EP1866078A2

EP1866078A2 - Absorbent moulded bodies method for production and use

Info

Publication number: EP1866078A2
Application number: EP06725081A
Authority: EP
Inventors: Helmut Stach
Original assignee: Fuesting Bernd; Muenn Peter
Current assignee: Fuesting Bernd; Muenn Peter
Priority date: 2005-03-16
Filing date: 2006-03-15
Publication date: 2007-12-19
Also published as: US20080274345A1; DE102005000022A1; WO2006097493A3; US8012246B2; WO2006097493A2

Abstract

The invention relates to an absorbent moulded body, a method for production and use thereof, comprising micro- or meso-porous adsorbents. Said moulded bodies serve as process heat and refrigeration sources, whereby a vapour working medium is expelled from the moulded body by the introduction of heat energy and optionally condensed and the working medium, optionally previously vaporised, is absorbed in gaseous form. The moulded body comprises crystalline powder and/or granules together with a conducting surface (3) within a cage (2), connected to the surface and the powder and/or granules are bonded by the binder in the form of a random bed.

Description

Sorbent molding, method of manufacture and use

description

The invention relates to a sorbent molding, a process for the preparation and its use, comprising microporous or mesoporous adsorbents. This shaped body is used to store useful heat and useful cooling, wherein a vaporous working fluid expelled by supplying heat energy from the molding and optionally condensed and the working fluid, which was optionally previously evaporated, is sorbed in gaseous form.

As umhüllbare, stackable or packable moldings they are used for sorptive heat storage using preferably aqueous-vaporous working fluid, so in the heating, cooling and air conditioning, especially for the use of natural warmth, such as natural or solar heat. For energy storage purposes, there are applications wherever thermal energy needs to be available for temporary periods of use that do not match periods of heat generation or their provision. Economic objectives of the use of moldings containing microporous or mesoporous sorbents consist in achieving high space-time yields for the material and energy conversion of the devices operated with them, including for heat storage. In this case, the outer shape of the sorbent moldings and their geometric dimensions can expediently be matched to the associated heat-exchanging devices, such as the geometry of inner tube walls of heat accumulators.

State of the art

The state of the art in the field of silicate heat storage media is characterized by microporous and mesoporous sorbents, from which the water of crystallization can be removed by the action of heat without damaging the framework structures. Commonly used are silica gels and zeolites, which correspond to a modern state of application for heat storage.

zeolites:

For the production of zeolites is on the company publications "Baylith ^® information", including "80.100 - General Product Description", "81.503 - Technical Properties" and "81.505 -Apparticular Properties", Bayer -Werke Leverkusen, as well as on "Zeosorb Molecular Sieves", Bayer AG Bitterfeld- Wolfen, referenced.

To achieve high space-time yields for substances and heat, especially in catalytically influenced processes alumo-silicates are used as zeolites. These have anion skeletons, which are preferably subjected to a chemical modification (DE 44 33 120 Al). Common techniques for siliceous sorbents are impregnation of a matrix with activating components, such as by infiltration techniques to achieve cation exchange. For the purpose of a high storage capacity for heat so magnesium-containing zeolite granules (DE 33 12 875 Al) are used. Hydrophilic salt hydrates, which are subjected to reversible hydration, are incorporated into a matrix, which can be absorbed by temperature. In DE 43 05 264 Al examples are given in which calcium chloride in powdered zeolites (DE 43 05 264 Al) or in silica gel (DE 197 34 887 Al) are introduced. The chemical composition of a zeolite of the type NaX is z. Nai ₂ (AlO ₂ ) i ₂ (SiO ₂ ) i ₂ .zH ₂ O consisting essentially of SiO ₄ and AlO ₄ tetrahedra. The pore diameters are in a favorable adaptation to the size of the water molecules depending on the type of molecular sieve 3 to 10 Ä. Their thermal stability is up to temperatures of 850 ° C, their hydrothermal stability only up to about 400 ° C.

