DE102014211278A1 - Compact catalyst test stand and filling it - Google Patents

Abstract

The present invention relates to the use of reactors in which at least one reaction space extends as a turn, preferably of reactors with multiply wound reaction spaces, in particular spirally wound reactor tubes, for testing catalysts, in particular for parallel testing, and a method for filling such Reactors with at least one turn, which are difficult to access and thus difficult to fill with conventional methods, especially when the contents are powdery, in particular a fixed catalyst bed.

Description

The present invention relates to the use of reactors in which at least one reaction space extends as a turn, preferably of reactors with multiply wound reaction spaces, in particular helically wound reactor tubes, for testing catalysts, in particular for parallel testing of catalysts. The present invention also relates to a method for filling such reactors with at least one turn, which are difficult to access and thus difficult to fill with conventional methods, in particular when the contents are powdery, for example in the case of a catalyst fixed bed.

Reactors, in particular reactors with powdery and / or particulate solid filling, in particular fixed-bed filling, as are of relevance for example for catalyst test stands, are characterized according to the prior art in that they are arranged in one plane and parallel to one another , In this case, individual reactors have reactor chambers arranged in a straight alignment (typically vertically "linearly" arranged) which, owing to their arrangement, can be filled, emptied, heated, cooled and controlled comparatively easily.

However, such a "vertical" or "straight" arrangement and shape limits the applications of such reactors in catalyst test stands, especially because a certain "height" of the catalyst bed is always necessary and on the dimensioning of the entire test a great impact has, or is relevant. Especially when catalysts are to be filled and tested on a gram scale or larger scales.

Such parallel arranged in a plane reactors are for example from the DE 198 09 477 known, in which case the rectilinear reactor channels as bores in a solid metal block (possibly with inserts) are present. A method for filling parallel arranged in a plane reactor tubes is from the EP 1 796 897 known.

A corresponding test in "U" -shaped reactors is out Jozsef M. Berty: Experiments in Catalytic Reaction Engineering, Elsevier Science (1999), ISBN 0-444-54137-3, page 31 ff known.

In the light of the known prior art, it is an object of the present invention to provide significantly smaller and / or more compact test stands for catalysts, in particular those having a lower height or installation height, and yet the testing of catalysts in the "gram range" Thus, greater than 0.1 g, preferably greater than 0.2 g, more preferably greater than 0.5 g allow, and also allow an effective parallel testing of catalysts.

This object is achieved by the use of at least one reactor in which at least one reaction space extends as a circle segment ("turn").

Preferably, the reaction space is on a circular arc, or represents a 3-dimensional helical arrangement, which arrangement is preferably helical, i. the radii of the turns of the screw are the same or similar. Archimedean, logarithmic, Fermat or hyperbolic spirals are also preferred, as are three-dimensional arrays such as Archimedean sphere spirals, conical spirals and loxodromes.

Preferably, at least one reactor has at least one multiply wound reaction space, more preferably with at least one spiral wound reactor tube, and is used in a catalyst test stand, this reactor due to its compact dimensions, here due to the "loop-shaped" or "spiral ", in any case, tortuous arrangement, even in a small volume segment, in particular a furnace temperature range, can be integrated, creating a test stand is provided, especially in comparison to the classical design of test reactors space saving, easy to temper because of more homogeneous temperature field and thus saves energy and complex control technology.

With regard to the reaction space, that is to say the volume segment located inside a reactor and to be filled with catalyst, according to the invention there are no restrictions except that it is at least 5 times, preferably at least 10 times, more preferably at least 5 times in the direction of flow of the fluid flowing through the reaction space 100 times larger dimensioned than perpendicular thereto. Particularly preferably, the reaction space is substantially tubular, ie perpendicular to the flow direction characterized by a characteristic diameter, which is then at least 5 times, 10 times or 100 times smaller than the length of the tubular reaction space.

Another advantage of a spiral reaction space is that when operated as a tap reactor all lines of the taps to an analysis unit can easily be made the same length, which automatically ensures that similar pressure drop prevails on the lines and ensures that the residence time of the fluid mixtures in the analysis line for all lines is the same length.

It is particularly preferred that at least two, more preferably at least four, more preferably at least 16 such reactors, in each of which at least one reaction space extends as a turn, be tested in a catalyst test stand parallel to each other, wherein preferably at least on the reactant Side the reaction spaces in fluid communication with each other.

• • zumindest einen Reaktionsraum, der sich als Windung erstreckt, vorzugsweise ausgestaltet als ein mehrfach gewundener Reaktionsraum, vorzugsweise aus- gestaltet als zumindest ein spiralförmig gewundenes Reaktor-Rohr;
• • zumindest eine Einheit zur Analyse, wobei diese Einheit zur Analyse den zumindest einen solchen Reaktionsraum vollständig umschließt, vorzugsweise der Reaktionsraum Bestandteil dieser Einheit zur Analyse ist.

