EP3021962A1 - 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 - Google Patents

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

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Publication number
EP3021962A1
EP3021962A1 EP14758483.3A EP14758483A EP3021962A1 EP 3021962 A1 EP3021962 A1 EP 3021962A1 EP 14758483 A EP14758483 A EP 14758483A EP 3021962 A1 EP3021962 A1 EP 3021962A1
Authority
EP
European Patent Office
Prior art keywords
adsorption
adsorbent
zeolite
adsorptionskältemaschine
refrigerant
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Withdrawn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
EP14758483.3A
Other languages
German (de)
English (en)
Inventor
Niels Braunschweig
Eric WEISHEIT
Thomas Heinz HERZOG
Jochen Jänchen
Wolfgang Lutz
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.)
INVENSOR GmbH
Original Assignee
INVENSOR GmbH
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 INVENSOR GmbH filed Critical INVENSOR GmbH
Priority to EP14758483.3A priority Critical patent/EP3021962A1/fr
Publication of EP3021962A1 publication Critical patent/EP3021962A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • F25B35/00—Boiler-absorbers, i.e. boilers usable for absorption or adsorption
    • F25B35/04—Boiler-absorbers, i.e. boilers usable for absorption or adsorption using a solid as sorbent
    • 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
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • 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
    • F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
    • F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt
    • F25B17/083—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt with two or more boiler-sorbers operating alternately
    • 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
    • F25B30/00—Heat pumps
    • F25B30/04—Heat pumps of the sorption type
    • 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

