EP4212799A1 - Traitements catalytiques d'adsorbants - Google Patents

Traitements catalytiques d'adsorbants Download PDF

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Publication number
EP4212799A1
EP4212799A1 EP23151124.7A EP23151124A EP4212799A1 EP 4212799 A1 EP4212799 A1 EP 4212799A1 EP 23151124 A EP23151124 A EP 23151124A EP 4212799 A1 EP4212799 A1 EP 4212799A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
gold
oxide supported
working fluid
silver nanoparticles
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
EP23151124.7A
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German (de)
English (en)
Inventor
Thomas Badenhop
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.)
Vaillant GmbH
Original Assignee
Vaillant GmbH
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Filing date
Publication date
Application filed by Vaillant GmbH filed Critical Vaillant GmbH
Publication of EP4212799A1 publication Critical patent/EP4212799A1/fr
Pending 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
    • F25B49/00—Arrangement or mounting of control or safety devices
    • F25B49/005—Arrangement or mounting of control or safety devices of safety devices
    • 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
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • 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
    • F25B25/00—Machines, plants or systems, using a combination of modes of operation covered by two or more of the groups F25B1/00 - F25B23/00
    • F25B25/005—Machines, plants or systems, using a combination of modes of operation covered by two or more of the groups F25B1/00 - F25B23/00 using primary and secondary systems
    • 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
    • F25B2500/00—Problems to be solved
    • F25B2500/22—Preventing, detecting or repairing leaks of refrigeration fluids
    • F25B2500/222—Detecting refrigerant leaks
    • 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