The present object is also achieved by a system comprising:

• At least one reaction space that extends as a turn, preferably designed as a multiply wound reaction space, preferably configured as at least one spiral-wound reactor tube;
• At least one unit for analysis, this unit for analysis completely enclosing the at least one such reaction space, preferably the reaction space is part of this unit for analysis.

Preferably, the system additionally comprises at least one catalyst which is in powder form or in solid particulate form, preferably present as a solid in a solid bed, and introduced into said reaction space. It is in no way excluded that said system can also have multiple catalysts.

The unit of analysis may be any analytical unit commonly used for testing fluid product streams. Examples include: gas chromatograph, mass spectrometer, UV-VIS spectrometer, IR spectrometer. Combinations thereof are especially preferred.

The use according to the invention and the system according to the invention also make it possible to install larger reaction spaces in the immediate vicinity of units for analysis, or even to integrate them in units for analysis, for example to integrate them in GC ovens and to heat them isothermally, and thus analyze them in the immediate vicinity.

The present invention will be described below with reference to further embodiments. The following figures serve the exemplary illustration of the invention.

1 shows a schematic representation of a device with a loop or spiral constructed tap reactor. The illustrated embodiment relates to a tap reactor having three cylindrically shaped turns and ten taps. Connected to the reactor are the filling and the compression tool.

2 shows a schematic representation of an apparatus for filling loop or spiral reactors, in particular comprising a reservoir ( 7 ), which has a funnel-shaped element ( 5 ) with the dosing unit ( 4 ), the dosing unit ( 4 ) over the connection ( 8th ) with the cavity ( 9 ) connected is.

3 shows a schematic representation of another embodiment of the in 2 shown device, which also has a line ( 13 ) having. The administration ( 13 ) causes advantageous pressure equalization between dosing unit and reservoir.

4 shows a schematic representation of a device analogous to the device of 2 and 3 , which as a further element a pressure vessel ( 21 ) and valve ( 23 ), wherein these elements allow a recording of compressed gases to generate gas pressure pulses.

5 shows a fourfold apparatus with four tap reactors ( 61 ) and a manifold or supply rail ( 60 ).

From the field of reactors used to investigate reaction kinetics, curved or helical reaction tubes are known in principle and often have to have a minimum length required for this type of assay, which is the conventional length range of reactors in a range from 0.2 m to 0.8 m. Examples of such reactors are so-called "tap reactor", which have a length in the range of 0.5 m to 10 m and whose inner diameter is in the range of 0.5 mm to 20 mm.

Zapfstellenreaktoren are known from the prior art, for example Solc. Jozsef M. Berty: Experiments in Catalytic Reaction Engineering. 292 pages, Elsevier Science (1999), ISBN 0-444-54137-3, p. 31 et seq

However, such curved or helically extending reaction tubes are not hitherto used in the prior art for testing catalysts, in particular solid-bed catalysts, since it has hitherto not been possible to reproducibly introduce a solid into such difficult-to-reach reaction spaces. In particular, however, for the parallel, ie comparative testing of catalysts, it must be ensured that in each reaction chamber of a parallel arrangement (2, 4, 8, 16, 32 ... reaction spaces) reproducibly the same amount of catalyst in a bed of the same density. If this is not guaranteed, reaction results can not be meaningfully compared.

Catalyst test stands in the sense of the present invention are preferably in "benchscale", so they can be positioned on a laboratory bench. It is particularly preferred that amounts of catalyst in the range of 0.1 g to 1 kg can be handled. The amount of catalyst is preferably in the range from 0.2 g to 500 g, more preferably in the range from 0.3 g to 250 g and in particular in the range from 0.5 g to 100 g. This catalyst is preferably present as a solid pulverulent or particulate substance, in particular as a fixed bed catalyst.

As already mentioned above, for the purposes of the present invention, for the at least one reactor, preferably for an arrangement with 2, 4, 16, 32 or more reactors (for parallel testing), a reaction space which extends as a turn is preferred, and preferably is designed as a multiply wound reaction space, and more preferably as a helical (or helical) coiled reactor tube, with a length of 10 cm to 2 m, preferably 15 cm to 1.5 m, further preferably from 20 m to 1.2 m, for the length of the reaction space (extension in the flow direction), and with a characteristic measure of the spatial extent perpendicular to the flow direction of 1 mm to 50 mm, preferably from 2 mm to 15 mm, these characteristic extent perpendicular to the flow direction in the case of a tube is the inner diameter of the tube.

