DE102007033368B4 - A method of providing a sorbent material for a storage container - Google Patents

Abstract

A method of providing a sorbent material (11) to a storage container (10), the sorbent material (11) comprising a sorbent and adsorbate adsorbed thereto in the form of a gaseous fuel, preferably hydrogen, with spent sorbent material in the storage container (10) is discharged from the storage container (10), wherein the spent sorbent material outside the storage container (10) is reloaded with the gaseous fuel and then the loaded with the gaseous fuel sorption material (11) for the storage container (10) is provided, wherein the discharge of the storage container (10) of the spent sorbent material is carried out by blowing in the gaseous fuel.

Description

The The present invention relates to a method for providing a Sorption material for a storage container, wherein the sorbent material is a sorbent and a sorbent adsorbed thereon Adsorbate in the form of a gaseous one Fuel, preferably hydrogen, includes.

she refers to the technical field of storage and deployment gaseous Fuels or fuels, in particular hydrogen. In this In particular, the present invention relates to a context storage container for gaseous fuels and its applications.

Storage tanks, for example be designed as so-called adsorption. of course is the invention is not limited to this particular application. Basically the storage system according to the present Invention for any type of storage applicable, in which a - especially from an inner container and External container existing - used storage tank becomes a medium to be stored, for example, a gas liquid or maybe but also a different kind of filling in a solid.

following however, the invention will be mainly illustrated for clarity an adsorption storage system described.

Especially The present invention relates to the technical field of hydrogen storage, which has gained significantly in importance recently.

hydrogen is considered zero emission fuel in terms of emissions of toxic or the climate affecting process gases, because at its use, for example in thermal internal combustion engines, in fuel cell applications or the like, almost only water is produced.

consequently is the creation of suitable storage means for efficient storage Hydrogen is an important target which must be reached before a widespread use of hydrogen as a fuel can adjust.

It is already known in principle to adsorb hydrogen to suitable adsorbents (for example based on carbon) - also called sorbents or sorbents in the context of the invention. Such adsorption materials are, for example, activated carbon. Adsorption in the light of the present invention means the addition of gases or solutes at the interface of a solid or liquid phase, the sorbent. The sorbent, for example, serves as storage material for the hydrogen. The term "sorbent" - in the plural "sorbents" - is thus used in the context of the present invention to designate the adsorption or storage agent (eg activated carbon) as such (sometimes the term "sorbent" is also used interchangeably in the context of the present invention more specific term "adsorbent" or "adsorbents"used); By contrast, in the context of the present invention-in contrast to the term "sorbent" -the term "sorption material" is used to designate the sorbent together with the adsorbed substance or gas, the so-called adsorbate (for example, the adsorbent with the gaseous fuel or fuel adsorbed thereon, such as the activated carbon with the hydrogen adsorbed thereon, ie expressed as an equation: Sorbent (eg activated carbon) + adsorbate (eg H 2 ) = Sorbent material.

The Storage or sorption material is preferably in a storage container, the Adsorption storage, housed in which the hydrogen stored becomes.

The Removal of the hydrogen takes place via the so-called desorption. This is the opposite of the adsorption Process. If in the further course of the description on the process of adsorption Of course, the process of desorption should always be pointed out also be taken into account. During desorption, the hydrogen adsorbed on the adsorption material is hydrogenated with the application of energy from the sorbent or sorption material released or released or separated.

The problem with the adsorption of media on adsorbent materials often lies in the management of the heat of reaction occurring, ie adsorption or desorption energies during the adsorption or desorption. Thus, it can come to local cooling or overheating of the adsorbents, since the adsorbents, such as activated carbon with high specific surface area, ha only poor thermal conductivity ben. The convection as a means of heat transfer in the gas phase is severely limited due to the large friction losses on the pore walls of the adsorbents. The kinetics of adsorption and desorption are significantly limited by the slow gas transport through the porous structure of the adsorbents.

