EP4209728A1 - Pompe à chaleur avec adsorbeur et catalyseur - Google Patents

Pompe à chaleur avec adsorbeur et catalyseur Download PDF

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Publication number
EP4209728A1
EP4209728A1 EP23150229.5A EP23150229A EP4209728A1 EP 4209728 A1 EP4209728 A1 EP 4209728A1 EP 23150229 A EP23150229 A EP 23150229A EP 4209728 A1 EP4209728 A1 EP 4209728A1
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EP
European Patent Office
Prior art keywords
adsorbent
oxidation catalyst
adsorption zone
oxidation
heat pump
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.)
Pending
Application number
EP23150229.5A
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German (de)
English (en)
Inventor
Arnold Wohlfeil
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Vaillant GmbH
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Vaillant GmbH
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Filing date
Publication date
Application filed by Vaillant GmbH filed Critical Vaillant GmbH
Publication of EP4209728A1 publication Critical patent/EP4209728A1/fr
Pending legal-status Critical Current

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    • 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
    • F25B30/02—Heat pumps of the compression 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
    • F25B49/00—Arrangement or mounting of control or safety devices
    • F25B49/005—Arrangement or mounting of control or safety devices of safety devices

Definitions

  • the invention relates to irregular states in refrigeration circuits in which a dangerous working fluid acting as a refrigerant is circulated in a thermodynamic cycle, such as the Clausius-Rankine cycle.
  • thermodynamic cycle such as the Clausius-Rankine cycle.
  • These are mainly heat pumps, air conditioning systems and refrigerators, as they are common in residential buildings.
  • the invention relates to use in a heat pump placed inside a dwelling.
  • Residential buildings are private houses, apartment building complexes, hospitals, hotel complexes, gastronomy and combined residential and commercial buildings in which people live and work permanently, in contrast to mobile devices such as car air conditioning systems or transport boxes, or industrial systems or medical devices. What these cycle processes have in common is that they generate useful heat or cold using energy and form heat transfer systems.
  • the heat pump itself as well as its installations for the users are set up inside a building, which results in high safety requirements.
  • the DE 10 2011 116 863 A1 describes a method for securing a device for a thermodynamic cycle which is operated with a process fluid which contains or consists of at least one environmentally hazardous, toxic and/or flammable substance.
  • a process fluid which contains or consists of at least one environmentally hazardous, toxic and/or flammable substance.
  • an adsorbent with the process fluid in particular ammonia, propane or propene, brought into contact and the substance is selectively bound by the adsorbent.
  • the adsorbent is regenerated after use.
  • Zeolite also in combination with imidazole or phosphates, as well as CuBTC and activated carbon are proposed as adsorbents; the adsorbent can be provided in the form of a bed, a shaped body, a paint, a spray film or a coating.
  • the support structure of the shaped body can consist of a microstructure, lamellar structure, tube bundle, tube register and sheet metal and must be mechanically stable and greatly increase the surface area.
  • the potentially contaminated air is usually circulated continuously, but it can also be initiated by a sensor that switches on the ventilation after a threshold value has been reached or if an accident is detected.
  • the adsorption can be carried out inside or outside a closed space.
  • the EP 3 486 564 A1 describes the lining of the heat pump housing with activated carbon, in which the activated carbon is preloaded with an inert gas, which is displaced by the working fluid that has escaped during loading. This reduces the heat generated during adsorption.
  • the EP 3 486 582 A1 describes a system with which the loading of the adsorber can be determined using a weight measurement.
  • the EP 3 581 861 A1 describes a heat pump canister stuffed with activated carbon mold pads.
  • the EP 3 748 257 A1 describes a device in which the adsorber opens a gas outlet via an adsorber in the event of a pressure increase in the heat pump container.
  • the EP 3 693 683 A1 describes protective layers in an adsorber that is open to the environment.
  • the EP 3 693 687 A1 describes an adsorber which is arranged in the heat pump housing and has cooling.
  • the breakthrough curve moves quickly through the adsorption, but remains relatively flat.
