EP2580160A1 - Dispositif de séchage contenant un alumino-phosphate - Google Patents

Dispositif de séchage contenant un alumino-phosphate

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Publication number
EP2580160A1
EP2580160A1 EP11725727.9A EP11725727A EP2580160A1 EP 2580160 A1 EP2580160 A1 EP 2580160A1 EP 11725727 A EP11725727 A EP 11725727A EP 2580160 A1 EP2580160 A1 EP 2580160A1
Authority
EP
European Patent Office
Prior art keywords
sapo
drying
alumino
phosphate
adsorption
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.)
Withdrawn
Application number
EP11725727.9A
Other languages
German (de)
English (en)
Inventor
Arno Tissler
Silke Sauerbeck
Rolf Kurzhals
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.)
Sued Chemie IP GmbH and Co KG
Original Assignee
Sued Chemie IP GmbH and Co KG
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 Sued Chemie IP GmbH and Co KG filed Critical Sued Chemie IP GmbH and Co KG
Publication of EP2580160A1 publication Critical patent/EP2580160A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/0018—Controlling processes, i.e. processes to control the operation of the machine characterised by the purpose or target of the control
    • A47L15/0021—Regulation of operational steps within the washing processes, e.g. optimisation or improvement of operational steps depending from the detergent nature or from the condition of the crockery
    • A47L15/0042—Desorption phases of reversibly dehydrogenated drying material, e.g. zeolite in a sorption drying system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00—Drying solid materials or objects by processes not involving the application of heat
    • F26B5/16—Drying solid materials or objects by processes not involving the application of heat by contact with sorbent bodies, e.g. absorbent mould; by admixture with sorbent materials
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/42—Details
    • A47L15/48—Drying arrangements
    • A47L15/481—Drying arrangements by using water absorbent materials, e.g. Zeolith
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/261—Drying gases or vapours by adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • 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
    • 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
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20746—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20753—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20784—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20792—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/56—Use in the form of a bed
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/66—Other type of housings or containers not covered by B01J2220/58 - B01J2220/64

Definitions

  • the present invention relates to a drying device with thermal management comprising an aluminophosphate as adsorbent for the energetically improved drying of articles and devices.
  • the present invention relates to a method for the liberation of objects and devices from residual moisture, as well as a method for the regeneration of a water-containing aluminophosphate.
  • Zeolites which include alumino-phosphates, form a structurally diverse family of complex silicate minerals. They occur naturally, but are also produced synthetically. Depending on the type of structure, the minerals of this group can store up to 40 percent of the dry weight of water that is released when heated to 350 to 400 ° C. The regeneration produces material that can be used again for drying.
  • alumino-silicate zeolites but also the group of alumino-phosphates show structural diversity and good adsorption capacity. Structures of this group are classified according to the International Union of Pure and Applied Chemistry (IUPAC) according to the "Structure Commission of the International Zeolite Association" because of their pore sizes, having pore sizes of 0.3 nm to 0.8 nm as microporous compounds.
  • IUPAC International Union of Pure and Applied Chemistry
  • the crystal structure and thus the size of the pores and channels formed is controlled by synthesis parameters such as pH, pressure and temperature. Additional factors such as the use of templates in the synthesis, as well as the Al / P / (Si) ratio additionally determine the resulting porosity. They crystallize in more than two hundred different variants, in more than two dozen different structures that have different pores, channels and cavities.
  • Alumino-phosphates are charge-neutral due to the balanced number of aluminum and phosphorus atoms.
  • the isomorphous exchange of phosphorus with silicon produces silico-aluminophosphates (SAPO).
  • SAPO silico-aluminophosphates
  • the exchange results in surplus negative charges, which are compensated by the incorporation of additional cations into the pore and channel system.
  • the degree of phosphorus-silicon substitution thus determines the number of cations needed to balance, and thus the maximum loading of the compound with positively charged cations, e.g. Hydrogen or metal ions.