As already stated above, the sorbents are mostly porous formed and have a high specific surface area. she are therefore often very poor thermal conductivity. If hydrogen or another gas is adsorbed on it, then occurs adsorption heat on, which in turn causes the Material heated and the adsorbed gas is partially desorbed again. One must therefore try the heat carry away. The same applies to desorption. At this you have to Heat on bring the adsorbent materials to effect desorption.

To the Storage of gases by adsorption - especially on so-called High-surface materials - will the temperature of the storage system and the storage medium, for example of a gas, advantageously lowered to cryogenic areas to better storage capacity to reach. This requires the removal of a large amount in energy. Added to this is the adsorption from the storage medium released energy, which also has to be dissipated. To drive away the storage medium must be the storage system however, energy is supplied to increase its temperature to room temperature range and to provide the necessary desorption energy.

In order to these two dynamic processes the storage system as possible can take place quickly, is an efficient energy supply or energy dissipation required.

There are already known in the prior art a number of solutions that deal with the storage of hydrogen, in particular with the adsorption and Desorptionsproblematik. For example, in the WO 2005/044454 A2 a storage system for storing a medium, for example hydrogen, and a method for loading / unloading a storage system with a storage medium are described. The storage system has a storage container, which is advantageously designed as a pressure vessel. In this storage container is a storage material in the form of a sorbent. A gas to be stored, for example hydrogen, is introduced into the storage container and adsorbed on the sorbent under suitable conditions. To remove the gas, this is subsequently desorbed first. The sorbent remains in the storage tank the whole time, the adsorption thus takes place within the storage tank.

Also in the DE 10 2005 023 036 A1 is assumed by a remaining in a tank system sorbent or sorbent material. The large amounts of heat of adsorption resulting from the loading must be removed from the tank system. This requires a heat exchanger in the tank system and costs a lot of time when refueling. In the DE 26 15 630 A1 a cooling device for cooling a high pressure tank will be described.

The DE 10 2006 010 636 A1 relates to a sorption storage unit for gases with a sorbent for reversibly receiving the gases to be stored. The sorbent is formed on the basis of discrete sorbent particles. These sorbent particles are incorporated in or fixed to a solid gas-permeable three-dimensional support with foam structure.

Furthermore, the concerns DE 10 2005 004 592 A1 a storage and / or pressure increasing device for hydrogen, which consists of at least one pressure-resistant vessel containing a cyclically hydrogen de absorbing or absorbing under Wärmezu- or removal, in which respect a hydride-forming metal alloy can be used. The substance is to be acted upon by heat removal and hydrogen supply under a lower gas pressure with hydrogen and caused by heat to hydrogen delivery under higher gas pressure, cyclically changing at least a portion of the hydrogen absorbing material is subjected to a higher temperature. The cyclic hydrogen degrading or absorbing material is under normal conditions in liquid state.

The DE 100 21 289 A1 relates to a tank system for consisting of small to very small solids, laden with a combustible gas bulk material that can be filled with hydrogen. In addition, this document relates to a device for unloading the bulk material. The filling volume of the tank is divided into two hermetically separated compartments so that they are alternately variable in their volumes between the value "almost zero" and the almost total filling volume of the tank and that the tank is connected to a device for discharging the bulk material , which should allow the entla return the bulk material to the tank.

Furthermore, the concerns DE 197 03 749 A1 a method for releasing hydrogen from a storage medium surrounded by a container, excluding the external atmosphere by increasing the temperature. The discharged storage medium should be multiply loadable and dischargeable and / or exchangeable for loaded storage material. The heating of the storage medium should be done in zones one after the other and the discharge pressure should be kept constant or approximately constant. The respectively located at low temperature region of the memory should be shut off gas-tight against the heating zone.

