DE202010016522U1 - Apparatus for the adsorption treatment of a fluid or fluid stream - Google Patents

Abstract

Apparatus for the adsorption treatment of a fluid or fluid stream, comprising
a container (11) for receiving adsorber material, wherein the container has a fluid inlet opening (14) and a fluid outlet opening (16), and
two fluid connection devices (17), one of the fluid connection devices being provided at the fluid inlet opening and the other of the fluid connection devices being provided at the fluid outlet opening,
wherein the fluid connection devices are fluid-tightly locked and configured such that they are each connectable and unlockable with a fluid line connection piece and can be unlocked or unlocked provided that they are connected to the respective fluid line connection piece.

Description

The present invention relates to a device for adsorption treatment of a fluid or fluid flow, a use of a device for adsorption treatment of a fluid or fluid flow, a method for regenerating and / or disposing, filling and / or installing a device for adsorption treatment of a fluid or fluid flow and a method for Adsorption treatment of a fluid or fluid stream, in particular natural gas or liquid gas for fuel cells. In particular, the invention relates to a device for desulfurization of a gaseous hydrocarbon stream and a corresponding method, in particular for use in combination with a fuel cell device.

Most fuel cells require hydrogen or hydrogen-rich gases as fuel for heat and power generation. Therefore, considerable efforts are currently being made to produce hydrogen from catalytic fuels such as diesel, gasoline, naphtha, LPG and natural gas in catalytic fuel conversion systems. In the long term, however, the successful use of fuel cells depends on the availability of renewable hydrogen.

The catalytic conversion of liquid or gaseous hydrocarbons to obtain a hydrogen-rich gas, such as the so-called reformate, takes place in several successive steps: the actual reforming reaction, a downstream water gas shift reaction and possibly a CO fine cleaning reaction such. B. the selective CO methanation reaction.

However, most of the primary sources of energy that can be used to catalytically generate hydrogen include amounts of sulfur. These are sometimes purposely added to the fuel as so-called odorants to warn people of potential leaks. Odoration serves as a safety measure when using otherwise odorless gases and refers to the addition of odoriferous substances (odorants), which should have a typical odor for the hazard. Odorants still cause alarm associations in humans to a great extent. Liquefied natural gas and gas therefore contain, in addition to natural sulfur compounds such as H ₂ S and COS, typically sulfur-containing odorants such as tetrahydrothiophene (THT) or mercaptans or mixtures of methanethiol, ethanethiol, propane-1-thiol and 2-methyl-propane-2-thiol, and tert-butyl mercaptan (TBM).

However, it is known that sulfur compounds cause irreversible deactivations in reforming catalysts as well as in the fuel cell itself. A suitable desulfurization stage is therefore a prerequisite for the use of hydrocarbons as fuel in a fuel cell. The process engineering of the desulfurization differ greatly depending on the hydrocarbon used. For desulfurization of natural gas and liquid gas, as simple as possible adsorptive desulfurization stages are sought, which can be operated at room temperature and room pressure with the highest possible selectivity.

Adsorptive desorbing processes with solid adsorbents are used in many fuel cell applications and are critical to process requirements, e.g. B. room temperature and room pressure, relatively easy to implement. For example, this describes WO 2010/023249 A1 an adsorbent material and a process for the desulfurization of hydrocarbonaceous gases. However, low temperatures and reaction pressures on the other hand mean comparatively low sulfur uptake capacities. The result is relatively large adsorber beds or fast replacement intervals. The capacity of each adsorbent depends strongly on the composition of the hydrocarbon and on the concentration and type of sulfur compounds. The materials used are z. As classical and impregnated activated carbon, zeolite, metal and misch metal (oxide) catalysts, clay minerals and combinations of materials in mixed bed and multi-component systems.

There is a need for adsorption treatment devices, e.g. B. detoxification of fluids or fluid streams, or for the desulfurization of hydrocarbons for fuel cells that allow safety-related measures and functionalities when installing or removing the devices in the gas line. The safe installation or the safe change process of the device is a central issue for a logistical concept for upgrading and retrofitting z. B. of fuel cell systems with sulfur filtration systems.

One of the most important challenges in building a logistics concept for the supply and disposal of fuel cell desulphurisation cartridges is the transport of used desulphurisation cartridges. The filter replacement is usually carried out by service technicians or gas technicians, who usually have no special training in handling dangerous goods can. For this reason, among other things, desulphurisation adsorbents are developed which are not subject to any dangerous goods classification. However, depending on the material, depending on the material, the adsorbents can accumulate various other toxic gas constituents in addition to sulfur compounds depending on the gas accompanying substances of the gas to be desulphurized, and thus alter their properties.

A general classification of the adsorbent in a used desulfurization can not be made for this reason. Depending on the adsorbent and gas composition, various other substances may or may not be adsorbed in addition to the sulfur compounds. In order to avoid possible exposure of persons, it must be ensured that replacement of the used adsorbent by opening the cartridge is only carried out by persons with expertise and safety equipment. There is therefore a need for safe equipment for adsorption treatment, e.g. B. equipment for the desulfurization of gaseous hydrocarbons.

The object of the invention is to provide a safe device for the adsorption treatment of a fluid, wherein the connection to a fluid line, the regeneration and / or disposal of the adsorbent and the changing process of the device as simple and safe as possible and the operation of the device with great reliability.

In one embodiment, there is provided an apparatus for adsorbing a fluid or fluid stream comprising a container for receiving adsorbent material, the container having a fluid inlet port and a fluid outlet port, and two fluid port devices, one of the fluid port devices being provided at the fluid inlet port and the other of the fluid port devices is provided at the fluid outlet opening, wherein the fluid connection devices are locked in a fluid-tight manner and are designed so that they are each connectable and unlockable with a fluid line connection piece and under the condition that they are connected to the respective fluid line connection piece, unlocked or unlocked.

One embodiment relates to the use of a device for the adsorption treatment of a fluid or fluid stream according to the preceding embodiment for the desulfurization of a combustion fluid, in particular natural gas or liquid gas, for fuel cells.

In a further embodiment, there is provided a method for regenerating and / or disposing, filling and / or installing a device for adsorbing a fluid or fluid stream according to the above-mentioned embodiment, comprising at least one of the steps of: removing the device for adsorption treatment of a fluid or fluid flow; the container of which contains adsorber material to be regenerated and / or disposed of by means of or in which an adsorption treatment has been carried out by detaching the fluid connection devices from fluid line connecting pieces connected to the device; Transporting the container with the adsorber material to be regenerated and / or disposed and locked fluid port devices while the container is being filled with treated or treated fluid; Transporting the container with the adsorbent material to be regenerated and / or disposed of and locking fluid connection devices to a regeneration and / or disposal station; Purging the container containing adsorbent material to be regenerated and / or disposed with inert gas, inert fluid or other gases such as air; Emptying the container from the adsorbent material to be regenerated and / or disposed of; Regenerating and / or disposing of the adsorbent material to be regenerated and / or disposed of; Filling the container with regenerated or unused adsorber material; Purging the container with inert gas, inert fluid, inert gas or the fluid freed from an adsorptive to be removed by the adsorption treatment, during and / or after filling the container with the regenerated or unused adsorbent material; Performing a pressure and / or leakage test to verify the tightness of the filled container with locked fluid connection devices; Transporting the container with the regenerated or unused adsorbent material and locked fluid connection devices while the container is filled with inert gas, inert fluid, or inert gas; Transporting the container with the regenerated or unused adsorber material and interlocking fluid connection devices to a device at or in which an adsorption treatment is to be performed; Connecting fluid line fittings to the device at or in which an adsorption treatment is to be performed; Installing the device for adsorption treatment of a fluid or fluid stream on or in a device at or in which an adsorption treatment is to be performed while the container is filled with regenerated or unused adsorber material and an element selected from inert gas, inert fluid, inert gas or the fluid is freed from an adsorbent to be removed by the adsorption treatment by connecting the fluid connection devices to fluid line fittings connected to the device.

In a further embodiment, there is provided a process for adsorbing a fluid or fluid stream, in particular for desulfurizing natural gas or liquid gas for fuel cells, comprising: providing a device for adsorption treatment of a fluid or fluid stream according to the above-mentioned embodiment, wherein the vessel is provided with an adsorbent material for adsorption treatment of fluids, connecting a fluid supply line to a first fluid line fitting and a fluid discharge line to a second fluid line fitting, connecting the first and second fluid line fittings to the two fluid connection devices of the device for adsorbing a fluid or fluid flow, thereby unlocking the fluid connection devices, and introducing a fluid inlet Fluids in or passing a fluid through the device for adsorption treatment of the fluid.