  • the incorporation of the cations allows the properties of the silico-aluminophosphates (SAPO) to be adjusted and changed.
  • the framework structures of alumino-phosphates are composed of regular, three-dimensional spatial networks with characteristic pores and channels, which can be linked together in one, two or three dimensions.
  • the above-mentioned structures arise from corner-sharing tetrahedral building blocks (A10 4 , P0 4 , possibly Si0 4 ), consisting of four times coordinated by oxygen aluminum and phosphorus, and optionally silicon.
  • the tetrahedra are called primary building blocks, the linkage of which leads to the formation of secondary building units.
  • Alumino-phosphates and silico-aluminophosphates are typically obtained by hydrothermal synthesis, starting from reactive aluminophosphate gels, or the individual Al, P, and optionally Si components, which are used in stoichiometric proportions.
  • the crystallization of the resulting aluminophosphates is carried out by adding structure-directing templates,
  • Crystallization nuclei or elements achieved (see, for example, DE 102009034850.6).
  • Alumo-phosphates are often used in
  • the adsorption capacity of the aluminophosphates is particularly good due to the microporous framework structure. On the large surface many molecules can be adsorbed. When water molecules hit the surface of alumino-phosphate, they are adsorbed. There is an exothermic deposition on the surface, giving off the kinetic energy of the water molecules and their adsorption, which is released in the form of heat of adsorption. The adsorption is reversible. Desorption is the reverse process. Generally, adsorption and desorption are in a competitive equilibrium that can be controlled by temperature and pressure.
  • zeolites Due to their low toxicity and easy handling, zeolites are used in daily life in various areas for drying.
  • Zeolites are known in the art because of their hydrophilic properties. They become the Drying solutions or used for dehumidifying closed rooms, as well as for drying textiles after a washing process or dishes in dishwashers.
  • Zeolites assist in the drying of textiles, since they are usually dried at low temperatures and with little movement of the wet textiles. Excessively high temperatures cause sensitive tissue to shrink and become unusable. Alternatives are the static execution of the drying process which, however, the drying time is increased because the textiles the water contained can be removed only superficially.
  • WO 2009/010446 discloses an adsorption dryer which is used for drying textiles using vacuum and a heating device.
  • a zeolite is additionally used as adsorbent.
  • the desorption of water from the framework structure of the zeolite is then carried out by a longer treatment at high temperatures of 350 ° C to 400 ° C.
  • Zeolites can also be used in dishwashers for better drying of the dishes (DE 20 2208 011 159 Ul).
  • a treatment at high temperatures 350 ° C to 400 ° C is necessary, which causes additional energy costs.
  • the object of the present invention was therefore to provide a drying device which, by using an energy-efficient drying method, enables energy and cost-reduced, as well as efficient, time-saving, uniform and gentle drying of objects and devices.
  • Thermal management drying device comprising an adsorption vessel containing a (silico) aluminophosphate as adsorbent.
  • thermal management is understood to mean the utilization of residual heat, for example, after a rinsing process in a dishwasher, or in a drying apparatus, such as a
  • thermal management it is further understood that the utilization of residual heat facilitates the regeneration of the water-containing alumino-phosphate, and the residual heat already desorbs some of the adsorbed water from the water preheated hydrous alumino-phosphate.
  • the residual adsorbed water can be removed by low heat consumption, keeping energy costs low.
  • thermal management means that heated air streams containing residual moisture can already regenerate the water-containing adsorbent. These residual moisture-containing air streams, which are conducted from the receiving space containing objects and devices with residual moisture to the adsorption device, heat up the adsorbent which contains the adsorbent Residual moisture from the air streams absorbs, and at the same time is regenerated by the heat.
  • thermal management is also understood to mean the use of the adsorption heat of an adsorbent resulting from the adsorption of water on a surface. This heat of adsorption is released in the form of heat, and can be used to form thermally contacting receiving spaces These chambers are reheated by the heat of adsorption and can thus be more easily removed from residual moisture.
