WO2016074918A1 - Dispositif thermoélectrique - Google Patents

Dispositif thermoélectrique Download PDF

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Publication number
WO2016074918A1
WO2016074918A1 PCT/EP2015/074870 EP2015074870W WO2016074918A1 WO 2016074918 A1 WO2016074918 A1 WO 2016074918A1 EP 2015074870 W EP2015074870 W EP 2015074870W WO 2016074918 A1 WO2016074918 A1 WO 2016074918A1
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WO
WIPO (PCT)
Prior art keywords
thermoelectric device
heat exchanger
storage vessel
thermoelectric
exhaust gas
Prior art date
Application number
PCT/EP2015/074870
Other languages
English (en)
Inventor
Mathias WEICKERT
Stefan Marx
Ulrich Müller
Adam Lack
Joseph Lynch
William Dolan
Michael SANTAMARIA
Original Assignee
Basf Se
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Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2016074918A1 publication Critical patent/WO2016074918A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N5/00—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy
    • F01N5/02—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy the devices using heat
    • F01N5/025—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy the devices using heat the device being thermoelectric generators
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0203—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels characterised by the type of gaseous fuel
    • F02M21/0215—Mixtures of gaseous fuels; Natural gas; Biogas; Mine gas; Landfill gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0218—Details on the gaseous fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M31/00—Apparatus for thermally treating combustion-air, fuel, or fuel-air mixture
    • F02M31/02—Apparatus for thermally treating combustion-air, fuel, or fuel-air mixture for heating
    • F02M31/12—Apparatus for thermally treating combustion-air, fuel, or fuel-air mixture for heating electrically
    • F02M31/125—Fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/13—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/30—Use of alternative fuels, e.g. biofuels

Definitions

  • thermoelectric device comprising a hot side and a cold side, wherein the hot side is thermally coupled to an exhaust gas system of an internal combustion engine, a vehicle and a use of the thermoelectric device.
  • Thermoelectric generators or devices and Peltier arrangements have been known for a long time, p- and n-doped semiconductors, which are heated on one side and cooled on the other side, transport electric charges through an external circuit, so that electrical work can be performed on a load in the circuit.
  • the efficiency thereby achieved for the conversion of heat into electrical energy is thermodynamically limited by the Carnot efficiency.
  • efficiencies up to approximately 6% have been achieved.
  • Peltier arrangement works as a heat pump and is there- fore suitable for cooling equipment parts, vehicles or buildings. Heating by means of the Peltier principal is also more favorable than conventional heating, because more heat is always transported than corresponds to the energy equivalent supplied.
  • thermoelectric generators are used in space probes for the generation of direct currents, for the cathodic corrosion protection of pipelines, for the energy supply of light and radio buoys, and for the operation of radios and televisions.
  • the advantages of thermoelectric generators reside in their extreme reliability. They operate irrespective of atmospheric conditions such as relative humidity; no material transport susceptible to interference takes place, rather only charge transport.
  • the thermoelectric device typically comprises p-and n-type pieces, which are connected electrically in series and thermally in parallel.
  • a conventional structure comprises two ceramic plates, between which the individual pieces are fitted alternately. Two pieces are in each case contacted electrically conductively via the end faces. Besides the electrically conductive contacting, various further layers are normally also provided on the actual material, which serve as protective layers or as solder layers. The electrical contact between two pieces is established via a metal bridge.
  • a thermoelectric material inside the thermoelectric device provides the actual effect. An electric current and a heat flux flow through the material in order to fulfil the function of the overall structure.
  • thermoelectric devices in motor vehicles such as automobiles and trucks, in the exhaust system or the exhaust gas recirculation, in order to obtain electrical energy from a part of the exhaust gas heat.
  • the hot side of the thermoelectric device is connected to the exhaust gas or tailpipe, while the cold side is typically connected to a cooler.
  • the thermoelectric device is installed for use behind the exhaust gas catalytic converter in the exhaust system.
  • the amount of electricity which can be generated depends on the temperature of the exhaust gas and the heat flux from the exhaust gas to the thermoelectric material.
  • adsorbed natural gas ANG
  • CNG compressed natural gas
  • a solid, such as activated carbon or metal organic framework material is packed in a vessel to increase the storage density, enabling lower pressure operation with the same capacity or higher amounts of stored gas at the same pressure.
  • Sorption which can be adsorption and/or absorption, is an exothermic process. Any sorption or desorption, as well as any compression and decompression, is accompanied by temperature changes in a storage system.
  • the heat of sorption has a detrimental effect on performance dur- ing both charge- and discharge cycles of storage vessels, especially when the storage vessel comprises a sorption medium.
  • the way of filling a storage system at a fuel station influences strongly the total fuel amount in the storage vessel that is available from the storage vessel at the end of a filling process.
  • the fuel temperature in the storage vessel increases due to the heat of compression and/or sorption.
  • the temperature in the storage vessel increases during filling to approximately 50°C above ambient temperature due to the heat of compression.
  • the temperature in the storage can increase further to an absolute temperature of approximately 90°C due to the additional heat of sorption.
