DE102016110062B3 - Reactor for a storage material which absorbs or releases heat with absorption or desorption of a reaction gas, preferably for a metal hydride, process for its production and use as well as filling device - Google Patents

Abstract

The invention relates to a reactor for a storage material, comprising a particular soldered plate heat exchanger (1) having a number of mutually at least substantially parallel plates (3), between which gap channels (4) are defined, wherein the gap channels (4) in a Group of primary gap channels (4a), which are fluidly connected in parallel and together form a primary flow channel, and a group of secondary split channels (4b), which are fluidly connected in parallel and together form a secondary flow channel, and wherein the primary gap channels (4a ) and the secondary gap channels (4b) are arranged alternately with each other, and wherein the primary or the secondary gap channels (4a, 4b) at least partially with a granular, in particular powdered storage material, which absorbs heat absorption or desorption of a reaction gas, preferably a metal ydrid, are filled. Furthermore, the invention relates to a method for producing such a reactor and its use and a filling device (8).

Description

The invention relates to a reactor for a storage material which absorbs or releases heat by absorption or desorption of a reaction gas, preferably a metal hydride, a process for producing such a reactor, and the use thereof. Moreover, the invention relates to a filling device.

Vehicle interior air conditioning presents a major challenge, in particular in the field of electromobility. On the one hand, there is the problem that the use of conventionally electrically operated air conditioning systems can reduce the range of the vehicles, in particular by 35% to 50%. On the other hand, the conventional air conditioning systems require the use of environmentally harmful and sometimes even toxic refrigerants. In light of this, there is a need for alternative air conditioning technologies that can be used primarily in electric or hybrid vehicles but also, for example, in vehicles with conventional internal combustion engines.

The use of storage materials which absorb or release heat by absorption or desorption of a reaction gas, in particular the use of metal hydrides, represents a promising approach in this context. The reaction gas is usually reversibly bound in an exothermic reaction into the storage material. The air conditioning effect is then based on the endothermic reverse reaction with heat absorption from the environment. The drive of such systems takes place in the so-called closed systems by a heat source and in open systems by a pressure difference.

As an example of such storage materials, metal hydrides may be mentioned which are used in particular together with hydrogen as the reaction gas, wherein the gaseous hydrogen is reversibly bound in a metal in an exothermic reaction and the air conditioning effect on the endothermic back-reaction of the resulting metal hydride takes place while absorbing heat from the environment.

Systems for the air conditioning of a vehicle interior based on metal hydride are, for example, from DE 60 2005 004 667 T2 . DE 26 31 359 A1 and US 4 436 539 A known.

However, it has been found that a core aspect of air conditioning based on storage materials, in particular metal hydrides, is the provision of suitable reactors, which on the one hand contain the storage material to which the reaction gas is to be supplied for the reaction or from which the reaction gas has to be removed, and on the other hand Allow heat transfer from or to a heat transfer fluid. In order to develop systems that are as efficient and safe as possible, two aspects have to be considered when designing the reactors.

On the one hand, the storage materials, in particular metal hydrides, have a comparatively low thermal conductivity of about 1 W / mK, which is why, in compact systems with a high specific power, in particular with regard to mobile use, the shortest possible transport paths from the storage material reaction bed to the heat transfer fluid are realized should. However, the storage material, in particular metal hydride, expands during the reaction, in particular hydrogenation, which conflicts with this design feature. The extent may be in the range of 10% to 35%. As a result, comparatively large forces act on the reactor wall and resulting stresses can lead to deformation and possibly to damage of the reactor or of an overall system comprising this. This may be accompanied by the exit of the reaction gas, in particular hydrogen and thus a potential hazard to the environment.

The expansion of metal hydrides is described in the article "Experimental investigation of the swelling / shrinkage of a hydride bed in a cell during hydrogen absorption / desorption cycles" by B. Charlas, O. Gillia, P. Doremus and D. Imbault, Int. J. Hydrogen Energy, 2012 treated.

The article "Metal hydride based heating and cooling systems: A review" by P. Muthukumar and M. Groll, Int. J. Hydrogen Energy, 201, which also discusses the application of the air conditioning of a vehicle interior. It can be seen from this publication that comparatively high specific powers are determined not only by the material properties of the hydrides used, but above all by a suitable reactor design. Low cycle times, both small dimensions and a low weight of serving as a refrigerator reactors can be achieved. This is of considerable importance with regard to mobile applications. From the publication, inter alia, a shell-and-tube heat exchanger with a metal hydride bed, through which the tube bundle to be flowed through by a heat transfer fluid, emerges as the reactor. At these reactors, however, it is sometimes considered disadvantageous that shell-and-tube heat exchangers are comparatively expensive. Also, the technology was demonstrated and demonstrated only on a laboratory scale.

Therefore, despite efforts to date, there is still a need to provide reactors with improved properties.

Starting from the prior art, it is an object of the present invention to provide a reactor of the type mentioned, which is characterized by a high specific power and a low cycle time and at the same time can be produced comparatively simple and inexpensive. In addition, it is an object of the invention to provide a method for producing such a reactor.

This object is achieved by a reactor for a storage material which absorbs or releases heat by absorption or desorption of a reaction gas, preferably for a metal hydride, comprising a particular soldered plate heat exchanger having a number of mutually at least substantially parallel plates, between them Cleavage channels are defined, wherein the gap channels are divided into a group of primary gap channels, which are fluidly connected in parallel and together form a primary flow channel, and a group of secondary gap channels, which are connected in parallel in flow and together form a secondary flow channel, and wherein the primary Gap channels and the secondary gap channels are arranged alternately with each other, and the primary flow channel having a primary inlet and a primary drain port and the secondary flow channel with a secondary supply and a secondary ren drain port is connected, and wherein the primary or the secondary gap channels at least partially filled with a granular, in particular powdery storage material which receives under absorption and desorption of a reactant gas or emits heat, preferably are filled a metal hydride.

In other words, the basic idea of the present invention is to use a plate heat exchanger as a reactor for a granular, in particular pulverulent, storage material.

Heat exchangers, also known as heat exchangers, include a primary and a secondary flow channel which are physically separate but thermally coupled together. In a plate heat exchanger, the two flow channels are each formed by a plurality of side by side or superimposed, flow-parallel connected primary or secondary gap channels, wherein the primary and secondary gap channels alternate. In the conventional operation, which is known from the prior art, heat transfer fluid flows through both the primary and secondary slot channels, and there is an efficient exchange of thermal energy between the fluid flowing through the primary and secondary fluid channels. For the supply and removal of heat transfer fluid in the primary and secondary flow channel usually a primary and a secondary inlet and outlet connection is provided and these are connected to the respective flow channel. The primary or secondary inlet and outlet connection can be arranged in particular at opposite end regions of the primary or secondary flow channel.

According to the invention, not all of the gap channels are to be flowed through by a heat transfer fluid during operation, but there is a storage material, which is preferably a metal hydride, in one of the two flow channels. For example, in particular all primary gap channels or all secondary gap channels of the plate heat exchanger are at least partially filled with storage material. For example, the primary or the secondary gap channels are each filled to about 90 or 95% with the granular, in particular powdered storage material, that is, for example, 5 to 10% of the volume of each gap channel remain free of granular, especially powdered storage material. It should be noted that the porosity of the memory material in the uncompressed state, for example, may be about 70%, so this may have an air content of 70%, so that the actual resulting degree of filling is well below, for example, 90%.

The other flow channel, however, remains free of the storage material and is to flow through during operation of a heat transfer fluid, in particular, while the endothermic back-reaction takes place while absorbing heat from the environment, whereby the heat transfer medium is cooled. Whether the storage material is provided in the primary or the secondary flow channel of the plate heat exchanger plays - especially in a completely symmetrical configuration - not matter.

Since the storage material expands during the absorption-desorption cycles and comparatively high operating pressures of, for example, 30 bar can occur, according to the invention soldered plate heat exchangers are preferably used. These offer not only a relatively high strength, by which it is possible comparatively large pressure changes without Damage to survive, the further advantage of a particularly high density, which is in the use of hydrogen as a reaction gas of great importance.