  • the adsorption heat can also be used to heat liquids, eg operating fluids such as dishwashing water in dishwashers leads advantageously to the fact that energy costs can be reduced.
  • thermal management as used herein further includes utilizing the heat of adsorption of an adsorption-type drying device to preheat operating fluids, heat being dissipated by direct thermal contact of the adsorption vessel with the operating fluid-containing vessel, thereby guaranteeing thermal exchange advantageous in dishwashers for heating rinse water o.ä. respectively.
  • thermal management is understood to mean the use of adsorption heat to preheat dry air streams or carrier gas streams, for example air streams in tumble dryers.Thus, by exploiting the heat of adsorption, drying of the articles and equipment can be even easier and faster.
  • the drying device according to the invention has over the drying devices of the prior art has the advantage that energy and cost reduced, as well as efficient, time-saving, uniform and gentle, using an energy-efficient drying process, articles and equipment can be freed of residual moisture.
  • aluminophosphates are suitable for use as adsorbents for the drying of articles and equipment. Due to their good adsorption capacity of water, alumino-phosphates can be used very well as adsorbents for removing residual moisture from objects and equipment. Since the adsorption capacity is many times higher than the adsorption capacity of zeolites, the amount of adsorbent required can be reduced with the same adsorptivity.
  • regeneration is understood to mean the recovery of ready-to-use adsorbent from water-containing adsorbent
  • the water-containing aluminophosphate is rendered operational again by the action of heat
  • the adsorbed water is removed by desorption and the adsorbent is thus recovered.
  • aluminophosphates which are used in a drying apparatus according to the invention can be regenerated even at a low desorption temperature of 20.degree. C. to 150.degree. Due to their lower desorption temperature compared to zeolites, the energy costs that have been incurred so far for the regeneration of the adsorbent can be reduced.
  • the alumino-phosphate can be regenerated even at low temperatures of 20 ° C to 150 ° C, preferably 50 ° C to 100 ° C, preferably to 70 ° C. As a result, the energy costs for the regeneration of alumino-phosphate can be kept very low.
  • the drying process comprises a process for the regeneration of water-containing aluminophosphate in the drying apparatus using thermal management, comprising the steps of a) regenerating the hydrous aluminum phosphate by means of a heat treatment,
  • the alumino-phosphate can be used again in the drying process according to the invention.
  • Thermal management materials are used for the adsorption of water, as already due to residual heat in the drying devices according to the invention by means of preheated Air flow is a regeneration.
  • the drying device according to the invention provides sufficient heat even after the drying process, so that the water-containing aluminophosphate can still be regenerated by means of the warm air streams.
  • the alumino-phosphate is warmed up and can be regenerated by a heat treatment at relatively low temperatures in the range of 50 ° C to 100 ° C. This saves energy, electricity costs and time, and leads to a particularly efficient drying of objects and equipment, since the adsorbent is ready for use after a short time.
  • the temperatures required for regeneration lie in a range of 50 ° C to 100 ° C, so that the water-containing adsorbent can already be regenerated with moist, heated air (with up to 63% humidity).
  • the adsorbent objects and equipment are particularly evenly freed from residual moisture, since the moisture from the receiving space containing the items and equipment with residual moisture is immediately absorbed by the adsorbent, and then transported by air flow from the drying device.
  • the air dried by the adsorbent air can be returned to the receiving space back to absorb moisture there again.
  • the adsorbent decreases
  • the air is not only dried, but also heated. It is particularly advantageous that this dried, preheated air in the receiving space can absorb more moisture, as it is even drier than the "outlet" air.
  • the adsorbent used is preferably an aluminophosphate which is a regenerable silico-aluminophosphate (SAPO).
  • SAPO regenerable silico-aluminophosphate
  • Regenerable means that the water-containing adsorbent reversibly releases the adsorbed water under heat. This recovers the alumino-phosphate, or silico-alumino-phosphate, and can be used again for drying.