In cyclical processes, such as in the loading of heat storage by desorption with the working water vapor and its discharge by adsorption on zeolites cycle numbers of 4,000 to 10,000 are often reached. The almost completely adsorbed water is released by zeolites, however, only when using process temperatures of 200 ° C to 450 ° C. Thus, the sorption capacity of zeolites are only partially used when using solar generated low temperature heat. Zeolite-like metallosilicates behave thermally similar and less effective. Metallophosphates: The replacement of silicon by phosphorus ions leads to zeolite-like molecular sieves such as aluminophosphates (ALPO). Replacement of aluminum with silicon provides silicoalumophosphates (SAPO). The chemical composition of ALPO corresponds essentially to xR ^• Al ₂ O ₃ ^• 1.0 ± 0.2 P ₂ O ₅ ^• yH ₂ O [0009] (R = amine or ammonium salt), that of the anhydrous SAPO about 0 - 0.3R (Si _x Al _y P ₂ ) O ₂ . AlO ₄ tetrahedra are assembled with PO ₄ tetrahedra. at In addition, the metalloaluminophosphates (MeALPO) of composition 0-0.3R (Me _x Al _y P _z ) O ₂ are replaced by a variety of elements. All metallophosphates have in common that new structures with outstanding properties for the storage of water are formed. Above all, storage materials are selected whose pore diameters are advantageously 2 to 13 Å. At temperatures up to 1000 ° C thermal stability is still present. Their hydrothermal stability up to temperatures of 600 ° C is very high. Flat sorption horseshoe curves occur during sorption. As far as the state of knowledge is concerned, it is confirmed by measuring samples that with repeated adsorption and desorption up to 60,000 cycles practically no changes in the isothermal forms for water are detectable. It is of particular advantage that the sorption isotherms for water have an S-shaped course with a sudden increase within a very short pressure interval. Within this range is achieved by pressure reduction by a few mbar extensive desorption at normal temperature. In comparison with silica gel, 4 to 6 times the amount of water is stored. Metallophosphates are particularly preferable because of their favorable desorbability at low temperatures in solar heat storage devices. It is envisaged that storage systems and also sorption heat pumps based on the new sorbents due to a high temperature lift can be built considerably smaller.

Granules / shaped bodies:

Artificially produced and their purpose adapted sorbents are common in a fine-grained crystalline powder form, which usually does not exceed a crystal size of a maximum of 500 microns possible. However, for effective use in heat storage devices, bedding of these crystals also allows only limited flow rates of the vaporized work equipment because of limited void volumes and high flow resistances. Pelleted granules which are processed with binders as random clusters into porous shaped bodies can be used to advantage. These moldings should have larger transport pores and cavities and flow channels, which allows higher speeds for the flow of the working fluid and upstream routes for the mass transfer of the working fluid water vapor can be significantly shortened. The total process time is limited by the exchanges for fabric and heat and is determined by the pore size of the sorbents themselves. An advantage of using molded articles is their packability between heat-conducting devices and the interchangeability of individual ones Components, especially for the purpose of interpretation and scale-up in modular heat accumulators. It also appears possible to limit the need for heat-conducting internals in heat accumulators by enlarging the molded body. So far, only so-called "zeolite shaped bodies" are an independent category within the outlined state of the art.

Heat conduction:

In random sorbent beds with high storage capacity is the

Thermal energy loss introduced into the interior, transmitted to the interior of the heat transfer medium flowing through the interior and as possible not irreversibly released back to the environment (eg, DE 34 18 005 Al, DE 36 43 668 Al, DE 44 37 950 Al, EP 0 091 095 A). To achieve a high energy storage density, an optimal ratio of heat transfer surfaces to the storage volume is set. The heat guidance in a longitudinal and in the transverse directions is designed so that forming material and temperature gradients quickly compensate each other. Nevertheless, it is disadvantageous that during the cyclic load change, a pronounced and non-ideal transition behavior is recorded in the dynamics of heat accumulators. Particularly in the case of an increase in scale in one of the geometrically provided main expansions, undesirable intermediate states occur in which the temperature deviation due to the impeded heat transfer is not predominantly stepwise and is smeared locally and temporally.

With metallic deformable packing larger dimensions already the disadvantages are overcome, resulting in mineral sorbents by poor heat conduction. The filler usually consist of a skeleton (DE 100 21 260 Al), on which there are boundary surfaces that are transparent to currents and at the same time touch each other at their edges. The surfaces are good heat-conducting, with the partially open body spatially not interfere. The deformability of the packing, as well as a Füllkörperhülle (DE 100 21 260 Al), ensures a dense packing of individual elements in the reaction chamber and the formation of a plurality of heat-transferring contact surfaces in the spatial dimensions of heat storage.

Binder:

A disadvantage of all sorbents, that they can be difficult to incorporate into moldings. In this case, the initially flowable binder remains a considerable space-filling component of the molded article, which reduces the degree of utilization of the sorbents by blocking exchange-active micro- and mesopores.

In most cases, the use of already granulated or pelleted with a binder crystals leads to these disadvantages. Due to the larger geometric dimensions of granules, although larger void volumes occur, which are advantageous for the flow guidance because of lower pressure losses, but affect the economics of the device as a whole unfavorably in terms of lower packing density.