  • the temperature increase constitutes a limitation especially for the ANG technique as for example carbon fiber tanks are presently only approved to operate at temperatures to up to 80°C.
  • a charge cycle normally will be performed in a fuel station, at least for mobile applications, where the released sorption heat can be removed. Contrary to the charge cycle, the rate of discharge is dictated by the energy demand of the application.
  • Heat management system have to be optimized with regard to a minimum of required space and a minimum of additional weight in mobile applications, a minimum of additionally required electrical power and limited costs.
  • WO 2014/057390 A1 describes a sorption store for storing gaseous substances, wherein the tank comprises separating elements, which are configured in such a way that the interior of the tank is divided into at least one pair of channels.
  • a method for removing gas from the sorption store is described, wherein the channel walls are flowed through by a heat transfer medium.
  • thermoelectric module which is thermally conduc- tively connected to a micro-heat exchanger. Further, an exhaust system of an internal combustion engine, preferably of motor vehicles, comprising the thermoelectric module, is described.
  • a thermoelectric generator is mentioned to produce electrical energy from heat of exhaust gases. An improved fuel economy can be achieved for a variety of engines including diesel, spark ignition, gas turbine and Stirling. Waste heat utilization concepts can include preheating, regeneration, turbo charging, turbo compounding and Rankine engine compounding. Electrical power, which is produced from the exhaust gas heat can be tapped into a battery to run a dc motor.
  • thermoelectric device with an increased energy output and which is able to benefit from temperature changes occurring in a storage vessel comprising a sorption medium.
  • thermoelectric device comprising a hot side and a cold side, wherein the hot side is thermally coupled to an exhaust gas system of an internal combustion engine and the cold side is thermally coupled to a storage vessel, wherein a sorption medium is disposed in the storage vessel and the storage vessels contains a fuel for the internal combustion engine.
  • thermoelectric device and the storage vessel are mounted to one vehicle, which is driven by the internal combustion engine.
  • the internal combustion engine runs with the fuel, which is contained in the storage vessel. Exhaust gas produced by the internal combustion en- gine is led through the exhaust gas system of the vehicle.
  • the vehicle can additionally comprise an electric motor with corresponding electric drive system.
  • the internal combustion engine is used to drive the vehicle, the fuel is consumed and the storage vessel is emptied while driving.
  • An emptying of the storage vessel corresponds to a desorption process in the interior of the storage vessel as the fuel was sorbed to the sorp- tion medium.
  • the term "sorption” generally covers adsorption as well as absorption. Sorption is an exothermic process whereas desorption is an endothermic process. Therefore, during driving the vehicle and desorption of the fuel from the sorption medium, the temperature of the sorption medium and the fuel still contained in the storage vessel decreases.
  • this temperature decrease can be used to produce electrical energy and to run the thermoelectric device, which uses heat from an exhaust gas system in the vehicle more efficiently. It is a further advantage of the invention that by the described thermal coupling between the storage vessel and the thermoelectric device heat is transferred into the storage vessel. Due to the heat transfer to the storage vessel a larger amount of the fuel can be discharged from the storage vessel as desorption of the fuel from the sorption medium is accelerated. As a smaller amount of the fuel remains in a sorbed state on the sorption medium in the storage vessel, the range the vehicle can cover after one stop for filling the storage vessel is enlarged.
  • the cold side is thermally coupled to the storage vessel by a heat exchanger.
  • the heat exchanger can be an internal heat exchanger, located in the storage vessel comprising piping loops or double walls in the interior of the storage vessel, which can be filled with a heat transfer fluid. It is also possible to equip the storage vessel with a double wall mantle.
  • the heat exchanger is an external heat exchanger applying the fuel from the storage vessel as a first heat transfer medium.
  • the storage vessel is equipped with an outlet and an inlet, which both comprise shut-off elements which can be operated separately. During driving, fuel can be taken from the storage vessel via the outlet with the outlet shut-off element open and the fuel taken from the storage vessel can be led through the external heat exchanger.
  • a first part of the fuel taken from the storage vessel can further be conducted to the internal combustion engine and a second part of the fuel taken from the storage vessel can be conducted back into the storage vessel through the inlet.
  • the two parts of the fuel taken from the storage vessel can be divided before or after a passage trough the external heat exchanger. Both parts or only one of the parts can be conducted through the external heat exchanger.
  • the second part of the fuel taken from the storage vessel reentering the storage vessel now has a higher temperature compared to the fuel still stored in the storage vessel. Therefore, the interior of the storage vessel and the sorption medium heat up and further fuel is desorbed from the sorption medium.
  • thermoelectric, device is electrically connected to a battery which is electrically connected to an electric motor.
  • the internal combustion engine is for example combined with the electric motor as auxiliary drive when the vehicle is a hybrid vehicle.
  • vehicle typically comprises rechargeable batteries which, as electrochemical cell, convert chemical energy into electric energy.
  • the thermoelectric device is preferably coupled to an electric system, which can comprise the battery and which supplies the electric motor or an air conditioning system or other electrically driven components of the vehicle or combinations thereof. Also a supply from the thermoelectric device to a dynamo of the vehicle might be considered.
