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EP1765492A1 - Corps moules a partir de poudres ou granules, leur procede de production et leur utilisation - Google Patents

Corps moules a partir de poudres ou granules, leur procede de production et leur utilisation

Info

Publication number
EP1765492A1
EP1765492A1 EP04738915A EP04738915A EP1765492A1 EP 1765492 A1 EP1765492 A1 EP 1765492A1 EP 04738915 A EP04738915 A EP 04738915A EP 04738915 A EP04738915 A EP 04738915A EP 1765492 A1 EP1765492 A1 EP 1765492A1
Authority
EP
European Patent Office
Prior art keywords
sorbent
shaped body
binder
granules
force field
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP04738915A
Other languages
German (de)
English (en)
Inventor
Helmut Stach
Peter Muenn
Jan Mugele
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuesting Bernd
Original Assignee
Fuesting Bernd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuesting Bernd filed Critical Fuesting Bernd
Publication of EP1765492A1 publication Critical patent/EP1765492A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28023—Fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B37/00—Absorbers; Adsorbers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/003—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249954—With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y10T428/249956—Void-containing component is inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y10T428/249956—Void-containing component is inorganic
    • Y10T428/249957—Inorganic impregnant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/24997—Of metal-containing material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249975—Void shape specified [e.g., crushed, flat, round, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249986—Void-containing component contains also a solid fiber or solid particle