For the purposes of the present invention, the multiply wound, preferably the spirally wound reaction space, or the reactor tube, on at least two curved segments, which constitute a continuous winding in the context of the present invention, which extends over a 360 ° segment ("winding "), Preferably at least three turns, more preferably from two to ten turns, more preferably from two to five turns. The resulting helical or spiral reactor is schematically shown in FIG 1 shown.

The diameter of such a reactor, determined by the outer diameter of the largest such "turns" (spiral), is preferably in a range of 5 cm to 50 cm, preferably 10 cm to 30 cm, more preferably 15 cm to 20 cm.

Preferably, the inventive test scale for catalysts on an industrial scale (typically for 60 g of catalyst per reaction space) has a dimension which corresponds to the furnace chamber of a gas chromatograph. In this case, the reactor can be arranged without difficulty in the interior of the furnace.

The loop or spiral reactor according to the invention is preferably operated under elevated pressure relative to the ambient pressure and / or elevated temperature relative to the ambient temperature. Temperature and pressure limitations of the reaction space result, for example, from the production process of the reaction space. For example, a steel pipe that is cold-rolled has a lower pressure stability than a steel pipe that is hot-wound. For cold-rolled steel reactors, the preferred operating pressure is in the range from 1 bar to 300 bar, preferably from 1 bar to 200 bar.

In a preferred embodiment, the loop or spiral reactor has at least one "bleed point", ie removal point for liquid and / or solid samples along the direction of flow of the reaction mixture in the reactor, preferably at least 2, 3, 5 or 10 such taps, said In a further preferred embodiment, taps are operatively connected to a multiport valve (for example a valve of the manufacturer VICI Valco Instruments Co. Inc.). Such a reactor is also known as a "tap reactor". This arrangement of such "tapping" (57) is also in 1 shown

Particularly advantageous is an arrangement of taps which allow sampling along the flow direction, i. along the reaction progress, allows, as such an arrangement in particular allows to carry out meaningful kinetics studies.

Preferably, the sampling takes place in the gas phase, but also a removal of liquid is possible, preferably via a collecting device for liquids. In particular, the reactors can be operated as gas-solid, liquid-solid and as gas-liquid-solid reactors in swamp, trickle bed and as highly loaded liquid column.

In an advantageous embodiment, sampling lines are provided at different locations of the tap reactor, which are in operative connection with at least one selector valve. Preferably, the individual sampling lines have the same length and / or the same diameter.

The sampling lines preferably have a length in the range of 10 cm to 200 cm. In a preferred arrangement, the multiport valve is in the door of a furnace, preferably a convection oven, more preferably a GC oven, arranged. In this embodiment, the accessibility of the furnace interior is such that further technical elements of the catalyst testing apparatus are arranged there, such as, in particular, gas saturators or heat exchangers for preheating gas streams

As already mentioned above, the known high-throughput systems, which are known to the person skilled in the art for testing catalysts, are based on straight, in particular substantially vertically arranged reactors (reaction tubes). To operate these "straight" reactors as tapping reactors, it would be necessary to arrange the heating around the taps as heating sleeves, which is associated with great technical effort or disadvantages. The disadvantages are that a much greater effort is required than is necessary in connection with a loop or spiral reactor which is heated by a fluid medium. In addition, the "spiraling" spiral or helical construction is very space saving and has other advantages, which are explained below.

In one embodiment of the invention, the loop-shaped or helical / helical reactor is heated with a heat transfer medium (for example, with gas) and realized in this way a possible isothermal temperature field. The heating of such a reactor can also take place via another fluid heat transfer medium, such as a liquid (oil, water), a melt (salt, metal) or a solid heat transfer medium such as sand, silicon or silicon carbide powder or metal powder or a gas such as nitrogen or air ,

The introduction of the loop or spiral reactor according to the invention in the heat transfer medium is relatively simple and the reactor can be accommodated to save space. Cassette-type modules are preferred, in particular for a high-throughput system for testing catalysts, which also makes it possible to test at different temperatures, in each case in a module in a system.

Also preferred is the inhomogeneous heating of such cassettes by applying an inhomogeneous temperature field, preferably using solid heat transfer medium. The modules can be stacked horizontally or vertically and / or ranked

Preferably, at least one thermocouple is in operative connection with at least one tapping point, which enables sample removal and simultaneous temperature measurement, in particular also of the catalyst bed, at this point.

Method and Apparatus for Filling a Curved Reactor A particular problem in the field of catalyst testing, especially for heterogeneous catalysis, is that the reactors must be charged with a fixed bed, for example with catalyst pellets. Such a charging of a reactor with a pulverulent or pellet-like solid is technically easy to realize for a suitably dimensioned linear reactor, but not for a tortuous, in particular loop-shaped reactor.