  • the advantage of this is that the adsorbate only heats up slightly as a result, the disadvantage is that very large amounts of adsorbent would be required for complete separation, which would be uneconomical and impractical.
  • a high partial pressure on the other hand, a lot can be adsorbed, but the adsorbate heats up considerably, which reduces the absorption capacity. There is an unwanted feedback.
  • a desorption of already separated adsorbent takes place at the same time, so the breakthrough curve pushes a kind of bow wave in front of it as it travels through the adsorber.
  • the adsorbed working fluid is desorbed from the adsorbate as soon as the partial pressure falls again, since there is then no back pressure.
  • the open, flow-through adsorber as well as the introduced adsorber cushions or walls coated with adsorbent cannot hold the adsorbed working fluid permanently, but only ensure that no ignitable mixture can form. It would therefore be desirable if the adsorber were able to destroy the separated substance immediately after the separation process, i.e. to switch to chemisorption after adsorption.
  • the dilemma is that oxidation of the adsorptive could lead to significant heat generation, since alkanes are ideal fuels as working fluids.
  • the extremely low temperatures in the freezer compartment mean that the pressure of the refrigerant is below atmospheric pressure and practically no refrigerant escapes in the event of a leak.
  • the heater for defrosting the storage compartment also heats the catalytic converter for any necessary catalytic decomposition of the refrigerant.
  • this trick cannot be transferred and applied at the usual temperatures of a heat pump.
  • the DE 69 60 740 T2 describes a filtering process for gas in the engine compartment of a vehicle and presents, among other things, a catalytic treatment of hydrocarbons, noble metals such as platinum, palladium and rhodium serve as catalysts, as well as metallic, high-melting carriers for this purpose.
  • a catalytic treatment of hydrocarbons noble metals such as platinum, palladium and rhodium serve as catalysts, as well as metallic, high-melting carriers for this purpose.
  • an auxiliary heated surface is required for this.
  • the construction can be carried out in accordance with conventional honeycomb catalytic converters, as has long been the state of the art in vehicle exhaust gas purification.
  • the catalytic reaction can also be preceded by adsorption with subsequent desorption.
  • the object of the invention is therefore to provide a device and a method for safe and efficient adsorptive gas treatment in a heat pump, which is installed in a residential building, and in which a left-handed thermodynamic cycle in a closed, hermetically sealed working fluid circuit using an inflammable, hydrocarbon-containing Working fluid is carried out. This should no longer have the problems described above.
  • the adsorptive When using the adsorption process in the housing of a heat pump or in connection with it inside a building, the adsorptive is slowly broken down with low leakage rates resulting in a very flat breakthrough curve in the adsorber, whereby it is assumed that atmospheric oxygen is available for oxidation is.
  • Configurations relate to an enclosed adsorption zone, which the air-hydrocarbon mixture can flow against, around or through, and a gas-permeable casing of this enclosed adsorption zone, with an adsorbent and an oxidation catalyst being provided within the enclosed adsorption zone.
  • Oxidation catalysts for alkanes are mainly used industrially to produce alkenes, for example propane is processed into propylene in a propane dehydrogenation, or butane is partially oxidized into butylene or butadiene.
  • the known processes are carried out catalytically, care being taken to ensure the highest possible selectivity and avoiding the formation of oxidation products such as carbon monoxide or carbon dioxide.
  • the catalysts used for this achieve the desired activity in temperature windows of at least 150 degrees Celsius.
  • oxidation that is as complete as possible at room temperatures is desired. Even the case of an incomplete oxidation in the form of a partial oxidation is acceptable as long as the partially oxidized products remain on the adsorbent, i.e. are either also adsorbed or are liquid or form solids, and if the heat of reaction remains low.
  • the amount of catalyst should therefore be small compared to the adsorbent. Therefore, it is envisaged that the ratio of oxidation catalyst to adsorbent is between 1:10 and 1:1000, calculated on the mass fraction. But it doesn't have to be the same everywhere.
  • Catalytic compounds containing Fe(III), Cu(II), Ce(IV), PB(IV), Rh or Pd or mixtures thereof are used in the device. They are either applied directly to the adsorbent, i.e. using the adsorbent as a carrier substance, or other carrier materials are used which are mixed with the adsorbent. Activated carbon is used as an adsorbent.