Definitions

  • Adsorption chiller with an adsorbent and method for generating cold and use of a dealuminated zeolite as adsorbent in a Adsorptionshimltemaschine
  • the invention relates to an adsorption chiller comprising one or more
  • Heat exchanger comprising a zeolite-type aluminosilicate Y from the group of faujasites as adsorbent.
  • the invention relates to a method for
  • a conventional Adsorptionskarltemaschine consists of at least one ad / Desorber unit, an evaporator, a condenser and / or a combined evaporator / condenser unit, which are housed in a common container or in separate containers, which then with pipes o. ⁇ . are connected to each other for the refrigerant flow.
  • the refrigerant is selected so that it changes its state of aggregation when passing through the cyclical working processes in the adsorption chiller and is gaseous or liquid depending on the working condition.
  • chillers which are generally used for heating and / or cooling of buildings.
  • Chillers implement thermodynamic cycles, where, for example, heat is absorbed below the ambient temperature and released at a higher temperature.
  • the thermodynamic cycles correspond to those of a heat pump.
  • Known in the art refrigerators are z.
  • adsorption refrigeration systems diffusion absorption refrigeration machines, adsorption refrigeration or Feststoffsorptionskapen, adsorption heat pumps, adsorption cold storage, adsorption heat storage, and
  • adsorption gaseous refrigerant
  • the desorption accordingly as dissolution of a solid.
  • the refrigerant which absorbs heat at low temperature and low pressure and releases heat at a higher temperature and pressure, is selected so that the ad- or desorption is accompanied by an aggregate state change. If water is used as the coolant, for example, with the adsorption of the refrigerant, a condensation and the desorption of an evaporation of the refrigerant is connected.
  • the adsorption refrigeration machines described in the prior art generally work according to the following mode of operation:
  • the refrigerant is converted by the supply of heat evaporated.
  • the energy required for this is taken from a heat exchanger which is connected to an external cooling circuit. Its cooling medium is deprived of energy by the evaporation of the refrigerant.
  • the vaporous refrigerant is fed into a first adsorption / desorption unit. There, the vaporous refrigerant is adsorbed by an adsorbent. Energy is released through this process.
  • a second adsorption A second adsorption
  • Desorption unit can regenerate at the same time, i. the refrigerant is released from the adsorbent by supplying heat. This process is called desorption. The thus liberated vapor refrigerant is fed into a condenser in which the
  • vaporous refrigerant condenses with release of energy.
  • the condensed refrigerant is then returned by means of a condensate return in the evaporator.
  • the refrigerant circulates in a closed circuit, which usually works without pumps. The course of the thermodynamic processes is thereby solely by the
  • the container can be hermetically sealed and gas-tight. This is a significant advantage of such
  • Adsorption chillers over conventional heat pump technology. When using, for example, water as a refrigerant, the adsorption chiller works
  • the refrigerant which can be referred to as fluid within the meaning of the invention, is present in the adsorption chiller both as vapor, solid and as liquid.
  • the use of two parallel adsorption / desorption units enables continuous operation of the adsorption chiller. One of the two units adsorbs with the release of energy, while the other is regenerated and thus prepared for recharging with the refrigerant.
  • adsorbent materials are described in the prior art, which are water-insoluble and finely porous and have a very large inner surface.
  • Advantageous materials include activated carbon, zeolites, alumina or silica gel, aluminum phosphates, silico-aluminum phosphates (SAPO), metal silico-aluminum phosphates, mesostructure silicates, organometallic scaffolds and / or microporous material comprising microporous polymers.
  • Micropores have a diameter of up to 2 nm, while mesopores have a diameter of up to 2 nm
  • Diameter of about 2 to 50 nm and macropores have a diameter greater than 50 nm.
  • Alumo-silicates occur in nature in many different structures, but are also produced synthetically. They have a high adsorptivity and can take up reversibly up to a third of their dry weight of water due to their large inner surface. When heated, the water is released again without damaging the zeolite structure of the alumino-silicate.
  • Zeolites are crystalline aluminosilicates consisting of a microporous framework consisting of AIO4 and SiCU tetrahedra. The aluminum and silicon atoms are linked together by oxygen atoms. The ratio of silicon to aluminum atoms allows a classification of the zeolites into subgroups.
  • Si / Al ratio is 1.
  • zeolites of types A and X Type Y zeolites are characterized by an Si / Al ratio greater than 1, in particular greater than 2.2. This has the consequence that in the framework structure of the zeolite, the silicon outweighs the aluminum.
  • Zeolites with a Si / Al ratio of greater than 1 are characterized by a higher stability, whereby a Si / Al ratio of up to 3 can be achieved by conventional production methods known to those skilled in the art. Faujasit is one