Definitions

  • the invention relates to a process for the production of moldings from powders and / or granules, in particular of sorbent moldings of microporous or mesoporous adsorbents and Kompositadsorbentien, which serve to store useful heat and useful refrigeration, wherein vaporized working medium by supplying heat energy from the Sorbent moldings are expelled and optionally condensed and Hämit ⁇ tel, which were optionally previously evaporated, are sorbed in gaseous form, and the ent speaking sorbent shaped article.
  • aluminosilicates such as zeolites
  • modifications of such zeolites for the purpose of high heat storage capacity can be carried out by the exchange of monovalent cations, in particular of cations of the I main group of the periodic table by polyvalent cations, at least favorably by cations of the IL main group.
  • Al magnesium-containing zeolite granules are used to generate useful heat and / or useful cold.
  • Conventional techniques of modifying silicate sorbents consist of a batch process with suitable activating components to achieve a cation exchange.
  • hydrophilic substances such as salt hydrates, which undergo reversible hydration can be incorporated into a matrix that can be absorbed by temperature.
  • hydrophilic substances such as salt hydrates
  • Examples are given in DE 43 05 264 Al, in which calcium chloride in powdered zeolites (DE 43 05 264 Al) or in silica gel (DE 197 34 887 Al) is introduced.
  • the modification of prefabricated granules provided with a binder or of pellets is likewise possible.
  • Synthetically produced sorbents adapted to their intended use are generally produced in a fine-grained crystallized form, which usually does not exceed a crystal size of approximately a maximum of 500 ⁇ m.
  • beds of these crystals also allow only limited flow rates of the vaporous working medium due to limited void volumes.
  • Sorbent moldings which have larger transport pores and also cavities, such as flow channels, can already be used more advantageously, with higher flow velocities of the vaporous working medium being ensured.
  • inorganic and dimensionally stable binders such as aluminum oxide hydrate, clays and silica gel.
  • binders such as aluminum oxide hydrate, clays and silica gel.
  • the binder In the case of embedding activated charcoal in silica matrices (DE 30 15 439 A1) or aluminum oxide hydrate matrices (US Pat. No. 4,499,208 A) or bentonites (DE 15 67 491 A1) and special clays (metakaolinite, DE 33 12 639 A1), the binder also blocks to a high degree the exchange-effective micropores of the adsorbent.
  • sorbent shaped bodies which are provided with fluid-permeable sheaths of ceramic or metallic materials for the purpose of good material or energy exchange via the walls delimiting them (EP 0 140 380 A).
  • the sheaths already produce one improved structural stability against mechanical Einwir ⁇ and at least partially overcome the already recognized disadvantages of the binder.
  • gas bubbles from ceramic casting compounds can be removed by the action of force fields, for example by a centrifugal device. In this way, hollow ceramic articles are produced in the form of bodies of revolution. Preforms are already being used which are impregnated with the casting compound and thermally precured at low temperatures. An embedding of powders or granules in binders curable at low temperatures is, however, not provided for.
  • binders are desired which cure at low temperatures without substantially reducing the sorption capacity.
  • the desorption of the vaporous working medium in silicate storage media can be desirable below 1000 0 C, must be provided for some active components of the sorbent molded as complete as possible desorption and a desired high cyclic recovery of working capacity temperatures of about 200 0 C.
  • the considerable load changes and thus temperature changes of about 15O 0 C influence the long-term binding capacity of powders or granules in the sorbent mold sustainable.
  • Porous sorbent carrier structures must therefore also have a high stability, whereby stresses caused by temperature changes are to be absorbed by the stabilized walls in the interest of long service life of the shaped bodies.
  • the invention is therefore based on the object to eliminate the mentioned disadvantages of be ⁇ written technical solutions.
  • the object was achieved by moldings which were obtained by premixing powders and / or preformed granules with binders (liquid or pasty constituents) in the process of preconsolidating the binders by the action of an external force field distributed voids in the form of void volume aus ⁇ forming vacuoles arise, wherein in the preferred direction of the force field, the porous Walls of the moldings auf ⁇ have a higher proportion of solidifying binder auf ⁇ than in the interior and the unequally distributed cavities are fixed in the molded body by simultane- ous or in a preferred direction temporally subsequent solidification of the walls and the interior.
  • binders liquid or pasty constituents
  • microporous or mesoporous adsorbents and composite adsorbents are used as powders and / or granules, which serve to store useful heat and useful refrigeration, so that a sorbent shaped body is formed.
  • the binders were reduced to a small and necessary level and can therefore be used in small proportions .
  • the binders in the moldings according to the invention are localized and are preferably located in the edge zones, where they are essential for maintaining the stability of the molded article and thus its effect. Binders used are binders known to be curable at low temperatures.
  • sorbent siliceous powders or preformed sorbent granules in the form of a gel, a cylinder or a different form,
  • At least one binder on a preferably siliceous prepolymerized base such as on a water glass base
  • the inventive method for producing the shaped body is that the solid components of the molding are dry pre-mixed and placed on a porous or per ⁇ for investigating carrier.
  • a force field acts, at least in the form of the earth's gravity field or in the form of a negative pressure on the ax of a liquid separation of solids by filtration.
  • the main dimensions of the shaped body are essentially determined by two main dimensions of the carrier, to which a smaller main extent is oriented in the direction of the surface normal.
  • the flowable and low viscous binder is added and penetrates the entire void volume. A density coating of the binder in the direction of the force field effect is generated, wherein a portion of the binder passes through the carrier and is separated.
  • the carrier is connected to the powder and / or the granules on the still pasty and at least pre-bonded binder.
  • the powder and / or the granules are applied to a porous wall which has a planar surface. It is advantageously set a void volume, which is directed normal to the effect of the force field and within the two main dimensions of the molded body preferred and planar oriented freely flowed through.
  • the solid premixed components are placed in a still resting mold of a spinner whose walls are porous or perforated.
  • This mold corresponds largely to the shape and dimensions of the desired shaped body.
  • the flowable and low-viscosity binder is added and penetrates the entire void volume.
  • the density coating of the binder is then achieved by the centrifugal effect.
  • a void volume which can be flowed through freely is set, which is directed normal to the action of the force field and radially with respect to the shaped body.
  • the setteurströmbare gap volume corresponds approximately to that of a bed of powder or a disordered bed of granules.
  • a larger proportion of the binder is thus removed via openings of the porous or perforated carrier or the periphery of the hollow mold, so that transport pores preferably arise.
  • the process of pre-curing is initiated by a thermal and / or chemical treatment of the binder.
  • the solidified preform is removed and subjected to a final thermal treatment.
  • a distribution of the binder in the shaped body which is an exponential in the third and smaller main dimension of the shaped body or deviates from a radially uniform exponential.
  • the physical effect is utilized that surface tension forces of liquids on the wetted solid and in cavities are associated with capillary forces in gaps and correspondingly also gap flows and form a common equilibrium of forces.
  • higher proportions of the binder occur, correspondingly lower at the upper boundary or in axially adjacent areas.
  • the gap volume at the boundaries of the smaller main dimension or in the peripheral areas is reduced, whereby the bond strength between the powders and / or granules with the carrier and the other solid constituents is increased by bridging or also filling up the proportions present here Pore is increased.