  • thermoelectric device comprises p- and n-conducting thermoelectric material pieces which are alternately connected to one another via electrically conductive contacts, and the thermoelectric device is thermally conductively connected to a micro heat exchanger, which comprises a plurality of continuous channels having a diameter of at most 1 mm, through which a second heat transfer medium can flow, which is preferably the exhaust gas.
  • micro heat exchanger By using micro heat exchangers, it is possible to ensure an improved heat flux from the exhaust gas to the thermoelectric device, with at the same time a sufficiently low temperature loss.
  • the term "micro heat exchanger” is intended to mean heat exchangers which have a plurality of continuous channels with a diameter of at most 1 mm, particularly preferably at most 0.8 mm.
  • the minimum diameter is set only by technical feasibility, and is preferably of the order of 50 ⁇ , particularly preferably 100 ⁇ .
  • the micro channels may have any suitable cross section, for example round, oval, polygonal such as square, triangular or star-shaped, etc.
  • the shortest distance between opposite edges or points of the micro channel is considered as the diameter.
  • the micro channels may also be formed so as to be flat, in which case the diameter is defined as the distance between the bounding surfaces. This is the case in particular for heat exchangers which are constructed from plates or layers.
  • the second heat transfer medium flows through the continuous micro channels while transferring heat to the heat exchanger.
  • the heat exchanger is on the other hand thermally connected to the thermoelectric device, so that good heat transfer is obtained from the heat exchanger to the thermoelectric device.
  • the micro heat exchanger is formed integrally with the thermoelectric device.
  • the micro heat exchanger is formed integrally with the thermoelectric device in a way that the micro heat exchanger has an integrally molded container which receives the p- and n-conducting thermoelectric material pieces, which are alternately connected to one another via electrically conductive contexts, to form an integrated assembly of micro heat exchanger and thermoelectric device.
  • the micro heat exchanger and container may be constructed in any suitable way from any suitable materials. It may for example be made from a block of a thermally conductive material, into which the continuous channels are introduced.
  • Suitable materials are for example plastics, for example polycarbonate, liquid crystal polymers such as Zenith ® from DuPont, polyether ether ketones (PEEK), etc.
  • Metals may also be used, such as iron, copper, aluminum or suitable al- loys such as chromium-iron, Fecralloy®.
  • Ceramics or inorganic oxide materials may furthermore be used, such as aluminum oxide or zirconium oxide or cordierite. It may also be a composite material made of a plurality of the aforementioned materials.
  • the micro heat exchanger is preferably made of a high temperature-resistant alloy (1000-1200°C), Fecralloy®, iron alloys containing Al, stainless steel, cordierite.
  • the microchannels may be introduced into a block of a thermally conductive material in any suitable way for example by laser methods, etching, boring, etc.
  • the micro heat exchanger and container may also be constructed from differ- ent plates, layers or tubes, which are subsequently connected to one another, for example by adhesive bonding or welding.
  • the plates, layers or tubes may in this case be provided in advance with the microchannels and then assembled.
  • the container which receives the p- and n-conducting thermoelectric material pieces is integrally moulded to at least one of the plates, layers or tubes.
  • the micro heat exchanger and container from a powder by means of a sintering method.
  • Both metal powders and ceramic powders can be used as the powder. Mixtures composed of metal and ceramic, composed of different metals or composed of different ceramics are also possible. Suitable metal powders comprise, for example, powders composed of ferritic steels, Fecralloy® or stainless steel.
  • SLS Selective Laser Sintering
  • micro heat exchanger and container affords the advantage of a good thermal conductivity.
  • ceramics have a good heat storage capability, and so they can be utilized, in particular, to compensate for temperature fluctuations.
  • plastics are used as material for the micro heat exchanger and container, it is necessary to apply a coating that protects the plastic from the temperatures of the exhaust gas flowing through the micro heat exchanger. Such coatings are also referred to as "thermal barrier coating”. On account of the high temperatures of the exhaust gas, it is necessary to coat all surfaces of the micro heat exchanger composed of the plastics material.
  • External dimensions of the micro heat exchanger are preferably from 60 x 60 x 20 to 40 x 40 x 8 mm 3 .
  • the specific heat transfer area of the micro heat exchanger, in relation to the volume of the micro heat exchanger, is preferably from 0.1 to 5 m 2 /l, particularly preferably from 0.3 to 3 m 2 /l, in particular from 0.5 to 2 m 2 /l.
  • Suitable micro heat exchangers are commercially available, for example from the Institut fur Mikrotechnik Mainz GmbH (IMM).
  • the IMM offers various geometries of microstructured heat exchangers, and in particular microstructured high-temperature heat exchangers for a maximum operating temperature of 900°C.
  • These high-temperature heat exchangers have dimensions of about 80 x 50 x 70 mm 3 and function (for other applications) according to the counterflow principle. They have a pressure loss of less than 50 mbar and a specific heat transfer area of about 1 m 2 /l.
  • Other micro heat exchangers are exhibited by VDIA DE-Technologiemaschinetechnik Informationstech- nik GmbH.