Thus, it is another object of the present invention to provide a method for charging a tortuous reactor described above, or generally a poorly accessible, non-substantially rectilinear reactor.

In contrast to a poorly accessible reactor, a freely accessible reactor is characterized in that the reaction space is arranged linearly and the inner volume of the reaction space (in the unfilled state) is completely visible from the inlet opening and in the direction of the viewing axis. As examples of such freely accessible reactors is called a straight tube, or a block having straight bores.

The present invention thus also relates to an apparatus and a method for introducing / introducing powdery goods, preferably pulverulent catalysts, into curved and / or not easily accessible reaction spaces or reaction spaces in reactors, in particular in the curved and miniaturized catalyst test stands according to the invention.

Not easily accessible reaction spaces or reaction spaces are characterized in that they have windings which are arranged more or less regularly and by which a direct access to the line area is "shadowed". The shadowing means that the areas for technical applications are not accessible in the same way as is the case with the linear reaction spaces.

From the prior art, the filling of packed columns is known, which are used in chromatography. For example, liquid slurries of the powdered bulk material are formed and these liquid slurries are then conveyed in the form of the liquid phase by means of pumps in the curved pipe sections. However, this is associated with the disadvantage of the presence of an often undesirable liquid phase.

It is also known to fill curved conduits with powders via funnels and using vibration devices. However, these methods are difficult to use under spatially limited conditions.

Thus, it is an object of the invention to provide an apparatus and a method by which the filling of curved reaction spaces is improved.

The object mentioned here and further objects are / is achieved by providing an apparatus and a method for filling curved reaction spaces.

• • zumindest einen Dosiergutspeicher (4),
• • zumindest ein Vorratsgefäß (7),
• • wobei Dosiergutspeicher (4) und Vorratsgefäß (7) über zumindest ein Trichterelement (5) miteinander stoffschlüssig verbunden sind,
• • wobei der Dosiergutspeicher (4) weiterhin über zumindest ein Wirkverbindung (8) mit dem zu befüllenden Reaktionsraum (9) stoffschlüssig verbunden ist,
• • und der Dosiergutspeicher (4) eine weitere Verbindung (3) aufweist, und zwar zu einer Vorrichtung zu Druckluftzufuhr (1),

wobei das Innenvolumen des Vorratsgefäßes (7) im Bereich von 10 ml bis 500 ml liegt, vorzugweise im Bereich von 20 ml bis 200 ml, und
wobei das Innenvolumen des Dosiergutspeichers (4) im Bereich von 5 ml bis 400 ml liegt, vorzugsweise 5 ml bis 50 ml.According to the invention, the device for filling at least one reaction space limited in its accessibility, in particular a curved / tortuous reaction space, has at least the following components:

• At least one dosing storage ( 4 )
• At least one storage vessel ( 7 )
• • where dosing storage ( 4 ) and storage vessel ( 7 ) via at least one funnel element ( 5 ) are materially connected to each other,
• • where the dosing storage ( 4 ) via at least one active compound ( 8th ) with the reaction space to be filled ( 9 ) is cohesively connected,
• • and the dosing storage ( 4 ) another compound ( 3 ), to a device for compressed air supply ( 1 )

wherein the internal volume of the storage vessel ( 7 ) in the range of 10 ml to 500 ml, preferably in the range of 20 ml to 200 ml, and
where the internal volume of the dosing storage ( 4 ) is in the range of 5 ml to 400 ml, preferably 5 ml to 50 ml.

The dimensioning of storage vessel and Dosiergutspeicher is particularly adapted to the inventive use (testing of catalysts in compact reactors) and the inventive system.

It is particularly preferred that the storage vessel ( 7 ) and the dosing storage ( 4 ) via an active connection element ( 13 ), which a pressure equalization between storage vessel ( 7 ) and the dosing storage ( 4 ), wherein the active connection element ( 13 ) has a control element in a preferred embodiment.

The different embodiments of the device according to the invention are in the 2 to 5 shown.

In particular, the device is suitable for filling reaction chambers which are of tubular construction, these preferably having a length in the range of 0.5 m to 10 m and a diameter in the range of 5 mm to 25 mm. The associated therewith powder packets preferably have a bed volume in the range 0.5 cm ³ to 1000 cm ^3, preferably from 1 cm ³ to 500 cm ^3, and even more preferably from 5 cm ³ to 250 cm ^3.