Even flowable and curable binder have been enriched only in the permeable surface of sorbent moldings to improve their surface stability and overall structural stability. This can be achieved by means of a force field process, such as by sedimentation or filtration (DE 103 01 099 A1). It preforms are used, which are soaked with the spatially unevenly distributed mass of the binder and thermally precured at low temperatures.

Substance and energy exchange: There are known sorbent moldings which are provided with fluid-permeable sheaths of ceramic or metallic materials for the purpose of good material or energy exchange over the walls delimiting them (EP 0 1 403 80 A).

In the heat storage by means of highly effective ALPO or SAPO, which are of higher hydrothermal stability, particularly binders are desired which cure at low temperatures, without significantly reducing the sorption and are also present in the lowest possible proportions in the molding. ^Λ

regeneration:

Although the adsorption of the vaporous working medium in silicate storage media can be carried out desirably at normal temperature, must be provided for the active components of the sorbent moldings as complete as possible desorption and a desired high degree of recovery of cyclic work ability at higher temperatures, usually of about 500 ° C. The considerable loading and thus temperature changes have a lasting effect on the long-term integratability of powders or granules in the porous molding. The moldings must have a high stability, because caused by heat exchange stresses internal defects occur. These must be collected in the interest of long service life of the moldings of the stabilized walls. Thus, the increase in heat or cold storage due to increase in sorption capacity and increase in energy storage density is also sought under improved mechanical properties of the moldings. The disadvantage still remains the poor heat conduction in particular larger moldings, since they insulator predominantly consist of mineral constituents.

task

The invention is therefore based on the object, said structural mechanical and heat and fluidic disadvantages of the described solutions to be sorbed moldings to eliminate, for sorbents with improved efficiency and improved heat transfer is provided.

Shaped body structure:

The object is achieved by a shaped body having a metallic grid-like cage structure and an inner likewise net-like guide surface for the heat. The guide surface according to the invention is a means for better management of heat flows and to increase the stability and shape of the molding.

Geometrically, the guide surface is formed of longitudinally extending and between edges spanned generating guidelines at least second order, which are bounded at the two transverse edges by second-order curves. These edges represent circular, elliptical or parabolic segments. The two borders of the cage structure are in each case in at least three upper points with the one limiting edge and in three lower points with the second delimiting edge of the guide surface in contact. In the longitudinal direction and thus the main extent of the shaped body, the guide surface in the form of a spatially curved diagonal surface. The diagonal surface consists of two uniform parts, which are symmetrically mirrored around the central transverse axis in one of the transverse expansions.

Physically seen, the guide surface is a minimum surface for the heat conduction in a cylindrical or rectangular body. Within the molded body, the guide surface is based in the contact points about resiliently on the cage structure and is optionally connected to the edges of this structure. With a low cost of materials optimally high heat conduction is adjusted within the molding and passed to the outer body of the molding limiting cage structure. Overall, a longitudinal stable and good heat conductive grid structure inside and outside of the molding.

The cage structure may consist of a knitted fabric, mesh, knitted fabric, fleece or scrim, which is preferably lattice-like or net-like and metallic. The structure is at least single-layered, but can also be executed in several layers, such as by winding. The heat transfer tubes can be conventional pipes, but also specially designed pipes that allow improved flow and heat management within the heat accumulator. Thus, the tubes may be called bellows, the interior of which produce a highly turbulent flow with the working fluid and thus allow improved heat transfer through the tube walls. A similar effect is achieved by sintered tubes, which have wall roughness inside. Also, the molded body can be fitted in Lammelienartige structures that connect analogous to heating systems with each other fluidically related pipes. For example, pipes arranged in parallel or meandering can be connected to one another via registers for the inlet and outlet of the heat carrier.

Within the cage structure with the guide surface is the highly active sorbent in the form of agglomerated crystals or pelleted granules, which are bound together by a binder in the form of a random cluster.

The geometric limitations of the shaped body may be barrel-shaped, cylindrical, prismatic or polyhedral. The cage structure with the guide surface and with the powders or granules contained in the interior are limited deformable at least in the process of their preparation. These therefore preferably satisfy the conditions of a quadrangular or triangular pitch arrangement of the internal heat-conducting devices on floor mirrors of heat accumulators. They nestle in shape so at least in individual contact points to the peripheries of heat transfer tubes.