The DE 25 22 972 A1 relates to a method for supplying an internal combustion engine with hydrogen obtained from a metal hydride. In this connection, fresh hydride in powder form is to be conveyed from a first vessel into a reactor of small capacity and heated therein, and the hydrogen released thereby is supplied to the engine. The spent hydride should be pumped from the reactor to a second vessel.

Finally, the concerns DE 694 09 907 T2 a microporous activated carbon in which more than 50% of the total pore volume consists of pores having a width of the order of greater than 8 Å to 20 Å and greater than 95% of the total pore volume of pores having a width of up to 50 Å the coal is derived from lignocellulosic material.

One great Problem of Sorptionsspeichern is the discharge of the refueling process released sorption heat. The Sorptionsenthalpie released during refueling must be short term dissipated become. For this process is a heat exchanger with correspondingly large cooling capacity necessary. In addition to the task, large amounts of coolant carry away, extended the need for heat dissipation Refueling process essential. In addition, the additional reduced Volume and weight requirements are volumetric and gravimetric storage capacity and increased In addition, the costs to be incurred for the decentralized Thermal management.

Of the present invention has for its object to provide a solution by means of which the aforementioned disadvantages are at least largely avoided or at least toned down can be. In particular, a solution for storing gases, in particular hydrogen, are provided by means of which the resulting heat of sorption in particular without time problems and with low cost and energy expenditure are dissipated can.

These The object is achieved by the method for providing a sorbent material for a storage container according to the independent claim 1. Further features, embodiments, embodiments and details of Invention will become apparent from the dependent claims.

The The present invention is based on the idea that with gas, For example, hydrogen, loaded sorbents in an external System, for example, a gas station, are stored and then compared with consumed Sorption material in a storage container, such as a mobile tank, to be replaced. This can be a filling process, for example a refueling process, be drastically shortened. The consumed or desorbed sorption materials are then in the external system - and not more, as usual, in the storage tank myself - again loaded with gas, such as hydrogen, and stand for one refilling process to disposal. For this purpose, trained or selected sorbents are in a special way required, which are also provided by the present invention become.

One greater Advantage of the present invention, for example, a complete recycling system, in the discharged sorbents or sorbents again against loaded sorbents or sorption materials are exchanged. From time to time, for example, a certain percentage of the Sorbents are exchanged for freshly prepared sorbents. Due to the high abrasion resistance of the invention used Sorbents can be used for years for a product batch of sorbents.

following various process aspects are described, such as a sorbent material can be provided and how a storage container with filled with such a material can be.

The present invention relates to a method for providing a sorbent material for a storage container, wherein the sorbent material, a sorbent and an adsorbate adsorbed thereto, in particular a gaseous fuel, preferably hydrogen, wherein in the storage container befindliches, consumed sorbent material is discharged from the storage container, wherein the spent sorbent outside the storage container with a gaseous fuel, in particular hydrogen, is charged again, and then with a gaseous fuel , in particular with hydrogen, loaded sorption material is made available for the storage container, wherein the discharge of the storage container of the spent sorption material by blowing the gas, in particular the hydrogen, takes place.

Regarding the secondary Operation of the method is based on the following directed.

Advantageous becomes the gas laden sorption material until further Use cached in a memory device. These Storage device can in the case of a gas station part of a appropriately designed dispenser be or at least in connection with this.

Preferably becomes the spent sorbent material discharged from the storage device before re-loading with a gas of a quality control subjected. This is in connection with the invention used System explained below, so that on the corresponding remarks referenced becomes.

In Another embodiment, the discharged from the memory device spent sorbent material before reloading with a Gas undergo a regeneration process. This too will in the context of the system used according to the invention below explains so that on the corresponding versions is referenced.

Advantageous The sorbent material may recharge before reloading with gas a predetermined temperature to be cooled. This is related with the invention used System also explained below, so that on the corresponding versions is referenced.

Regarding the Operation of the method is also on the following versions fully incorporated by reference and referenced.