The reaction space to be filled ( 9 ), as in 2 shown, has an input via a connector ( 8th ) in operative connection with the Dosiergutspeicher ( 4 ) stands. The reaction space to be filled further has at least one outlet ( 10 ) located at a distance from the entrance, for example at a pipe at the other end.

The one or more outputs ( 10 ) preferably have elements ( 11 ), which retain the powdery material but allow gases or liquids (carrier fluids) to pass through. These retention elements may for example comprise or be sieves, frits, cotton wool or the like.

Furthermore, in a preferred embodiment, the dosing stock ( 4 ) via a line ( 3 ), which acts as an operative connection, with a switching valve ( 2 ) in connection. On the input side there is a pressure supply / fluid supply for the carrier fluid. The supply line and the pressure supply for the carrier fluid are in the unit ( 1 ) summarized.

The valve ( 2 ) preferably has the functionality that the valve makes it possible to generate pressure pulses, so a pressure increase, a target pressure and a pressure drop.

This means that it is possible to build up a specific pressure in the system by means of the valve in a predetermined period of time, in particular in the operative connection ( 3 ), as well as the active compound ( 8th ), and in another phase to drop the pressure by shutting off the fluid flow to the ambient pressure.

The period of time within which inside the device, in particular in the operative connection ( 3 ), as well as the active compound ( 8th ), an increased pressure relative to ambient pressure or the previously prevailing pressure, is referred to as "pressure phase". The time length of the printing phase preferably ranges from 1 ms to within the range of 100 s. Preferred is a time range of 100 ms to 10 s, more preferably 50 ms to 5 s.

The pauses between the pressure phases are preferably in the same time range as the pressure surges themselves. However, it is not mandatory for the pauses between two pressure phases to have the same length as the pressure phases. In any case, it is preferred that the pressure in the device rises rapidly, ie the pressure for establishing the pressure phase should reach 80% of the equilibrium pressure in 1 ms, preferably 10 ms, preferably in 500 ms. A sequence of pressure phase and pressureless phase is referred to as pressure pulse in the sense of the present invention.

The storage vessel ( 7 ) has an active compound ( 5 ) with the dosing product storage ( 4 ) in connection. The storage vessel is preferably oriented so that the content under the action of gravity in the Dosiergutspeicher ( 4 ). Accordingly, embodiments are preferred for the storage vessel, the "trickling" of the content ("bulk") in the Dosiergutspeicher ( 4 ) facilitate. In particular, funnel-like formations of the bottom of the container are preferred. The active compound ( 5 ) has the same cross-sectional area as the Dosiergutspeicher, preferably, the value of half the cross section, more preferably, the value of the third part of the cross section.

In a preferred embodiment, the storage vessel ( 7 ) subjected to a pressurization.

A preferred storage vessel ( 7 ) has an inner volume in the range of 10 ml to 500 ml, preferably the inner volume is in the range of 20 ml to 200 ml. The Dosiergutspeicher preferably has an inner volume in the range of 5 ml to 400 ml, preferably from 5 ml to 50 ml.

3 shows the device as related to above 2 describe, however, with the preferred embodiment that between storage vessel ( 7 ) and dosing storage ( 4 ) a line ( 13 ) is provided for pressure equalization, which conveys a "trickling" of the bulk material from the storage vessel into the Dosiergutspeicher.

In 4 a variant for the generation of gas pressure pulses is shown. The volume ( 21 ) is on the one hand via a valve ( 22 ) in operative connection, in this case with a gas supply. On the other hand, there is an operative connection to the valve ( 2 ). Into the volume ( 21 ) is disabled when the valve is 2 ) over the valve ( 22 ) Admitted gas. In this way, a pressure in the volume ( 21 ) built up. With locked valve ( 22 ), the pressure from the volume ( 22 ) over the valve ( 2 ) and over the line ( 3 ) into the dosing product memory ( 4 ) dismiss. In this embodiment, no further switching operations to generate a pressure pulse are required.

In 5 is an embodiment with four reactors arranged in parallel ( 61 ). The reactors ( 61 ) are replaced by the supply line ( 60 ), each having a supply line ( 62 ) to the reactors. The individual tap connections in this particular embodiment become a common derivative ( 63 ) guided.

In the variant according to the 2 or 3 the slope of the pressure pulse next to the cross section of the valve is determined by its switching time. For example, directly controlled solenoid valves are preferred.

With regard to all the above-mentioned embodiments, the active compound ( 8th ) preferably has a maximum length of 20 cm, preferably 10 cm, more preferably 1 cm. The cross section of this active compound ( 8th ) is between three times to one tenth of the diameter of the inlet to the reaction space, preferably between twice to one fifth, preferably the same to a quarter of the value of the entrance to the reaction space ( 8th ).