  • alumino-phosphates (general formula (AIPO 4 - /) are understood as meaning microporous aluminophosphates.
  • alumino-phosphate in the context of the present invention is understood as meaning a crystalline substance from the group of aluminum phosphates with a spatial network structure.
  • the three-dimensional structure has annular 8-unit units, as well as singly and doubly bound six-membered rings, which are connected to regular, three-dimensional space networks.
  • the spatial network structure has characteristic pores and channels that again through the corner-sharing tetrahedron (A10 4 , Si0 4 , P0 4 ) one-, two- or
  • the Al / P / Si tetrahedra are referred to as primary building blocks whose combination leads to the formation of secondary building units.
  • silico-aluminophosphates corresponding to the general formula (Si x Al y P z ) C> 2 (anhydrous) are obtained by isomorphous exchange of phosphorus with, for example, silicon.
  • alumino-phosphates which have a partial replacement of phosphorus by silicon, with a Si / (Al, P) ratio of 0.01: 1 to 0.5: 1, preferably from 0.02: 1 to 0 , 1: 1.
  • microporous silico-aluminophosphates of the following type may be employed, SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO -31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56.
  • SAPO-5 SAPO-11 or SAPO-34.
  • SAPO-5 SAPO-11
  • SAPO-34 due to their good properties as adsorbents and the low regeneration temperature.
  • the use of microporous aluminophosphates with CHA structure is particularly suitable.
  • the aluminophosphates according to the invention may also have other metals.
  • Part of the phosphor can also be replaced by titanium, iron, manganese, copper, cobalt, chromium, zinc and / or nickel. These are commonly referred to as SiAPOs, FeAPOs, TiAPOs, MnAPOs, CuAPOs, CoAPOs, CrAPOs, ZnAPOs, CoAPOs or NiAPOs.
  • MAPO-5, MAPO-8, MAPO-11, MAPO-16, MAPO-17, MAPO-18, MAPO-20, MAPO-31, MAPO-34, MAPO-35, MAPO-36, MAPO -37, MAPO-40, MAPO-41, MAPO-42, MAPO-44, MAPO-47, MAPO-56 (where M Si, Ti, Fe, Mn, Cu, Co, Cr, Zn, Ni).
  • MAPO-5, MAPO-11 and MAPO-34 are particularly preferred.
  • the aluminophosphates according to the invention may contain further metals.
  • the ion exchange with titanium, iron, manganese, copper, cobalt, chromium, zinc and nickel are particularly suitable.
  • the aluminophosphates may also be doped, in which metal is incorporated in the framework.
  • metal is incorporated in the framework.
  • dopings with titanium, iron, manganese, copper, cobalt, chromium, zinc and nickel are particularly suitable.
  • microporous MAPSOs Ti, Mn, Cu, Cr, Zn, Co, Ni
  • M Ti, Mn, Cu, Cr, Zn, Co, Ni
  • MAPSO-5 MAPSO-11 or MAPSO-34.
  • the aluminophosphate of the present invention may further contain at least one other metal selected from a group containing titanium, iron, manganese, copper, cobalt, chromium, zinc, and nickel.
  • at least one other metal selected from a group containing titanium, iron, manganese, copper, cobalt, chromium, zinc, and nickel.
  • the adsorption properties of alumino-phosphates are improved. These are commonly referred to as FeAPOs, TiAPOs, MnAPOs, CuAPOs, CoAPOs, CrAPOs, ZnAPOs or NiAPOs. Particularly suitable is FeAPO-5.
  • the alumino-phosphate is used according to the invention as a fixed bed or loose bed of material.
  • a loose alumino-phosphate bed or alumo-phosphate introduced in the fixed bed is particularly suitable because it can be easily introduced into the adsorption tank.
  • the aluminophosphate is present in the drying device according to the invention as loose granules in the form of beads, cylinders, beads, threads, strands, platelets, cubes or agglomerates, since this increases the adsorptive surface of the aluminophosphate, which allows a particularly efficient absorption of moisture.