Other features and advantages will become apparent from the following description of embodiments, the figures and the subclaims.

All non-mutually exclusive features of embodiments described herein may be combined. Like elements of the embodiments are given the same reference numerals in the following description. Elements of one embodiment may be used in the other embodiments without further mention. Embodiments of the invention will now be described in more detail by the following examples with reference to figures, without wishing to restrict thereby. Show it:

1 a schematic representation of a device according to an embodiment;

2 a schematic representation of a device according to an embodiment;

3 a schematic representation of another device according to an embodiment;

4a a schematic representation of another device according to an embodiment;

4b a schematic representation of another device according to an embodiment;

5a a schematic representation of a device according to an embodiment;

5b a schematic representation of a device according to an embodiment;

5c a schematic representation of a device according to an embodiment;

5d schematic representations ( 5D0 to 5d3 ) of a device according to an embodiment;

5e Representations of an example of a device according to the embodiment of the 5d ; and

6 a percentage scaling of the THT (tetrahydrothiophene) breakthrough capacity of Example 1 of WO2006 / 028686 depending on the space velocity and the L / D ratio.

In the following description of embodiments, the terms adsorbent, adsorbent, sorbent and adsorber material are used interchangeably. Furthermore, the device for the adsorption treatment of a fluid or fluid flow is also referred to below as a cartridge. The fluid connection devices are described below with reference to gas sockets with an angled at 90 ° angle form, but not limited thereto.

In addition, embodiments of the invention are described below with reference to the desulfurization of a fuel gas for fuel cells, without limiting the invention thereto. In addition, in the following description of embodiments, a gas is used as the fluid, without limiting the invention thereto. Furthermore, embodiments of the invention will be described below in connection with the adsorptive treatment of a fluid stream, but may also be used to treat a stationary fluid.

In one embodiment, an apparatus for the adsorption treatment of a fluid or fluid stream is provided, comprising a container for receiving adsorber material, wherein the container a Fluid inlet opening and a fluid outlet opening, and two fluid connection devices, wherein one of the fluid connection devices is provided at the fluid inlet opening and the other of the fluid connection devices is provided at the fluid outlet opening, wherein the fluid connection devices are fluid-tightly locked and formed so that they are each connectable to a fluid line connector and unlocked and provided that they are connected to the respective fluid conduit fitting, unlocked or unlocked. The fluid connection devices may also be designed so that they are fluid-tight, provided that they are not connected to the respective fluid line connection piece.

The device for the adsorption treatment of a fluid or fluid stream can be used for desulfurization of a combustion fluid, in particular natural gas or liquid gas, for fuel cells. The device may also be equipped only with a fluid connection device. The device for the adsorption treatment of a fluid or fluid flow is also referred to here as an adsorption treatment device or apparatus.

Embodiments of the present invention enable adsorption treatment of fluids with an intrinsically safe device, e.g. As for the desulfurization of hydrocarbons, which is closed gas-tight after removal from the gas line. For example, the intrinsically safe device locks automatically during manual removal from the gas line due to the function. Exposure to pollutants and the escape of combustible gases are thus safely avoided. The apparatus according to embodiments may be shipped to a disposal company after removal, opened by trained persons, and the adsorbers subjected to appropriate refurbishment before the apparatus is refilled with new material and can be re-fed to the cycle.

In embodiments, the unlocked fluid port devices may secure the fluid conduit fittings, e.g. B. against unwanted detachment. Furthermore, the fluid connection devices can be designed such that the fluid line connection pieces are secured when the fluid connection devices are unlocked. In addition, the fluid connection devices can be designed such that they can be locked manually or automatically by means of the respective fluid line connecting pieces, for. B. by actuation or detachment of the respective fluid line fittings. In embodiments, at least one of the fluid connection devices is designed such that it can be connected and unlocked successively or simultaneously with the respective fluid line connection piece.

1 shows a cartridge as an example of an embodiment of the adsorption treatment apparatus 10 , The cartouche 10 includes a container 11 whose walls are made of a material, eg. As stainless steel, which consist of the interior 12 the container suitable for the dense absorption of gases. The container may be made of plastic or metal, for example, particularly preferred materials are PE (polyethylene) z. PE 80, PE 100, PE-Xa, PE-Xb, PE-Xc, aluminum, anodized aluminum, stainless steel, copper, or other materials approved for natural gas. A combination of the materials mentioned is also conceivable.

The container 11 has a fluid inlet opening an inlet opening 14 and as the fluid outlet opening an outlet opening 16 , At the openings 14 and 16 is in each case as a fluid connection device, a gas outlet 17 gas-tight. The gas sockets 17 each have a fluid flow channel 19 and can be at one end 13 to the container 11 be welded or removable with the container 11 , z. B. by means of an in 1 not shown gas-tight thread, gas-tight connected. The gas sockets 17 are at each other, the container 11 opposite end 15 in there unconnected state each gas-tight locked, which in 1 schematically and exemplarily with bars 18 is shown as closing body. The gas sockets 17 are designed so that they each end 15 with a gas plug 20 can be connected and unlocked as a fluid line connection piece and under the condition that they are connected to the respective gas plug 20 are unlocked. Alternatively, the gas outlets 17 be designed so that they are provided with the respective gas plug 20 are connected, are unlocked.

In embodiments, the fluid connection devices may be on the container 11 welded and / or glued. As a result, no destructive disassembly of the secure fluid connection device is possible.

In one embodiment of the device, the fluid connection devices each have a fluid flow channel and a movable closing body, wherein the closing body fluid-tightly closes the fluid flow channel and the fluid connection devices are formed such that the respective Closing body is moved by connecting the fluid connection device with the fluid line connection piece and opens the fluid flow channel, and / or is moved by releasing the fluid line connection piece and closes the fluid flow channel. The closure body may be biased such that when the fluid connection device is not coupled to a corresponding fluid line connector, the fluid connection device is locked and, when the fluid line connector is released, is automatically locked.

2 schematically shows an embodiment of the gas outlet 17 and the gas plug 20 , the representations in 2 from left to right the process of connecting the gas plug 20 with the gas socket 17 illustrate. In this embodiment, the end is 15 the gas socket 17 if it is not with the gas plug 20 connected to the through the gas plug 17 sliding latch 18 sealed as closing body gas-tight. The sliding latch 18 is inside a latch device 21 biased, for example, with a spring (not shown), and slidably mounted up to a stop point. The bolt 18 is biased so he, if not a gas plug 20 with the gas socket 17 connected to the opening of the container 11 opposite end 15 of the gas plug 20 gastight closes. To the gas plug 20 with the gas socket 17 to connect, in this embodiment, first the gas plug 20 next to the bar 18 introduced into an opening of the locking device (left illustration in 2 , The gas plug 20 will be like this before the end 15 the gas socket 17 shifts that latch 18 is moved to its stop point and the opening of the gas socket is exposed and aligned with the gas plug (middle illustration in 2 ). Finally, the gas plug 20 in the flow channel 19 advanced the gas socket and a gas-tight connection of the gas plug 20 with the gas socket 17 is manufactured (right representation in 2 ). To secure the gas plug 20 against pulling out the prestressed latch 17 engage in a corresponding groove (not shown) on the gas connector. In the present embodiment, the gas outlets 17 So designed so that they on the condition that they with the respective gas plug 20 are unlocked. To detach the gas plug 20 this is from the gas outlet 17 pulled, the prestressed latch 18 is thereby displaced again in front of the opening of the gas socket, whereby the gas socket automatically locks gas-tight.

In other embodiments, in the container 11 opposite end 15 the gas socket 17 a stopcock, z. Example, a ball valve, a plug cock or a piston cock be integrated, wherein a ball, a plug or a piston is used as a movable closing body accordingly.

According to one embodiment (not shown) are at least one gas outlet 17 and the associated gas connector designed as a combined plug and rotary coupling, wherein the plug and rotary coupling has an internal, closed in the uncoupled state and opened in the coupled state ball valve. In one example (not shown), the gas plug has an inner coupling piece and the gas socket has an outer coupling piece as plug-in coupling parts. In addition, the plug and rotary coupling in the end includes 15 the gas socket 17 a ball valve as a rotary coupling part. The ball valve and the inner and outer coupling pieces are designed such that the ball valve by rotation of the inner coupling piece of the gas plug in the outer coupling piece of the gas socket 17 is opened and so the gas outlet 17 is unlocked.