  • zeolites of the types X and Y are counted among the faujasites.
  • a disadvantage of the prior art is that the proposed adsorbents have a low adsorption capacity. As a result, it is not possible to provide small adsorption chillers because large amounts of the adsorbent must be used. In addition, high costs in equipping the adsorption chiller with the
  • the adsorption capacity of an adsorbent depends inter alia on the structure, in particular the pore structure, of the adsorbent. It has been shown that larger pores have a higher adsorption capacity than smaller pores. To date, the art has described essentially microporous materials with pore diameters less than 2 nm.
  • SAPO-34 commonly used as a catalyst, for example, amorphized in the presence of water or in an aqueous phase at temperatures between 30 and 50 0 C to 70% and is thus useless as an adsorbent.
  • SAPO-34 has limited diffusion of water as it has a pronounced microporous system.
  • Adsorbent has a low desorption temperature for regeneration.
  • the object of the invention is therefore, an adsorption with a
  • the invention relates to an adsorption refrigerator comprising one or more heat exchangers comprising a zeolite-type aluminosilicate of the faujasite group as adsorbent, wherein the adsorbent is a dealuminated zeolite (DAY zeolite) and a Si / Al Ratio of 2.5 to 4 has.
  • adsorption refrigerator comprising one or more heat exchangers comprising a zeolite-type aluminosilicate of the faujasite group as adsorbent, wherein the adsorbent is a dealuminated zeolite (DAY zeolite) and a Si / Al Ratio of 2.5 to 4 has.
  • an adsorption chiller with a zeolite type Y alumino-silicate from the faujasite group can be provided as an adsorbent having a Si / Al ratio of 2.5 to 4, and advantageously a low desorption temperature, good adsorption ability, good diffusion properties of the refrigerant used in the adsorption chiller, and good hydrothermal stability in the presence of water.
  • the zeolite of the Y type has increased mesopores through dealumination. Furthermore, it was completely surprising that the adsorption behavior of the zeolite changes due to the dealumination of the zeolite or of the silicate framework, in particular its affinity for the refrigerant of the adsorption chiller, preferably water.
  • the desorption temperature of the dealuminated zeolite could be shifted by the dealumination to lower temperatures, so that a
  • Adsorption chiller according to the invention also achieves optimum performance even at low inlet temperatures.
  • the adsorption refrigeration machine according to the invention is preferably operated with waste heat from industrial plants, combined heat and power plants or other plants. A shift in the desorption temperatures to low values is advantageous since most of the waste heat has a temperature of less than 80 ° C.
  • the plant efficiency and the efficiency are particularly high when the adsorption chillers waste heat of low temperature is supplied.
  • the term "efficiency” refers to the ratio of thermal energy supplied as waste heat and useful thermal energy.
  • the adsorption chiller waste heat is supplied from a low temperature, advantageously reduce the losses of thermal energy, resulting from the fact that in the adsorption chiller not only the adsorbent must be heated, but inevitably the internal components of the chiller are heated.
  • outlet temperatures of heated chiller components do not contribute to the adsorption performance of the adsorption chiller, thus reducing the efficiency of the machine.
  • Heat exchangers in the context of this invention are devices in which thermal energy is transferred from one material stream to another. This is in the invention
  • Adsorptionshimltemaschine for example in the adsorption / desorption, the Condenser and the evaporator of the case.
  • the choice of dealuminated zeolite with a Si / Al ratio between 2.5 and 4 not only leads to an improved adsorption capacity of the zeolite, but also to a simplified one
  • zeolites of the Y type with a Si / Al ratio in the range of 2.5 to 4 can be dealuminated in water vapor at temperatures of 300 to 800 degrees Celsius without the zeolite lattice framework collapsing.
  • This surprising stability of the dealuminated zeolite with said Si / Al ratio is due to long silicate chains having at least 132 silicon atoms, wherein 60 aluminum atoms can be removed, since at least 132 silicon atoms, more preferably at least 150 Silicon atoms, forming a contiguous substructure of silicon in the zeolite framework, which advantageously remains stable even when the aluminum atoms are removed from the grid. It is a merit of the present invention to provide these
  • a zeolite of the type NaY was used as the dealuminated zeolite.
  • Base material used. Na stands for sodium in this context.
  • aluminum is present as the central atom in an AIC tetrahedron, with the aluminum bearing a negative charge as the element of the third main group of the periodic table of the elements due to the bonding with four oxygen atoms.
  • positively charged cations for example sodium, are needed. These cations, which may preferably be both alkali or alkaline earth metals, are not incorporated into the main lattice of the crystal, but remain in place
  • Lattice cavities contains.