  • the aluminophosphate can be used in the drying device according to the invention as a binder-containing or binder-free granules, which simplifies the installation in the drying apparatus and the introduction into the adsorption.
  • the aluminophosphate may also be present in a coating on a shaped body.
  • the molding can take any geometric shape, such as hollow body, plates, nets or honeycombs.
  • the application is usually carried out as a suspension (washcoat) or can be carried out using any other method known to the person skilled in the art.
  • the use as a shaped body is advantageous, since so the adsorbent in the adsorption in the
  • Adsorption can be integrated to save space in the drying device according to the invention.
  • the drying device has a receiving space for receiving objects and devices to be dried, which are to be freed of residual moisture.
  • the one receiving space of the invention is the one receiving space of the invention.
  • Drying apparatus comprises two interconnected receiving spaces, one of which comprises an adsorption device containing an adsorption vessel containing an aluminophosphate as adsorbent.
  • the residual moisture of the objects and devices to be dried is transported to the connected further receiving spaces by means of an air flow and adsorbed by the adsorbent.
  • the drying device may include a receiving space through which the objects and equipment with residual moisture for drying can be transported.
  • the water is taken up by the adsorbent from the moist air, while the dried and heated by the heat of adsorption air is guided back into the receiving space to moisture again there take.
  • This drying device can be used to dry the articles and devices with residual moisture particularly quickly and efficiently.
  • the drying device may include a further associated receiving space for items and equipment with residual moisture.
  • a simultaneous use of supply air and exhaust air can be carried out a continuous drying and loading of the drying device. While in the first receiving space by a stream of air moist air is fed to the adsorbent, the other receiving space can be loaded. The dry, preheated air is led to the other receiving space, where it absorbs moisture again, while the first receiving space can be unloaded and loaded.
  • a drying device is particularly important for the catering, since the largest quantities of crockery and cutlery must be dried as soon as possible. To make further steps unnecessary, the drying must be evenly, without water stains o.ä. to be left behind.
  • the drying device according to the invention further contains a heating device.
  • the purpose of this is to dry the objects and equipment that are to be freed of residual moisture faster, for faster drying.
  • the heating device can be used for warming up the articles and devices, and is preferably a heat radiator, a hot air blower, an infrared radiator or a
  • the heater can also be used time-controlled, for example, only after a predetermined time after the start of drying. Further, the heater can be set to be a consistently constant one Temperature, while avoiding overheating of the objects and equipment to be dried.
  • the power of the heating device is adjusted so that according to the invention the drying proceeds faster and / or optionally the regeneration of the adsorbent can be carried out with it.
  • Drying device has a device for generating air currents.
  • This device may be a blower, an air pump, a compressor or a compressor, and serves to transport the moist air from the receiving space to the connected further receiving spaces and / or to be transported out of the drying device or transported back into the receiving spaces.
  • an overpressure can prevail in the receiving spaces.
  • the moisture is passed through the air flow under pressure to the adsorption device, where it is adsorbed by the adsorbent.
  • the water-containing adsorbent can be regenerated.
  • a heating fan can be used, which fulfills both the function of heating, as well as the generation of an air flow.
  • a negative pressure in the drying device according to the invention can be generated by means of the blower or a vacuum device.
  • the heating device contained in the drying device can be used to preheat the articles and equipment for easier drying, as well as to regenerate the water-containing adsorbent under desorption. This can be done during operation with removal of the aqueous air stream from the adsorption, or after a drying process.
  • the regeneration of the adsorbent can be done directly before a drying process, since so the residual heat of regeneration used for preheating the objects and equipment with residual moisture can be used, allowing easier drying.
  • the regeneration of the adsorbent can already take place before a rinsing process, since the energy used to heat the rinsing water can thus be used simultaneously for the regeneration of the adsorbent.