In addition, in the present example, the plug and rotary coupling is designed so that the gas plug is secured during rotation of the gas outlet. For example, during rotation, a biased pin on the gas plug engage in a recess in the gas socket to secure the gas plug to the gas socket against unwanted detachment. This pin is solvable again only by a combined rotational and pushing movement out of the recess.

In the present example, a groove is also provided on the inner coupling piece of the gas connector, into which a corresponding projection provided in the gas socket can engage during insertion of the gas connector. In addition, a red and a green marking are provided on the gas connector. The gas socket has a viewing window that corresponds to the markings depending on the position of the gas plug in the gas socket.

For connecting the gas plug to the gas socket of the present embodiment, the gas plug is aligned so that the groove can engage in the projection of the gas socket. Then the gas plug is inserted into the gas socket so far that the red mark appears in the viewing window. This connects the gas plug to the gas outlet while the gas outlet 17 is gas-tight locked. Then the gas plug is in the gas socket 17 rotated, with the gas outlet through Opening the ball valve is unlocked and the gas plug is secured against detachment at the same time. This condition is indicated by the appearance of the green mark in the viewing window. The gas socket 17 is thus designed in the present embodiment such that it can be unlocked provided that it is connected to the gas connector.

According to the present embodiment, to detach the gas plug, it is rotated in the gas socket, in a direction opposite to the rotation upon unlocking. The ball valve is closed thereby, whereby the gas socket is locked gas-tight. At the same time the gas plug is unlocked and the red mark appears in the viewing window. Then the connection of the gas plug with the gas socket can be solved.

The gas plugs are connected according to embodiments in each case with a gas line as a fluid line, which in 2 not shown. In embodiments, the two fluid line connecting pieces are thus designed such that they are each connected to one of the two fluid connection devices and a fluid line, for. B. a flexible gas hose, are connectable. Furthermore, the unlocked fluid connection devices can secure the fluid line fittings connected to them. In the example of 2 is this backup, as described above, by snapping the latch 17 in a groove on the gas plug 20 realizable.

According to embodiments, the container contains 11 one or more adsorber materials (not shown in the figures), e.g. As adsorbent for the desulfurization of liquefied gas, gas or natural gas. Further, the container may contain a plurality of adsorber materials, and the adsorbent materials may be in a mixed bed or as a multicomponent adsorber material. The adsorbent materials used are z. As classical and impregnated activated carbon, zeolite, metal and misch metal (oxide) catalysts, and other known materials and combinations of materials in mixed bed and multicomponent systems. The materials should be mentioned only by way of example and the invention is not limited with respect to the materials. Examples of adsorptive desulfurization adsorbents and systems are in WO 2004/060840 A2 . WO 2006/028686 A1 and US 2009272675 A1 described, the complete disclosure of which is incorporated herein by reference.

Further, according to embodiments, the adsorption treatment apparatus may comprise a thermally activating fluid shut-off device and / or a fluid flow monitor. The thermally triggered fluid shut-off device can be a thermally triggered shut-off device (TAE) 30 be like her with the cartouche 101 in 3 is shown schematically. The thermally triggered shut-off device 30 contains a solder, which melts in case of fire and breaks the gas flow. Furthermore, as an alternative or in addition to the thermally triggering shut-off device as the fluid flow monitor optionally a gas flow monitor (not shown in FIG 3 ), which automatically cuts off gas flow immediately if the gas line is intentionally or accidentally damaged. The operation of a thermal shut-off device and a gas flow monitor are z. B. in DVGW worksheet G600 April 2008 described in detail.

In one embodiment, the container for reversible filling with the adsorber material may comprise an opening and closing element having a safety device to prevent tampering, selected from: a cover of the opening and closing element and a special screw, which are opened exclusively with special tool can. The security device may also be a seal.

For the (re-) filling and emptying of the container with the adsorbent, in one embodiment, the cartridge can be designed so that the container 11 can be opened at one point by means of a screw of the cartridge. Examples of this embodiment are in 4a and 4b as cartridges 103 and 105 shown. The containers of the cartridges 103 and 105 exist, as in particular from 4b it can be seen, in each case from two halves 40 and 42 , The half 40 has an internal thread and half 42 has an external thread and the halves 40 and 42 can be gas-tightly screwed together via these threads. This gland contains additional security elements to avoid external manipulation. In the example of 4a is a removable cuff 50 provided above the screw connection which surrounds the circumference of the container and by means of a special screw connection 52 is or can be attached over the screw connection. The special fitting 52 can only be opened with appropriate tools that are not commercially available. The security element for protection against opening by unauthorized persons can according to the example of 4b also a cover 54 be on one of the halves of the cartouche 105 is attached and the screwing of the two halves 40 and 42 covered. Another embodiment relates to a combination of cover and sleeve with special screw.

To attach the cartridge z. On a wall, a hook may be attached to the cuff, to which the cartridge can be attached to a corresponding eyelet (not shown) provided on the wall. The eyelet can of course also be attached to the cuff and the hook on the wall. This type of suspension is z. B. from Wandfeuerlöschgeräten known. The defined attachment of such a suspension has the advantage that the gas plug of the gas inlet and outlet of the cartridge can not be accidentally connected incorrectly when the corresponding gas supply lines are mounted so that the port is matched to the suspension, z. B. by a defined length of the gas hose. Of course, different from each other fluid connection devices for the gas inlet and outlet of the cartridge can be used. In a further embodiment of the invention, therefore, the fluid connection devices and / or the associated fluid line connection pieces for the fluid inlet opening and for the fluid outlet opening are formed in different geometries. So a confusion of the connections can be excluded. The correct flow is particularly important for the flow through multicomponent adsorber systems. In another embodiment of the invention, the gas sockets are rotatably mounted on the cartridge, so that the service technician has the greatest possible flexibility in terms of connections of the gas hoses and space when installing the cartridge.

According to embodiments, the container 11 be formed so that it is vertically installable and adjacent to the fluid inlet opening a cavity or a cavity with or limited by a flexible and / or porous inert material or plastic foam filling have, for. B. for collecting condensate. Examples of these embodiments are in the 5a and 5b as cartridges 107 and 109 shown, which subsequently to the fluid inlet opening 14 have an unfilled or filled cavity. A corresponding cavity may alternatively or additionally be provided at the fluid outlet opening. Such cavities lead individually or in combination also to an improvement in the flow distribution of the gas flowing through. In a variant of these embodiments, the cavity may have a condensate drain.

How out 5a is recognizable, is the interior of the container 11 the cartouche 107 through a porous, inert and fluid and / or gas-permeable partition wall 60 in two chambers 62 and 64 divided. The chamber 62 serves to accommodate the Adsorbermaterials while the chamber 64 at the entrance 14 adjacent, serves to trap condensate. The chamber 64 is an unfilled cavity in the operating condition of the cartridge.

In the 5b illustrated cartridge 109 Contains adjacent to the inlet 14 a cavity or space 66 which is equipped with porous and / or flexible inert material or a plastic foam filling. Therein, after the entry of the fluid or gas into the cartridge 109 In the fluid or gas contained liquid fractions are collected as condensate. As a porous and / or flexible inert material or as a plastic foam filling are, for example, synthetically produced substances with cellular structure and / or low density based on a plastic. Examples of such a plastic are flexible polyurethane foam, polypropylene (PP), polyethylene (PE), cross-linked polyethylene (PE-X), and polyethylene terephthalate (PET). Particularly preferred are elastomers, such as. As flexible polyurethane foam, or foams based on or include ceramic or metal.

Dimensions and / or lengths described herein are examples and may include common manufacturing and measurement tolerances.

In one embodiment, the outer length of the container between the fluid inlet opening and the fluid outlet opening is in a range of 700 to 800 mm. For example, the length between the fluid inlet opening and the fluid outlet opening is 729 mm, 717 mm, 723 mm, 750 mm or 756 mm.

In a further embodiment, the device including the fluid connection devices has a length in the range of 850 mm to 900 mm, for example 871 mm.

In embodiments, the container has an outer diameter of 110 mm and / or an inner diameter of 90 mm.