  • the base material is made using a seed solution or by the addition of seeds of a zeolite of the NaX type.
  • a seed of NaX preferably consists of a zeolite of the type X, in the lattice cavities of which Na ions are used Stop the purposes of charge equalization.
  • seeds of a zeolite of the NaX type are added to the batch for initialization of the crystal growth.
  • Type X zeolites have a Si / Al ratio of 1 such that the addition of the NaX nuclei crystallizes a faujasite-type product.
  • the forming zeolite material therefore advantageously has a Si / Al ratio of 1 in the core of the crystal, which
  • Composition corresponds to the virtually unchanged zeolite of the type NaX.
  • the Si / Al ratio of "undefinite" is advantageously present at the crystal surface. This Si / Al ratio, which changes from the inside to the outside, advantageously leads to the formation of a Si / Al gradient, which has a significant influence on the loss of micropores and the Formation of mesopores during dealumination
  • the targeted generation of the Si / Al gradient results in the formation, advantageously in the inner core region of the zeolite, of an aluminum-rich region, the composition of which is decisively shaped by the NaX seed with a Si / Al ratio of 1.
  • This material in the core of the zeolite is inherently unstable in water vapor and therefore not suitable for use in adsorption chillers.
  • the area of the material surface is characterized by being substantially free of aluminum. This corresponds to an Si / Al ratio of "infinite.”
  • the zeolite with the desired Si / Al ratio of 2.5 to 4 advantageously forms, which is advantageously stable in water vapor and has a good adsorption capacity and a low desorption temperature.
  • the positively charged sodium ions which are present as countercations for charge compensation of the negatively charged aluminum ion in the center of the Al0 4 ⁇ tetrahedron in the cavities of the silicate lattice, are preferably replaced by positively charged ammonium ions NH 4 + .
  • steaming refers to the treatment of zeolite NH 4 Y in water vapor at temperatures of 300 to 800 "Celsius. Above 250 “Celsius, the ammonia ion is decomposed to give off ammonia, and the proton form of the zeolite is aluminum from the zeolite framework due to acid hydrolysis
  • the exchange of the sodium by ammonium is preferably carried out by stirring NaY in aqueous solution of ammonium sulfate in three stages of 30 min - 2.5 hours, preferably 45 min - 1, 5 hours, more preferably 1 hour at room temperature. Neither the increase in time to 5 hours nor the increase in temperature to 80 ° C led to higher exchange values.
  • the term “lattice” refers to the spatial structure of aluminum and silicon atoms in combination with oxygen, in which positively charged ions are advantageously present in cavities for charge compensation, which are advantageously movable within the lattice.
  • These cations are preferably positively charged sodium, hydrogen and ammonium ions, and grids and mobile cations together are referred to herein as "frameworks”.
  • Vapor phase as it is present in an adsorption / desorption of a Adsorptionshimltemaschine record.
  • the invention relates to a
  • Adsorptionshimltemaschine in which the adsorbent thermo-chemically by a
  • the dealuminated zeolites prepared in a medium temperature range of 400-500 ° C have the best properties for use in an adsorption chiller when using water as a refrigerant in the adsorption chiller is used.
  • the dealuminated zeolite obtained has a surprisingly high adsorption capacity, but also allows the desorption of the water at temperatures of 100 ° C. and below It was not foreseeable for the average person skilled in the art that it would not be the more dealuminated zeolites with their large number of terminal hydroxyl groups. Groups, which were presumed to be preferred sorption centers for the water molecules, have the greatest potential for use in adsorption chillers.
  • the outstanding suitability of the dealuminated zeolites produced at temperatures between 400 and 500 centigrade is due to a restructuring of the lattice framework, whereby the leaching out of the aluminum from the lattice leads to the installation of holes and imperfections These holes remain in the lattice and eventually become larger, which impairs the adsorptivity of the zeolite, since no water can be bound in these holes.At low temperatures, the structure heals and the aluminum migrates to the surface of the zeolite with the temperature range of 400 to 500 "Celsius by lucky grip found a medium temperature range in which an effective dealumination of the base material is advantageously already possible, an increased impurity growth along with a reduction in the number of Me soporens and the available mesopore volume, however, does not yet take place.
  • Adsorbents in an adsorption chiller proved that the preferred
  • Adsorbent has no regularly shaped mesopores or Mesoporenpatenteden and that are distributed in the zeolite with a Si / Al ratio of 2.5 to 4 mesopores beyond inhomogeneous over the zeolites. It has been found that such an inhomogeneous distribution of mesopores over the adsorption material leads to surprisingly good adsorption performance when using the material in an adsorption chiller, which does not provide good adsorption performance to the average person skilled in the art