The reactor according to the invention can preferably be used in a vehicle, in particular electric or hybrid vehicle, as the thermochemical refrigerating machine of the air conditioning system for the vehicle interior.

A metal hydride, for example Hydralloy C5 (a TiMn alloy) or a LaNi alloy (for example LaNi4.75Al0.25) can be used as the storage material, the dehydrogenation of the metal hydride as a reaction type, in particular for cooling a heat transfer fluid flowing through the other flow channel of the heat exchanger is used. In addition to metal hydrides, other storage materials can be used. According to the invention, it is possible in particular to use any type of gas-solid reaction in which short loading or unloading times and thus preferably low gap thicknesses are desired. In addition to the dehydrogenation of metal hydrides with an example reaction of MgH ₂ ⇌ Mg + H ₂ and a temperature range of the indicated reaction of 200-400 ° C are purely exemplary of other possible types of reactions, the dehydration of metal hydroxides with an example reaction of Mg (OH) ₂ ⇌ MgO + H ₂ O and a temperature range of the indicated reaction of 250-300 ° C, the decarboxylation of metal carbonates with an example reaction of MgCO ₃ ⇌ MgO + CO ₂ and a temperature range of the indicated reaction of 350-450 ° C, reforming processes with an example reaction of CH ₄ + H ₂ O ⇌ CO + 3H ₂ and a temperature range of the indicated reaction of 700-1000 ° C, gas dissociation (catalytic) with an example reaction of 2SO ₃ ⇌ 2SO ₂ + O ₂ and a temperature range of the indicated reaction of 500-900 ° C, the deoxygenation of metal oxides with an example reaction of BaO ₂ ⇌ BaO + 0.5O ₂ and a temperature range of the indicated Reak tion of 750-850 ° C or the dehydration of salt hydrates with a sample reaction of SrBr ₂ · 1H ₂ O ⇌ SrBr ₂ + 1H ₂ O and a temperature range of the displayed response of 150-300 ° C mentioned.

The use according to the invention of a plate heat exchanger as a reactor for a storage material, in particular as a metal hydride reactor, offers numerous advantages. On the one hand, plate heat exchangers are comparatively inexpensive, in particular within the same power classes, considerably cheaper than tube bundle heat exchangers, for example, while at the same time having a high specific / volumetric power density. In addition, plate heat exchangers are characterized by a significantly lower pressure loss on the part of the heat transfer fluid. This makes it possible, with the same pump power to improve the heat transfer fluid side and to increase the specific or volumetric performance, especially if a plate heat exchanger is used, the plates are not flat, but have a wave-shaped profile, whereby the turbulence of the heat transfer fluid is increased when it flows through the primary or secondary flow channel and the heat transfer is improved. Also, this type of heat exchangers, in which the thickness of the gap channels, for example, in the order of a few millimeters, for example 1.5 to 2 mm may be, while the plate length or plate width, for example, in the order of a few tens or a few centimeters, for example 10th can be up to 15 cm or 5 to 10 cm, volume-related, the highest heat-transmitting surface.

In tests of the Applicant has been found that under the inventive use soldered plate heat exchangers as metal hydride reactors - depending on the boundary conditions - cycle times of 60 seconds and specific power of 1300 W / kg _{metal hydride} can be achieved. This illustrates the excellent suitability of relatively inexpensive plate heat exchangers as reactors for the metal hydride-based air conditioning.

An embodiment of the reactor according to the invention is characterized in that the plates have the same outer dimensions, wherein in each plate four, in particular round holes are provided, which are arranged in identical positions in all plates, so that the holes of corresponding locations are aligned and transversely define by the plates and the gap channels extending, in particular cylindrical, primary inlet or outlet channel or secondary inlet or outlet channel. In particular, the holes may be provided in the edge region of the plates. If the plates have a square or rectangular shape, the holes are preferably provided near the four corners of each plate.

Furthermore, it can be provided that in at least one inflow or outflow channel a cylindrical tube-shaped filter cartridge is arranged, which is dimensioned in particular such that it sits positively in the inlet or outlet channel and which is preferably made of a sintered metal. On the one hand, the filter candle prevents the granular, in particular pulverulent, storage material provided in the primary or secondary gap channels from migrating from the gap channels into the primary or secondary inlet or outlet channel and, secondly, sufficient mass transport of the reaction gas through the filter gas-permeable filter candle realized in the respective gap channels. The Filter cartridge is seated to reliably prevent the material migration from the gap channels drainage channel, expediently form fit in the primary or secondary inlet or outlet channel. The filter candle preferably made of a sintered metal can also be welded to the plate heat exchanger, for example with one of the plates or an inlet or outlet connection, for fixing.

A further embodiment is characterized in that in at least one inlet or outlet channel a plurality of superimposed, in particular made of Teflon, Füllscheiben is arranged, the outer contour of the inner contour of the holes in the plates and their thickness in particular the sum of the thickness of two gap channels and corresponds to two plates. The filling disks seated in the inflow or outflow channel have been gradually used in particular in the context of a gap-channel-wise filling process of the primary or secondary flow channel with granular, in particular powdered, storage material, whereby they each have closed a filled gap channel and prevent the finished state of the reactor. analogous to a filter cartridge - in an expedient manner positive fit in the inlet or outlet channel the outlet of the storage material from the gap channels. In this case, the thickness of the filling disks corresponds in particular to the sum of the thickness of two gap channels and two plates, since in the filling process a gap channel in each case filled with storage material and then in the region of that inflow or outflow channel, via which the filling was made, by a Füllscheibe korrespondierender Thickness in the inlet and outlet channel was used. In addition to the closing of the last-filled gap channel, the precipitation discs during the gap-filling process expediently also ensure that the overlying area of the respective inlet or discharge channel up to the next to be filled gap channel whose thickness corresponds to the sum of the intermediate gap channel and a plate , is bypassed. Accordingly, in an advantageous embodiment, they have a thickness which corresponds to the sum of the thicknesses of two gap channels and two plates.

In a further development, the plate heat exchanger further comprises an at least substantially parallel to the plates extending top in which four holes are provided which are aligned with the holes in the plates, and in particular four projecting from the top cylindrical, each embracing a hole Provided connecting pieces, which each form the primary or secondary inlet or outlet port and are preferably provided with an external thread, in particular, the holes in the plates and the holes in the top have the same diameter.

In a particularly advantageous embodiment, the plates of the plate heat exchanger are further aligned vertically and / or the plate heat exchanger associated with a magnetic device by means of which the plate heat exchanger is acted upon or acted upon by a magnetic field. The magnetic device is expediently designed and arranged such that the plate heat exchanger is acted upon by a magnetic field such that the magnetic field resulting Lorentz force is directed to the memory material, in particular metal hydride particles orthogonal to the plates, so that the particles against a the plates defining the respective gap channel are "pressed" and slipping of the particles is prevented. Alternatively, the plate heat exchanger can be subjected to a magnetic field such that the resulting Lorentz force is directed parallel to the plates and opposite to the hydrogen supply in the absorption and the hydrogen removal during desorption, in which case the orientation of the magnetic field when changing from absorption to the desorption would have to be inverted accordingly.

In combination with a vertical orientation of the plates, a supply of the reaction gas from below has proved to be particularly useful. This is preferably done via one of the inlet or outlet connections, which are given for example by provided with an external thread connecting piece. For example, the plate heat exchanger may be cuboid with rectangular, vertically aligned plates and there are provided on a likewise vertically oriented front four connecting pieces, which form the inlet and outlet connection to the primary and secondary flow channel. The supply of the reaction gases is then preferably via the lower connection piece of the filled with storage material flow channel.

Are the plates and thus defined by these gap channels vertically oriented and the reaction gas is supplied from below, is achieved by the cyclic hydrogen supply during absorption and the hydrogen pressure counteracting gravitational force a steady remixing of the storage material, in particular metal hydride, or counteracted a potential accumulation of material ,

Alternatively or in addition to a vertical orientation of the plates and thus gap channels, the plate heat exchanger can also be acted upon by a magnetic field associated therewith a magnetic device. This can on the one hand a material agglomeration, in particular in the air conditioning operation, counteracted and on the other hand, a homogeneous distribution of the storage material, in particular metal hydride, is achieved at the plate surface of a gap channel. In turn, a homogeneous distribution ensures optimum heat transfer from the storage material to the heat transfer fluid flowing through the gap channels of the other flow channel and thus to a maximum specific output. The Lorentz force resulting from the applied magnetic field should expediently be greater than the weight or pressure force.