  • Micro heat exchangers are furthermore offered by Ehrfeld Mikrotechnik BTS GmbH, Wendelsheim and SWEP Market Services, a branch of Dover Market Services GmbH, Fijrth.
  • the micro heat exchanger known from the above sources can be adapted for use in the thermoelectric device.
  • an integrally moulded container can be preformed or formed on the micro heat exchanger.
  • the assembly of micro heat exchanger and thermoelectric device is a "one piece" component which is preferably obtained in one process by Selective Laser Sintering (SLS).
  • SLS Selective Laser Sintering
  • the micro heat exchanger is preferably configured so that it can be connected to the thermoelectric device in a way which has the best possible thermal conduction. Depending on the structure and material constitution, it may be thermally conductively connected directly to the thermoelectric device. It is also possible for the thermoelectric device to be flat and, on the thermoe- lectric material pieces, to have a carrier plate on the hot side which is thermally conductively connected to the micro heat exchanger.
  • thermoelectric device Preferably in the container, hot side electrically conductive contacts are placed, an extract solid matrix structure is inserted afterwards, which has recesses to house the p- and n-conducting thermoelectric material pieces inserted therein, cold side electrically conductive contacts are placed on the p- and n-conducting thermoelectric materials and finally cold side electrical insulation is applied, in order to form the thermoelectric device.
  • the container can have any desired redimensional shape, as long as it can house the thermoe- lectric material pieces, the electrical contact and the other layers described.
  • the container has the form of a box, into which the thermoelectric device is filled.
  • the bottom of the box is electrically insulated by an insulating layer made of for example ceramics, glass etc., by known coating processes like spraying, CVD, PVD, galvanic processes, casting, etc.
  • electrically conductive contacts forming the hot side electrically conductive contacts of the thermoelectric device, are placed on the respective positions in the container or box.
  • These electrically conducting contacts can be made of any desired electrically conducting materials like metals, i.e. copper, iron, nickel, etc. These contacts may be placed in the container or fixed by gluing or soldering or by placing in respective recesses of the container.
  • an eggcrate solid matrix structure is inserted, which fills the container but has recesses to house the p- and n-conducting thermoelectric material pieces inserted therein.
  • the eggcrate solid matrix structure can be formed of any suitable material like ceramics, polymers, aerogel, wood, foam or metal like steel.
  • the eggcrate solid matrix structure has recesses of the size of the p- and n-conducting thermoelectric material pieces.
  • the eggcrate can be formed from one or more pieces which can be layered onto each other.
  • the eggcrate can have recesses or holes of any possible diameter and geometry.
  • the eggcrate solid matrix material is selected from polymers or ceramics due to the low thermal connectivity, minimizing heat losses.
  • thermoelectric material pieces are then inserted in the recesses of the eggcrate matrix structure, in alternating n- and p-order.
  • the material pieces can be contacted with the electrically conductive contacts in any suitable manner, like soldering, gluing, clamping or pressing.
  • thermoelectric device Cold side electrically conductive contacts are placed on the p- and n-conducting thermoelectric materials, so that also the cold side of the thermoelectric devices is electrically connected. Finally, a cold side electrical insulation is applied, in order to form the thermoelectric device.
  • This insulating layer may be formed of ceramics, glass, glimmer or other coatings.
  • the pressure loss generated through the continuous micro channels of the heat exchanger for a gas flowing through is preferably at most 100 mbar, in particular at most 50 mbar. Such pressure losses do not lead to an increased fuel consumption of the internal combustion engine. Such a pressure loss can be realized, in particular if the micro heat exchangers are arranged such that the channels through which the exhaust gas flows run parallel and are connected to an inlet on one side and to an outlet on the other side.
  • the length of the micro channels through which the exhaust gas flows is in this case preferably at most 60 mm, in particular at most 40 mm. If more than one micro heat exchanger is used, the micro heat exchangers are likewise connected in parallel and connected to a common inlet and a common outlet, such that the channels of the individual heat exchangers likewise run parallel.
  • the heat-exchanging surface of the micro heat exchanger may be installed directly in the exhaust system or tailpipe of the internal combustion engine. It may be installed fixed or removably.
  • the heat-exchanging surface may also be firmly encapsulated with the thermoelectric device.
  • One or more of the thermoelectric devices, for example connected in succession, may be integrated into the exhaust system of the internal combustion engine. In this case, thermoelectric devices comprising different thermoelectric materials may also be combined.
  • thermoelectric materials which are suitable for the temperature range of the exhaust gas of the internal combustion engine.
  • thermoelectric materials are manganese silicides, bismuth, nickel, platinum, carbon, aluminum, rhodium, copper, gold, silver, iron, nichrome and constantan. It is preferred that the thermoelectric device comprises a thermoelectrically active material, which is selected from the group consisting of silicides, lead germanium tellurides, bismuth tellu- rides, such as bismuth lead tellurides, zinc antimonide and single crystalline clathrates in the BaGaGe system showing a high thermoelectric figure, optimized single crystalline Peltier materials and combinations thereof.