One filling process of the type described above, such as a refueling process, sets good Transport properties and safe handling of the sorption materials from the storage tank of the system - about the Gas station - about one conveyor system in the mobile tank ahead. This is for example with conventional activated carbon powders hardly possible, because the particle size of the powder varies greatly. The resulting problems were a separation the particles during transport (for example, only small particles are transported in the gas stream to the mobile tank), partially Agglomeration and heavy wear of the fittings used such as pressure reducers, valves and pumps by a deposit of Particles of different dimensions. By the use of the invention used Sorbents and sorbents can make the filling process significantly better will be realized.

Advantageous the discharge and filling take place of the storage container by means of a system described below, so that on the corresponding versions is fully incorporated by reference and referenced.

Advantageous can the storage tank filled with a sorption material which is by means of one as described above Method has been provided so that to the corresponding embodiments is fully incorporated by reference and referenced.

Preferably is prior to unloading the storage container of spent sorbent material the remaining amount in the storage tank remaining, adsorbate adsorbed on the sorbent material and / or unadsorbed, gaseous Fuel, especially hydrogen, determined. For example may be a determination of the residual amount of stored gas, such as hydrogen, done by pressure and temperature measurement of the storage medium.

The discharge of the storage container of spent sorbent material is effected by blowing in gas or fuel, in particular hydrogen, used with regard to the sorption material. The discharge of the sorption material or sorbent in the storage container takes place, for example, by blowing in hydrogen. Due to the special shape and position of the gas guide, approximately in the form of a Nozzle, the sorbent material or sorbent is fluidized and discharged through the gas stream via the outlet. The pressure of this discharge circuit need not necessarily be 40 bar, but it can for example be adapted to the residual pressure in the storage tank to prevent adsorption or further desorption of the sorbent material during the discharge process.

Advantageous can the storage tank between the discharge and the refilling to a predetermined Temperature brought, in particular cooled. After removal an advantageous portion of the sorbent material or sorbent (For example, about 98%), the storage container (ie the empty pressure vessel) by Blow in gas, such as cold (77 K) hydrogen, cooled. there becomes cold (77 K) gas (hydrogen gas) with adapted flow rate and volumetric flow from the delivery system over that provided for the gas inlet execution in the storage tank blown by the heat flow dQ / dt from the pressure vessel to the cold gas (hydrogen gas) heat is dissipated, which through the exhaustion of the now warmed up Gas (hydrogen gas) through the intended implementation of the storage container is transported away.

Preferably may be refilling of the storage container with unconsumed sorbent material at an elevated pressure from greater / equal 40 bar.

The Unused sorbent material is advantageous in comparison increased to ambient pressure Pressure, preferably at a pressure of greater than or equal to 40 bar, for example at a pressure of 40 bar, transported to the storage tank and in this filled. It follows thus the injection of fresh, for example with hydrogen, fully loaded sorbent material at, for example, 40 or 100 bar pressure over the for the filling intended implementation. This sorbent material has been advantageous in the delivery system already pre-cooled to 77K and at 40 bar with gas (hydrogen) loaded. Therefore, a Transport of sorption material from the delivery system in the storage container the tank system also at elevated pressure, about 40 bar, to avoid desorption of the gas (hydrogen). Otherwise, could be renewed adsorption in the storage tank to an increase the temperature and consequently to a shorter service life or smaller Loading density and, in the case of a mobile tank system in a vehicle, thus lead to a lower range of the vehicle. Conceivable would be too a load on the delivery system at pressures greater than 40 bar, the pressure when refueling the storage tank then could be lowered to 40 bar. Consequently, would a portion of the adsorbed gas (hydrogen) from the sorbent material desorb and lower the temperature in the storage tank below 77K. at a lower temperature in the storage tank could at the same pressure (40 bar) a larger amount stored on gas (hydrogen) or the life of the tank system elevated become.