If the plate heat exchanger subjected to a suitable magnetic field, can be dispensed with a vertical orientation of the plates. Since the storage material is held magnetically in the gap channels in this case, can also be dispensed with filling discs in the inlet or outlet channel of the filled with the storage material flow channel.

Furthermore, it can be provided that the plates have a corrugated profile, whereby the turbulence of the heat transfer fluid is increased when it flows through the gap channels defined by the plates. This in turn improves the heat transfer from the storage material to the heat transfer fluid or vice versa.

Another object of the invention is the use of a reactor according to the invention as a thermochemical refrigerator, in particular for the air conditioning of the interior of a vehicle, preferably electric or hybrid vehicle.

• – ein Wärmeübertrager, der einen primären Strömungskanal, welcher mit einem primären Zu- und einem primären Ablaufanschluss verbunden ist, und einen sekundären Strömungskanal, welcher mit einem sekundären Zu- und einem sekundären Ablaufanschluss verbunden ist, aufweist, wird bereitgestellt,
• – ein granulares, insbesondere pulverförmiges Speichermaterial, welches unter Absorption bzw. Desorption eines Reaktionsgases Wärme aufnimmt bzw. abgibt, insbesondere ein Metallhydrid, wird bereitgestellt, und
• – der primäre oder der sekundäre Strömungskanal des Wärmeübertragers wird zumindest teilweise mit dem Speichermaterial befüllt, indem das Speichermaterial über den primären Zu- oder Ablaufanschluss bzw. den sekundären Zu- oder Ablaufanschluss in den primären bzw. sekundären Strömungskanal eingebracht wird, während an demjenigen Anschluss, über welchen die Einbringung erfolgt, ein Überdruck angelegt wird, insbesondere durch Zufuhr eines unter Druck stehenden Inertgases, und/oder während an dem anderen Anschluss des Strömungskanals, der mit dem Speichermaterial befüllt wird, ein Unterdruck angelegt wird, insbesondere unter Verwendung einer Vakuumpumpe.

The above-mentioned second object is achieved by a method for producing a reactor for a storage material which absorbs or releases heat while absorbing or desorbing a reaction gas, in particular for a metal hydride, preferably for producing a reactor according to the present invention, comprising the steps

• A heat exchanger having a primary flow channel connected to a primary inlet and a primary drain port and a secondary flow channel connected to a secondary inlet and a secondary drain port is provided,
• A granular, in particular powdery, storage material which absorbs or gives off heat by absorption or desorption of a reaction gas, in particular a metal hydride, is provided, and
• The primary or the secondary flow channel of the heat exchanger is at least partially filled with the storage material by the storage material is introduced into the primary or secondary flow channel via the primary inlet or outlet port or the secondary inlet or outlet port, while at that terminal, via which the introduction takes place, an overpressure is applied, in particular by supplying a pressurized inert gas, and / or at the other terminal of the flow channel, which is filled with the storage material, a negative pressure is applied, in particular using a vacuum pump.

It has been found that a granular, in particular powdery, storage material, preferably a metal hydride, can be introduced into the flow channel of an already manufactured heat exchanger in a particularly efficient and at the same time comparatively simple manner by supplying the storage material to the flow channel, while a pressure gradient in this prevails. About the pressure gradient, the storage material in the possibly narrow or complex shaped flow channel, reliably and particularly evenly introduced and clogging of the flow channel during the filling process is reliably avoided.
It also prevents the formation of material accumulations, which can lead to damage to the reactor during operation.

By carrying out the method according to the invention, it is possible, in particular, to fill the gap channels of a plate heat exchanger with them, despite the generally small gap thicknesses of, for example, a few millimeters and the agglomeration tendency of the granular, in particular pulverulent, storage materials. As a result, it becomes possible to use plate heat exchangers as reactors for a storage material such as metal hydride.

For the generation of the pressure gradient, an overpressure is applied according to the invention, in particular at that connection of the flow channel via which the storage material is supplied thereto. The overpressure is obtained in an advantageous embodiment in that the connection, via which the introduction of the storage material takes place, a pressurized inert gas is supplied. This can be realized, for example, by connecting this connection directly or indirectly with a compressed gas cylinder filled with the inert gas.

Alternatively or additionally, a negative pressure can be applied to the other connection of the flow channel. A negative pressure may be obtained using, for example, a vacuum pump which is connected to the other port.

For example, the storage material can be introduced into the primary flow channel via the primary feed connection, while the feed connection is connected to a compressed gas cylinder containing an inert gas and / or while the primary discharge connection is connected to an operating vacuum pump.

If, for example, a sufficiently high overpressure can be achieved, the generation of a negative pressure can also be dispensed with.

For example, if a metal hydride is used as a storage material, the use of an inert gas is particularly useful, since under reaction with air can form a permanent oxide layer on the metal hydride, which inhibits the reaction with hydrogen.

In an expedient embodiment, the steps of the process according to the invention for producing a reactor are carried out completely under an inert gas atmosphere, for example in a closed chamber.

The introduction of the storage material into one of the flow channels of the heat exchanger can preferably be carried out using a suitable filling device having, for example, a feed tube or the like, via which the granular, in particular pulverulent storage material can be introduced into the primary or secondary flow channel. If a plate heat exchanger is provided in the context of the inventive method, the storage material is introduced into the primary or secondary gap channels, in particular using a filling device with a feed tube, which is introduced for the gap channel-wise storage material supply in an inflow or outflow channel extending transversely through the plates and gap channels can be.

According to a particularly advantageous embodiment of the method according to the invention, it is provided that the storage material, before it is introduced into the primary or secondary flow channel of the heat exchanger, is pre-cycled by undergoing several absorption-desorption cycles, in particular 20 to 30 absorption-desorption cycles , The pre-cycling, ie carrying out several absorption-desorption cycles before introduction into the heat exchanger, can take place in particular in at least one pre-cycling reactor provided for this purpose.

Storage material beds, in particular metal hydride beds, expand in each absorption cycle and fall together again upon desorption. The expansion during the absorption in the first cycle is the strongest and then gradually decreases with further cycles. For example, in a titanium-manganese alloy, the volume change upon activation, ie, the first cycle, breaking up the existing oxide layer is up to 20%. In this case, considerable forces act on the wall of the container in which the activation takes place, which are caused by the particle decomposition of the metal hydride during the activation process. If the activation takes place only after the storage material has already been introduced into the heat exchanger in the manner according to the invention, damage to the heat exchanger can occur in the worst case. Therefore, in a particularly preferred embodiment of the method according to the invention, since the volume change decreases as the number of cycles increases with increasing number of cycles, and approaches an asymptotic value, the storage material, in particular metal hydride, undergoes a plurality of absorption-disoption cycles before it is introduced into the heat exchanger , In this way it is achieved that the volume changes occurring in the heat exchanger are reduced and thus damage to the heat exchanger can be reliably prevented.

The pre-cycling according to this particularly preferred embodiment offers yet another advantage. As a result of the preceding cycling, the initially comparatively large particles of the storage material, in particular metal hydride, which may for example initially have diameters of up to 20 mm, disintegrate into particles of smaller dimensions, which are filled considerably more easily, if at all, into the flow channel of a heat exchanger can. In particular, in the event that it is the heat exchanger to a plate heat exchanger, the gap channels thicknesses in the range of only a few millimeters, z. B. 15 mm, the pre-cycling offers a significant advantage for the subsequent filling.

Since the volume change is greatest during the first cycles, the pre-cycling of the storage material conveniently takes place in a dedicated pre-cyclic reactor characterized by a strength which exceeds that of the heat exchanger of the reactor according to the invention.

In a further advantageous embodiment of the method according to the invention is a particular brazed as a heat exchanger A plate heat exchanger provided comprising a number of mutually at least substantially parallel plates, between which gap channels are defined, wherein the gap channels in a group of primary gap channels, which are connected in parallel in fluid and form the primary flow channel, and a group of secondary gap channels, the flow are connected in parallel and together form the secondary flow channel, are divided, and wherein the primary gap channels and the secondary gap channels are arranged alternately with each other, in particular the memory material is successively introduced into the primary gap channels or successively in the secondary gap channels.