The flow of the working fluid takes place in cavities, preferably in the form of pocket or gusset spaces or on the tolerance column, which are formed between the moldings and the heat transfer tubes. The mass transfer of the molding takes place so primarily on its front and side surfaces, the heat exchange via the cage structure connected to the guide surface with the adjacent heat transfer tubes. Due to the high affinity of the sorbent for the working medium vapor and thus the high driving forces of the sorption always sufficient free cross-sections for the flow through all cavities are set with the working fluid.

The outer geometric dimensions of the molding exceed the size of the granules to a considerable extent. It is set as a high volume density and a high degree of space utilization for the sorbents in the heat storage. However, the mesh sizes of the cage structure are smaller than the major dimensions of the granulated sorbent particles. When using powders in the molding, the mesh size of the cage is only set to a minimum necessary level for the purpose of passing the working medium vapor. The mesh size of the guide surface exceeds the size dimension of powders and can also exceed the size of granules and should allow an unobstructed flow through the molding in the preferred direction. It is expedient to provide the Sorbensinnere with separate flow guides. These facilitate the access of the working fluid into the spaces of the shaped body, which are still outside the sorption front in the direction of its main dimension. Overall, a proportional cross-flow of the working fluid is thus achieved, which reach the heat accumulator both via the front surfaces and via the side surfaces of the molded body.

Production method:

The lattice cage of the molding is prefabricated by rolling a flat and preferably metallic network or from another wire-shaped edged mold carrier. The network of the mold carrier may also be a knitted fabric, mesh or knit or else a scrim or nonwoven. Appropriately, it is a cut net-like stocking material. The guide surface introduced into the mold carrier is licked, stapled, needled or simply opened at the borders of the cage. Particles used and to be incorporated in the moldings are aluminosilicate powders or preformed sorbent granules, in a spherical, cylindrical, cylindrical or deviating prismatic geometry, and are preferably ALPO, SAPO and MeAPO.

The prefabrication of the molding is carried out by the mineral powders and / or the preformed granules are premixed with liquid low-viscosity binders or from its moderately viscous or pasty components and the mixture is filled into the cage with the guide surface. The flowable viscous binder initially penetrates the total gap volume. The binder should preferably be enriched in the edge zones of the shaped body in order to ensure access of the working medium via micropores and mesopores with only slight inhibitions for the diffusion. Depending on the dimensions of the sorbent particles, the filling can be effected by impressions by means of a punch or piston movement of one or expediently from both of the transversely extended boundary surfaces of the shaped body.

It is preferably used at low temperatures pre-drying and curable known binders. These are usually prepolymers of alkali-containing silicates such as water glass or organosilicon viscose Anteigmittel, such as silicones. Other binders used are phenol-formaldehyde resins, polyvinyl resins and polyacrylates with little desired internal bond strength for the sorbents. Polyurethanes and latexes also only moderately increase the strength within the molding. Cellulose derivatives as matrix formers for powders and granules are only temporarily remaining binders during the process of preconsolidation in the molding and can be partially removed by dissolution. The undesired blocking of micro - and mesopores in the sorbent by the binder thus remains largely limited. A chemical treatment of the binder may be caused by the fact that during the partial removal of the binder additional adhesion-promoting and solidifying, but liquid chemically reactive substances are introduced into the components of the molding. In the case of water-glass-containing binders, this can be done by acids or bases which accelerate polymerization and condensation of the silicate functional groups present. In other silicate and solidifiable binders, this can be accomplished by adding liquid reactive components to form prepolymers.

In the Wandberandungen the binder is localized and preferably used in higher proportions where it is essential for maintaining the structural stability of the molding and thus its structure-forming effect. Due to higher temperature resistance, conventional inorganic binders are preferably used in these boundaries, such as alumina hydrate, clays and silica gel. Likewise, embeddings in matrices of silica or alumina hydrate, but also in bentonites and special clays, such as metakaolinite. Carbonation is also possible with the particles of binding and originally water-soluble pitch acids.

Liquid binders are introduced into the wall boundaries by means of infiltration, pasty optionally by overpressure and under application of a pressure pad within a press room to one or both of the transverse boundary surfaces. The binder is enriched in a relatively thin surface layer and penetrates especially in the use of granules in areas with higher interfacial forces and thus adhesive forces. It preferably adheres to the contact points of crystals and granules and fills only limited the interiors of the molding and the necessary for the mass transfer voids between the solid constituents. Moderately pasty binders are already applied during prefabrication to the lattice structure of the molding and pressed under pressure into the outer surfaces.

It is adjusted by means of located between the granules binders of the molding a gradual or abruptly directed into the interior distribution before or during the structural solidification, in the central core zones of the molding lower binder content of a first binder, in the peripheral edge zones however, higher levels of a second binder may be present.