With The present invention may advantageously be a recycle of the Energy carrier gas when using pressure bodies with poor thermal conductivity (eg CFRP materials) achieved by pre-cooled hydrogen become. By external loading of the storage material with hydrogen and the consequent elimination of heat of reaction in the storage container (dQ / dt; dt <10 min) the for the cold entry required volume flows, however significantly lower and correspond in their magnitude then approximately the required heat flows (dQ / dt; dt ~ several hours = several hundred kilometers) for desorption, So that the for the Warmth- and mass transport needed Apparatuses and cross sections can be significantly reduced. Thereby This results in weight savings as well as a reduction in the complexity of the storage system. In order to decrease the production costs or the costs to be invested and the operating expenses combined with increased service life ("Boil-off time") due the lower heat flow over the narrow dimensioned pipe connections.

in the The scope of the present invention is a storage container for Saving a sorption material used, wherein the storage container with a pressure vessel, a connector to an external delivery system and at least one sorbent material which, at least during the proper use of the storage container in this is stored, as well as with a transport guide to Loading and / or unloading the storage container with sorption material equipped, wherein the sorbent material is a sorbent and a Adsorbate adsorbed thereon, in particular a gaseous fuel, preferably Hydrogen, included. The storage tank is characterized by the fact that on the one hand at least a second guide for feeding and / or discharge a gas (gas guidance) is provided and that on the other hand the sorbent based on high-performance adsorbents the basis of activated carbon in the form of discrete activated carbon granules, preferably in spherical form, wherein at least 70% of the total pore volume high-performance adsorbents through micropores with pore diameters formed of ≤ 20 Å In other words, they are highly microporous high performance adsorbents are used).

According to a preferred embodiment, the high-performance adsorbents used according to the invention have a total pore volume according to Gurvich of at least 0.7 cm ³ / g, wherein at least 70% of this total pore volume is formed by micropores with pore diameters of ≦ 20 Å.

As the applicants surprisingly and unexpectedly found, a highly microporous activated carbon is suitable of the aforementioned kind in a special way for the present invention, on the one hand such an activated carbon an extremely high loading capacity with respect to the relevant fuel or fuel gases, in particular hydrogen, and on the other such activated carbon one for the purposes of the invention has optimal adsorption and desorption behavior. Furthermore the activated carbon in question has an extremely high abrasion resistance and features over it excellent wear characteristics, what their long-term use, especially over several months or even Years, and continues to allow for recycle. Due to the abrasion resistance and freedom from dust of the high-performance adsorbents used according to the invention is also an impurity of the equipment used components efficiently avoided and also the risk of inflammation or explosions excluded or at least largely minimized. After all facilitates the spherical shape of the sorbents used the loading and Discharge process not inconsiderable. Further associated with the use of activated carbon according to the invention Advantages will be discussed later in the detailed characterization the invention used Activated carbon explained and arise for the expert in the study of the description, the claims and the figure representations.

A suitable for the purposes of the invention activated carbon is particularly in the 20 2006 016 898 U1 (Attention: Priority: 10 2006 048 790.7 of 12.10.2006) of 4 November 2006, the entire disclosure of which is hereby incorporated by reference, and is moreover disclosed by Blücher GmbH, Erkrath, and Adsor-rech GmbH, Premnitz , commercially available.

Of the used according to the invention storage container is designed so that he from the outside supplied Sorption material to which a gas is adsorbed, can absorb. In its operating state, the storage container is sorption material filled and may be adsorbed gas, for example hydrogen, as needed to a consumer. When the storage tank is new filled must become, the spent sorbent material is removed therefrom and through replaced new, non-used sorption material. Also in this regard is the storage tank designed in a special way. How this is realized in detail can, is on the basis of some advantageous, but not exclusive Examples in the further course of the description explained in more detail.

First is advantageously provided that the storage container a inner container for receiving the sorbent, which then the actual pressure vessel represents. Furthermore, advantageously, a second, outside of the inner container provided outer container provided which primarily has the function of an insulation container. The outer container can also serve the inner container from damage to protect.