The plates of the heat exchanger provided have then in particular the same outer dimensions, wherein in each plate four, in particular round holes are provided, which are arranged in identical positions in all plates, so that the holes of corresponding locations are aligned and a transversely through the plates and the Define gap channels extending, in particular cylindrical primary inlet or outlet channel or secondary inlet or outlet channel.

The storage material is preferably introduced by means of a filling device, in particular successively in the primary or secondary gap channels comprising a feed tube whose outer diameter is adapted to the inner diameter of aligned holes in the plates and the top, wherein the feed tube for the filling operation by the primary or secondary Zu - or drain port is introduced into the primary or secondary inlet or outlet channel.

• – das Zuführrohr wird zur Befüllung des untersten Spaltkanals, welcher von der Oberseite am weitesten entfernt liegt, soweit in den primären oder sekundären Zu- oder Ablaufkanal eingeführt, bis der wenigstens eine Abstandssteg an der der Unterseite des Plattenwärmeübertragers zugewandten Stirnseite des Zu- oder Abführkanals in Anlage kommt,
• – in diesem Zustand wird eine vorgegebene Menge Speichermaterial über das Zuführrohr in den untersten Spaltkanal eingebracht,
• – anschließend wird das Zuführrohr aus dem für den Befüllvorgang verwendeten Zu- oder Ablaufkanal entfernt,
• – in denjenigen Abschnitt des für den Befüllvorgang verwendeten Zu- oder Ablaufkanals, welcher sich im Bereich des untersten Spaltkanals erstreckt, wird eine insbesondere aus Teflon bestehende Füllscheibe, deren Außenkontur der Innenkontur der Löcher in den Platten und deren Dicke insbesondere der Summe der Dicke zweier Spaltkanäle und zweier Platten entspricht, eingesetzt,
• – anschließend wird das Zuführrohr erneut in den für den Befüllvorgang verwendeten Zu- oder Ablaufkanal eingeführt und zwar so weit, bis der wenigstens eine Abstandssteg an der Oberseite des Füllkörpers in Anlage kommt,
• – in diesem Zustand wird eine vorgegebene Menge Speichermaterial über das Zuführrohr in den drittuntersten Spaltkanal eingebracht,
• – anschließend wird das Zuführrohr aus dem für den Befüllvorgang verwendeten Zu- oder Ablaufkanal entfernt,
• – in denjenigen Abschnitt des für den Befüllvorgang verwendeten Zu- oder Ablaufkanals, der sich im Bereich des drittuntersten Spaltkanal erstreckt, wird eine weitere insbesondere aus Teflon bestehende Füllscheibe, deren Außenkontur der Innenkontur der Löcher in den Platten und deren Dicke insbesondere der Summe der Dicke zweier Spaltkanäle und zweier Platten entspricht, eingesetzt, und
• – die vorgenannten Schritte werden gegebenenfalls noch so oft wiederholt bis sämtliche primären oder sämtliche sekundären Spaltkanäle mit einer vorgegebenen Menge Speichermaterial befüllt sind.

In a particularly advantageous development, a filling device with a feed tube is used, from which one end face protrudes at least one spacer web in the axial direction, preferably at least two spacer webs protrude in the axial direction, wherein the extension of the Abtandsstegs or the spacer webs in the axial direction corresponds to the thickness of a gap channel , and wherein the following steps are performed:

• - The feed tube is to fill the lowest gap channel, which is furthest away from the top, as far as introduced into the primary or secondary inlet or outlet channel until the at least one spacer bar on the underside of the Plattenwärmeübertragers facing end of the supply or discharge channel in Plant comes
• - In this state, a predetermined amount of memory material is introduced via the feed tube in the lowest gap channel,
• Subsequently the feed tube is removed from the inlet or outlet channel used for the filling process,
• - In that section of the inflow or outflow channel used for the filling, which extends in the region of the lowest gap channel, a particular Teflon existing filling disk whose outer contour of the inner contour of the holes in the plates and their thickness, in particular the sum of the thickness of two gap channels and two plates, when inserted,
• - Subsequently, the feed tube is again introduced into the inlet or outlet channel used for the filling and that until the at least one spacer bar comes into contact at the top of the packing,
• - In this state, a predetermined amount of memory material is introduced via the feed tube in the third lowest gap channel,
• Subsequently the feed tube is removed from the inlet or outlet channel used for the filling process,
• In the section of the inflow or outflow channel used for the filling process, which extends in the region of the third lowermost split channel, a further filling plate, in particular made of Teflon, whose outer contour of the inner contour of the holes in the plates and their thickness, in particular the sum of the thickness of two Splitting channels and two plates corresponds, used, and
• - The above steps are optionally repeated until all primary or all secondary gap channels are filled with a predetermined amount of storage material.

In particular, an inventive filling device described below is used.

• – einen Rohr-förmigen, bevorzugt Zylinderrohr-förmigen Grundkörper,
• – ein in dem Grundkörper angeordnetes Zuführrohr, dessen Außenkontur an die Innenkontur des Grundkörpers angepasst ist und welches in dem Grundkörper in axialer Richtung derart bewegbar ist, dass es in eine Position gebracht werden kann, in welcher es aus dem einen Ende des Rohr-förmigen Grundkörpers herausragt,
• – einen sich an dem anderen Ende des Rohr-förmigen Grundkörpers in axialer Richtung anschließenden Düsenkörper, der einen Düseninnenraum mit einem sich in Richtung des Grundkörpers kegelförmig verjüngenden Abschnitt und einem Verbindungskanalabschnitt, welcher den sich verjüngenden Abschnitt mit dem Innenraum des Grundkörpers verbindet, umfasst, und der wenigstens eine seitliche, in den Düseninnenraum mündende Zuführöffnung für ein Inertgas aufweist, und
• – einen Trichterkörper, der sich an der von dem Grundkörper abgewandten Seite in axialer Richtung an den Düsenkörper anschließt und einen Trichterinnenraum umfasst, der einen mit dem Düseninnenraum verbundenen, sich in Richtung des Düsenkörpers verjüngenden Abschnitt aufweist.

Another object of the present invention is a filling device for filling the gap channels of a particular soldered Plattenwärmeübertragers with a granular, in particular powdered storage material which absorbs or releases heat absorption or desorption of a reaction gas, preferably with a metal hydride comprising

• A tube-shaped, preferably cylindrical tube-shaped basic body,
• - A arranged in the body feed pipe whose outer contour is adapted to the inner contour of the base body and which is movable in the base body in the axial direction such that it can be brought into a position in which it from the one end of the tube-shaped base body protrudes,
• - One at the other end of the tube-shaped body in the axial direction adjoining nozzle body having a nozzle interior with a conically tapering in the direction of the body portion and a connecting channel portion which connects the tapered portion with the interior of the body, and having at least one lateral, opening into the nozzle interior feed opening for an inert gas, and
• - A funnel body, which adjoins the side facing away from the base body in the axial direction of the nozzle body and comprises a funnel interior having a nozzle connected to the interior, tapering in the direction of the nozzle body portion.

It has been shown that a filling device designed in the manner according to the invention is particularly suitable for filling the gap channels of a plate heat exchanger at least partially with a granular, in particular pulverulent, storage material.

For this purpose, the filling device, preferably the base body, is advantageously connected to one of the four connecting pieces of a plate heat exchanger to be filled and the supply tube movably held in the base body is moved into those inflow or outflow channel which extends below the relevant connecting piece and at least substantially transversely the plates and thus gap channels runs, introduced. Storage material, which is introduced into the funnel body of the filling device, in particular from above, is poured through the nozzle body, the base body and the feed tube to the primary or secondary gap channel to be filled, in a first step in particular to the lowest of the primary or secondary Split channels, which is furthest away from the connecting piece. If the lowest primary or secondary gap channel has been filled, a filling disc is used according to the invention in the respective channel and then the next, lying on the lowest primary or secondary gap channel primary or secondary gap channel can be filled. Since each between two primary slit channels is a - not to be filled - secondary, which is to be skipped, or vice versa, following the filling of the lowest gap channel that of the third lowest, then the fifth lowest and so on, until the colonel or ever whether an even or odd number of gap channels is present, the second gap channel has arrived from above and all primary or all secondary gap channels are filled with storage material.