  • the annealing is preferably carried out by monosilicic acid molecules H4S1O4, which can migrate in the lattice and have a high reactivity. These settle under the influence of the process water advantageously in the holes and defects and close them Impurities, so that one of the NaY starting sample comparable crystal structure with
  • the invention relates to a
  • Adsorption chiller wherein a partial pressure of water vapor during the temperature treatment in the production process of the adsorbent is 0.1 to 1 bar.
  • the thermodynamic process control in the production of the adsorbent always results from a
  • Temperature range of 300 to 800 ° Celsius, or the particularly preferred temperature range of 400 to 500 ° Celsius results and corresponds with this.
  • Adsorption chiller wherein the adsorbent consists essentially of the components silicon, aluminum, sodium, hydrogen and oxygen.
  • Adsorbent is not an ambiguous formulation, since he recognizes by the overall disclosure of the teaching of the invention that the adsorbent is an aluminosilicate zeolite type Y from the group of faujasites, as a chemical compound a certain
  • the hydrogen and sodium compensate for the charge of aluminum, which is negatively charged by its quadruple bond in the AIC tetrahedron.
  • the hydrogen forms with the oxygen in the zeolite framework Si-OH groups, which positively influence the desired formation of mesopores on the crystal surface.
  • a dealuminated zeolite which preferably consists of substantially five elements and has outstanding usability in adsorption chillers as adsorbents.
  • the experts had previously assumed that a
  • Aluminum, sodium, hydrogen and oxygen produced dealuminated zeolite is a cost effective alternative to, for example, titanium or phosphorus zeolites described in the prior art.
  • the invention relates to a
  • Adsorption chiller with an adsorbent having both micropores, and mesopores having both micropores, and mesopores.
  • the micropores are preferably located inside the adsorbent, and the mesopores are preferably present on the surface of the adsorbent. It was quite surprising to be able to provide a dealuminated zeolite as adsorbent in adsorption chillers, advantageously both via micropores, as well as mesopores and over outstanding ones
  • micropores of the zeolite according to the invention advantageously have a diameter of less than 1.2 nm.
  • the mesopores advantageously have diameters in the range of 2 to 5 nm.
  • mesoporous silicates are known to the experts, who however are not suitable for use as adsorption agents in adsorption chillers because they are hydrophobic due to their small number of OH groups.
  • the mesoporous silicates known in the art have a low hydrothermal long-term stability and a low selective water adsorption and require a higher desorption temperature due to the condensation of the refrigerant used in the water, for example, in the mesopores.
  • the adsorption material may advantageously be applied differently, that is, it may be a granular bed or the adsorbent may be present in the form of extrudates, spheres, chips and / or attached as a solid layer on the heat exchanger. It may also be preferred that the adsorbent rests on the heat exchange. Due to these different types of application, the adsorption machine can be adapted to different requirements. So the machine can be adapted to the location or the refrigerant. In addition, the layer thickness of the adsorbent material is critical to the performance of the adsorbent material.
  • the adsorbent according to the invention is not limited to one type of heat exchangers, but the adsorbent can be used for example both in conjunction with tube heat exchangers, as well as in conjunction with fin heat exchangers.
  • the adsorbent according to the invention can be used both for single-chamber systems, for example with two adsorbers, but also for two- or multi-chamber systems, each with only one adsorber of a Adsorptionshimltemaschine. Besides, it can be used easily and quickly in other types of adsorption machines. Essentially, the machines do not have to be modified in terms of apparatus.
  • the invention relates to a
  • Adsorptionshimltemaschine with an adsorbent which is bound with a binder, wherein the binder is preferably selected from the group of clay minerals, in particular silica sol and alumina hydrate.
  • the dealuminated zeolite having a Si / Al ratio of 2.5 to 4 is preferably present as a powder.
  • the binder preferably acts as a carrier material and gives the zeolite stability and strength. The deformation of the zeolite powder into balls, for example, takes place according to two strategies: bonding with classical clay in the Eyrich mixer (rolling process),
  • the binder An important role in the molding process plays in particular the binder. This must be suitable on the one hand for the ball formation of the drops and on the other hand is responsible for the molding strength. In addition to the use of balls, however, the application in the form of solid layers on the heat exchangers may be preferred. It has been found that the adsorbent according to the invention is surprisingly suitable for being applied in the form of solid layers in an adsorption refrigeration machine.
  • a binder can be provided which, on the one hand, is suitable for use with spheres, extrudates or solid layers
  • beneficial properties are its good binding properties and its favorable price.