  • a thermoelectrically active material which is selected from the group consisting of silicides, lead germanium tellurides, bismuth tellu- rides, such as bismuth lead tellurides, zinc antimonide and single crystalline clathrates in the BaGaGe system showing a high thermoelectric figure, optimized single crystalline Peltier materials and combinations thereof.
  • Preferred materials are further magnesium silicides, manganese silicides, half-Heusler compounds of the general formulae (Zr m Hf 1-m )NiSn with 0.2 ⁇ m ⁇ 0.8 and (Co n Fei -n ) TiSb with 0.3 ⁇ n ⁇ 0.9. Silicides and half-Heusler compounds are preferred as they are environmentally compatible.
  • thermoelectric material 5 to 6 % of heat taken from an exhaust gas stream can be transformed into electric energy. This value is predominantly limited by the selection of the thermoelectric material. Especially suitable materials can provide a transformation of up to 10 %. At a temperature difference between 100°C and 650°C, commercially available materials can provide an efficiency of 6 to 7 % for the transformation of heat into electric energy. Considering heat losses in the system, an overall efficiency of 5 % can be achieved. Typically a cooling capacity of 10 to 15 kW is required on the cold side of the thermoelectric device for applications in cars.
  • a protective layer for protecting against excessive temperatures is provided between the thermoelectric device and the micro heat exchanger.
  • This layer also referred to as a phase-change layer, is preferably made of inorganic metal salts or metal alloys having a melting point in the range of from 250°C to 1700°C.
  • Suitable metal salts are for example fluorides, chlorides, bromides, iodides, sulfates, nitrates, carbonates, chromates, molyb- dates, vanadates and tungstates of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium. Mixtures of suitable salts of this type, which form double or triple eutectics, are preferably used.
  • thermoelectric device may be encapsulated with the protective layer, in particular when using metals such as nickel, zirconium, titanium, silver and iron, or when using alloys based on nickel, chromium, iron, zirconium and/or titanium.
  • the micro channels of the micro heat exchanger are coated with a motor vehicle exhaust gas catalyst.
  • the micro channels are preferably coated with an exhaust gas catalyst, which in particular catalyzes one or more of the conversions: NOx to nitrogen, hydrocarbons to C0 2 and H 2 0, and CO to C0 2 . Particularly preferably, all these conversions are catalyzed.
  • Suitable catalytically active materials such as Pt, Ru, Ce, Pd are known, and are described for example in Stone, R. et al., Automotive Engineering Fundamentals, Society of Automotive En- gineers 2004. These catalytically active materials are applied in a suitable way onto the micro channels of the micro heat exchanger. Preferably, application in the form of a washcoat may be envisaged. In this case, the catalyst is applied in the form of a suspension as a thin layer onto the inner walls of the micro heat exchanger, or onto its channels. The catalyst may then consist of a single layer or various layers with identical or varying composition. The applied catalyst may then fully or partially replace the normally used exhaust gas catalytic converter of the internal combustion engine during use in a motor vehicle, depending on the dimensioning of the micro heat exchanger and its coating.
  • thermoe- lectric device Due to the washcoat directly provided in the micro heat exchanger, the hot side of the thermoe- lectric device can be further heated up, due to the catalyzed reaction occurring at the washcoat.
  • the micro heat exchanger may be installed in the exhaust system at the position of the original exhaust gas catalytic converter. In this way, a high exhaust gas temperature can be supplied to the micro heat exchanger. The temperature may be increased even further by the chemical conversion at the exhaust gas catalyst of the micro heat exchanger, so that much more efficient heat transfer takes place than in known systems.
  • the thermoelectric device may also be used in reverse for preheating the exhaust gas catalyst during a cold start of an internal combustion engine, preferably of a motor vehicle.
  • the thermoelectric device is used as a Peltier element.
  • the exhaust system is intended to mean the system which is connected to the outlet of an internal combustion engine and which the exhaust gas is processed. The pressure loss in the exhaust system of the internal combustion engine is low, in particular when the micro heat exchanger is coated with the washcoat of the exhaust gas catalyst.
  • the structure of the exhaust system can be simplified significantly by the one integrated component. Since the integrated component can be integrated closer to the internal combustion engine in the exhaust system, higher exhaust gas temperatures can be supplied to the thermoelectric device. By the reverse use of the thermoelectric device as a Peltier element, the exhaust gas catalyst can be heated during a cold start of the engine.
  • the sorption medium in the storage vessel is selected from the group consisting of activated charcoals, zeolites, activated aluminia, silica gels, open-pore polymer foams, metal hybrids, metal organic frameworks (MOF) and combinations thereof. Especially preferred are metal organic frameworks.
  • Zeolites are crystalline aluminosilicates having a microporous framework structure made up of AI04 and Si04 tetrahedra. Here, the aluminum and silicon atoms are joined to one another via oxygen atoms. Possible zeolites are zeolite A, zeolite Y, zeolite L, zeolite X, mordenite, ZSM (Zeolites Socony Mobil) 5 or ZSM 1 1.