  • the drying device according to the invention can be used for the removal of residual moisture from objects and devices even after a cleaning of the objects and devices.
  • the drying device according to the invention may be a dishwasher or a tumble dryer, which can be used for drying and / or cleaning dishes or textiles.
  • the object of the present invention is further achieved by a method for drying articles and devices with residual moisture using a drying device comprising the steps of a) Preparing to be dried objects and devices with residual moisture,
  • objects and devices to be liberated from residual moisture are provided in a receiving space.
  • the process of the invention involves a further step of adsorbing residual moisture through the aluminophosphate to yield hydrous alumino-phosphate.
  • a stream of air can agitate the residual moisture adhered to the articles and equipment, whereby it can be more easily adsorbed by the alumino-phosphate. This speeds up the drying process of the articles and equipment since the alumino-phosphate can adsorb more water per unit time.
  • the objects and equipment with residual moisture can, if necessary, be heated by a warm air stream. Furthermore, due to the warm air flow, the residual moisture adhering to the objects and devices is led out of the receiving space to the adsorption device, in which the provided alumino-phosphate adsorbs the residual moisture to obtain water-containing aluminophosphate.
  • the drying of the articles and devices with residual moisture can take place with renewed insertion of the dried air.
  • the warm, dry air decreases in the Receiving room moisture on, is led to the adsorption, in which the moisture is absorbed by the adsorbent.
  • Adsorption of the moisture now releases heat of adsorption, which now warms up the dried air.
  • This dry, preheated air is returned to the receiving room, where it can absorb moisture again. This makes the drying of items and equipment even more efficient.
  • the residual moisture adsorbed reversibly by the alumino-phosphate is between 5% and 30% of the residual moisture adhering to the objects to be dried.
  • the alumino-phosphate is used in an amount by weight of 0.1 to 10 kg, preferably 0.3 to 5 kg, and most preferably 0.5 to 2.5 kg. This depends on the amount of objects and equipment to be dried.
  • the amount of adsorbent is adjusted according to the number of drying operations, the amount of items to be dried and equipment, and especially to the size of the drying device.
  • a large amount of alumino-phosphate can be used, preferably in an amount by weight of 10 to 100 kg, if the adsorbent does not have to be regenerated after each individual drying operation, but without regeneration the moisture e.g. also reliably adsorbed in large quantities.
  • the adsorbent may be used in an amount that is the amount of water to be absorbed equivalent. Furthermore, a multiple of it can be used. For this purpose, the simple to fifty times the amount of water to be absorbed can be used. Thus, 1 liter of water to be removed may correspond to an amount of 1 kg to 50 kg of the adsorbent, preferably 1 kg to 20 kg of adsorbent per 1 liter of water.
  • Figure 1 the water adsorption rate and water desorption rate of a silico-alumino-phosphate, as a function of temperature and absorbed volume of water in weight percent [wt%], at 4.1 mbar and at 11.6 mbar steam pressure.
  • Figure 2 the water adsorption rate and water desorption rate of the prior art zeolite 13X, as a function of temperature and absorbed volume of water in weight percent [wt%], at 4.1 mbar and at 11.6 mbar Water vapor pressure.
  • a pressure chamber of the type "IGA003" from Hiden Analytical was used.
  • the necessary water vapor was generated in situ from a liquid reservoir.
  • the measurement was carried out statically in vacuo.Vacuum-tightness and high vacuum were measured before the measurement set ( ⁇ 1CT 5 mbar, external at the high vacuum connection with a Pfeiffer device type "IKR 261").
  • the water vapor pressure was controlled internally by means of two pressure sensors of the type "Baratron” from MKS.
  • the temperature in the chamber was adjusted with thermostats of the type RTE-111 from Neslab.
  • SAPO-34 from Süd-Chemie AG was used.
  • the regeneration of the hydrous alumino-phosphate can be carried out by heat treatment at low temperatures of 50 ° C to 100 ° C when a low pressure is applied.