The supply opening for an inert gas provided in the nozzle body is expediently connected to an inert gas pressure bottle during a filling operation, whereby according to the invention a pressure gradient is obtained in the flow channel formed by the gap channels.

With the help of the pressure difference is thereby reliably prevented that the gap channel becomes clogged during the filling process.

The feed tube of the filling device according to the invention has, in an expedient embodiment, a length in the range of 5 to 50 cm, in particular 10 to 30 cm, preferably 10 to 20 cm. These dimensions make it possible, in particular, to achieve all of the gap channels of a plate heat exchanger having a total thickness in this range, if the feed tube for a gap channel filling in a transverse to the plates extending inlet or outlet channel, which is preferably defined by aligned holes in the plates is introduced.

In a further development of the filling device according to the invention it is provided that at least one in the axial direction of the feed tube projecting spacer web is provided at the end remote from the nozzle body, in particular two projecting in the axial direction of the feed tube spacer webs are provided whose axial extent in particular 0, 5 to 5 mm, preferably 1 to 2.5 mm.

By using the feed tube with at least one, preferably two spacer webs, a targeted filling of only one gap channel with a defined, predefined amount of metal hydride can take place. If two, in particular, opposing spacer webs are provided, two openings, in particular of equal size, are produced in the radial direction, via which the defined filling of exactly one gap channel can take place. The overlying gap channels are closed by the feed tube and are not filled at the same time with storage material.

Furthermore, means may be provided for closing the connecting channel section, which in particular comprise a radial threaded bore opening into the connecting channel section and a threaded pin screwed or screwed into the threaded bore or a threaded screw screwed or screwed into the threaded bore. It is thus achieved that storage material, which was introduced into the filling device via the funnel body, in particular was poured in, initially does not enter the base body and the feed tube but remains in the nozzle body. In this state, an overpressure can then be applied, in particular via the inlet opening provided for an inert gas in the nozzle body, and the storage material can be opened by opening the connecting channel section Body and the feed tube are selectively introduced into a gap channel of the plate heat exchanger.

The funnel body and the nozzle body are connected to each other in an advantageous embodiment via a pipe-shaped, in particular cylinder tube-shaped connecting body, in which a fitting, in particular a ball valve is provided. The ball valve serves the purpose of being able to seal the interior of the nozzle body against the environment before the overpressure is applied, after a predetermined amount of storage material has been introduced into the filling device according to the invention via the funnel body.

According to a further embodiment, the tube-shaped base body is provided at its free end portion with an internal thread. This embodiment makes it possible to connect the filling device in a particularly simple manner for a filling process with a plate heat exchanger. These wise usually for the primary and the secondary flow channel in each case two connecting pieces, which are provided with the one Außengwinde to unscrew connecting lines for the supply of a heat transfer fluid to this. If the base body is provided with an internal thread which is designed to correspond to the external thread of the connecting piece, it can be screwed onto a connecting piece of the plate heat exchanger in a convenient manner, in order to introduce the storage material into the gap channels by means of this.

Finally, the filling device according to the invention can be characterized in that the nozzle body at its end facing the base body has a projection whose outer contour is adapted to the inner contour of the pipe-shaped base body and on which the base body is attached.

If a plate heat exchanger is filled with a storage material while carrying out the method according to the invention and using a filling device according to the invention, the entire filling process can be carried out under an inert gas atmosphere, for example in a sealed chamber, which in particular pre-cycled storage material in several, the number of filling gap channels corresponding separate containers are provided, each containing just the amount of storage material, which is provided for a gap channels. Then, for the filling of each gap channel, one of the containers can be connected to the filling device, in particular the funnel body, and via the application of the overpressure with a pressurized inert gas, an inert gas atmosphere is created only in the container containing the storage material, in the filling device and in the Plate heat exchanger generated.

Thus, in this case, the containers with the storage material exchanged without the action of foreign gas and the filling discs can be used after filling each gap channel in one of the inlet or outlet channels of Plattenwärmeübertragers also without the action of foreign gas, a lock with two valves between the Containers and the filling provided.

If a plurality of containers is provided, each of which contains the amount of storage material provided for a gap channel, the containers may in particular be pre-cycled reactors in which the pre-cyclization of the storage material has been carried out.

It has proven to be particularly advantageous if the primary or the secondary flow channel forming primary or secondary gap channels of a particular soldered Plattenwärmeübertragers are performed by carrying out the inventive method and use of a filling device according to the invention with the granular, in particular powdered storage material. This ensures that, despite the comparatively small gap thicknesses, a particularly efficient and rapid filling with the storage material can take place, at the same time achieving particularly uniform and permanent material distribution in each of the gap channels, which in turn counteracts material accumulation and potentially damaging the reactor becomes.

In a particularly advantageous embodiment, a reactor according to the invention with a preferably soldered plate heat exchanger, the primary or secondary gap channels were filled while carrying out the method and use of the filling device according to the invention with a particular pre-cycled storage material, aligned in operation so that the plates are oriented vertically and / or the plate heat exchanger is acted upon via a magnetic device associated therewith with a magnetic field.

Another object of the invention is a vehicle, in particular electric or hybrid vehicle, which comprises a reactor according to the invention. This then preferably serves as a thermochemical refrigeration machine for the air conditioning of the vehicle interior.

In the drawing, the invention with reference to an embodiment is illustrated in more detail. In a purely schematic representation:

1 a sectional view through a plate heat exchanger,

2 a view of the plate heat exchanger 1 .

3 the plate heat exchanger from the 1 and 2 during the filling according to the invention with a metal hydride using a filling device according to the invention,

4 an enlarged sectional view of the filling device according to the invention 3 .

5 an enlarged external view of the filling device according to the invention from the 3 and 4 .

6 an illustration of the gap-wise filling operation of the plate heat exchanger from the 1 to 3 with metal hydride using the filling device according to the invention,

7 a graph showing the percentage change in volume of the memory material as a function of the number of cycles passed (without scaling).

The 1 shows in a purely schematic sectional view of a soldered plate heat exchanger 1 , as well known from the prior art. In the illustrated embodiment, it is concretely a plate heat exchanger of the series VM of the company VAU.

The plate heat exchanger 1 has a roughly cuboid housing 2 on which - as in the supervision of the plate heat exchanger 1 in 2 recognizable - characterized in horizontal section by rounded corners. Inside the cuboid housing 2 a plurality of at least substantially parallel plates extends 3 between which gap channels 4 are defined. All plates 3 have the same outer dimensions, have an approximately rectangular shape and in the illustrated embodiment, a length of about 30.8 cm, width of about 7.2 cm and thickness of about 13.5 mm. The plates 3 are arranged at a distance of about 1.5 mm to each other, so that thickness of the plurality of gap channels 4 each 1.5 mm. The plates also have a wave-shaped profile, which can not be taken from the figures for reasons of simplified depictability. Due to the wavy profile of the plates 3 can the turbulence of a the slit channels 4 be increased by flowing heat transfer fluid.

The gap channels 4 of the plate heat exchanger 1 are also in a group of primary splitting channels 4a and a group of secondary split channels 4b divided, which are arranged alternately with each other. The in 1 the uppermost split channel is a secondary split channel 4b , the underlying a primary splitting channel 4a and so on. The group of primary splitting channels 4a or the group of secondary gap channels 4b are further connected in parallel in terms of flow and together form a primary or secondary flow channel.

The through the plurality of primary gap channels 4a formed primary flow channel is further with a in the 2 recognizable primary inlet port P1 and a primary outlet port P2 connected. Likewise, the secondary flow channel formed by the plurality of secondary gap channels is connected to a secondary inlet port S1 and a secondary drain port S2.

In every plate 3 There are four round holes each 5 provided, of which two each only in the sectional view 3 can be seen. The four holes 5 are in all plates 3 in identical places, leaving the holes 5 Corresponding bodies - as in 3 recognizable - aligned and each one across the plates 3 and thus the gap channels 4 define extending cylindrical primary or secondary inlet or outlet channel, which are each below the primary and secondary inlet and outlet port P1, S1, P2, S2.