The molded article is preconsolidated by pressing the mesh cage together with the sorbent and with heating. The standing under heat, at least bivalve cheek plates also heat the lattice cage of the molding, wherein on the guide surface at the same time a very good heat input in the interior under intense heat balance for the purpose of drying the binder. It is also possible to additionally apply the grid structure together with the binder on the molding and to press. It is followed by a post-drying at elevated

Temperatures on and / or activation of the molding. This can be done in a favoring this gas atmosphere. All associated with heat compensation forming operations carried out due to improved heat conduction even with larger dimensions of the molding in shortened periods, in comparison with conventionally produced moldings without guide surface.

It arises in the delimiting walls of the sorbent molding a stable and mechanically more resilient shell region, which is directed in the direction of the original pressing action. In the central, axially adjacent areas, however, the binder content is reduced. In a modification of the molding are in its interior for the purpose of improved heat conduction in addition also fine-fibrous and / or finely dispersed metal components in the millimeter range, which are above the size of silicate crystals, but below the main dimension of granules and the proportionate with the guide surface of the molding in contact. Optionally, additionally deformed strip, fiber or sheet-like constituents of metals or other heat-conductive materials are used whose main dimensions are above those of granules. Other constituents of the shaped body are wetting agent and adhesion promoter components for the constituents of the shaped body between the sorbent particles.

Since the preconsolidation of the binder takes place with simultaneous preheating of the preform and the required preheating temperatures for water glass binders are below 200 ° C and preferably 150 ° C, no damage is expected in particular of aluminophosphates, Silikoalumophosphaten or Metalloalumosilikaten. For the heating and activation temperatures between 400 ° C and 600 ° C are preferably used in an inert gas atmosphere, which also lead to no structural changes. Particularly favorable effects are achieved in that the active components of the sorbent shaped body, in contrast to the prior art at elevated temperatures during the charging and discharging of the heat storage their lattice structure not or very little change, so that a long life of the molding, its increased effectiveness is achieved at the same time increased lifespan.

The features of the invention will become apparent from the claims also from the description, wherein the individual features each represent alone or to several advantageous combinations in the form of combinations executions for which protection is sought with this document. 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 of moldings by means of a cage and a guide surface), which influence each other and in their new overall effect, a utility advantage and the desired success result, which is that even higher space-time yields in the storage of useful heat and useful cold as described in the prior art, can be achieved. The advantages of the sorbent molding according to the invention thus consist in an optimally possible interaction of thermal conduction and the reaction engineering effect of aluminophosphates, silicoaluminophosphates or metalloalumosilicates as well as in their fluidic effect in the material and heat exchange with the aim of high space - time yields in the Storage of useful heat and useful refrigeration to achieve. The increased by the introduction of the guide surface manufacturing cost is thereby relativized or compensated that large dimensions of the molding are provided.

The process is not limited to the production of sorbent moldings. There may be other, for. B. non-adsorbent granules containing moldings are prepared in the same or similar procedure by infiltration within a lattice structure. It form a total of sintered-like shaped bodies of coarse-disperse granules, which are characterized by a low binder content and a high void volume, the walls are reinforced by higher proportions of solidified binder.

embodiments

The invention is explained in more detail by way of example, without being limited to the exemplary embodiments. In the accompanying drawings show:

Fig. 1: The sorbent molded body with cage and guide surface in an exploded view Fig. 2 (a) to Fig. 2 (d): Embodiments of various molded bodies with flow channels in oblique views of the guide surface

Fig. 3: A heat transfer tube with adjacent shaped body in a schematic representation

4 (a) and 4 (b) show embodiments of the cage grid structure in quadrilateral and FIG

triangular pitch

Fig. 5 (a) and Fig. 5 (b): successively arranged moldings in top views with a bottom mirror of a heat storage in quadrilateral and triangular division

example 1 The prior art of a sorbent cylindrical shaped body 1 according to FIG. 1 is characterized in that in the cage 2 and between powders or granules of the sorbent 7 with possible additionally introduced thermally conductive solids at least one guide surface 3 is missing and still a uniform distribution of the binder consists. In this case, before or during the hardening process of the binder, intermediate spaces can also be formed which are penetrated by the vaporous working medium. According to the prior art, these gaps are still unfavorably present in a small proportion and extent and form only reduced transport routes, so that the possible durchströmbare gap volume remains limited as a result of a high binder content. The heat balance with a metallic and transparent sheath is still insufficient.