  • extrudate refers to elongated pellets having a circular base area, and these extrudates are preferably produced in a diameter of 0.3 to 3 mm, particularly preferably in a diameter of 0.5 to 1 mm known as by the method of Extrusion such cylinder-like pellets are made from the adsorptive material bound with the binder.
  • extrudates are particularly advantageous since the extruders produced with the dimensions described above have a particularly high bulk density and thus a high in a small space
  • clay minerals generally have naturally-caused contaminants that affect their catalytic properties. It has also been suggested by those skilled in the art that clay minerals produce thermal conversion products that have only very low adsorption capabilities and therefore are not suitable as adsorbents for use in an adsorption chiller.
  • Adsorptionshimltemaschine wherein the heat exchanger is an adsorption / desorption unit, a condenser and / or an evaporator.
  • the invention relates to a method for generating cold by means of a Adsorptionshimltemaschine, wherein the adsorbent a
  • Desorption of 40 to 140 ° C preferably from 50 to 1 10 ° C, more preferably from 55 to 90 ° C and most preferably from 60 to 80 ° C.
  • a method for producing cold in the specified temperature ranges is particularly advantageous since the adsorption refrigerating machine according to the invention is preferably operated with waste heat and most of the "waste heat" generated in industrial or other applications lies in the temperature ranges mentioned Accordingly, the method of producing refrigeration satisfies, in a particularly advantageous manner, a long-term, urgent need of operators of all plants which produce waste heat which hitherto could not be used effectively to a satisfactory extent can be regenerated to the specified temperature ranges.
  • the adsorbent exhibits a certain load change behavior in a favorable relative pressure range.
  • relative pressure describes the relationship between the equilibrium pressure of the adsorbent material and the saturation pressure of the refrigerant
  • loading describes the ratio between the mass of the refrigerant and the mass of the adsorbent material.
  • the adsorption material preferably has between the relative pressure 0.03 and 0.5, in particular between the relative pressure 0.1 and 0.25, a loading change of at least 0.1 (10%), preferably at least 0.2 (20%) on.
  • the invention relates to the use of a dealuminated zeolite (DAY zeolite) as adsorbent in one
  • Adsorption chiller water is used as a refrigerant.
  • Fig. 1 shows a schematic structure of an adsorption refrigerator, on the
  • Heat transfer agents preferably the adsorbent of the invention
  • FIG. 1 shows the schematic structure of an adsorption refrigeration machine according to the invention (10).
  • the adsorption chiller (10) shown by way of example consists of at least one evaporator (14) and one condenser (12).
  • the exemplary adsorption chiller (10) includes two adsorption / desorption units (16, 18). In these two adsorption / Desorptionsakuen (16, 18) are heat exchangers (20, 22). These are shown in Figure 1 with an adsorbent (24, 26), which is exemplified in different ways on the heat exchangers (20, 22) attached.
  • a first heat exchanger (20) is located in a first adsorption / desorption unit (16) and is provided with the adsorption material (24) in the form of a bed.
  • the second heat exchanger (22) is located in a second adsorption / desorption unit (18) and is provided with the adsorbent (26) in the form of a layer.
  • FIG. 1 shows have shown that the heat exchangers (20, 22) present in the adsorption chiller (10) are provided with differently applied adsorption means (24, 26).
  • Heat exchangers (20, 22) is applied in the same way.
  • a refrigerant e.g. Water, or brine
  • the vaporous refrigerant is then passed, for example, into a first adsorption / desorption unit (16). There, the vaporous refrigerant is adsorbed by the on the first heat exchanger (20) applied adsorbent (24). If as
  • Refrigerant water is used, the water is stored in the pores of the adsorbent (24) in the liquid state. This adsorption releases energy. This can be used for heating or cooling depending on the design and design of the adsorption refrigeration machine (10) according to the invention.
  • the second adsorption / desorption unit (18) can regenerate.
  • the process of regenerating an adsorbent (24, 26) requires the supply of heat.
  • the refrigerant stored in the liquid state of matter in the adsorbent (24, 26) is expelled from the adsorbent (24, 26). This process is called desorption.
  • the refrigerant Due to the desorption, the refrigerant is present in the gaseous state in the second adsorption / desorption unit (18).
  • the gaseous refrigerant is passed into the condenser (12). It is condensed there, releasing energy again.
  • the refrigerant, which is now in the liquid state is returned to the evaporator (14) via a condensate recirculation device.
  • the adsorption chiller (10) When an adsorption chiller is operated with water as the refrigerant, the adsorption chiller (10) preferably operates in the vacuum range. The course of the adsorption and desorption is determined solely by the temperature of the adsorbent (24, 26) which is applied to the heat exchangers (22, 20) of the two adsorption / desorption units (16, 18). LIST OF REFERENCE NUMBERS