In one embodiment, a total length L1 of the cartridge including the fluid connection devices may be 871 mm. A length L2 of the container between the fluid inlet opening and the fluid outlet opening may be 729 mm. The fluid connection devices may each have an angled by a 90 ° angle shape, for. B. have an L-shape with two legs. One of the fluid connection devices, for. B. the fluid connection device at the fluid inlet opening can be mounted in the cartridge Condition parallel to the length of the container have a length L3 of 53 mm. If this fluid connection device has an L-shape, a length L4 of the fluid connection device between the free leg of the L-shape and the container is 21 mm. The other of the fluid connection devices, e.g. As the fluid connection device to the fluid outlet opening, in the mounted state on the cartridge parallel to the length of the container have a length L5 of 89 mm. If this fluid connection device has an L-shape, the length L6 of the fluid connection device between the free leg of the L-shape and the container is 56 mm. As an example, in 5c schematically the cartridge 110 with L-shaped fluid connection devices are not shown to scale with the above external dimensions L1 to L6.

In a further embodiment, the container is 717 mm long and a first opening selected from the fluid inlet opening and the fluid outlet opening comprises a tube piece with a length of 33 mm. Furthermore, a compression connector can be provided in the pipe section and connected to the associated fluid connection device.

According to one embodiment, a screw connection or bulkhead screw connection is provided in a second opening selected from the fluid inlet opening and the fluid outlet opening. The bulkhead fitting can extend the tank by 6 mm.

Furthermore, in embodiments of the device, the fluid connection devices 17 each have an angled by 90 ° angle shape. In addition, the fluid connection devices 17 at their respective free end in each case a connection opening, for. B. with an inner diameter of 20 mm, for connection to the respective fluid line connection piece. The distance between the centers of the connection openings, for example, in the embodiment of the 5c between 835 and 850 mm or approximately 839 mm.

5d shows schematically as another embodiment of the device for adsorption treatment, a cartridge 111 in the total or partial representations of 5D0 to 5d3 , The container of the cartridge 111 includes, as in the cross-sectional view of 5D0 is shown, a piece of pipe 1 , on one end of which is an end cap 2 and at the other end an end cap 3 are provided. The end cap 3 and the associated end of the pipe section 1 are connected together by welding. The pipe piece 1 and the endcap 2 have complementary threads and are interconnected, using an O-ring 5 for sealing between the pipe section 1 and the end cap 2 is provided. For the O-ring 5 is in the end cap 2 an annular groove provided.

In the end cap 3 is the fluid inlet opening 14 provided with a bulkhead fitting 6 is provided in a length L15 of 6 mm from the fluid inlet opening 14 protrudes. In the bulkhead fitting 6 is as a fluid connection device 17 a safety socket 9 intended. The fluid outlet opening 16 is in the present embodiment with a pipe piece 8th welded by 33 mm in length. In the pipe section 8th is a compression connector 7 inserted, with the as a fluid connection device 17 a second safety socket 9 connected is. One sieve with a mesh size of 0.5 mm is in the cartridge inside the end cap 3 in front of the fluid inlet opening 14 and approximately in the middle of the interior of the cartridge 111 intended.

The container of the cartridge 111 ie the connected system from the pipe section 1 , the end caps 2 and 3 and the pipe section 8th has a length L11 of 750 mm. The pipe piece 1 has a length L12 of 598.5 mm. The end cap 3 has a length L13 of 100 mm, while the end cap 2 has a length L14 of 105 mm. The pipe piece 1 and the endcap 3 have an inner diameter of 90 mm. The end cap 2 on the other hand has an internal diameter of 96 mm. The pipe piece 1 , and the end caps 2 and 3 each have an outer diameter of 110 mm. The pipe piece 8th , the press connector 7 and the safety sockets 9 each have an inner diameter of 20 mm. The annular groove for the O-ring 5 has an inside diameter of 104 mm. The O-ring may be made of a flexible material which is resistant to the fluid to be treated, e.g. B. Teflon.

5d also includes detailed representations 5d1 . 5d2 and 5d3 , The detailed representation of the 5d1 shows a plan view of the end cap 2 the cartouche 111 with the safety socket provided 9 , The detailed presentation 5d2 illustrates an enlarged section Z of the pipe section 8th and the press connector 7 , as a lateral plan view along the arrows A on the 5d1 , 5d3 represents an overall perspective view of the cartridge 111 represents.

5e illustrates an example of the device according to the embodiment of the 5d with technical details. The dimensions of the individual components with the reference numerals 1 to 9 are explained in detail in the parts list. The example of 5e has a general tolerance according to ISO 2768-m , At least one of the safety sockets 9 may be an all-gas safety socket GT DN 15. Table: Parts list of Fig. 5e Pos. amount unit designation 1 1 piece Pipe piece DN 110 × 10.0 2 1 piece End cap, long DN 110 × 10.0, with thread 3 1 piece End cap, long DN 110 × 10.0, without thread 4 2 piece Screen with mesh size 0.5 mm 5 1 piece O-ring, diameter 96 × 5 6 1 piece Bulkhead connection SV12MS PN 16/40 7 1 piece Press connector 20 × 1/2 "IG 8th 1 piece Pipe piece, diameter 20, 33 mm long 9 2 piece Safety gas socket DN 15

Surprisingly, it has been found that a flow through the cartridge from bottom to top has positive effects on the desired homogeneous flow of the adsorbents. According to a particularly preferred embodiment, therefore, the cartridge is designed so that it can be installed vertically and flowed through from bottom to top. Furthermore, it can, as explained above, between the gas inlet opening 14 and Adsorber an optionally filled with porous inert material or thus limited cavity for collecting condensate. Is the cavity as a flexible porous inert material, z. As flexible porous plastic foam, this may be additionally advantageous in terms of filling and abrasion resistance of the adsorbents. For example, in the case of a filling of the adsorbents between a flexible inert material layer in a cavity at the bottom and a correspondingly identical layer in a cavity at the head of the cartridge, the adsorber particles are clamped between the two layers. The flexibility of such an inert material layer, e.g. As a plastic foam, offers advantages in terms of abrasion resistance of the adsorber z. B. during transport of the cartridge. In addition to the formation of abrasion and the entry of dust can be reduced in subsequent catalyst stages, especially when the plastic foam simultaneously shows filtration effect and thus prevents powdered components of the adsorbent are discharged with the gas.

According to a particular embodiment, the cartridge may comprise: a resealable container with two safety gas connections, i. H. at the gas inlet and gas outlet, a gas inlet and / or gas outlet zone to improve the flow distribution of the gas flowing through, a simple suspension and / or several security elements to protect against opening by unauthorized persons.

According to another embodiment, there is provided a method for regenerating and / or disposing, filling and / or installing the apparatus for the adsorption treatment of a fluid or fluid stream comprising at least one of the steps of: filling the container with the adsorber material, e.g. Under inert gas, inert fluid, inert gas or the fluid freed from an adsorptive to be removed by the adsorption treatment; Rinsing the container during and / or after filling the container with the adsorber material, for. With inert gas, inert fluid, inert gas or the fluid freed from an adsorptive to be removed by the adsorption treatment; Performing a pressure and / or leakage test to verify the tightness of the filled container with locked fluid connection devices; Installing the device for adsorption treatment of a fluid or fluid stream before or in a dedicated device while the container is filled with adsorber material and an element selected from inert fluid, inert gas or the fluid freed from an adsorptive to be removed by the adsorption treatment; and installing the apparatus for adsorption treatment of a fluid or fluid stream according to the above embodiment before or in the housing of a fuel cell and / or before or after a gas compressor of a fuel cell.

Filling the container with adsorbent means here that the container is completely or incompletely filled with adsorbent material such that in both cases in the container free volume for fluid or gas is present. Thus, the container may also be filled with gas or fluid.

In another embodiment, there is provided a method of regenerating and / or disposing, filling, and / or installing the apparatus for adsorbing a fluid or fluid stream comprising at least one of the following steps.

One of the steps involves removing the apparatus for adsorption treatment of a fluid or fluid stream, the container of which contains adsorber material to be regenerated and / or disposed of, from a device on which or in which an adsorption treatment has been carried out by releasing the fluid connection devices 17 of fluid line fittings 20 which are connected to the device. The release of the fluid connection devices 17 from the fluid line fittings 20 can be done while the container is filled with treated or treated fluid.