Again 3 can be removed, is in the primary flow channel, which extends below the primary drain port P2, a filter cartridge F, whose outer contour is adapted to the inner contour of the primary flow channel used. The filter candle F is made of a sintered metal.

In the top 2a of the plate heat exchanger 1 are further - as in the plates 3 - four round holes 6 of which in 3 again only two can be recognized. The four holes 6 in the top 2a aligned with the holes 5 in the plates 3 and are each from one of the top 2a protruding cylindrical connecting piece 7 encompassed, which is provided with an external thread. The holes 6 in the top 2a and the holes 5 in the plates 3 are characterized by the same diameter. out.

Both the holes 5 as well as the holes 6 are further - as in 2 recognizable - in the corner areas of the plates 3 or top side 2a of housing 2 arranged. Accordingly, there are primary and secondary inlet and outlet channel respectively in opposite end regions of the primary gap channels 4a or secondary gap channels 4b formed primary or secondary flow channel.

While with the primary inlet channel and the primary outlet channel only the primary gap channels 4a are connected to the secondary inlet channel and the secondary outlet channel, only the secondary gap channels 4b connected. Like in the 3 shown purely schematically, these are those adjacent plates 3 which, for example, a secondary splitting channel 4b define, in the region of the primary inlet and outlet channel connected to each other, for example, soldered together or the like. Analogous to this are - what in 3 not shown - those adjacent plates in the area of the secondary inlet and outlet channels 3 interconnected, which is a primary splitting channel 4a define.

According to the present invention, the in the 1 to 3 illustrated plate heat exchanger 1 filled with a metal hydride to obtain a metal hydride reactor. Specifically, while carrying out the method according to the invention and using a filling device according to the invention, the primary gap channels 4a of the plate heat exchanger 1 with Hydralloy C5 from GfE, a TiMn alloy with the composition Ti0.95Zr0.05Mn1.48V0.43Fe0.08Al0.01 (although the constituents may vary slightly depending on the charge).

For the filling process, the plate heat exchanger 1 from the 1 to 3 provided and a filling device according to the invention 8th will - as in 3 shown - on the connection piece 7 the primary inlet port P1 screwed. Enlarged illustrations of the filling device according to the invention 8th in the section and the outside view can the 4 and 5 be removed. The 4 corresponds to a section along the line AA in 5 ,

The filling device according to the invention 8th comprises a cylindrical tube-shaped base body 9 who, as in 4 recognizable - is provided at its free end with an internal thread. In the main body 9 is a cylindrical feed tube 11 arranged, the outer contour of the inner contour of the body 9 is adapted and which on the body 9 is movable in the axial direction so that it can be brought into a position in which it from the in the 3 and 4 right-pointing end of the body 9 protrudes. A corresponding position can be 3 be removed. At that from the main body 9 outstanding end of the feed tube 11 are two in the axial direction of the feed tube 11 protruding, opposing spacer webs 11a and 11b provided, the axial extent of the thickness of a gap channel 4 of the plate heat exchanger 1 , So in the illustrated embodiment is 1.5 mm. In the 4 is from the feed tube 11 just a section shown so that the spacer bars 11a . 11b are not recognizable there.

At the free end of the opposite end of the cylindrical tube-shaped body 9 , which in the 4 and 5 to the left and in the 3 points upward, joins the main body 9 in the axial direction, a nozzle body 12 at. This is done by two nested nozzle body parts 12a and 12b formed and defines a nozzle interior 13 with one in the direction of the main body 9 cone-shaped tapered section 13a and a cylindrical connecting channel section 13b , the tapered section 13a with the interior of the cylindrical tube-shaped body 9 connects and has an inner diameter which is significantly smaller than that of the cylindrical tube-shaped body 9 , The interior 13 further comprises a first cylindrical portion 13c larger diameter and a second cylindrical section 13d smaller diameter, which is that of the main body 9 side facing away from one another to the conically tapered section 13a connect.

The nozzle body part 12 indicates his in 4 pointing to the right end of a cylindrical tubular projection on which the base body 9 , like in the 4 recognizable, is plugged. In the nozzle body 12 , specifically in the in the 4 further left nozzle body part 12b , is also a side feed opening 14 intended for an inert gas.

In the nozzle body 12 , specifically in the nozzle body part 12a , Further, in the connection channel section 13b opening threaded hole G provided in which a not shown in the figures threaded pin is screwed to the connection between the nozzle interior 13 and the interior of the body 9 to close.

The filling device according to the invention 8th also includes a funnel body 15 with at least substantially cylindrical outer contour, which has a funnel-shaped funnel interior which tapers in the direction of the nozzle body 15a defined, and a substantially cylindrical tube-shaped connecting body 16 , the funnel body 15 with the nozzle body 12 combines. In the connecting body 16 is a fitting, in this case provided a ball valve, of which in the 4 only the lever 17 to open and close is shown. In the schematic representation of the filling device 8th in 3 is the connecting body 16 with the lever 17 not shown.

As already mentioned, in the illustrated embodiment, the primary gap channels forming the primary flow channel 4a filled with powdered metal hydride.

In this case, according to the invention, a pulverulent metal hydride is provided which has been pre-cycled by being subjected to several absorption-desorption cycles in a pre-cyclic reactor, not shown in the figures, for this purpose. Specifically, in the illustrated embodiment, a metal hydride is provided and into the primary gap channels 4a of the plate heat exchanger 1 filled, which has previously undergone 30 absorption-desorption cycles. As the volume change decreases due to the decreasing particle rearrangement with increasing number of cycles, and approaches an asymptotic value, which is due to the unscaled graph 7 , which shows the volume change in percent over the number of cycles, is illustrated purely schematically, is achieved by filling with a pre-cyclized metal hydride that in the plate heat exchanger 1 occurring volume changes are comparatively low and thus damage the heat exchanger 1 reliably prevented. Another advantage of the pre-cycling is that the initially comparatively large particles of metal hydride, which may for example initially have diameters of up to 20 mm, decay through them into particles of smaller dimensions, which are considerably easier in the primary gap channels 4a can be introduced.

The pre-cycled metal hydride is supplied via the primary feed port P1 by means of the filling device 8th into the primary slit channels 4a introduced, while according to the invention at the primary inlet port P1, an overpressure and at the primary outlet port P2, a negative pressure is applied. In the illustrated embodiment, this is achieved by the feed opening 14 in the nozzle body 12 via overpressure line 18 which can be opened and closed by a valve, not shown in the figure, with a gas cylinder containing an inert gas 19 is connected (see. 3 ). At the same time, the primary drain port P2 is with a vacuum pump 21 connected, as in the 3 only indicated purely schematically. Accordingly, arises in the primary gap channels 4a of the plate heat exchanger 1 a pressure gradient, which according to the invention a fast and efficient filling of the primary gap channels 4a with the powdered metal hydride - without adding a single slit channel 4a - allows.

The gap-wise filling of the primary gap channels 4a in the context of the inventive method is in the 6 illustrated schematically.

For the filling of the lowest primary gap channel 4a becomes the feed tube 11 the filling device according to the invention 8th , whose basic body 9 on the connecting piece 7 the primary inlet port P1 is screwed, as far inserted in the primary inlet channel until the two spacer webs 11a . 11b come into contact with the lower face of the primary inlet channel. Since the axial extent of the spacer webs 11a . 11b just the thickness of a gap channel 4 corresponds, ends the feed tube 11 in this position just at the top of the lowest gap channel 4 , as in 6 recognizable on the far left.