  • a stable shell region of the molded body which can be subjected to greater mechanical load, is produced, which is directed in the direction of the original force field effect.
  • the binary proportion is reduced.
  • the binder is depleted and penetrates into areas with higher interfacial forces and thus adhesive forces. It hardens preferentially at the contact points of crystals and granules, thereby also only partially filling the interstices between the solid constituents.
  • the chemical treatment of the binder can take place in that during the partial removal of the binder, additional liquid substances solidifying the binder during the force field action are introduced into the constituents of the shaped body.
  • additional liquid substances solidifying the binder during the force field action are introduced into the constituents of the shaped body.
  • this can be done by acids or bases which accelerate polymerization and condensation of the silicate functional groups present.
  • silicate and solidifying binders this can be effected with the addition of other liquid reactive components to the prepolymers.
  • the flat edge zone or the peripheral regions of the molding may also be limited by the binder to be impregnated, additional sheaths, which are introduced into the hollow shape of the spinner on the flat carrier or before the spinning process.
  • the sheaths can consist of single-layered or multilayered Ge, braids, knitted fabrics, fleeces or mats, which are preferably metallic for reasons of improvement of the heat conduction. It is also possible to provide braided or latticed or otherwise perforated sheaths. In the case of a sorbent shaped article, additional heat-conducting solids can likewise be introduced.
  • These preferably consist of finely fibrous and / or finely dispersed metal constituents which lie in the submillimeter range of the powder bed or below the main dimension of the granules. They increase the thermal conductivity between sorbent and binder, but mainly only in the vicinity of individual and adjacent granules.
  • deformed strip-like, fibrous or sheet-like constituents of metals or other thermally conductive materials whose major dimensions are above those of the granules may be incorporated into the sorbent molding. These take over the heat conduction over larger areas of the geometric expansion and are of particular importance in the case of sorbent shaped bodies with larger dimensions.
  • the sorbent shaped body which consist of a mesh or lattice-like transparent, flow-permeable material, or of another material provided with perforations, which is likewise preferably metallic. These improve overall the mass transfer and the heat transfer. Their proportion of material in the molded body can be small in order to keep the binder portion adhering to this material low during manufacture despite the pores that are permeable to the binder.
  • Amount as the pre-solidification of the binder is carried out under gleichzeiti ⁇ according preheating the preform and the necessary pre-heating temperatures are of water-glass-containing binder to 200 0 C, preferably 15O 0 C, no damage is expected in particular of modified aluminosilicates and / or aluminum silicates.
  • aluminosilicates with a Si / Al ratio of at least 1 to 4 and / or mesoporous aluminosilicates with a Si / Al ratio of 15 to 30 are used.
  • the aluminosilicates are preferably zeolites modified by cation exchange with an average pore radius of less than 7.2 nm.
  • the replacement cations are at least twice positively charged.
  • the active component may consist of a composite adsorbent, so that it is possible to introduce finely dispersed hydrophilic salts into its pores and cavities or onto the inner and outer surfaces of a sorbent carrier.
  • the advantages of the sorbent formed body according to the invention thus consist in an optimal combination of the reaction-technical effectiveness of modified aluminosilicates and / or aluminum silicates and their fluidic effect during mass and heat exchange with the aim of achieving high space-time yields in the storage of To achieve useful heat and useful refrigeration.
  • Non-adsorbent granules containing moldings are prepared in the same or similar procedure by force field processes at partial removal of Bin ⁇ deffens. It form a total of sintered-like shaped moldings from coarsely dispersed granules, which are characterized by a low binder content and a high void volume, the walls are reinforced by higher and solidified binder proportions.
  • the essence of the invention consists of a combination of known (shaped bodies of powders and / or granules, binders, etc.) and new elements (the production the shaped body under the action of a force field), which influence one another and, in their new overall effect, result in a use advantage and the desired success, which is achieved by achieving high space-time yields in the storage of useful heat and useful refrigeration.
  • the sorbent tablets according to the invention are suitable for storing useful heat or useful refrigeration.
  • vaporous working agents are expelled from the sorbent shaped body by supplying heat energy and optionally condensed, and the working agents, which may have previously been vaporized, are sorbed in gaseous form.
  • FIG. 1 shows a section through a sorbent shaped body according to the prior art.
  • FIG. 2 shows a section through the sorbent molding according to the invention.
  • FIG. 3 shows a rotationally symmetrical sorbent shaped body according to FIG. 1b with additionally introduced flow guides.
  • the state of the art of the sorbent shaped article 1 according to FIG. 1 is characterized in that an axially and radially uniform distribution of the binder 3 exists between the granules 2 and the additionally introduced heat-conducting solids ⁇ not shown). It is also possible here before or during the hardening process of the binder to form vugs 4, which are penetrated by the vaporous working medium. According to the prior art, these vacuoles 4 are still unfavorably present in a small proportion and extent and form only reduced transport pores, so that the possible void volume remains limited due to a high binder content.
  • a concentration of the binder 3 in the shell 5 of the sorbent formed body 1 occurs, which causes stabilization and solidification of the shell in the peripheral Berei ⁇ chen.
  • the binder 3 preferably adheres to the denser adjacent granules and the other introduced solids and in the gusset spaces such that larger clearances around the gussets, larger transport pores and overall larger and freely flow-through void volumes arise.
  • the increase in the relative mass of the binder is at a relative radius (based on the distance central axis - periphery of sorbent molding) of 0.9 a maximum of 7%, their reduction at a relative radius of 0.1 not more than 4%.
  • Traces of the relative resistance coefficients and the relative gap volume show, depending on the cross-sectional average relative Geschwin ⁇ speed of the vaporous working medium at an increase of this speed by 100%, a lowering of the relative resistance coefficient by a maximum of 6% and an increase in the relative gap volume by a maximum of 9%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un corps moulé, notamment des corps moulés sorbants constitués d'adsorbants microporeux ou mésoporeux et d'adsorbants composites destinés à l'accumulation de chaleur utile et de froid utile. Le corps moulé présente une fraction réduite de liants. Les corps moulés sorbants ont des cavités de répartition irrégulière se présentant sous la forme de vacuoles formant des volumes de vacuité. Le procédé de production des corps moulés consiste à appliquer des constituants solides prémélangés du corps moulé sur un support poreux ou perforé ; à effectuer après l'adjonction du liant, la présolidification du liant sous l'effet d'un champ de force externe, ce champ de force entraînant la création des cavités de répartition irrégulière et le constituant liant situé sur le support qui représente la paroi du corps moulé, étant plus élevé qu'à l'intérieur du corps moulé. Le corps moulé sorbant selon l'invention présente l'avantage de lier de manière optimale l'efficacité en termes de techniques réactionnelles d'alumosilicates et/ou d'aluminiumsilicates modifiés et leur action liée à la technique d'écoulement dans le cas d'échange de matière et de chaleur avec pour objectif d'obtenir des rendements espace-temps élevés lors de l'accumulation de chaleur utile et de froid utile.
EP04738915A 2004-07-09 2004-07-09 Corps moules a partir de poudres ou granules, leur procede de production et leur utilisation Ceased EP1765492A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/DE2004/001535 WO2006005275A1 (fr) 2004-07-09 2004-07-09 Corps moules a partir de poudres ou granules, leur procede de production et leur utilisation