  • Suitable activated carbons are in, particular, those having a specific surface area above 500m 2 g "1 , preferably about 1500m 2 g "1 , very particularly preferably above 3000m 2 g "1 . Such an activated carbon can be obtained, for example under the name Energy to Carbon or MaxSorb.
  • Metal-organic frameworks are known in the prior art and are described for example in US 5,648,508, EP-A 0 700 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000), pages 3 to 20, H. Li et al., Nature 402, 1 (1999), page 276, M. Eddaoudi et al., Topics in Catalysis 9, (1999), pages 105 to 1 1 1 , B.
  • MOF metal-organic frameworks
  • MOF-177, MOF- A520, KHUST-1 , Sc-terephthalate, AI-BDC and AI-BTC Preferred metal-organic frameworks
  • MOFs Apart from the conventional method of preparing the MOFs, as described, for example, in US 5,648,508, these can also be prepared by an electrochemical route. In this regard, reference may be made to DE-A 103 55 087 and WO-A 2005/049892.
  • the metal organic frameworks prepared in this way have particularly good properties in respect of the sorption and desorption of chemical substances, in particular gases.
  • Particularly suitable materials for the adsorption in storage vessels are the metal-organic framework materials MOF A520, MOF Z377 and MOF C300.
  • MOF A 520 is based on aluminium fumarate.
  • the specific surface area of a MOF A520 measured by porosimetry or nitrogen adsorption, is typically in the range from 800 m 2 /g to 2000 m 2 /g.
  • the adsorption enthalpy of MOF A520 with regard to natural gas amounts to 17kJ/mol. Further information on this type of MOF may be found in "Metal-Organic Frameworks, Wiley-VCH Ver- lag, David Farrusseng, 201 1 ".
  • MOF Z377 in literature also referred to as MOF 177, is based on zinc-benzene-tribenzoate.
  • the specific surface area of a MOF Z377 is typically in the range from 2000 m 2 /g to 5000 m 2 /g.
  • the MOF Z377 typically posses an adsorption enthalpy between 12 kJ/mol and 17 kJ/mol with respect to natu- ral gas.
  • MOF C300 is based on copper benzene-1 ,3,5-tricarboxylate and for example commercially available from Sigma Aldrich under the tradename Basolite® C300.
  • the sorption medium can generally be disposed in the storage vessel in forms of powder, pellets, shaped bodies or monoliths or combinations thereof.
  • the sorption medium is present as a bed of pellets and the ratio of the permeability of the pellets to the smallest pellet diameter is at least between 1 * 10 "11 m 2 /m and 1 * 10 "16 m 2 /m, preferably between 1 * 10 "12 m 2 /m and 1 * 10 "14 m 2 /m, and most preferably 1 * 10 "13 m 2 /m.
  • the rate at which the gas or fuel penetrates into the pellets during filling depends on the rapidity with which the pressure in the interior of the pellets becomes the same as the ambient pressure. With decreasing permeability and increasing diameter of the pellets, the time for this pressure equalization and thus also the loading time of the pellets increases. This can have a limiting effect on the overall process of filling and discharging.
  • the storage vessel is a pressure vessel for the storage of fuel at a pressure in the range of up to 500 bar, preferably in a range of 1 bar to 400 bar, most preferably in the range of 1 bar to 250 bar. In other embodiments, also the range of 1 bar to 100 bar is preferred.
  • cross-sectional areas are suitable for the storage vessel, for example circular, elliptical or rectangular. Irregularly shaped cross-sectional areas are also possible, e. g. when the storage vessel is to be fitted into a hollow space of a vehicle body. It is also possible to divide the total storage volume filled with the sorption medium into more than one storage vessel. For higher pressure above about 100 bar, circular and elliptical cross-sections are particularly suitable.
  • the vessel size varies according to the application. Diameters of the vessel of approximately 50 cm are typical for tanks in trucks and approximately 20 cm for tanks in cars, respectively. In cars volumes between 20 liters and 40 liters are provided, whereas storage vessel of a volume between 500 liters and 3000 liters can be found in trucks.
  • the fuel comprises a gas selected from the group consisting of natural gas, shale gas, town gas, methane, ethane, hydrogen, propane, propene, ethylene, carbon dioxide and combinations thereof.
  • the storage vessel can comprise any fuel that is suitable for combustion in the internal combustion engine, and which adsorbs or absorbs onto or into the sorption medium.
  • the fuel is generally present in the storage vessel in a gaseous form and/or in a sorbed state but due to compression, also small amounts of liquid can occur.
  • the fuel comprises methane and/or hydrogen to an extent of more than 70 vol.-%.
  • the invention further relates to a vehicle comprising the thermoelectric device.
  • the vehicle also comprises a battery and/or an electric motor.
  • the invention also relates to a use of a thermoelectric device according to the invention for generating electricity from heat of exhaust gas, preferably in a motor vehicle such as an automobile, truck or three-wheeler.
  • the thermoelectric device is used in the motor vehicle, when the temperature of is hot side is at least 400 °C, more preferably at least 500 °C. Generally, this is not the case directly after starting the internal combustion engine but when the internal combustion engine is running at preferably at least 50 % of its full load, more preferably at least 60 %.