The compressed air filling in the context of the present invention has the advantage that the powdery material does not come into contact with a liquid which can easily change the surface of the material or even clog the pores. In addition, no cleaning or drying of the catalyst bed or the powder bed is required after the compressed air filling.

Method for filling curved reaction spaces

• • druckloser Transfer von pulverförmigem Gut von einem Vorratsgefäß (7) über einen Trichter (5) in einen Dosiergutspeicher (4), der mit dem zu füllenden Reaktionsraum (9) und mit einer Einrichtung zur Erzeugung von Druckimpulsen verbunden ist,
• • zumindest einmalige Druckbeaufschlagung des Dosiergutspeichers (4) und Transfer des pulverförmigen Guts vom Dosiergutspeicher (4) in den zu füllenden Reaktionsraum (9),
• • zumindest einmaliges, bevorzugt mehrmaliges Wiederholen der Verfahrensschritte (i) und (ii).

The present invention also relates to a method for filling a curved and restricted in its accessibility reaction space, this method being characterized by the following steps:

• • pressureless transfer of powdered material from a storage vessel ( 7 ) via a funnel ( 5 ) into a dosing storage ( 4 ), with the reaction space to be filled ( 9 ) and connected to a device for generating pressure pulses,
• • at least one pressurization of the dosing material storage ( 4 ) and transfer of the powdery material from the dosing material storage ( 4 ) in the reaction space to be filled ( 9 )
• At least once, preferably several times, repeating the method steps (i) and (ii).

In a preferred embodiment, pressure buildup in the apparatus may cause fluid to flow into the hopper and lift the powder.

After the pressure has been reduced again, powder trickles into the space of the dosing storage. As a result of the second pressure pulse, the powder now present in the metered product store is conveyed into the reaction space. At the same time, the powder already in the reaction space is compressed by the pressure surge. After at least two, preferably at least four pressure pulses, the reaction space is completely filled and the powder already present in the reaction space is compressed.

The pressure pulses used for filling can have an absolute pressure in the range of 1 bar to 200 bar. The absolute pressure preferably has values in the range from 1 bar to 50 bar, more preferably from 2 bar to 10 bar, in particular from 3 bar to 6 bar.

In a further preferred form of the device, the storage vessel ( 7 ) via an active compound ( 5 ) with the dosing product storage ( 4 ) in operative connection. The cross-section of the active compound has similar dimensions as the active compound ( 3 ). This connection serves to counteract the pressure pulse which penetrates from below into the storage vessel, a different pressure pulse from above, so that the powdery material is not ejected upwards out of the vessel.

In the preferred embodiment with pressure compensation, the storage vessel ( 7 ) via a removable lid ( 12 ), the pressure-tight and -dicht the vessel.

Interaction of inventive reactor / test stand and filling process

There are synergy effects between the filling device according to the invention (or the corresponding method) and the reactor according to the invention with at least one turn / loop, since their practical use for catalyst testing is made possible due to the improved production of reactor packs in loop-shaped reactors.

Another preferred aspect of the invention also relates to the use in liquid-solid systems in which liquids are passed through solids beds or Trickle-Bed applications in which liquids and gases are passed through the catalyst bed. In particular, the applications GTL (gas-to-liquid), FT (Fischer-Tropsch-Verfaren) or HBF columns are also preferred.

A preferred field of use of the reactor systems according to the invention relates to carrying out kinetic measurements. It is also possible to determine a so-called global kinetics for certain catalyst systems. Particularly preferably, such data can be used to determine the microkinetics.

A particularly advantageous use of the systems according to the invention in research and technology is given since particularly flexible and versatile. In particular, for the performance of kinetic studies house-building properties. Due to the introduction of large amounts of catalyst, it is possible to obtain test data that have a high technical relevance and therefore a high relevance. Limitations can be given if there are very large heat of reaction in the reactions carried out. However, it should then be possible for a person skilled in the art to modify the dimensioning of the reactor or to dilute the catalyst material with inert material in order to specifically contribute to system optimization by modifying and adapting the experimental conditions and to use the system according to the invention in a reproducible method.

Arrangement of reactors in more complex systems

Furthermore, it should be noted that the invention is not limited to the description in the description and the drawings, but the reactors may be arranged in more complex systems, which may be present in quite different embodiments. In one of these more complex embodiments, two or more reactors are helically wound together so that the reactors so arranged produce a multi-threaded helix. For example, an embodiment of two reactors is in the form of a DNA double helix as a two-turn helix. The more complex arrangements may be in the form of twisted pairs or twisted triplets. The more complex arrangement provides another contribution to making the reactor arrangements more compact than simple reactors. The more compact design also facilitates the modularization of the components, which in turn leads to a reduction of the systems, which can also be arranged in a flexible manner. The filling of the reactors could already be solved with the help of the filling method according to the invention and the filling device according to the invention, which is also part of the present disclosure.