  • the oxidation catalyst is supported on the adsorbent.
  • This includes shaped bodies of a bed, such as cylindrical pellets, or honeycomb shaped bodies with flow channels, or shaped cushions or foams or other known carriers for adsorbents and catalysts.
  • the oxidation catalysts can also be applied to separate shaped bodies which, for example, are admixed to a bed. For example, if activated charcoal is used as an adsorbent in the form of a bed, small amounts of other shaped bodies on which catalysts are applied can be admixed to the bed.
  • the adsorption zone is formed by a sorption channel which has a gas inlet and insert baskets which are filled with adsorbent and oxidation catalyst are filled, and a gas outlet that is open to the atmosphere.
  • the sorption channel can be equipped with additional equipment, such as protective layers, baffles, etc.
  • one embodiment provides that the bulk density of catalyst increases with the bed height, ie the length of the flow, and the bulk density of catalyst at the adsorber outlet assumes the highest value. This ensures that the lowest reaction heat occurs at the adsorber inlet, where most of the heat of adsorption occurs, while the catalytic degradation is strongest at the adsorber outlet, where initially only little adsorption takes place. In this way, the heat load is best distributed over the adsorber bed height.
  • the covers can be fitted with a catalyst. If adsorber walls are used, the catalyst should be arranged on the side facing the vessel wall, since the heat of reaction can best be dissipated via the vessel wall or other walls. If shaped bodies are used for adsorption, the catalyst must be installed at the flow outlet or on the side walls in a higher concentration than in the middle or at the flow inlet.
  • the adsorption zone is then formed by a shaped body with inner and outer inflow surfaces. It can also be provided that the shaped body is attached to the inner wall of the housing of a heat pump and the bulk density of oxidation catalyst on the adsorbent increases with proximity to the wall. All of these measures and designs can also be used side by side in combination.
  • the temperature of the adsorbent is measured. If this rises too much, a small amount of inerting nitrogen is added, which slows down the oxidation by lowering the partial pressures of the reactants, especially oxygen. If the addition amount is small, influences the adsorption, on the other hand, hardly does.
  • the temperature measurement and the addition of nitrogen can also take place in different places or layers.
  • the nitrogen to be added, if necessary, is kept under high pressure, which during the expansion during the addition also leads to a cooling of the adsorbent due to the Joule-Thomson effect.
  • the adsorber can also be cooled alternatively or additionally with known cooling devices according to the prior art, as described above.
  • Fig.1 shows a heat pump 1 with an encapsulated housing 2 in which a refrigeration circuit 3 is operated with the flammable refrigerant R290.
  • This refrigeration circuit comprises a compressor 4, a condenser 5, an expansion valve 6 and an evaporator 7.
  • the encapsulated housing is provided with a connection 8 to a sorption channel 9.
  • the sorption channel 9 contains a bed with the adsorbent activated carbon and an oxidation catalyst made of iron (III), which is applied to the activated carbon.
  • the concentration of the doping increases with the run length. Cleaned air can leave the sorption channel 9 via the outlet 10 . Normally there is hardly any flow through the sorption channel.
  • the pressure in the encapsulated housing 2 increases and drives the resulting air-R290 mixture into the sorption channel 9, where it is adsorbed in the lower area.
  • the adsorbent heats up and the applied catalyst causes a slow reaction, oxidation products of the R290 up to to the carbon dioxide. If larger amounts should occur due to a larger leakage, which is extremely rare, the heat of adsorption causes significant heating, which also accelerates oxidation and can cause further heating.
  • an injection 11 of nitrogen or another inert gas is provided in order to modulate this reaction.
  • a temperature reduction can also be achieved by pressure relief during injection, which on the one hand increases the capacity of the adsorbent and on the other hand the reaction heat of the oxidation reduced.
  • a temperature measuring point T is provided in the sorption channel 9 in order to detect such excessive heating in good time.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation Of Gases By Adsorption (AREA)
EP23150229.5A 2022-01-07 2023-01-04 Pompe à chaleur avec adsorbeur et catalyseur Pending EP4209728A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102022100269.1A DE102022100269A1 (de) 2022-01-07 2022-01-07 Katalytische Abluftbehandlung für eine Wärmepumpe

