l'on sèche des gels qui contiennent de l'isopropanol comme fluide.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on sèche des gels d'acide silicique.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'on a recours à un fluide de séchage pour l'apport de chaleur convective.
  6. Procédé selon la revendication 5, caractérisé en ce que l'on a recours comme fluides de séchage à des C1-C6-alcanoles, -éthers, -cétones, -aldéhydes, -alcanes, -alcènes, -esters ou amines ou du dioxyde de carbone.
  7. Procédé selon la revendication 5 ou 6, caractérisé en ce que l'on utilise comme fluide de séchage le même que le fluide contenu dans les particules microporeuses.
  8. Procédé de préparation de particules microporeuses en réseau dans l'espace par
    (a) préparation particules microporeuses contenant un liquide dans les pores ou un fluide,
    (b) le cas échéant lavage et/ou dessalage des particules évoquées dans l'étape (a) contenant un liquide dans les pores au moyen d'un solvant ou d'eau,
    (c) le cas échéant échange partiel ou complet du liquide des pores ou du solvant ou de l'eau dans les particules par un fluide à la réception de particules microporeuses contenant un fluide,
    (d) séchage des particules microporeuses contenant un fluide et
    (e) le cas échéant séparation des gaz et/ou de substances sorbées des particules séchées à l'étape (d),
       caractérisé en ce que l'on réalise le séchage à l'étape (d) comme défini dans l'une des revendications 1 à 7 et que l'on réalise les étapes (b), (c) et (e) dans un lit mouvant dans le sens contraire de celui dans lequel on a fait passer un flux de solvant et/ou un flux d'eau dans l'étape (b) sur les particules évoquées dans l'étape (a), dans l'étape (c) on passe les particules en sens inverse du fluide, et dans l'étape (e) on passe les particules dans un flux de gaz inerte.
  9. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que pour la réalisation du procédé un dispositif est utilisé, qui comporte un réservoir à pression avec un réservoir interne (1) et un réservoir externe (2) porteur de pression ainsi que des dispositifs de mesure et de régulation appropriés de même que des dispositifs de pompes et de chauffage (6, 7), le réservoir interne étant prévu pour l'admission des particules à sécher et une fente étant prévue entre le réservoir interne et le réservoir externe.
  10. Procédé selon la revendication 9, caractérisé en ce que le réservoir interne est constitué d'acier inoxydable et le réservoir externe porteur de pression d'acier résistant à la chaleur.
  11. Procédé selon la revendication 9 ou 10, caractérisé en ce qu'une régulation de la différence de pression est placée entre le réservoir interne et le réservoir externe.
EP99915573A 1998-03-11 1999-03-11 Procede pour secher et preparer des particules microporeuses Expired - Lifetime EP1062181B1 (fr)

Applications Claiming Priority (3)

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DE19810564A DE19810564A1 (de) 1998-03-11 1998-03-11 Verfahren zur Trocknung und Herstellung von mikroporösen Teilchen sowie eine Vorrichtung zur Trocknung
DE19810564 1998-03-11
PCT/EP1999/001591 WO1999046203A2 (fr) 1998-03-11 1999-03-11 Procede pour secher et preparer des particules microporeuses et dispositif approprie pour le sechage

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EP1062181A2 EP1062181A2 (fr) 2000-12-27
EP1062181B1 true EP1062181B1 (fr) 2004-06-02

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DE (2) DE19810564A1 (fr)
DK (1) DK1062181T3 (fr)
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DE19810565A1 (de) * 1998-03-11 1999-09-16 Basf Ag Verfahren zur Trocknung und Herstellung von mikroporösen Teilchen
JP4857459B2 (ja) * 2000-03-06 2012-01-18 栗田工業株式会社 水熱反応方法および装置
US7326673B2 (en) * 2001-12-31 2008-02-05 Advanced Technology Materials, Inc. Treatment of semiconductor substrates using long-chain organothiols or long-chain acetates
US7557073B2 (en) * 2001-12-31 2009-07-07 Advanced Technology Materials, Inc. Non-fluoride containing supercritical fluid composition for removal of ion-implant photoresist
EP1585926A4 (fr) * 2002-12-19 2007-09-19 Karges Faulconbridge Inc Systeme pour extraction liquide et procedes
US7776218B2 (en) * 2003-12-19 2010-08-17 Kfi Intellectual Properties L.L.C. System for liquid extraction, and methods
US20040241742A1 (en) * 2003-05-30 2004-12-02 Peck Bill J. Ligand array processing methods that include a low surface tension fluid deposition step and compositions for practicing the same
US20060084707A1 (en) * 2004-10-15 2006-04-20 Aspen Aerogels, Inc. Methods for manufacture of aerogels
US7877895B2 (en) 2006-06-26 2011-02-01 Tokyo Electron Limited Substrate processing apparatus
US7908765B2 (en) * 2006-12-22 2011-03-22 Collette Nv Continuous granulating and drying apparatus
US8596468B2 (en) * 2007-06-27 2013-12-03 J.M. Huber Corporation Composite caustic silica gel manufacturing method and gels made thereby
US7803343B2 (en) * 2007-06-27 2010-09-28 J.M. Huber Corporation Silica gel manufacturing method and gels made thereby
JP5811620B2 (ja) 2010-12-13 2015-11-11 富士ゼロックス株式会社 シリカ粒子の製造方法
JP2012151398A (ja) * 2011-01-21 2012-08-09 Toshiba Corp 超臨界乾燥装置及び方法
WO2014030192A1 (fr) * 2012-08-24 2014-02-27 パナソニック株式会社 Corps poreux en silice et microphone optique
CN107824129B (zh) * 2017-12-04 2024-03-12 陕西盟创纳米新型材料股份有限公司 一种醇超临界法生产气凝胶的干燥系统

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US4610863A (en) * 1985-09-04 1986-09-09 The United States Of America As Represented By The United States Department Of Energy Process for forming transparent aerogel insulating arrays
DE4316540A1 (de) * 1993-05-18 1994-11-24 Hoechst Ag Verfahren zur unterkritischen Trocknung von Aerogelen
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DE19810564A1 (de) 1999-09-16
DK1062181T3 (da) 2004-08-16
ATE268310T1 (de) 2004-06-15
KR100604727B1 (ko) 2006-07-28
WO1999046203A3 (fr) 2000-04-06
DE59909648D1 (de) 2004-07-08
JP3535829B2 (ja) 2004-06-07
EP1062181A2 (fr) 2000-12-27
WO1999046203A2 (fr) 1999-09-16
KR20010041782A (ko) 2001-05-25
ES2222027T3 (es) 2005-01-16
JP2002505956A (ja) 2002-02-26
US6438867B1 (en) 2002-08-27

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