  • thermoelectric device for cool- ing a storage vessel during filling.
  • the thermoelectric device may be used in reverse for preheating the exhaust gas system or the exhaust gas catalyst, in case the micro heat exchanger comprises a washcoat, during a cold start of an internal combustion engine and simultaneously for cooling the storage vessel in order to reduce the time required for filling the storage vessel with the fuel.
  • a voltage difference is applied to the thermoelectric device the storage vessel and/or the sorption medium is cooled.
  • the thermoelectric device is used as a Peltier element.
  • Figure 1 shows a scheme of a vehicle comprising a thermoelectric device according to the invention
  • Figure 2 shows a thermoelectric device comprising p- and n-type pieces
  • FIG 3 shows thermoelectric devices with micro heat exchanger
  • Figure 4 shows a tailpipe with thermoelectric devices and micro heat exchangers and
  • Figure 5 shows another embodiment of a tailpipe with thermoelectric devices and micro heat exchangers.
  • Figure 1 shows a drive system 19, for instance for a hybrid vehicle, having an internal combustion engine 9, an electric motor 17, a battery 15, a storage vessel 1 1 , a heat exchanger 13, a thermoelectric device 1 according to the invention with a hot side 3 and a cold side 5 as well as an exhaust gas system 7.
  • the drive system 19 is equipped with a motor unit 23, which comprises the internal combustion engine 9 and the electric motor 17.
  • Such drive systems 19 are particularly suitable for hybrid vehicles in which both combustion energy and electric energy are utilized for powering the vehi- cle.
  • the internal combustion engine 9 can supply energy to a drive axle 25 of the hybrid vehicle by combustion of a fuel, which is stored in the storage vessel 1 1.
  • the storage vessel 1 1 comprises a sorption medium, preferably metal organic framework material. Additionally or alternatively, the electric motor 17 can apply energy to the drive axle 25 of the hybrid vehicle by means of electric energy stored in a battery 15.
  • the storage unit 27 comprises the storage vessel 1 1 and the battery 15 for storing electric energy.
  • the storage vessel 1 1 is filled with the fuel, which can be fed to the internal combustion engine 9 via a line 3133. The fuel is consumed by the internal combustion engine 9, wherein exhaust gas is produced, which is removed from the internal combustion engine 9 through the exhaust gas system 7. During driving, the fuel is taken off from the storage vessel 1 1 , which leads to a temperature decrease in the storage vessel 1 1 due to desorption of the fuel from the sorption medium.
  • thermoelectric device 1 heats up due to the hot exhaust gas coming from the internal combustion engine 9.
  • the vehicle is further equipped with the thermoelectric device 1.
  • the hot side 3 of the thermoelectric device 1 is thermally coupled to the exhaust gas system 7 and the cold side 5 is thermally coupled to the storage vessel 1 1 by the heat exchanger 13.
  • cool fuel from the storage vessel 1 1 is pumped through the heat exchanger 13. Due to the temperature difference between the storage vessel 1 1 and the exhaust gas system 7, when the internal combustion engine 9 is running, electric energy can be produced by means of the thermoelectric device 1 and for example stored in the battery 15.
  • Figure 2 shows a thermoelectric device 1 comprising p- and n-conducting type pieces 21 , which are connected electrically in series and thermally in parallel.
  • its structure comprises two ceramic plates 35, between which the individual pieces are fitted alternately.
  • Two pieces 21 are in each case contacted electrically conductively via their end faces.
  • various further layers can be provided, which serve as protective layers or as solder layers.
  • An electrical contact between two pieces 21 is established via a metal bridge.
  • FIG. 3 shows thermoelectric devices 1 with a micro heat exchanger 29.
  • Two thermoelectric devices 1 are stapled and in between the two thermoelectric devices 1 a micro heat exchanger 29 is provided.
  • the thermoelectric devices 1 and the micro heat exchanger 29 form an assembly 43.
  • the micro heat exchanger 29 comprises a plurality of continuous channels 31 , which preferably have a diameter of at most 1 mm. Through the channels 31 a second heat transfer medium can flow, which is here a stream of exhaust gas 39.
  • the channels 31 of the micro heat exchanger 29 are preferably coated with a washcoat of a motor vehicle exhaust gas catalyst. Hot sides 3 of the thermoelectric devices 1 are in direct contact and thermally coupled to the micro heat exchanger 29.
  • thermoelectric devices 1 heat entering the channels 31 with the stream of exhaust gas 39 is transferred to the hot sides 3 of the thermoelectric devices 1.
  • Cold sides 5 opposing the hot sides 3 of the thermoelectric devices 1 are thermally coupled to a stream of a further heat transfer medium 41.
  • a cooling liquid for example cooling water
  • the stream of the further heat transfer medium 41 is thermally coupled to a storage vessel 1 1 comprising a sorption medium.
  • the stream of the further heat transfer medium 41 is cooled by the temperature decrease in the storage vessel 1 1 occurring due to desorption, when fuel is taken from the storage vessel 1 1.
  • the directions of the stream of exhaust gas 39 and the stream of the further heat transfer medium 41 are rectangular to each other in this illustrative embodiment.