According to the prior art, it has also been found, according to DE 103 01 099 A1, that in carrying out the associated method for the production by means of a force field process, a concentration of the binder is adjusted according to an exponential distribution over a transverse direction of the shaped body 1. This already causes a stabilization and solidification of the sheath in peripheral areas. In axially adjacent and central regions of the molded body 1, a depletion of the binder occurs. However, the binder preferably adheres to the more closely adjacent granules and the other introduced solids as well as in the gusset spaces in such a way that larger free spaces around the gussets, larger transport pores and overall larger and freely flow-through void volumes arise. Again, however, the heat balance with the metallic sheath is still unsatisfactory due to lack of fins.

Example 2

With reference to Figure 1 according to the invention consists of the molded body 1 of the cage 2 and the transparent guide surface 3. The ridge 4 and the ridge 4 'and the sole 5 are on the one hand with a lower part of the boundary 6 of the one of the transverse boundary surfaces Burr 4 and the ridge 4 'connected to the vertex 5' with an upper part of the other of the transverse boundary surfaces 6 'on the cage 2 of the molding 1. According to FIG. 4, the molded body 1 fits over the tolerance gap 22 to four heat carrier tubes 20 (FIG. 4 a) or 3 heat carrier tubes 20 (FIG. 4 b). According to Figure 3 exceeds the wall temperature of a heat transfer tube 20 above the bottom 21 at heat supply even under steady-state conditions that which was determined without the guide surface 3 (LF) and without filling with the sorbent 7. The sorbent used is an aluminosilicate having a pore volume of 0.3-0.4 cmVg and a mean pore diameter of 7.4 Å in a shaped body having the main dimensions of 300 mm × 400 mm. After the starting time of the thermal compensation of 20 s, the wall temperature exceeds that of a shaped body according to the prior art by 1.5 times.

Example 3

In a shaped body according to Example 2 are as sorbent an aluminosilicate in the form of hollow cylinders with dimensions of 6/3 or 7/4 mm an original bulk density of 400 - 550 kg / m ³ and a specific surface area greater than 700 m ³ / kg.

The increase in the relative mass of the binder water glass at a relative radius (based on the distance between the center axis periphery of the sorbent shaped body of 0.9) is a maximum of 8%, their share at a relative radius of 0.1 not more than 2%. Precursors of the relative resistance coefficients and the relative void volume (based on the prior art molding) show, depending on the average cross-sectional relative velocity of the vaporous working medium with an increase of this speed by 100%, a reduction of the relative resistance coefficient by a maximum of 6% and a Increase of the relative gap volume by a maximum of 9%.

Example 4

A modified according to Figure 4 and used according to Example 3 molded body 1 contains in the sorbent 7 to both mutually mirrored sides of the guide surface 3 on the one hand a flow channel 10 and on the other hand, a flow channel 10 '. Referring to Fig. 4 (a), the flow channels 10 and 10 'are in the shape of a cylinder. In the material and heat balance, after a process time of 144 s to 90%, an equilibrium setting for the working medium water vapor and the set temperature stroke is achieved. Example 5

A shaped body according to FIG. 4 (b) has between the flow channels 10; 10 'a passage 11 for the working fluid. According to Example 4 and after a process time of 5 160 s, a 90% equilibrium for the working medium water vapor and the temperature stroke is achieved.

Example 6

A shaped body 1 according to FIG. 4 (c) has flow channels 10; 10 'two opposite conical indentations. The equilibrium settings of Examples 2 and 4 are reached after 118 seconds.

Example 7

I ₅

A molded body 1 according to Fig. 4 (d) has three channels, each of the flow channels 10; 10 'with the passage 11 exist. Settings of the water vapor and temperature equilibria corresponding to the above examples are achieved after 120 s, comparable to example 5.

20

Example 8

According to Figure 5 are located on a bottom 21 of a heat storage between the heat transfer tubes 20 a plurality of moldings 1 and 1 'in each case a cage 2 and 2' and 2 ₅ arranged in a square pitch [Fig. 5 (a)] or in a triangular division [Fig. 5 (b)] of

Bodens 21. The moldings 1 and 1 'have no flow channels 10; 10 'and none

Passages 11.

In a test arrangement of a heat accumulator according to FIG. 5 (a) with 6

Shaped bodies in the longitudinal extent and 4 moldings with dimensions in one of the 30 transverse expansions according to Example 2 at the output corresponding settings of the water vapor and temperature equilibria are reached after about 6 minutes.

Example 9 According to Table 1, as measured data, the working capacities (loading cycles as differences in sorption capacity) at comparable sorption temperatures for adsorption and desorption for a conventional sorbent and two sorbents used here are compared. Given the reversibility of both processes, the work capacities of the SAPO and AL PO are increased by a factor of 4 to 6, respectively. As with reference to Example 10, Tab. 2, the storage density of a heat accumulator increases under otherwise comparable apparatus configuration by 30 to 40%.