Preferably is between the inner container and the outer container Isolation area provided. This isolation area can be, for example be formed as a kind of cavity in which an insulation material can be located. The insulation material can be solid, liquid or gaseous be. It is also conceivable that the Insulation area is formed in the form of an insulating layer, which is for example a film, mat or the like can act between foreign and inner container is arranged.

in the Some preferred embodiments of the storage container used according to the invention are described below. without that Invention is limited to these examples mentioned.

aim while a mechanical is possible simple loading and unloading system to elaborate designs as well to avoid moving parts inside the storage tank. The basic idea is it, the granular, preferably grain or spherical Sorption over a gas flow at virtually any pressure, especially about up to about 40 bar, to transport.

The storage container should basically have two openings / feedthroughs for media, which are referred to below as guides. A first tour is the so-called transport guide, which is primarily responsible for the transport of the sorption materials. This guide is used, for example, to transport the sorption material both from the filling station to the tank system and also from the tank system to the filling station. A second guide is formed by a gas guide over which Gases can be directed into and out of the container. This will be explained in more detail later in the description.

Advantageous can / can the transport guide and / or the gas routing tubular be educated. The invention is not limited to certain pipe sections limited. These arise rather from the fluidic requirements. Advantageously, however, a circular or oval cross-section is provided.

Preferably can / can the transport guide and / or the gas routing in the form of a nozzle be educated. This can be done Particularly advantageous a suitable flow course within the storage container realize.

Around an undesirable Discharge of sorbent material from the storage tank too can avoid, in the gas guide preferably at least one filter element for filtering sorption material and / or sorbent be provided.

The first implementation (Transport guide) is advantageous with a relative to the particle size of the sorbent material relatively large diameter equipped, for example, a diameter of at least the 50 times the particle size.

The second implementation (Gas guide) is advantageously designed nozzle-shaped and has a filter, the penetrating Sorptionsmaterialpartikel restrained. This nozzle serves at filling of the tank system (storage tank) as a gas outlet. When loading the tank system with fresh sorption material this will be over a flow over the first implementation (Transport guide) introduced into the tank system. A carrier gas required for this purpose (for example hydrogen carrier gas) leaves the system over the second execution (Gas guide). During a discharge of the tank system, gas, for example hydrogen gas, flows over the second, as a nozzle executed execution (Gas guide) in the tank system. Due to the high flow rate at the outlet and the Position of the nozzle In the tank system sorption material present in the tank system is whirled up and over the first implementation (Transport guide) through the gas flow transported from the tank system. Thus, the tank system can and unloaded.

In a further embodiment, the transport guide and the gas guide can be connected to one another in the storage container and form a pipe loop. This design makes the dynamic pressure drop in places with increased flow velocity according to the Bernoulli equation 1 2 pv 2 + ρgh + p = const. use (Venturi tube). It is advantageous to a closed pipe loop with minimal internal flow resistance.

Advantageous can / can in the pipe loop at least one rotatable flap, preferably two flaps, to change of the flow be provided within the pipe loop.

For example The pipe loop can be moved in two places by 90 ° rotatable, flow-driven flaps to be interrupted. The aim of these valves is the deflection of the flow (Sorption material + carrier gas) while of the filling process. The first flap closes the passage through the pipe system and thereby requires the introduction of the sorbent material in the storage tank. The carrier gas is about the second flap back transported into the pipe system and may for example be returned to the pump. When emptying of the storage container flows through the carrier gas the pipe loop in the opposite direction. A narrowing of the pipe loop (See the venturi principle described above) leads to the reduction of static Pressure in the pipe section and thereby suction of sorbent material from the storage container. The Sorption material is added to the carrier stream dispersed and discharged from the storage container.

One Filter in front of the flap (s) can prevent the unwanted discharge of sorbent material prevent. Advantageously, therefore, at least in the pipe loop a filter element for filtering sorbent material and / or sorbent be provided, wherein the filter element is preferably in the range the rotatable flap (s) is arranged.