Flexibility in process control and use of the reactor systems

Significant in connection with the present invention is also its flexible Use in very different processes - for example, for the separation of mixtures or to carry out kinetic studies. In a particular embodiment, the apparatus may be used to perform Simulated Moving Bed (SMB) experiments in which migration of the catalyst bed is controlled by valve switching and fluid flow guidance in a specific manner. It is possible that the educt is supplied via the taps in the course of the reaction and further switched after a certain time. This sometimes leads to a reversal of the flow direction. This flow reversal creates a time behavior that can equivalently be described as a moving bed. By switching the entry point - in the sense of the entrance towards the exit - the educts meet again and again on a "fresh" bed. In the mathematical description this seems like a moving bed. SMB processes are used in the field of HPLC chromatography - also on a semi-preparative scale.

Operation of the reactor system analogous to the stirred tank cascade

In addition, it is possible in a further process control to use the respective taps to supply the starting material in partial streams over the entire length of the reactor. By way of example of an oxidation reaction, this could mean, for example, that the substances to be oxidized are metered in at the inlet pipe of the reactor and the oxidizing agent is supplied in portions distributed over all tapping points. As a result, it is avoided, for example, that in the first part of the catalyst bed too high a heat of reaction occurs, as can be very easily the case with high reactivity.

Examples

In the present case, the device according to the invention was according to the 3 used for filling a tap reactor with a length of 1.20 m and an internal pipe diameter of 9.13 mm. The tap reactor, which had a spiral shape and each had a valve for sampling at a distance of 5 cm or 10 cm, had a reaction zone with a length of 1.00 m, which corresponds to a volume of 65.47 cm ³ to be filled. To the metering device, a reservoir was connected, which had an internal volume of 50 ml. As metering experiments, the metering of corundum with a particle size in the range from 250 μm to 500 μm was carried out in Example B1, in Example B2 a copper catalyst with a particle size from 250 μm to 500 μm was metered and in Example B3 a pumice was applied dipped copper catalyst with a particle size of 1.1 mm to 1.6 mm.

The device was equipped with a dosing system ( 4 ), which had a volume of 50 ml. The device was connected to a compressed air pressure line, which provided compressed air under a pressure of 4.0 bar.

In carrying out several examples, the tap reactor could be filled in a densely packed manner in a reproducible manner within a short time and with a number of 20 to 40 pressure surges.

To control the quality of the package, the length of the reactor bed in the reactor tube of a tap reactor was determined in each case, wherein the weight of the introduced into the catalyst tube powder amount was determined. On the basis of the weight amount of catalyst powder and the reactor bed length, the packing density was determined, since the tube diameter of the tap reactor is known. Comparative tests were carried out for packing in a linear tube reactor in which the same catalyst powder was compressed in each case within the reactor tube by means of a tamping compressor.

As a result, it was found that, as expected, the reactor packs which were produced in a linear reactor tube by means of tamping compressors, which are thus to be regarded as "ideally packed" reactor, a higher bulk density than those reactor packs by means of the inventive method in a tap reactor with Spiral winding were made. The bulk density obtained by the linear reactor tube was taken as the maximum packing density to be achieved. The maximum bulk density in the linear tube reactor was assigned a value of 100%. With regard to the bulk density, which was produced by means of the device according to the invention and the method according to the invention, a value could be achieved which was 62.2%. The measurements were repeated ten times and the bulk density variation was 2% to 3%. It should be emphasized that a deviation of 1% corresponds to a change in the packing density of 0.004 g / cm ³ . Thus, the inventive method has a very high reproducibility.

This shows that tightly packed spiral or loop-shaped reactors can also be used for catalyst testing and, in particular, for parallel testing since comparable catalyst beds can be set.

LIST OF REFERENCE NUMBERS

1

 Supply of a fluid supply (compressed air supply)

2

 switching valve

3

 Active connection between switching valve and dosing system memory

4

 Dosiergutspeicher

5

 Operative connection between storage vessel for powdered material and dosing product storage

6

 Powdery good

7

 Storage vessel for powdery good

8th

 Active connection between the dosing product storage and the reaction space to be filled

9

 to be filled reaction space

10

 Exit of the reaction space

11

 Elements for retaining powdered material

12

 Cover for closing the storage vessel

13

 Line for pressure equalization between dosing product storage and storage vessel

20

Connection to the switching valve ( 2 )

21

 Volume for storing gas under pressure

22

 Second valve

23

 gas supply

51

Supply line of a fluid supply (corresponds 1 )