  • the desorptive capacity of a water-containing aluminophosphate was tested as a function of the water vapor pressure.
  • the water vapor pressure in a pressure chamber was gradually adjusted from 29 mbar to 10 ⁇ 3 mbar at a temperature of 25 ° C.
  • the adsorbed water amount in adsorption-desorption equilibrium was measured.
  • the water uptake was measured at over 20 pressure points after one. After adjusting the water vapor pressure, the mass change was monitored for equilibrium adjustment for up to 60 min. It was found that, depending on the applied pressure, the adsorption-desorption equilibrium can be shifted.
  • Desorption equilibrium can be shifted by increasing the water vapor pressure for desorption.
  • test series were carried out at temperatures of 10 ° C to 110 ° C, respectively at 4.1 mbar and at 11.6 mbar.
  • the temperature was in the pressure chamber with a thermostat was set, and only after keeping the temperature constant for 10 minutes, a corresponding amount of adsorbent was added to the pressure chamber via a corresponding valve.
  • SAPO-34 was used.
  • the test series at 4.1 mbar water vapor pressure show that much water is adsorbed for low temperatures of 10 ° C to 40 ° C.
  • the values of the adsorbed water are here in a range of 30 wt .-% to about 35 wt .-% (see Figure 1).
  • the adsorption rate of adsorbed water drops from 30% by weight to about 5% by weight in the temperature range from 40 ° C. to 70 ° C. (FIG. 1).
  • SAPO-34 absorbs less water at higher temperatures and the adsorption rate drops. Adsorption and desorption compete with each other. The equilibrium shifts at higher temperatures towards desorption.
  • zeolite 13 X belongs to the FAU structural class, to the group of zeolite X, which in particular also contains the group of faujasites.
  • Zeolite 13 X has a pore size of 13 ⁇ , and is used as a molecular sieve for the adsorption of water and water vapor.
  • the comparative example of the zeolite 13 X shows (FIG. 2) that the adsorption rate is only slightly influenced by the temperature. Here there is no shift in the adsorption-desorption equilibrium within the investigated
  • FIG. 2 shows that the water vapor pressure has very little influence on the adsorption behavior of the zeolite 13 X.
  • the slow decrease in the adsorption rate indicates that a much higher temperature (>> 150 ° C) is needed to reverse the adsorption-desorption equilibrium. This means that in order to regenerate water-containing zeolite 13 X a much higher temperature is required than was tested in the test.

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Abstract

La présente invention concerne un dispositif comprenant un alumino-phosphate et bénéficiant d'une gestion de l'énergie thermique pour assurer le séchage efficace d'objets et d'appareils. L'invention a également pour objet un procédé de séchage pour obtenir des objets et appareils secs, ainsi qu'un procédé de régénération par désorption d'eau à partie d'alumino-phosphate contenant de l'eau.
EP11725727.9A 2010-06-10 2011-06-10 Dispositif de séchage contenant un alumino-phosphate Withdrawn EP2580160A1 (fr)

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DE102010023327A DE102010023327A1 (de) 2010-06-10 2010-06-10 Trocknungsvorrichtung enthaltend ein Alumo-Phosphat
PCT/EP2011/059705 WO2011154530A1 (fr) 2010-06-10 2011-06-10 Dispositif de séchage contenant un alumino-phosphate

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DE102010055729A1 (de) * 2010-12-22 2012-06-28 Süd-Chemie AG Trocknungsvorrichtung enthaltend ein Titano-Alumo-Phosphat
CN104562595B (zh) * 2014-12-23 2017-11-28 珠海格力电器股份有限公司 干衣机
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JP2016105037A (ja) 2016-06-09
DE102010023327A1 (de) 2011-12-15
JP2013529285A (ja) 2013-07-18
WO2011154530A1 (fr) 2011-12-15
CN103038171A (zh) 2013-04-10
US20130152420A1 (en) 2013-06-20

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