Table 1. Comparison of working capacities of the molding according to the invention with one of the prior art

Example 10

With reference to Table 2, some values determined for properties of sorbents used (SAPO and ALPO), such as the sorption capacity with the working medium water vapor, the integral molar adsorption heats and the desorption temperature are compared with those of conventional zeolitic sorbents.

It turns out that the adsorption capacities and the integral heat of adsorption for SAPO and ALPO are already advantageously high and correspond approximately to those of zeolites. By contrast, the desorption temperatures are comparatively low and are at least 100 ° C. to 130 ° C. below the corresponding temperatures for zeolites. Tab. 2. Comparison of aluminophosphates with measured data for sorbents according to the prior art

List of reference numbers:

1 Shaped body 6 Border r Shaped body 6 'boundary

2 cage 7 sorbents

2 'cage 10 flow guide

3 guide surface 10 'flow guide

3 'baffle 11 passage

4 ridge 20 heat transfer tube

4 'ridge 21 ground

5 sole 22 gusset room

5 'vertex

- for this purpose 29 claims -

Claims

claims

1. shaped body (1), comprising crystalline powders and / or granules and at least one binder, wherein powder and / or granules together with a surface (3) within

5 of a cage (2), which is connected to the surface and the powders and / or granules are bound by the binder in the form of a random pile.

2. Shaped body according to claim 1, characterized in that the binder is unevenly distributed between its peripheral radial and its central axial parts.

10

3. Shaped body according to claim 1 or 2, characterized in that it is the surface to a guide surface (3) and in the powders and / or granules to sorbing powder and / or granules, so that a sorbent molded body (1) is formed becomes.

i ₅

4. sorbent molding (1) according to claim 3, characterized in that a ridge (4) and a ridge (4 ¹ ) and a sole (5), on the one hand with a lower part of the boundary (6) of one of the transversely defining surfaces, the ridge (4) and the ridge (4 ¹ ) with a vertex (5 ¹ ) with an upper part of the other of the transverse boundary surfaces (6 ¹ ) on the cage (2) in contact or in contact.

20

5. Sorbent molded body (1) according to claim 3 and 4, characterized in that the cage (2) and the guide surface (3) consist of a layer of knitted fabric, woven, knitted fabric, nonwoven or scrim and are preferably formed grid-like or net-like and metallic ,

2 ₅ 6. sorbent molded body (1) according to one of claims 3 to 5, characterized in that the cage (2) is designed as a layer at least one layer.

7. sorbent molding (1) according to one of claims 3 to 6, characterized in that in the sorbent (7) to both mutually mirrored sides of the guide surface (3) at least

30 a flow channel (10) and on the other hand at least one flow channel (10 ') is present.

8. sorbent molding (1) according to claim 7, characterized in that the flow channels (10) and (10 ') have the shape of a cylinder, a cone or a prism.

9. sorbent molded body (1) according to claim 7, characterized in that at least one flow channel (10) and a flow channel (10 ') through the guide surface (3) through passages (11) communicate with each other.

5

10. sorbent molded body (1) according to one of claims 3 to 9, characterized in that this above a floor (21) via a tolerance column (22) to three heat transfer tubes (20) or to four heat transfer tubes (20) conforms.

lo

11. sorbent molded body (1) according to claim 10, characterized in that in a main extension of a device a plurality of moldings (1) one behind the other and in a transverse extension of the bottom (21) parallel to mold several moldings (1) to the heat transfer tubes (20).

i ₅

12. sorbent molding according to one of claims 3 to 11, characterized in that it is the sorbents to silicate microporous or mesoporous sorbents of the metallophosphate type and preferably of aluminophosphates (ALPO), silicoaluminophosphates (SAPO) or Metalloalumophosphaten (MeAPO) , which during a load change by sorption at elevated and reduced temperatures their

20 Grid structure does not change or changes only slightly.

13. sorbent molding according to claim 3, characterized in that the granules have the shape of sphere, cylinders, tons or of polyhedra.

2 ₅ 14 sorbing molding according to one of claims 3 to 13, characterized in that further integral parts constitute heat-conducting solids and preferably fibrous and / or disperse metal components are, whose dimensions are maximum for powder in the millimeter range.

15. Sorbent molding according to one of claims 3 to 14, characterized in that additionally deformed strip, iaser or sheet-like components of metals or other heat-conductive materials are present, which are at least in the millimeter range and above the main dimension of the granules.