52

Switching valve (corresponds 2 )

53

 Dosiergutspeicher

54

Active compound (corresponds 3 )

55

Storage vessel or Dosiergutspeicher (corresponds 4 )

56

spiral reaction space (corresponds 9 )

57

 Drain pipes of taps

58

 selector valve

59

 Active link to analytical instruments

60

 Supply line (supply rail)

61

 reactors

62

 Feedstock supply lines to the reactors, which may also contain distribution elements

63

 Derivation of the products

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 19809477 [0004]
• EP 1796897 [0004]

Cited non-patent literature

• Jozsef M. Berty: Experiments in Catalytic Reaction Engineering, Elsevier Science (1999), ISBN 0-444-54137-3, page 31 et seq. [0005]
• Solc. Jozsef M. Berty: Experiments in Catalytic Reaction Engineering. 292 pages, Elsevier Science (1999), ISBN 0-444-54137-3, p. 31 et seq. [0024]

Claims (13)

Use of at least one reactor in which at least one reaction space extends as a turn, preferably of at least one reactor having at least one multiply wound reaction space, preferably at least one reaction space extending spirally or helically or over at least one 360 ° arc, preferably such a convoluted one Reactor tube, for testing catalysts. Use according to claim 1, for the parallel testing of catalysts, wherein at least two, preferably at least 12, more preferably at least 24 reaction spaces are present as reaction spaces with turns, preferably as multiply wound reaction spaces, more preferably as helically wound reactor tubes. System comprising: At least one reaction space which extends as a turn, preferably designed as a multiply wound reaction space, preferably designed as at least one spiral-wound reactor tube; At least one unit for analysis, this unit for analysis completely enclosing the at least one such reaction space, and preferably the reaction space is part of this unit for analysis. System according to claim 3, further comprising at least one catalyst, which is in powder form or in solid particulate form, preferably as a solid in a solid bed, and is introduced in said reaction space. A system according to claim 3 or 4 for use in testing at least one catalyst, preferably for parallel testing of a plurality of catalysts, the system having at least 2, 4, 16 or 32 reaction spaces.  System according to at least one of claims 3 to 5, wherein at least one unit for analysis is a gas chromatograph. Device for filling at least one reaction space limited in its accessibility, in particular a curved / convoluted reaction space, wherein the device comprises at least the following components: at least one dosing material reservoir ( 4 ); At least one storage vessel ( 7 ), • where dosing storage ( 4 ) and storage vessel ( 7 ) via at least one funnel element ( 5 ) are materially connected to one another, wherein the dosing goods storage ( 4 ) via at least one active compound ( 8th ) with the reaction space to be filled ( 9 ) is materially connected, • and the dosing material storage ( 4 ) another compound ( 3 ), to a device for compressed air supply ( 1 ), wherein the internal volume of the storage vessel ( 7 ) in the range of 10 ml to 500 ml, preferably in the range of 20 ml to 200 ml, and wherein the inner volume of the Dosiergutspeichers ( 4 ) is in the range of 5 ml to 400 ml, preferably in the range of 5 ml to 50 ml. Apparatus according to claim 7, characterized in that the storage vessel ( 7 ) and the dosing storage ( 4 ) via the active connection element ( 13 ), wherein the active connection element ( 13 ) has a control element in a preferred embodiment. Apparatus according to claim 7 or 8, characterized in that the compressed air supply a compressed air reservoir ( 21 ) and a switching valve ( 22 ) having. Device according to one of claims 7 to 9, characterized in that the device is in connection with a reaction space, more preferably with a system according to one of claims 3 to 6, and that the reaction space has a length in the range of 0.5 m to 10 m and a diameter in the range of 5 mm to 25 mm. A process for filling a curved and limited in its accessibility reaction space, this method being characterized by the following steps: • pressureless transfer of powdered material from a storage vessel ( 7 ) via a funnel ( 5 ) into a dosing storage ( 4 ), with the reaction space to be filled ( 9 ) and is connected to a device for generating pressure pulses, at least one pressurization of the dosing stock ( 4 ) and transfer of the powdery material from the dosing material storage ( 4 ) in the reaction space to be filled ( 9 ), At least once, preferably several times, repeating the method steps (i) and (ii). A method according to claim 11, characterized in that at least one for the transfer of filling material from the Dosiergutspeicher ( 4 ) In the reaction chamber inserted pressure pulse has an absolute pressure in the range of 1 bar to 200 bar. A method according to claim 11 or 12, characterized in that the duration of a Pressurization is in the range of 0.2 s to 7,200 s, preferably in the range of 0.5 s to 3,600 s.

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