In this state is - when the ball valve is open and closed state of the connecting channel section 13b when the threaded screw is screwed into the threaded hole G, a predetermined amount of powdered metal hydride in the funnel-shaped interior 15a of the funnel body 15 the filling device according to the invention 8th given. Then the ball valve is activated by operating the lever 17 closed and both the pressure line 18 as well as the connecting channel section 13b be opened by unscrewing the threaded screw. The metal hydride powder then passes into the body 9 and the feed tube 11 , Because of the spacer bars 11a . 11b radial openings to the lowest gap channel 4 give the metal hydride powder in this, which in the 6 is indicated on the left according to arrows. In this case, by the pressure gradient set according to the invention a fast, efficient and uniform filling of the lowest gap channel 4 allows with the metal hydride, which reliably prevents the gap channel 4a added during the filling process. By using the feed tube 11 with the two spacer bars 11a . 11b and thereby resulting radial openings can be targeted filling only the lowest primary gap channel 4a with a defined amount of pre-cycled metal hydride. The overlying gap channels 4 are closed and therefore not filled with metal hydride.

Is the predetermined amount of metal hydride powder in this inventive way in the lowest primary gap 4a has been introduced, the feed tube 11 removed from the primary inlet channel by being pulled out of this and the filling device 8th is from the spigot 7 unscrewed. In the section of the primary inlet channel, which is in the region of the lowest primary gap channel 4a extends, then a present from Teflon existing filling disc 20 used, in particular by being inserted from above into the primary inlet channel. The filling disc 20 has an outer contour of the inner contour of the holes 5 in the plates 3 corresponds and whose thickness in the present case the sum of the thickness of two gap channels 4 and two plates 3 corresponds to what purely schematically the 6 can be removed.

After the filling disk 20 was used, the filling device 8th back to the primary inlet port P1 defining the connecting piece 7 screwed on, and the feed tube 11 is re-introduced into the primary inlet channel, this time until the spacer bars 11a . 11b at the top of the packing 21 come into contact. In this position, a predetermined amount of powdered pre-cycled metal hydride is again placed in the second lowest primary slit channel 4a let in what is in the 6 again indicated by corresponding arrows.

Subsequently, the feed tube 11 removed from the primary inlet channel and the filling 8th is unscrewed again and a second filling disc 20 Teflon can be used in the primary inlet channel to fill the next, third lowest primary slot 4a as in the third illustration from the left in 6 shown.

These steps are repeated until all primary slit channels 4a of the plate heat exchanger 1 - According to the invention in each case under prevalence of a pressure gradient in the primary gap to be filled - have been filled with pre-cycled metal hydride.

Finally, the filling device according to the invention 8th one last time from the spigot 7 unscrewed and the primary inlet port P1 is provided with a closure 21 with a female thread closed by the spigot 21 is screwed on this. This is in the 6 to recognize on the far right.

The vacuum pump 21 can then be removed from the primary drain port P2 and in operation, this port is used for the hydrogen supply and removal. In this case, the filter cartridge F provided in the primary drainage channel ensures that no metal hydride from the primary gap channels 4a enters the primary drainage channel and at the same time sufficient mass transport into the primary gap channels 4a is realized.

By carrying out the process according to the invention, a reactor according to the invention is obtained which comprises a brazed plate heat exchanger 1 includes, whose primary gap channels 4a are filled with a pre-cyclized metal hydride. The secondary gap channels 4b remain according to the invention free of metal hydride and are flowed through during operation of the reactor by a heat transfer fluid, which in particular via the secondary inlet port S1 and is discharged via the secondary drain port S2. Under supply (absorption) or removal (desorption) of hydrogen via the primary drain port P2 of which the secondary gap channels 4b thereby flowing heat transfer fluid absorbed or released by the metal hydride.

The resulting reactor according to the invention is characterized by a particularly high specific / volumetric power density and, at the same time, is considerably cheaper than, for example, a reactor comprising a shell-and-tube heat exchanger. The pressure loss on the part of the heat transfer fluid is in contrast significantly lower in the reactor according to the invention.

In operation, the reactor according to the invention is advantageously oriented such that the plates 3 of the plate heat exchanger 1 are vertically oriented. The supply and discharge of hydrogen is also ideally carried out from below. The reactor is thus suitably oriented in such a way that the plates 3 are oriented vertically and the primary drain port P2, under which the primary drain passage and thus the filter cartridge F extends, lies below. This is the case when the reactor is placed in the 1 and 2 right side 2 B of the housing 2 is provided. This orientation and feed offers the advantage that a constant remixing of the metal hydride is achieved or a potential accumulation of material is counteracted by the cyclical supply of hydrogen during the absorption and the weight force opposing the hydrogen pressure.

As an alternative to the illustrated embodiment, the plate heat exchanger 1 be associated with a magnetic device, via which it can be acted upon by a magnetic field. In this way, on the one hand, a material agglomeration in air conditioning operation can be counteracted and, on the other hand, a homogeneous distribution of the metal hydride on the plate surface of a gap channel 4 achieved. A homogeneous distribution in turn ensures optimal heat transfer from the metal hydride powder to the secondary gap channels 4b During operation, flowing through heat transfer fluid and thus a maximum specific power. The magnetic device is expediently designed and arranged such that the plate heat exchanger 1 is subjected to such a magnetic field that the Lorentz force resulting from the magnetic field on the metal hydride particles orthogonal to the plates 3 is directed so that the particles against one of the respective gap channel 4 defining plates 3 "Pressed" and slipping of the particles is prevented. The Lorentz force resulting from the applied magnetic field should expediently be greater than the weight or pressure force.

Will the plate heat exchanger 1 applied with a suitable magnetic field, can be based on a vertical orientation of the plates 3 be waived.

Since the memory material in this case, magnetic in the gap channels 4 can also be held on the filling discs 20 dispensed with in the primary inlet channel.

In particular, in this case, both the primary inlet port P1 and the primary outlet port P2 can be used for the hydrogen supply, whereby the mass transfer can be further improved.

The reactor according to the invention can be used in particular in a vehicle, preferably an electric or hybrid vehicle, as a thermochemical refrigerating machine for the vehicle interior of the air conditioning system.

Claims (20)