16. sorbent molding according to one of claims 3 to 15, characterized in that a binder is preferably a pre-dry and low-temperature curable binder such as a prepolymer of alkaline silicates or silicones or a phenol-formaldehyde resin, polyvinyl resin, polyacrylate, polyurethane or a latex.

5

17. sorbent molding according to one of claims 3 to 15, characterized in that a binder is a cellulose derivative as a temporary remaining in the molding binder.

18. sorbent molding according to one of claims 3 to 15, characterized in that a binder is a water glass-containing binder.

19. sorbent molding according to one of claims 3 to 18, characterized in that a second binder is preferably a pre-shrinkable at higher temperatures and i ₅ curable binder and is localized and preferably used in higher proportions in the wall boundaries.

20. sorbent molding according to one of claims 3 to 18, characterized in that preferably conventional inorganic binders such as alumina hydrate, clays such

20 Metakaolinit, bentonite or embedding in matrices of silica or alumina hydrate can be used.

21. sorbent molding according to one of claims 3 to 18, characterized in that are used as binders carbonated pitch acids.

2 ₅

22. A method for producing a shaped article according to claim 1 or 2, characterized in that the solid premixed portions of the shaped body with small yet unconsolidated binder fractions and adhesion promoters in a carrier-like transparent wall together with a surface in the form of a spatially curved diagonal surface

30, here form a random pile with less solidification and in the presence of gaps at low binder contents, brought under the action of a predominantly radial pressure in a preliminary shape and pre-consolidated and optionally a second binder under radial and axial pressure in the peripheral - radial Parts of the wall is introduced, with another Solidification of the overall transparent wall of the molding in the form of a shell with increased strength and stability arises.

23. A method for producing a shaped article according to one of claims 3 to 18, 5 characterized by the following steps: a) prefabrication of a lattice structure in the form of a composite of the cage (2) with the

Guide surface (3), b) Design of a preform by introducing liquid and / or pasty

Constituents of binders with the solid constituents and of relatively small amounts of reactive coupling agent in the hollow mold of a tool, this with in

Direction of the pressure field perforated trained walling, c) pressing the preform in one or one of the transverse directions at the same time

Pressing of flow channels by means of stamping in the longitudinal direction, optionally with penetration of the guide surface (3), i ₅ d) and optionally with simultaneous or subsequent thermal pretreatment at temperatures of 150 ° C to 200 ° C for forming, e) completion of from Hollow mold removed molding by thermal

Post-treatment and activation at temperatures of 400 ° C to 600 ° C, optionally in an inert atmosphere of a gas.

20

24. A modified process for the production of moldings according to claim 23, characterized in that the operations are carried out sequentially: a ') design of a preform by introducing liquid and / or pasty

Bestanteilen first binder as well as in smaller proportions auxiliary reactive acting 2 ₅ adhesion promoter together with the guide surface (3) and with the solid components in a mold cavity, this perforated with perforated in the direction of the pressure field

Bewandung, b ') Pressing the preform in one or one of the transverse directions while simultaneously

Pressing in flow channels by means of stamping in the longitudinal direction, optionally 30 while penetrating the guide surface (3), c ') and optionally simultaneous or subsequent thermal pretreatment at

Temperatures of 150 ° C to 200 ° C for forming, d ') applying a second pasty binder on the removed from the mold

Forming and on this a prefabricated lattice structure or d ") application of a second pasty binder to the mold removed from the mold together with a lattice structure, optionally with renewed pressing and densification, e ') completion of the mold removed from the mold by thermal treatment and activation at temperatures of 400 ° C to 600 ° C, optionally in an inert atmosphere of a gas.

25. The method according to claim 23 or 24, characterized in that in water-glass binders preferably acids or bases or other liquid reactive lo components accelerate polymerization and condensation of silicate functional groups.

26. The method according to claim 25, characterized in that the preconsolidation of the binder is carried out with simultaneous preheating of the preform and for i ₅ waterglass-containing binder preheat temperatures required for this are below 200 ° C and preferably 150 ° C.

27. The method according to any one of claims 23 to 26, characterized in that for a heating and activation preferably in an inert gas atmosphere temperatures

20 be applied between 400 ° C and 600 ° C.

28. Use of the sorbent molding according to claims 3 to 22 for the storage of useful heat and useful cold

2 ₅ 29. Use of the shaped article according to claim 28, characterized in that vaporous working medium and preferably steam are expelled by supplying heat energy from the molding and optionally condensed and working fluid, which were previously evaporated, are gaseously sorbed.