Definitions

  • the invention relates to irregular states in refrigeration circuits in which a working fluid acting as a refrigerant is circulated in a thermodynamic cycle, such as the Clausius-Rankine cycle, and their adsorptive safety device.
  • 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.
  • 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 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 is brought into contact with the process fluid, in particular ammonia, propane or propene, and the substance is selectively bound by the adsorbent.
  • the adsorbent is regenerated after use.
  • Zeolite also in combination with imidazole or phosphates, and also CuBTC are proposed as adsorbents, as well as activated carbon; the adsorbent can be 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 DE 195 25 064 C1 describes a refrigeration machine with a gas-tight housing, which accommodates all refrigerant-carrying components of the machine, a space connecting the interior of the gas-tight housing with an outlet is provided, and the space is filled with a refrigerant-sorbing substance.
  • the amount of sorbing substance is dimensioned in such a way that the entire amount of refrigerant that may escape can be absorbed and kept away from the environment.
  • the space filled with the sorbing substance is open to the environment. For heavier-than-air refrigerants, the space is open at the bottom, for lighter-than-air ones, it is open at the top, so a conveying fan is not required.
  • the sorbent is introduced into the housing and completely encloses the refrigeration machine or the refrigerant-carrying equipment. Baffles are provided on its way out to prevent shunt flows and force escaping gas through the sorbent. A double-walled embodiment, in which the sorbent is arranged in the double jacket, is also possible.
  • a measuring device for refrigerant can be provided at the outlet of the space filled with the sorbing substance to the environment.
  • the JP 2000 105003 A describes a refrigeration unit, which is operated with a flammable working fluid, the unit can consist of two parts, one of which is placed inside a building and the other outside in the open air.
  • the inner walls of the inner housing are lined with adsorbent material and the lines of the part installed outside are coated with an adsorbent material.
  • Activated charcoal among others, is proposed as an adsorbent.
  • the EP 3 693 683 A1 describes a heat pump system with a heat pump with combustible refrigerant, the heat pump system comprising a sorbent bed with adsorbent for receiving leaking refrigerant, the heat pump system comprising protective layers arranged to protect the adsorbent from contamination. It is known that when activated charcoal is used as an adsorbent, the activated charcoal ages over time in the air because slow oxidation processes take place. Due to the requirements of a safety concept for the availability over the service life of heat pumps, however, degradation of the adsorbent must be avoided at all costs, especially if it could happen unnoticed.
  • VOC volatile organic compounds
  • water vapor from atmospheric humidity atmospheric oxygen, temperature changes, and others.
  • the VOCs are particularly critical. They mainly consist of hydrocarbons and have a boiling point between 50°C and 250°C. These include various aldehydes, ketones, aromatics, terpenes and alcohols.
  • the concentration of VOCs can be particularly high indoors.
  • the reason is new building materials and furniture and cleaning agents, but also paints and in professional environments toner dust, perfumes, laboratory chemicals and odors from manufacturing plants including tobacco smoke, in kitchen environments other contaminants are added.
  • an external adsorber is used, which vents to the outside. It is assumed below that the sorption bed is located in a channel with an inflow side and an outflow side, one side being connected to the interior of the heat pump housing and the other side being open to the installation space.
  • a known design is used, as is also the case, for example, in EP 3 693 683 A1 is shown, although the design is not important.
  • the contamination load of such sorption beds which are open inwards and outwards with respect to the housing is caused by diffusion and convection of contaminants, in the case of adsorption of co-adsorbents, from both channel openings into the sorption bed.
  • the contaminants can cause reversible or also irreversible degradations in the sorption capacity of the sorption bed compared to the escaping refrigerant.
  • the diffusion flow is driven solely by the concentration gradient, while convective inputs are caused by weather-induced air pressure or temperature gradients between the housing and the environment. The resulting pressure differences lead to compensating flows through the sorption bed and thus to the transport of contaminants into the sorption bed.
  • the following contaminants come into consideration from the housing in which the cycle process is carried out: monovalent and polyvalent alcohols, moisture, drawing fats, cutting oils, foaming agents and RCM oils. These loads are also all in the EP 3 693 683 A1 described.
  • the object of the invention is therefore to provide a secure against degradation adsorbent for heat pumps that are operated with a combustible or flammable refrigerant or hydrocarbons, such as R290, R600a, R1270 or R32, and a method for internal regeneration available, which no longer has the disadvantages described.
  • the solution is achieved through a device with suitable adsorbents, which are mixed with noble metal nanoparticles and make regeneration unnecessary.
  • the sorption channel can be arranged inside or outside of the heat pump housing.
  • the protective layers can be provided by the nanoparticles being produced beforehand and being introduced into the adsorbent in the process of its manufacture.
  • the carrier materials for the protective layers can be activated carbon or zeolite, and activated carbon is used for adsorption. Shaped bodies or a bed can be used.
  • the mass fraction of the nanoparticles should be between 0.5 and 1 mass percent, the nanoparticles must not clog the micropores of the adsorbent, they should ideally be 2 to 4 nanometers in size.
  • Such configurations relate to the catalytically active nanoparticles. These are contained rare earth metals, preferably gadolinium, or noble metals, preferably from the platinum group comprising platinum, palladium, rhodium and ruthenium.
  • rare earth metals preferably gadolinium
  • noble metals preferably from the platinum group comprising platinum, palladium, rhodium and ruthenium.
  • Mixtures of these named nanoparticles are preferably used in order to treat as broad a spectrum of VOCs as possible with them.
  • the mixes are there to match the installation conditions. The way it works is that under room air temperatures and conditions, catalytic oxidations are triggered, which oxidize the adsorbed VOCs to CO 2 and water vapour, whereupon the reaction products desorb and the protective layers regenerate at the same time. A degradation is prevented in this way. Since in this way no safety margin is required with regard to the dimensioning of the protective layers, these can be dimensioned significantly smaller, by a factor of about two to three, than without such equipment.
  • the adsorption layer of the adsorber is also equipped with nanoparticles containing noble metals.
  • adsorbed refrigerant e.g. R290
  • the adsorbent is regenerated as a result.
  • the adsorbent is thus also protected against co-adsorption of VOCs.
  • the dimensioning can be selected to be considerably smaller compared to pure activated carbon adsorption.
  • the nanoparticles are synthesized wet-chemically by reducing metal cations with sodium borohydride.
  • various metal precursors are reduced with sodium borohydride, which causes the formation of the nanoparticles, for example in the liquid phase in the case of gold-silver nanoparticles.
  • the aim here is to produce a homogeneous alloy composition with nanoparticles of less than 5 nm.
  • the best synthesis results are shown with sodium borohydride NaBH 4 as the reducing agent for tetrachloroauric acid HAuCl 4 and silver nitrate AgNOs.
  • the gold-silver nanoparticles are then deposited on a carrier material, such as titanium dioxide or directly on activated carbon, and are separated from the liquid phase using known methods. This method offers good control over the size and composition of the nanoparticles, which is important for the catalytic properties.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP23151124.7A 2022-01-13 2023-01-11 Traitements catalytiques d'adsorbants Pending EP4212799A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102022100735.9A DE102022100735A1 (de) 2022-01-13 2022-01-13 Katalytische Ausrüstungen von Adsorptionsmitteln