Another possible step of the method for regenerating and / or disposing, filling and / or installing the device for adsorption treatment comprises transporting the container with the adsorber material to be regenerated and / or disposed and locked fluid connection devices under safety precautions and / or under protective gas, inert fluid or inert gas. In the method for regenerating and / or disposing, filling and / or installing the device for adsorption treatment, all, single or multiple transport steps under safety precautions, such as. Example, under protective gas, inert fluid or inert gas, carried out, wherein the protective gas, inert fluid or inert gas can be provided within and / or outside of the container. Examples of other safety precautions during transport are: A suitable packaging with special protection for individual components, such as. B. the fluid connection devices, so that during transport no physical damage to the cartridge can occur; a mark with warnings, eg. B. "Do not open, cartridge may contain residues of hazardous ingredients"; and preventing gas exchange with the exterior of the container through intrinsically safe connections.

Further, in a step of the method for regenerating and / or disposing, filling and / or installing the apparatus for adsorption treatment, the container with the adsorber material to be regenerated and / or disposed and locked fluid connection devices can be transported to a regeneration and / or disposal station. There, for example, under protective measures, the device can be opened and the adsorber material exchanged or regenerated. The equipment may be present and used in the regeneration and / or disposal station necessary for the safe handling and regeneration of the apparatus for the adsorption treatment of a fluid or fluid stream and / or for the safe handling, regeneration and / or disposal of the adsorbent material. If the container for reversible filling with the adsorber material comprises an opening and closing element which has a security device to prevent tampering by unauthorized persons, special equipment or special tools may be present and used in the regeneration and / or disposal station for handling the safety device / which is not commercially available but only available to professionals. For example, the container of the device may comprise a safety device, selected from: a cover of the opening and closing element and / or a special screw, which can be opened only with special tool / can. The security device may also be a seal that can only be opened by professionals.

Examples of other possible protective or safety measures in the regeneration and / or disposal station are: flushing of the cartridge with inert gas before opening, because in some cases an adsorptive can cause an explosive gas mixture when opened or, for example, in the case of sulfur adsorbers, pyrophoric reactions drain with air; Opening and refilling the used or to be regenerated adsorber under common safety precautions for the staff in the regeneration and / or disposal station, such as personal protective equipment, such as goggles and respiratory protection, air exchange and extraction of possibly contaminated air; and oxidative aftertreatment of purge gas, possibly containing fluid residues from the cartridge.

Further, the method for regenerating and / or disposing, filling and / or installing the adsorption treatment apparatus may include at least one of: purging the container containing adsorber material to be regenerated and / or disposed with inert gas, inert fluid or inert gas; Emptying the container from the adsorber material to be regenerated and / or disposed of, e.g. B. under inert gas, inert fluid, or inert gas; Disposal and / or regeneration of the regenerated and / or or dislodging adsorbent material; Filling the container with regenerated or unused adsorber material, eg. Under inert gas, inert fluid, inert gas or the fluid freed from an adsorptive to be removed by the adsorption treatment; Purging the container with inert gas, inert fluid, inert gas or the fluid freed from an adsorptive to be removed by the adsorption treatment, during and / or after filling the container with the regenerated or unused adsorbent material; and performing a pressure and / or leakage test to verify the tightness of the filled container with locked fluid connection devices.

For example, the following sequence of removal of a used adsorber material from the cartridge is possible: first, the container is purged with N ₂ until the residual gas in the container is removed. Thereafter, the container is opened. Then the absorber material is removed from the container and filled in a special container for disposal. Further, in one example, the container is filled with the regenerated or unused adsorber material under air and then purged with inert gas. In this case, a small amount of residual air remain in the container, because the inert gas is mainly used to displace most of the air in the container for subsequent applications.

Furthermore, the method may comprise regenerating and / or disposing, filling and / or installing the device: transporting the container with the regenerated or unused adsorbent material and interlocked fluid connection devices to a device at or in which an adsorption treatment is to be performed; and / or connecting fluid line fittings 20 with the device. In addition, the apparatus for adsorption treatment of a fluid or fluid stream may be installed on or in the apparatus while the container is filled with regenerated or unused adsorbent material and an element selected from inert gas, inert fluid, inert gas or the fluid to be removed from one to be removed by the adsorption treatment Adsorptively freed, by connecting the fluid connection devices 17 with fluid line fittings 20 which are connected to the device.

Embodiments of the method for regenerating and / or disposing, filling and / or installing the apparatus for adsorption treatment allow the adsorbent treatment apparatus used adsorbing material to be removed from a facility at or at which the adsorption treatment has been carried out, and to a regeneration and / or or disposal station, while the adsorption treatment treated or treated gas is in the adsorption treatment apparatus. Further, embodiments of the method for regenerating and / or disposing, filling and / or installing the adsorption treatment apparatus allow the adsorption treatment apparatus containing unused or regenerated adsorbent material to be transported to a facility at or at which the adsorption treatment is to be performed, while inert gas is in the adsorption treatment device.

In an example of the method for regenerating and / or disposing, filling and / or installing the adsorption treatment apparatus, a cartridge containing adsorber material to be regenerated and / or disposed is disposed at a facility where desulfurization treatment has been performed. The cartridge includes the container 10 and the gas sockets 17 of the example of 4b , The gas plug 20 that with the device and the gas sockets 17 are connected by the gas outlets 17 dissolved while in the container natural gas is. Upon release, the fluid connection devices become 17 on the container 10 with the bars 18 closed, so that the cartridge is gas-tight locked. Then the cartridge is transported to the regeneration and / or disposal station. There, the natural gas contained in the cartridge is removed under safety precautions to prevent explosions or contact with personnel and the cartridge is optionally purged with inert gas. The cartridge is then opened by loosening the threaded closure. Now, the cartridge, optionally under a protective gas atmosphere, freed from the spent adsorber, filled with fresh or regenerated adsorber and then rinsed with inert gas. Finally, the cartridge is transported to a facility at or in which a desulfurization treatment is to be carried out and connected to the facility while inert gas is in the cartridge.

According to embodiments, the device to or at which an adsorption treatment is to be performed may be a fuel cell or a gas compressor of a fuel cell. The device for adsorption treatment of a fluid or fluid stream or the device to which an adsorption treatment is to be carried out may comprise an adsorptive detector or a sulfur detector, and the regeneration and / or disposal of the device for adsorption treatment of a fluid or fluid flow may be dependent on the detection of a Adsorptive or be carried out by sulfur compounds. Furthermore, the device on or in which an adsorption treatment is to be carried out, be provided with at least one shut-off valve, which is installed in the flow direction before or after the device for the adsorption treatment of a fluid or fluid flow.

In addition to filling, installation and removal, regeneration and disposal, a service cycle may also include safety measures, including safety precautions. An example of one embodiment is to perform a pressure and / or leak test prior to shipment of the cartridge. With such a test, the technical tightness can be checked. In a particularly advantageous embodiment of the invention, prior to delivery of the cartridge, a pressure and / or leakage test with N ₂ or other known inert gases such. As CO ₂ , He, Ne, or Ar take place. This has the advantage that after installation of the cartridge in the gas line and opening the gas tap in the cartridge no explosive mixture can occur or subsequent components can be damaged. If the filling of the cartridge, however, carried out under air and no flushing integrated into the filling process, the cartridge contains air, which can form explosive mixtures when mixed with the fuel gas or can cause problems in downstream equipment parts. If z. As a reduced and thus pyrophoric reforming catalyst, such as a Ni catalyst or a water-gas shift catalyst containing Cu / Zn, brought into contact with air, violent oxidation reactions can occur and cause metal burning in the worst case.

In a further preferred embodiment of the invention, the cartridge can be rinsed and delivered instead of inert gas with the main component of a gas to be treated. Example is sulfur-free natural gas or pure methane or technical, sulfur-free propane or butane for the use of LPG.

When loading the container with regenerated or unused adsorber material, one or more of the following steps may be performed: control of the weight by gravimetric or volumetric method; Shaking or vibrating while filling the container to ensure optimum settlement of the filling; and air extraction of particulate matter as a safety precaution.

A flushing process can be carried out after filling the container with adsorbent material with inert gas, such as N ₂ , and / or before performing a pressure or leakage test: For example, first the container is flushed with N ₂ until the defined oxygen content to be defined in the cartridge is, then the pressure with the same inert gas is increased to pressure and / or leakage test level. This is followed by the pressure or leakage test, z. Example, by determining the pressure difference, the pressure drop or a leakage rate at a suitable pressure. After successful pressure or leakage test, the N ₂ is drained again until approx. Room pressure is reached. The connections are closed and the cartridge is under N ₂ . Another rinse is typically not required.