  • Figure 4 shows a tailpipe 45 with thermoelectric devices 1 and micro heat exchangers 29, which are combined to assemblies 43.
  • a possible flow configuration of an exhaust gas stream 39 through the assembly 43 is shown.
  • the exhaust gas stream 39 is led through the tailpipe 45, which is arranged in a rectangular manner to the assembly 43 and which provides openings towards the micro heat exchangers 29.
  • three assemblies 43 are applied in parallel. After the exhaust gas stream 39 has left the assemblies 43, it is further con- ducted through the tailpipe 45 back to the direction the exhaust gas stream 39 came from.
  • Figure 5 shows another embodiment of a tailpipe 45 with thermoelectric devices 1 and micro heat exchangers 29, which are combined to assemblies 43.
  • an exhaust gas stream 39 is conducted through a tailpipe 45 to the assemblies 43 and through channels 31 of a micro heat exchanger 29.
  • the exhaust gas stream 39 is conducted from the assemblies 43 further in the same direction the exhaust gas stream 39 came from.
  • a storage vessel made of steel with an inner volume of 140 liters comprises a sorption medium with an adsorption enthalpy towards natural gas of 17 kJ/mol.
  • the sorption medium is provided in the storage vessel with a bulk density of 600 g/l and a heat capacity of 1 100 J/(kg * K).
  • 20 g natural gas is ad- sorbed per 100 g sorption medium.
  • the storage vessel provides a cooling capacity of 15 MJ, generated only by the desorption process.
  • the vessel with sorption medium can be heated up to 80°C by use of the thermoelectric device and a cooling capacity from the storage vessel of 15 MJ is possible.
  • a temperature of -10°C can alternatively occur due to conditions of the environment.
  • a cooling capacity of up to 15 MJ is provided due to the desorption process when a vehicle comprising the storage vessel is driven for a time of 100 minutes.
  • An output of 5 kW is possible, relating 30 MJ to 100 minutes.
  • the capacity of 5 kW had to be provided from an alternative cooling system in the vehicle applying for example bigger or more radiators, heat exchangers and other cooling components.
  • thermoelectric material pieces 21 p- and n-conducting thermoelectric material pieces

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

L'invention porte sur un dispositif thermoélectrique (1), qui comprend un côté chaud (3) et un côté froid (5) ; le côté chaud (3) étant thermiquement couplé à un système de gaz d'échappement (7) d'un moteur à combustion interne (9) et le côté froid (5) étant thermiquement couplé à un récipient de stockage (11), et dans lequel un milieu de sorption est disposé dans le récipient de stockage et le récipient de stockage contient un carburant pour le moteur à combustion interne (9). L'invention porte également sur un véhicule et sur une utilisation du dispositif thermoélectrique.
PCT/EP2015/074870 2014-11-11 2015-10-27 Dispositif thermoélectrique WO2016074918A1 (fr)

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CN107672439A (zh) * 2017-08-18 2018-02-09 广东卓梅尼技术股份有限公司 一种氢混合动力集成控制系统
DE102017200524A1 (de) * 2017-01-13 2018-07-19 Siemens Aktiengesellschaft Kühlvorrichtung mit einem Wärmerohr und einem Latentwärmespeicher, Verfahren zum Herstellen derselben und elektronische Schaltung
US10202324B2 (en) 2015-05-04 2019-02-12 Basf Se Process for the preparation of melonal
US10202323B2 (en) 2015-07-15 2019-02-12 Basf Se Process for preparing an arylpropene
US10556801B2 (en) 2015-02-12 2020-02-11 Basf Se Process for the preparation of a dealuminated zeolitic material having the BEA framework structure
US10737944B2 (en) 2015-12-08 2020-08-11 Basf Se Tin-containing zeolitic material having a BEA framework structure
US10766781B2 (en) 2015-12-08 2020-09-08 Basf Se Tin-containing zeolitic material having a BEA framework structure

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10556801B2 (en) 2015-02-12 2020-02-11 Basf Se Process for the preparation of a dealuminated zeolitic material having the BEA framework structure
US10202324B2 (en) 2015-05-04 2019-02-12 Basf Se Process for the preparation of melonal
US10202323B2 (en) 2015-07-15 2019-02-12 Basf Se Process for preparing an arylpropene
US10737944B2 (en) 2015-12-08 2020-08-11 Basf Se Tin-containing zeolitic material having a BEA framework structure
US10766781B2 (en) 2015-12-08 2020-09-08 Basf Se Tin-containing zeolitic material having a BEA framework structure
DE102017200524A1 (de) * 2017-01-13 2018-07-19 Siemens Aktiengesellschaft Kühlvorrichtung mit einem Wärmerohr und einem Latentwärmespeicher, Verfahren zum Herstellen derselben und elektronische Schaltung
CN107672439A (zh) * 2017-08-18 2018-02-09 广东卓梅尼技术股份有限公司 一种氢混合动力集成控制系统
CN107672439B (zh) * 2017-08-18 2020-10-27 广东卓梅尼技术股份有限公司 一种氢混合动力集成控制系统

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