Publications (1)

Publication Number Publication Date
EP4212799A1 true EP4212799A1 (fr) 2023-07-19

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Family Applications (1)

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EP23151124.7A Pending EP4212799A1 (fr) 2022-01-13 2023-01-11 Traitements catalytiques d'adsorbants

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EP (1) EP4212799A1 (fr)
DE (1) DE102022100735A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102023100551A1 (de) 2023-01-12 2024-07-18 Vaillant Gmbh Sorptive Abscheidung von gasförmigem Sicherheitskältemittel

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19525064C1 (de) 1995-07-10 1996-08-01 Joachim Dr Ing Paul Kältemaschine
EP0773062A1 (fr) 1995-11-07 1997-05-14 Agency Of Industrial Science And Technology, Ministry Of International Trade And Industry Matériau contenant des particules ultrafines d'or immobilisées et procédé pour sa production
DE19734974A1 (de) 1997-08-13 1999-02-25 Hoechst Ag Verfahren zur Herstellung von porös geträgerten Metall-Nanopartikel-haltigen Katalysatoren, insbesondere für die Gasphasenoxidation von Ethylen und Essigsäure zu Vinylacetat
JP2000105003A (ja) 1998-09-28 2000-04-11 Sanyo Electric Co Ltd 冷凍機ユニット
EP2045028A1 (fr) 2007-09-26 2009-04-08 Fujifilm Corporation Nanoparticules métalliques, leur procédé de production, dispersion aqueuse, procédé de fabrication de circuit ou électrode imprimée, et carte ou dispositif de circuit imprimé
WO2010006796A1 (fr) 2008-07-17 2010-01-21 Universität Duisburg-Essen Procédé de fabrication de substrats carbonés chargés d'oxydes métalliques et substrats carbonés fabriqués par ce procédé
EP2316567A1 (fr) 2003-09-26 2011-05-04 3M Innovative Properties Co. Catalyseurs d'or de l'échelle nano, agents d'activation, moyen de support et méthodologies apparentées utiles pour la fabrication de systèmes catalyseurs lorsque le catalyseur est déposé sur le moyen de support par le dépôt de vapeur physique
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
CN105299761A (zh) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 一种带中央空调建筑物的空气净化方法
EP3106780A1 (fr) * 2015-06-17 2016-12-21 Vaillant GmbH Installation de pompes a chaleur
EP3693683A1 (fr) 2019-02-06 2020-08-12 Vaillant GmbH Barrière de diffusion au moyen de couches de protection

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19525064C1 (de) 1995-07-10 1996-08-01 Joachim Dr Ing Paul Kältemaschine
EP0773062A1 (fr) 1995-11-07 1997-05-14 Agency Of Industrial Science And Technology, Ministry Of International Trade And Industry Matériau contenant des particules ultrafines d'or immobilisées et procédé pour sa production
DE19734974A1 (de) 1997-08-13 1999-02-25 Hoechst Ag Verfahren zur Herstellung von porös geträgerten Metall-Nanopartikel-haltigen Katalysatoren, insbesondere für die Gasphasenoxidation von Ethylen und Essigsäure zu Vinylacetat
JP2000105003A (ja) 1998-09-28 2000-04-11 Sanyo Electric Co Ltd 冷凍機ユニット
EP2316567A1 (fr) 2003-09-26 2011-05-04 3M Innovative Properties Co. Catalyseurs d'or de l'échelle nano, agents d'activation, moyen de support et méthodologies apparentées utiles pour la fabrication de systèmes catalyseurs lorsque le catalyseur est déposé sur le moyen de support par le dépôt de vapeur physique
EP2045028A1 (fr) 2007-09-26 2009-04-08 Fujifilm Corporation Nanoparticules métalliques, leur procédé de production, dispersion aqueuse, procédé de fabrication de circuit ou électrode imprimée, et carte ou dispositif de circuit imprimé
WO2010006796A1 (fr) 2008-07-17 2010-01-21 Universität Duisburg-Essen Procédé de fabrication de substrats carbonés chargés d'oxydes métalliques et substrats carbonés fabriqués par ce procédé
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
EP3106780A1 (fr) * 2015-06-17 2016-12-21 Vaillant GmbH Installation de pompes a chaleur
CN105299761A (zh) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 一种带中央空调建筑物的空气净化方法
EP3693683A1 (fr) 2019-02-06 2020-08-12 Vaillant GmbH Barrière de diffusion au moyen de couches de protection

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