The regeneration of the adsorber can be done thermally, for. B. with steam, air or other hot gaseous media at temperatures greater than 200 ° C. A disposal can z. For example, sulfur is roasted from a Cu / Mn adsorber, then Cu and Mn are melted by thermal processes, separated and recovered as a solution.

Examples of inert gas, inert fluid or inert gas are N ₂ , Ar, He, nitrogen enriched air (NEA), CO ₂ , or the respective pure gas to be treated with the adsorber material.

The cartridge can be installed either in front of the fuel cell (external) or in the fuel cell housing (internally). In the case of an external installation, it should be noted that the desulfurized gas no longer contains odorants after flowing through the cartridge and that no warning smell is emitted in the event of a leak. The gas line to the cartridge and before entering the fuel cell device may therefore be designed so that it contains no internals. One possible solution is, for example, the attachment of a gas hose or a similar line piece in the fuel cell housing, so that the attachment from the outside is not accessible. If the accessible free end of the gas hose to which the gas plug is mounted is connected to the provided gas socket on the cartridge, no non-odorized gas can escape. Since the gas line up to the gas socket contains no other installations or screw connections, the gas line can be classified as permanently leak-proof after the pressure test has been carried out. The change process and the operation of the cartridge can be done safely with the described structure.

In an internal installation, additional security measures such. B. gas warning sensors or suction of the housing air available. Gas leaks can do with it Detected independently of Odoriermittelgehalt or the formation of an explosive atmosphere can be prevented. In internal installations, a distinction is made according to embodiments as to whether the cartridge is installed before or after a gas compressor. In the case of installations upstream of a compressor, negative pressure may occur during operational malfunctions; in the case of an installation after a gas compressor, a slight overpressure may be assumed as the operating pressure.

In addition to the pressures, different operating temperatures result in the different installation variants. For installations in a fuel cell housing temperatures of up to 70 ° C are conceivable, while for external installations ambient temperatures z. B. prevail in basements.

Therefore, in embodiments, the cartridge and / or the adsorbent material used is at temperatures of -10 to + 90 ° C and a pressure range of -500 mbar above atmospheric pressure to +10 bar above atmospheric pressure, preferably at a temperature range of -10 to + 80 ° C. and a pressure range of -300 mbar above atmospheric pressure to +3 bar above atmospheric pressure, and particularly preferably at a temperature range of -10 to + 70 ° C and a pressure range of -100 mbar above atmospheric pressure to +100 mbar above atmospheric pressure. The unit "bar above atmospheric pressure" used here corresponds to the unit barg and means bar relative to atmospheric pressure.

In a further embodiment, there is provided a process for adsorbing a fluid or fluid stream, in particular for desulfurizing natural gas or liquid gas for fuel cells, comprising: providing the apparatus for adsorbing a fluid or fluid stream according to any of the embodiments described herein, wherein the vessel is provided with an adsorbent material Adsorption treatment of fluids is filled, connecting a fluid supply line with a first fluid line connection piece and a fluid outlet with a second fluid line connection piece, connecting the first and second fluid line connection piece with the two fluid connection devices of the device for adsorption treatment of a fluid or fluid flow and thereby unlock the fluid connection devices, and introduction of a fluid in or passing a fluid through the device for adsorption treatment of the fluid.

It is provided in one embodiment that the cartridge is operated in combination with a shut-off valve which is installed in front of the cartridge. In another embodiment of the invention, the cartridge can be operated in combination with a sulfur monitor. Operation in combination with a sulfur monitor allows dynamic cartridge cycling, depending on the amount of sulfur absorbed and regardless of regional differences in natural gas composition.

In accordance with embodiments described herein, the apparatus for adsorbing a fluid or fluid stream is configured or oriented such that the fluid is passed vertically through the apparatus from bottom to top.

If the fluid is passed vertically through the device from bottom to top, if the adsorbent bed z. B. by strong shaking or transport operations, on the wall of the cartridge container, in contrast to a horizontal installation and flow, no edge flow effect and thus no premature breaking of sulfur substances occur.

Furthermore, the flow management from bottom to top offers advantages in terms of reliability with regard to entrainment of condensed water in z. B. natural gas. It is known that water can occur in gas lines at least in gaseous form. In a possible condensation, z. B. during gas in cool areas of a basement room, accumulation and transport of liquid water in the gas, the adsorbents used can therefore be brought into contact with liquid water. In this case, the adsorbents can enter into unwanted reactions with water or lose their functionality and thus not maintain proper operation. To reduce the risk that the adsorbent comes into contact with liquid water, the procedure can be carried out so that the cartridge is traversed vertically from bottom to top. If, in addition, a cavity or a cavity filled or filled with highly porous inert material is provided between the gas inlet and the adsorber, any possible condensate can be retained therein. The combination of flow guidance from bottom to top with the described cavity can also have positive effects on the flow distribution in the gas inlet region. Surprisingly, it has been found that a flow through the cartridge from bottom to top has positive effects on the desired homogeneous flow of adsorbents, as already above in connection with the 5a and 5b was explained.

According to another embodiment of the methods described herein, the apparatus for adsorption treatment of a fluid or fluid stream is operated in combination with an adsorptive detector or a sulfur detector, and the replacement of the apparatus is performed depending on the detection of an adsorptive or sulfur compound. Further, the apparatus for adsorption treatment of a fluid or fluid flow may be operated in combination with a shut-off valve installed in the flow direction before or after the tank. By these measures, the safety of the operation of the device according to the invention can be increased.

In another embodiment of the process, in particular in combination with a sulfur detector, the fluid after passing through the device may have a purity of <50 ppb residual sulfur.

In a further embodiment of the method, the fluid is passed through the device at temperatures of -10 to + 90 ° C and a pressure in a pressure range of -500 mbar above atmospheric pressure to +10 bar above atmospheric pressure. As a result, a method for producing a desulfurized fuel gas for fuel cells is provided in which the fuel gas, in particular natural gas and LPG, by the use of suitable adsorbents at temperatures of -10 to + 90 ° C and a pressure range of -500 mbar above atmospheric pressure to +10 bar above atmospheric pressure, preferably at a temperature range of -10 to + 80 ° C and a pressure range of -300 mbar above atmospheric pressure to +3 bar above atmospheric pressure, and more preferably at a temperature range of -10 to + 70 ° C and a pressure range of -100 mbar above atmospheric pressure to +100 mbar above atmospheric pressure is desulfurized. For installations of the device according to the invention in a fuel cell housing namely temperatures of up to 70 ° C are possible, while in external installations ambient temperatures may prevail, for example in basements.

In embodiments, the container of the cartridge may be tubular or cylindrical, but other shapes of the container are conceivable. Equations and explanations given herein relating to tubular cartridge containers are to be understood as analogous to non-tubular cartridges.

According to one embodiment of the apparatus and method, the container may have a packed length to bulk diameter ratio (L / D ratio) of 0.1 to 40, and / or in the container may have a space velocity <10,000 h ^-1 relative to Total amount of adsorber be set. In an advantageous embodiment, the minimum L / D ratio is in a range of 1 to 20 and in a particularly advantageous embodiment in a range of 1 to 10. In a particularly preferred embodiment, the space velocity is less than 2,000 h ^-1 based on the total amount of adsorber material. According to a preferred embodiment of the invention, the bulk-to-particle diameter ratio has values greater than 10, in a particularly preferred embodiment values greater than 20. These embodiments cause a particularly favorable breakdown behavior of the device for the adsorption treatment of a fluid or fluid flow, as explained below.

L_Schüttung:

Durchströmte Länge der Schüttung in axialer Richtung

D_Schüttung:

Durchmesser einer zylinderförmigen Schüttung

The bedding-to-bedding ratio (L / D) ratio is the ratio of the length of the bed to its diameter. The equation for this is:

L _bed:

Flowed length of the bed in the axial direction

D _bed:

Diameter of a cylindrical bed

W₀:

Strömungsgeschwindigkeit des Fluids im leeren Rohr (Leerrohrgeschwindigkeit)

V_Gas:

Gasvolumenstrom

A:

Reaktorquerschnittsfläche

D_Reaktor:

Reaktordurchmesser

A higher L / D ratio means a longer path through the adsorber and thus a longer residence time (see below) in the adsorber bed. Therefore, an L / D ratio in the range of 0.1 to 40 has a positive effect on the breakthrough time. In a variation of the L / D ratio changes, in the case of a tubular container of the cartridge, the diameter of the bed or the container. This has a constant bed volume and gas flow a change in the flow rate result. This change is present both in the free cross-section of the container of the cartridge, which is also referred to here as a reactor, as well as within the bed. The following equation shows the dependence of the empty tube velocity on the volume flow and reactor diameter.