Reactor for a storage material, which absorbs or releases heat while absorbing or desorbing a reaction gas, comprising a plate heat exchanger (US Pat. 1 ) comprising a number of plates (at least substantially) parallel to each other ( 3 ), between which gap channels ( 4 ), the gap channels ( 4 ) into a group of primary splitting channels ( 4a ), which are fluidly connected in parallel and together form a primary flow channel, and a group of secondary gap channels ( 4b ), which are fluidly connected in parallel and together form a secondary flow channel, are divided, and wherein the primary gap channels ( 4a ) and the secondary gap channels ( 4b ) are alternately arranged with each other, and the primary flow channel having a primary inlet and a primary outlet port (P1, P2) and the secondary flow channel with a secondary inlet and a secondary drain port (S1, S2) is connected, and wherein the primary or the secondary gap channels ( 4a . 4b ) are at least partially filled with a granular storage material which absorbs or releases heat while absorbing or desorbing a reaction gas. Reactor according to claim 1, characterized in that the plates ( 3 ) have the same outer dimensions, wherein in each plate four in particular round holes ( 5 ) provided in all panels ( 3 ) are arranged at identical locations, so that the holes ( 5 ) are aligned and a right through the plates ( 3 ) and the gap channels ( 4 ) extending, in particular cylindrical, primary inlet or outlet channel or secondary inlet or outlet channel define. Reactor according to claim 2, characterized in that in at least one inflow or outflow channel a cylindrical tube-shaped filter cartridge (F) is arranged, which in particular is dimensioned such that it sits positively in the inflow or outflow channel and preferably made of a sintered metal is. Reactor according to claim 2 or 3, characterized in that in at least one inlet or outlet channel a plurality of superimposed, in particular made of Teflon, filling discs ( 20 ) whose outer contour of the inner contour of the holes ( 5 ) in the plates ( 3 ) and their thickness in particular the sum of the thickness of two gap channels ( 4 ) and two plates ( 3 ) corresponds. Reactor according to one of claims 2 to 4, characterized in that the plate heat exchanger ( 1 ) an at least substantially parallel to the plates extending top ( 2a ), in which four holes ( 6 ) provided with the holes ( 5 ) in the plates ( 3 ), and in particular four from the top ( 2a ) projecting cylindrical, in each case a hole encompassing connecting piece ( 7 ) are provided, which each form the primary or secondary inlet or outlet port (P1, P2, S1, S2) and are preferably provided with an external thread, and in particular the holes ( 5 ) in the plates ( 3 ) and the holes ( 6 ) in the top ( 2a ) have the same diameter. Reactor according to one of the preceding claims, characterized in that the plates ( 3 ) are vertically aligned and / or the plate heat exchanger ( 1 ) is associated with a magnetic device by means of which the plate heat exchanger ( 1 ) is acted upon or acted upon by a magnetic field. Use of a reactor according to one of claims 1 to 6 as a thermochemical refrigerator. Process for producing a reactor for a storage material which absorbs or releases heat while absorbing or desorbing a reaction gas, comprising the steps of - a heat exchanger ( 1 ), which has a primary flow channel, which has a primary inlet and a primary outlet connection (P1, P2) is provided, and a secondary flow channel, which is connected to a secondary supply and a secondary drain port (S1, S2) is connected, is provided, - a granular storage material, which absorbs heat or absorption or absorption of a reaction gas, is provided, and - the primary or the secondary flow channel of the heat exchanger ( 1 ) is at least partially filled with the storage material by the storage material via the primary inlet or outlet port (P1, P2) and the secondary inlet or outlet port (S1, S2) is introduced into the primary or secondary flow channel, while on the one Connection (P1, P2, S1, S2), via which the introduction takes place, an overpressure is applied and / or at the other port (P1, P2, S1, S2) of the flow channel, which is filled with the storage material, a negative pressure is created. A method according to claim 8, characterized in that the storage material before it in the primary or secondary flow channel of the heat exchanger ( 1 is pre-cycled by being subjected to several absorption-desorption cycles, in particular 20 to 30 absorption-desorption cycles, wherein the pre-cycling takes place in particular in at least one provided for this purpose Vorzyklier reactor. A method according to claim 8 or 9, characterized in that as a heat exchanger, in particular a soldered plate heat exchanger ( 1 ) comprising a number of plates (at least substantially) parallel to each other ( 3 ), between which gap channels ( 4 ), the gap channels ( 4 ) into a group of primary splitting channels ( 4a ), which are fluidly connected in parallel and together form the primary flow channel, and a group of secondary gap channels ( 4b ), which are fluidly connected in parallel and together form the secondary flow channel, are divided, and wherein the primary gap channels ( 4a ) and the secondary gap channels ( 4b ) are arranged alternately with each other, wherein in particular the storage material successively in the primary gap channels ( 4a ) or successively into the secondary gap channels ( 4b ) is introduced. A method according to claim 10, characterized in that a plate heat exchanger ( 1 ) whose plates ( 3 ) have the same outer dimensions, wherein in each plate ( 3 ) four in particular round holes ( 5 ) provided in all panels ( 3 ) are arranged at identical locations, so that the holes ( 5 ) are aligned and a right through the plates ( 3 ) and the gap channels ( 4 ) extending, in particular cylindrical primary inlet or outlet channel or secondary inlet or outlet channel define. A method according to claim 11, characterized in that the storage material by means of a filling device ( 8th ) in particular successively into the primary or secondary gap channels ( 4a . 4b ), which is a feed tube ( 11 ) whose outer diameter at the inner diameter of aligned holes ( 5 . 6 ) in the plates ( 3 ) and the top ( 2a ), the feed tube ( 11 ) is introduced for the filling process through the primary or secondary inlet or outlet port (P1, P2, S1, S2) in the primary or secondary inlet or outlet channel. Method according to claim 12, characterized in that a filling device ( 8th ) with a feed tube ( 11 ) is used, of which one end face at least one spacer web ( 11a . 11b protrudes in the axial direction, preferably at least two spacer webs ( 11a . 11b protrude in the axial direction, wherein the extension of Abt Abtstegs ( 11a . 11b ) or the spacer webs ( 11a . 11b ) in the axial direction of the thickness of a gap channel ( 4 ), the following steps being carried out: - the feed tube ( 11 ) is used to fill the lowest gap channel ( 4 ), which from the top ( 2a ) is farthest away, as far as introduced into the primary or secondary inflow or outflow channel, until the at least one spacer web ( 11a . 11b ) at the bottom of the plate heat exchanger ( 1 ) facing end of the supply or discharge channel comes into contact, - in this state, a predetermined amount of storage material via the feed tube ( 11 ) in the lowest gap channel ( 4 ) brought in, - then the feed tube ( 11 ) is removed from the inlet or outlet channel used for the filling process, - in that section of the inlet or outlet channel used for the filling process, which in the region of the lowest gap channel ( 4 ) extends, is a particular Teflon existing filling disc ( 20 ) whose outer contour of the inner contour of the holes ( 5 ) in the plates ( 3 ) and their thickness in particular the sum of the thickness of two gap channels ( 4 ) and two plates ( 3 ), then the feed tube ( 11 ) is again introduced into the inflow or outflow channel used for the filling process, namely until the at least one spacer web ( 11a . 11b ) at the top of the packing ( 20 ) comes into contact, - in this state, a predetermined amount of storage material via the feed tube ( 11 ) in the third lowermost splitting channel ( 4 ), then the feed tube ( 11 ) is removed from the inlet or outlet channel used for the filling process, - in that section of the inlet or outlet channel used for the filling process, located in the region of the third lowest gap channel ( 4 ), a further filling disk (in particular consisting of Teflon) is ( 20 ) whose outer contour of the inner contour of the holes ( 5 ) in the plates ( 3 ) and their thickness in particular the sum of the thickness of two gap channels ( 4 ) and two plates ( 3 ), used, and - the above steps are optionally repeated until all primary or all secondary gap channels are filled with a predetermined amount of storage material. Method according to one of claims 8 to 13, characterized in that a filling device ( 8th ) according to one of claims 15 to 20 is used to transfer the storage material into the primary or the secondary gap channels ( 4a . 4b ). Filling device ( 8th ) for filling the gap channels of a plate heat exchanger ( 1 ) with a granular storage material which absorbs or releases heat on absorption or desorption of a reaction gas, comprising - a tube-shaped base body ( 9 ), - one in the main body ( 9 ) arranged feed tube ( 11 ), the outer contour of the inner contour of the body ( 9 ) and which in the body ( 9 ) is movable in the axial direction in such a way that it can be brought into a position in which it can be moved out of one end of the basic body ( 9 ) protrudes, - one at the other end of the basic body ( 9 ) in the axial direction adjoining nozzle body ( 12 ), which has a nozzle interior ( 13 ) with a conically tapering section in the direction of the main body ( 13a ) and a connection channel section ( 13b ), which the tapered section ( 13a ) with the interior of the body ( 9 ), and the at least one lateral, opening into the nozzle interior feed opening ( 14 ) for an inert gas, and - a funnel body ( 15 ), which is at the of the main body ( 9 ) facing away from the nozzle body in the axial direction ( 12 ) and a funnel interior ( 15a ), one with the nozzle interior ( 13 ), in the direction of the nozzle body ( 12 ) has a tapered section. Apparatus according to claim 15, characterized in that on the of the nozzle body ( 12 ) facing away from the feed tube ( 11 ) at least one in the axial direction of the feed tube ( 11 ) projecting spacer bar ( 11a . 11b ) is provided, in particular two in the axial direction of the feed tube ( 11 ) projecting spacer webs ( 11a . 11b ) are provided, the axial extent is in particular 0.5 to 5 mm, preferably 1 to 2.5 mm. Apparatus according to claim 15 or 16, characterized in that means are provided to connect the connecting channel section ( 13b ), in particular one in the nozzle body ( 12 ) provided, in the connecting channel section opening radial threaded bore (G) and in the threaded bore (G) screwed or screwed threaded pin or in the threaded bore (G) screwed or screw threaded screw. Device according to one of claims 15 to 17, characterized in that the funnel body ( 15 ) and the nozzle body ( 12 ) via a pipe-shaped, in particular cylinder tube-shaped connecting body ( 16 ) are connected to each other, in which a fitting, in particular a ball valve is provided. Device according to one of claims 15 to 18, characterized in that the tube-shaped base body ( 9 ) is provided at its free end with an internal thread. Device according to one of claims 15 to 19, characterized in that the nozzle body ( 12 ) at its base ( 9 ) facing end has a projection, the outer contour of the inner contour of the tubular-shaped body ( 9 ) and on which the basic body ( 9 ) is attached.

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