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  • Inorganic Chemistry (AREA)
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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne une machine frigorifique à adsorption comprenant un ou plusieurs échangeurs de chaleur comportant un silicate d'aluminium de type zéolite Y du groupe des faujasites en tant qu'agent d'adsorption. L'agent d'adsorption est disposé sur les échangeurs de chaleur de la machine frigorifique à adsorption. Dans un autre mode de réalisation, l'invention concerne un procédé de production de froid au moyen d'un machine frigorifique à adsorption, et l'utilisation d'une zéolite désaluminée en tant qu'agent d'adsorption dans une machine frigorifique à adsorption.
EP14758483.3A 2013-07-19 2014-07-21 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 Withdrawn EP3021962A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14758483.3A EP3021962A1 (fr) 2013-07-19 2014-07-21 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

Applications Claiming Priority (5)

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DE102013107752 2013-07-19
DE102013107741 2013-07-19
EP14170579 2014-05-30
PCT/DE2014/100266 WO2015007274A1 (fr) 2013-07-19 2014-07-21 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
EP14758483.3A EP3021962A1 (fr) 2013-07-19 2014-07-21 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

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EP3021962A1 true EP3021962A1 (fr) 2016-05-25

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EP14758483.3A Withdrawn EP3021962A1 (fr) 2013-07-19 2014-07-21 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

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WO (1) WO2015007274A1 (fr)

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DE102016226163A1 (de) * 2016-12-23 2018-06-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wärmeübertrager, Klimamaschine und Verfahren zur Kondensation und Verdampfung
EP3725390A1 (fr) * 2019-04-15 2020-10-21 Linde GmbH Procédé et dispositif de traitement d'un mélange gazeux par modulation de pression sous vide comprenant un pompe à chaleur à sorption
DE102020007213A1 (de) 2019-12-17 2021-06-17 Silica Verfahrenstechnik Gmbh Verfahren und Vorrichtung zum Behandeln eines mit Schad- und/oder Nutzkomponenten belasteten Gases

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WO2002066152A2 (fr) * 2001-01-05 2002-08-29 Questair Technologies, Inc. Compositions de revetement adsorbantes, stratifies et elements d'adsorption comprenant ces compositions et leurs procedes de fabrication et d'utilisation

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DE4202671A1 (de) * 1991-05-27 1992-12-03 Degussa Formkoerper enthaltend dealuminierten zeolith y und das verfahren zu ihrer herstellung
DE4316138A1 (de) * 1993-05-14 1994-11-17 Basf Ag Verfahren zur Herstellung von Polytetrahydrofuran
DE112004002971A5 (de) * 2004-07-09 2007-07-12 Fuesting, Bernd Formkörper aus Pulvern oder Granalien, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102007012113B4 (de) * 2007-03-13 2009-04-16 Sortech Ag Kompakte Sorptionskälteeinrichtung
US8323747B2 (en) * 2010-06-25 2012-12-04 Uop Llc Zeolite containing wash coats for adsorber heat exchangers and temperature controlled adsorbers

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
WO2002066152A2 (fr) * 2001-01-05 2002-08-29 Questair Technologies, Inc. Compositions de revetement adsorbantes, stratifies et elements d'adsorption comprenant ces compositions et leurs procedes de fabrication et d'utilisation

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See also references of WO2015007274A1 *

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