W ₀ :

Flow velocity of the fluid in the empty tube (empty tube velocity)

V _gas :

Gas flow

A:

Reactor cross-sectional area

D _reactor :

Reactor diameter

A higher empty tube velocity can adversely affect the adsorbent breakthrough capacity because the molecules to be removed have less time available for sorption. This can thus have an accelerating effect on the breakthrough time.

W₀:

Strömungsgeschwindigkeit des Fluids im leeren Rohr (Leerrohrgeschwindigkeit)

V:

Schüttbettvolumen

A:

Reaktorquerschnittsfläche

A similar influence on the breakthrough capacity causes the choice of the space velocity. The space velocity (RG) is the reciprocal of the residence time and one of the most important operating parameters for catalysts and adsorbents. It is calculated according to the following formula:

W ₀ :

Flow velocity of the fluid in the empty tube (empty tube velocity)

V:

Packed bed volume

A:

Reactor cross-sectional area

The space velocity is usually given in the unit 1 / h and related to NL / h / L adsorbent. The empty tube velocity is often expressed indirectly in the chemical engineering by the space velocity, since this is directly proportional to the empty tube velocity and additionally expresses the connection with the used bed volume. However, there is no relation to the shape of the packed bed. As can be seen from the formula, it is directly proportional to the flow velocity. Therefore, a higher space velocity also has an accelerating effect on the breakthrough time. Measurements showed that low space velocities have a positive effect on the breakthrough capacity of the chosen adsorbent and retarding the breakthrough time. For this reason, in embodiments, low space velocities less than about 10,000 h ^{-1 are} chosen. Another important reason for the choice of low space velocities is the required service life of the adsorbent. The service interval, for example, of fuel cell house heating systems should not be less than one year. A certain minimum amount of adsorber is therefore necessary to realize the required gas purity over the period.

D_Schüttung:

Durchmesser einer zylinderförmigen Schüttung

d_P:

mittlerer Partikeldurchmesser.

According to a preferred embodiment of the invention, the bulk-to-particle diameter ratio has values greater than 10, in a particularly preferred embodiment values greater than 20. The bulk to particle diameter ratio is defined as follows:

D _bed :

Diameter of a cylindrical bed

d _P :

average particle diameter.

The porosity, also referred to as the degree of voiding, is higher on the wall of a fixed bed adsorber than in the remaining packed bed. Therefore, there may be so-called edge flow effects on the wall. These effects can be at an earlier breakthrough time z. B. lead a sulfur compound. The average porosity of ball piles is between 0.37 and 0.4. The marginal porosity is about 0.5 at these beds. Commercially available desulfurization adsorbents, such. B. the spherical material FCDS-GS12 Fa. SüdChemie AG has an average porosity of 0.32. In order to avoid edge flow effects, in one embodiment at least one D / d _P ratio greater than about 10 is maintained.

Examples

Experiments were performed on a desulphurisation test facility as examples of embodiments of the invention. The desulphurisation plant has four cylindrical cartridges as devices for adsorption treatment, which could be passed in parallel with different gases. The cartridges were each provided at the gas inlet opening and at the gas outlet opening with gas sockets and connected with corresponding gas plugs with a respective gas line. The gas sockets and gas plugs come from the manufacturer Viega, component: 1/2 '' Type TAE (G2016T) # 526 788, the gas pipes each consisted of gas hoses of the manufacturer Viega, component 1/2 "× 500 mm (G2023) # 531 904 ,

The aim of experiment 1 was to document the effects of the L / D ratio and the space velocity to show that both parameters have a direct influence on the adsorption performance, eg. B. on the desulfurization, the material or the cartridge. The aim of experiment 2 was to analyze the flow in the inlet area of the cartridge.

The incoming and outgoing gas could be specifically analyzed for sulfur compounds using a gas chromatograph connected to the gas outlet and gas inlet of the unit, equipped with a pulsed flame photometric detector (GC-PFPD). Mass Flow Controllers from Brooks made it possible to precisely control the gases supplied. As test adsorbents, a sequential desulfurization bed was used as in WO 2006/028686 A1 chosen in the ratio 3 to 1. The adsorbent material used consisted of Ca exchanged 13X zeolite (FCDS-GS12) according to Example 1 of WO 2006/028686 A1 sequentially in combination, with a mixed Cu / Mn metal oxide (FCDS-GS6) according to Example 2 of WO 2006/028686 A1 , The 13X zeolite had a Si: Al equivalence ratio of 1.17 and a calcium exchange of 70%, with the remaining metal ions comprising sodium and / or potassium. The Cu / Mn mixed metal oxide material had 34% by weight of manganese compounds 54% by weight of iron oxide comprising Fe ₂ O ₃ and 12% of aluminum oxide having a surface area of 294 m ² / g. Further test data are shown in Table 1. General test data print pressure P_Abs bar 2 temperature T ° C 40 bulk data bulk total V [Ml] 2.1 Bulk volume Ex. 1 WO06 / 028686 V_Bsp. 1 WO06 / 028686 [Ml] 1.5 Bulk volume Ex. 2 WO06 / 028686 V_Bsp. 2 WO06 / 028686 [Ml] 0.6 Particle size Ex. 1 WO06 / 028686 d_p_Bsp. 1 WO06 / 028686 [Mm] 0.8-1 Particle size Ex. 2 WO06 / 028686 d_p_Bsp. 2 WO06 / 028686 [Mm] 0.8-1 Bulk density Ex. 1 WO06 / 028686 p_schuett_Bsp. 1 WO06 / 028686 [G / ml] 0.65 Bulk density Ex. 2 WO06 / 028686 p_schuett_Bsp. 2 WO06 / 028686 [G / ml] 0.74 Test gas composition methane CH ₄ [%] 98% carbon dioxide CO ₂ [%] 1.00% nitrogen N ₂ [%] 0.75 tetrahydrothiophene THT [Ppm] 10 ethyl mercaptan EM [Ppm] 10 carbonyl COS [Ppm] 10 hydrogen sulfide H ₂ S [Ppm] 5 Table 1: General data of the desulphurisation tests

The sorbents were brought by grinding and sieving to the particle size fraction 0.8 to 1 mm. Since exact volume determination is very difficult with the small sorbent volumes, bulk bulk measurements were made with the materials and the sorbent levels were weighed for the tests. In this way it was possible to ensure that the same amounts of sorbent were used for each individual experiment.

Trial 1

Little is known about the concrete influence of the L / D ratio of bulk material reactors on the adsorber performance. However, this influence is very important for the design of an adsorption cartridge, which is why tests were carried out with L / D ratios (see Table 2). Space velocities were set in the range between 3000 and 15000 1 / h.

The tests were designed so that one space velocity and four fixed L / D ratios were measured per test run. Table 2 lists the test variants. Space velocity variation Test no. 1 2 3 Flow rate per reactor V. [L / h] 6.3 10.5 20.9 space velocity GHSV [L / h] 3000 5000 10000 L / D Variation reactor 1 2 3 4 Length to diameter ratio L: D [-] 2.0 3.9 3.9 7.4 Reactor diameter D [Mm] 11.0 8.8 8.8 7.1 Bulk length (/ height) L [Mm] 22.0 34.4 34.4 52.8 Table 2: Variants of the desulphurisation tests

After the test gas flowed through the cartridges filled with adsorbents, the breakthrough behavior was recorded with the GC-PFPD detector as a function of the L / D ratio. Breakthrough is the time or breakthrough capacity at which, for the first time, a specific sulfur compound in the gas is detected after the adsorber bed. The limit of quantification was 200 ppb per sulfur compound. From the defined gas volume and the defined sulfur components and concentrations in the gas can be calculated how much sulfur passes through the cartridge. This is called breakthrough capacity. From this, the load at break-through time can be calculated via the weighed sorbent mass.