Publications (1)

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EP1765492A1 true EP1765492A1 (fr) 2007-03-28

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EP04738915A Ceased EP1765492A1 (fr) 2004-07-09 2004-07-09 Corps moules a partir de poudres ou granules, leur procede de production et leur utilisation

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US (1) US8092903B2 (fr)
EP (1) EP1765492A1 (fr)
DE (1) DE112004002971A5 (fr)
WO (1) WO2006005275A1 (fr)

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DE102005000022A1 (de) * 2005-03-16 2006-09-28 Füsting, Bernd Sorbierender Formkörper, Verfahren zur Herstellung und Verwendung
DK2220343T3 (da) * 2007-10-03 2013-08-05 Isentropic Ltd Apparat til energilagring og fremgangsmåde til energilagring
WO2015007274A1 (fr) * 2013-07-19 2015-01-22 Invensor Gmbh Machine frigorifique à adsorption dotée d'un agent d'adsorption, procédé de production de froid et utilisation d'une zéolite désaluminée en tant qu'agent d'adsorption dans une machine frigorifique à adsorption
JP2015040646A (ja) * 2013-08-20 2015-03-02 株式会社豊田自動織機 化学蓄熱装置
TWI659778B (zh) 2014-04-09 2019-05-21 美商Ｗ Ｒ 康格雷氏公司 經改良之氣體或液體吸附和／或脫附用之沸石粒子及其應用與製造方法
CN107110613B (zh) * 2015-01-27 2019-08-13 古河电气工业株式会社 蓄热容器以及包括蓄热容器的蓄热装置
JP6868393B2 (ja) * 2016-12-28 2021-05-12 日本ペイントホールディングス株式会社 蓄放熱装置
EP3382314A1 (fr) * 2017-03-30 2018-10-03 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Production et utilisation améliorées de tcm

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Also Published As

Publication number Publication date
WO2006005275A1 (fr) 2006-01-19
US8092903B2 (en) 2012-01-10
US20070251837A1 (en) 2007-11-01
DE112004002971A5 (de) 2007-07-12

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