Publications (1)

Publication Number Publication Date
EP4209728A1 true EP4209728A1 (fr) 2023-07-12

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EP23150229.5A Pending EP4209728A1 (fr) 2022-01-07 2023-01-04 Pompe à chaleur avec adsorbeur et catalyseur

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EP (1) EP4209728A1 (fr)
DE (1) DE102022100269A1 (fr)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000320950A (ja) 1999-05-11 2000-11-24 Matsushita Refrig Co Ltd 冷蔵庫
DE102011116863A1 (de) 2011-10-25 2013-04-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Sicherung einer Vorrichtung für einen thermodynamischen Kreisprozess und abgesicherte Vorrichtung für einen thermodynamischen Kreisprozess
EP3486582A1 (fr) 2017-11-16 2019-05-22 Vaillant GmbH Détection des fuites au moyen de capacité adsorbante
EP3486564A1 (fr) 2017-11-16 2019-05-22 Vaillant GmbH Adsorption de fluide à refoulement de gaz inerte
EP3581861A2 (fr) 2018-04-23 2019-12-18 Vaillant GmbH Sorption du fluide
EP3693687A2 (fr) 2019-02-06 2020-08-12 Vaillant GmbH Refroidissement d'adsorbant
EP3693683A1 (fr) 2019-02-06 2020-08-12 Vaillant GmbH Barrière de diffusion au moyen de couches de protection
DE102019118984A1 (de) * 2019-02-06 2020-10-08 Vaillant Gmbh Diffusionssperre mittels Schutzschichten
EP3748257A1 (fr) 2019-06-03 2020-12-09 Vaillant GmbH Dispositif pour la performance sûre d'un procédé circulaire thermodynamique à rotation à gauche au moyen d'un fluide de travail inflammable avec adsorption de fluide
US20210108810A1 (en) 2019-10-14 2021-04-15 Bluezone Ip Holding Llc Method and apparatus for air treatment employing catalyst material

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000320950A (ja) 1999-05-11 2000-11-24 Matsushita Refrig Co Ltd 冷蔵庫
DE102011116863A1 (de) 2011-10-25 2013-04-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Sicherung einer Vorrichtung für einen thermodynamischen Kreisprozess und abgesicherte Vorrichtung für einen thermodynamischen Kreisprozess
EP3486582A1 (fr) 2017-11-16 2019-05-22 Vaillant GmbH Détection des fuites au moyen de capacité adsorbante
EP3486564A1 (fr) 2017-11-16 2019-05-22 Vaillant GmbH Adsorption de fluide à refoulement de gaz inerte
EP3581861A2 (fr) 2018-04-23 2019-12-18 Vaillant GmbH Sorption du fluide
EP3693687A2 (fr) 2019-02-06 2020-08-12 Vaillant GmbH Refroidissement d'adsorbant
EP3693683A1 (fr) 2019-02-06 2020-08-12 Vaillant GmbH Barrière de diffusion au moyen de couches de protection
DE102019118984A1 (de) * 2019-02-06 2020-10-08 Vaillant Gmbh Diffusionssperre mittels Schutzschichten
EP3748257A1 (fr) 2019-06-03 2020-12-09 Vaillant GmbH Dispositif pour la performance sûre d'un procédé circulaire thermodynamique à rotation à gauche au moyen d'un fluide de travail inflammable avec adsorption de fluide
US20210108810A1 (en) 2019-10-14 2021-04-15 Bluezone Ip Holding Llc Method and apparatus for air treatment employing catalyst material

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