Table 3 shows, for example, the measured breakthrough capacities of the desulfurization bed, which corresponds to Example 1 of WO2006 / 028686 was modeled as the ratio of mass compound to mass of the sorbent. The breakthrough capacities were determined on the basis of the breakthrough time. The breakthrough in this case was a concentration of 1 ppm THT (tetrahydrothiophene) at the cartridge exit. About the volume enforced up to this time and the content of sulfur compounds could be calculated, which had absorbed sulfur content of the adsorber. Values in% THT THT example 1 from WO 2006/028686 RG [1 / h] | L / D [-] 2 3.9 7.4 10000 12.5 13.1 14.0 5000 13.9 14.2 15.0 3000 13.7 14.6 15.6 Table 3: Breakthrough capacities for THT at breakthrough time 1 ppm

6 shows the influence of the space velocity as well as the L / D ratio pictorially, the breakdown capacity of the L / D ratio of 2 and the space velocity 10000 are respectively defined as 100%.

It could therefore be confirmed that higher breakthrough capacities result from higher L / D ratios. On the other hand, the height and the resulting pressure drop of the container of the cartridge are to be considered, so that an excessively long container of the cartridge is not desirable. It could be shown that an L / D ratio of about 4 represents a good compromise in the design of the cartridge.

Trial 2

The aim of experiment 2 was to analyze the flow in the inlet area of the cartridge. For fluidic investigations, a cylindrical cartridge prototype made of clear Plexiglas was manufactured. This made it possible to visually assess flow-dynamic gas distributions. The inside diameter of the prototype was 14, the length about 55 cm. The volume was about 8 liters. The cartridge had removable lids at both ends of the cylinder, allowing it to be opened and filled. In the lid gas sockets according to the invention, in the present examples gas sockets from Viega, were screwed, were introduced into the corresponding gas plugs with gas lines connected thereto.

With the help of artificially generated mist, the inflow into the cartridge was made visible. Various installations have been tested to check if they exert a comparable effect on the flow.

With the help of a Mass Flow Controller (MFC) from Brooks, the gas volume flow was regulated. The MFC was calibrated for this purpose to the medium used, nitrogen 3.0, with the aid of a DRYCAL flowmeter manufactured by Westphal in the volume flow range between 70 and 600 standard liters per hour. The nitrogen stream was mixed via a T-piece of fog from a commercial FOG-700 disco fogger. The gas / mist mixture entered the cartridge via the ports. A visual documentation was done by means of an HD camera, which is fixed on a tripod before the test setup. To increase the contrast, the cartridge was pasted with black construction paper.

A prerequisite of the experiment was that the mist in the gas medium mixed optimally and had no settling behavior. This could be confirmed by a test by filling the cartridge with mist and then stopping the gas flow. The fog "floated" then constant and showed no settling behavior.

A volume flow of 400 NL / h N _{2 was} set, which corresponds to a space velocity of approx. 50 NL / h / L. In the first test run, the inflow behavior of the gas was observed with an inflow from top to bottom through an inert porous layer of hard plastic foam which was provided in the container of the cartridge at a distance from the gas inlet opening. In comparison, in a second test run with a gas inflow from bottom to top, an inflow through an inert porous layer of hard plastic foam of the same material as in the first test run, which was provided in the cartridge at a distance from the gas inlet opening was performed. It was easy to see that the flow "shot through" more from top to bottom as it flowed in, ie distributed more unevenly in the container of the cartridge. An optimal and desired flow behavior was observed at inflow from bottom to top. Already within a few centimeters of the container height, a so-called plug flow, ie the formation of a gland-shaped mist cloud, set in at the bottom of the cartridge. A uniform loading of the adsorbent and thus an optimal utilization of the filling of the adsorbent is the result of such flow behavior.

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

• WO 2010/023249 A1 [0006]
• WO 2006/028686 [0027, 0116, 0116]
• WO 2004/060840 A2 [0046]
• WO 2006/028686 A1 [0046, 0111, 0111, 0111]
• US 2009272675 A1 [0046]
• WO 06/028686 [0111, 0111, 0111, 0111, 0111, 0111, 0111, 0111, 0111, 0111, 0111, 0111]

Cited non-patent literature

• ISO 2768-m [0066]
• PN 16/40 [0066]

Claims (15)

Apparatus for the adsorption treatment of a fluid or fluid stream, comprising a container ( 11 ) for receiving adsorber material, wherein the container has a fluid inlet opening ( 14 ) and a fluid outlet opening ( 16 ), and two fluid connection devices ( 17 ), wherein one of the fluid connection devices is provided at the fluid inlet opening and the other of the fluid connection devices is provided at the fluid outlet opening, wherein the fluid connection devices are fluid-tightly locked and designed such that they are each connectable and unlockable with a fluid line connection piece and provided that they the respective fluid line connecting piece are connected, unlocked or unlocked. Device according to claim 1, wherein the unlocked fluid connection devices secure the fluid line fittings; and or wherein the fluid connection devices are configured such that the fluid line connection pieces are secured when unlocking the fluid connection devices; and or wherein the fluid connection devices are designed such that they can be manually or automatically locked by means of the respective fluid line connecting pieces; and or wherein at least one of the fluid connection devices is designed such that it can be connected and unlocked successively or simultaneously with the respective fluid line connection piece. Apparatus according to claim 1 or 2, wherein the fluid connection devices each have a fluid flow channel ( 19 ) and a movable closing body ( 18 ), wherein the closing body fluid-tightly closes the fluid flow passage and the fluid connection devices are formed such that the respective closing body is moved by connecting the fluid connection device with the fluid line connection piece and opens the fluid flow channel, and / or moved by releasing the fluid line connection piece and closes the fluid flow channel. Device according to one of the preceding claims, further comprising two fluid line connecting pieces ( 20 ), which are formed so that they are each connectable to one of the two fluid connection devices and a fluid line. Device according to one of the preceding claims, the container containing one or more adsorber materials; and or the container contains one or more adsorbent materials for the desulfurization of liquefied gas, gas, natural gas or other hydrocarbons; and or the container contains a plurality of adsorber materials and the adsorbent materials are present in a mixed bed or as a multicomponent adsorber material. Device according to one of the preceding claims, further comprising a thermally triggering Fluidabsperreinrichtung ( 30 ) and / or a fluid flow monitor. Device according to one of the preceding claims, wherein the container for reversible filling with the adsorber material comprises an opening and closing element, which has a security device for preventing tampering, selected from: a cover ( 50 ; 54 ) of the opening and closing element and a special screw connection ( 52 ), which can only be opened with special tools. Device according to one of the preceding claims, wherein the container is formed so that it is vertically installable and adjacent to the fluid inlet opening a cavity ( 64 ) or a cavity ( 66 ) with a filling or boundary of porous and / or flexible inert material or plastic foam, for collecting condensate; and / or wherein the cartridge and / or the adsorbent material used are designed so that they can be used at temperatures of -10 to + 90 ° C and a pressure range of -500 mbar above atmospheric pressure to +10 bar above atmospheric pressure. An apparatus according to any one of the preceding claims, wherein the container has a packing length to packing diameter ratio of 0.1 to 40; and or wherein in the container a space velocity <10,000 h ^{-1 is set} based on the total amount of the adsorbent material; and / or wherein the bed-to-particle diameter ratio of the adsorber material is greater than 10. Device according to one of the preceding claims, wherein the outer length of the container ( 11 ) between the fluid inlet opening ( 14 ) and the fluid outlet opening ( 16 ) is in a range of 700 to 800 mm or 729 mm. Device according to one of the preceding claims, wherein the device including the fluid connection devices ( 17 ) has a length in the range of 850 to 900 mm or a length of 871 mm. Device according to one of the preceding claims, wherein the container ( 11 ) has an outer diameter of 110 mm and / or an inner diameter of 90 mm. Device according to one of the preceding claims, wherein the container ( 11 ) 717 mm long and a first opening selected from the fluid inlet opening and the fluid outlet opening a pipe section ( 8th ) with a length of 33 mm; and / or wherein in the pipe section ( 8th ) a compression connector is provided and with the associated fluid connection device ( 17 ) connected is. Device according to one of the preceding claims, wherein in a second opening selected from the fluid inlet opening and the fluid outlet opening a screw connection or bulkhead screw connection (US Pat. 6 ) is provided; and / or wherein the bulkhead fitting the container ( 11 ) extended by 6 mm. Device according to one of the preceding claims, wherein the fluid connection devices ( 17 ) each have a 90 ° angle angled shape; and / or wherein the fluid connection devices ( 17 ) at their respective free end in each case have a connection opening for connection to the respective fluid line connection piece, wherein the distance between the centers of the connection openings is between 830 and 850 mm or 839 mm.

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