Advantageously, the storage container, at least during the filling process and / or Entla tion process in a (r) inclination, based on a horizontal or vertical reference plane (depending on whether the storage container is arranged vertically or horizontally), be brought or aligned. A slight inclination of the storage tank and a favorable positioning of the Venturi piece near the lowest point take over the task of transporting the sorption material into the reach of the suction by using gravity on the inclined plane.

According to one Another embodiment may be provided that the transport guide and the gas supply in a single guide summarized are and that the guide as a recording for formed a filling / discharge nozzle is. This embodiment comes in particular with a further below described in more detail Filling / discharge nozzle for use. Advantage of this embodiment is the decoupling of for the filling and unloading needed Components from the storage container, and thus a significant saving in weight and heat capacity. The task the supply and discharge of sorbent material and carrier gas one in the storage container introduced Neck, which can also be designed flexibly and advantageous characterized in that the Length of the Neck in the storage tank can be readjusted to the sorption material as possible stir up and remove locally to be able to.

Advantageous For example, at least one sensor element for measuring operation-specific Properties of the storage tank and / or the sorbent material and / or the sorbent be. Such measurements can, as in the course even closer explained will be used to complete the filling and discharging process continue to optimize.

In In such a case, advantageously at least one interface for transmission from above the at least one sensor element detected values can be provided. This may be particularly advantageous to a data interface act.

Also if the storage tank for storing any gaseous Media can be used, this may be particularly preferred as a storage tank for a gaseous Fuel, especially for hydrogen, be educated.

As described above, in the context of the present invention, the adsorbents used are preferably high performance adsorbents based on activated carbon with a high microporosity, as they are the subject of DE 20 2006 016 898 U1 both are in the name of Blücher GmbH, Erkrath.

Such high-performance activated carbon adsorbents in the form of discrete activated charcoal grains, preferably in spherical form, are characterized by a high microporosity, wherein generally at least 70% of the total pore volume of the high-performance adsorbents used according to the invention are formed by micropores having pore diameters of ≦ 20 Å. According to a preferred embodiment of the present invention, the high-performance adsorbents used according to the invention have a total pore volume according to Gurvich of at least 0.7 cm ³ / g, wherein at least 70% of this total pore volume is formed by micropores with pore diameters of ≦ 20 Å.

In addition, the active carbon-based high-performance adsorbents of the abovementioned type used as sorbents in the context of the present invention have an average pore diameter of at most 30 Å and / or a BET surface area of at least 1500 m ² / g.

• – einen Anteil an Mikroporen mit Porendurchmessern von ≤ 20 Å von mindestens 70% des Gesamtporenvolumens, besonders bevorzugt ein Gesamtporenvolumen nach Gurvich von mindestens 0,7 cm³/g, wobei mindestens 70% dieses Gesamtporenvolumens durch Mikroporen mit Porendurchmessern von ≤ 20 Å gebildet sind, und/oder
• – einen mittleren Porendurchmesser von höchstens 30 Å und/oder
• – eine BET-Oberfläche von mindestens 1.500 m²/g.

The high-performance adsorbents based on activated carbon in the form of discrete activated charcoal grains, preferably in spherical form, used as sorbents in the context of the present invention are thus characterized in particular by the following parameters:

• A fraction of micropores with pore diameters of ≦ 20 Å of at least 70% of the total pore volume, more preferably a Gurvich total pore volume of at least 0.7 cm ³ / g, wherein at least 70% of this total pore volume is formed by micropores having pore diameters of ≦ 20 Å , and or
• An average pore diameter of at most 30 Å and / or
• - a BET surface area of at least 1,500 m ² / g.

The high-performance adsorbents or activated carbons used according to the invention are distinguished, in particular, by a large overall porosity and a simultaneously large BET surface area. As will be explained below, despite the high porosity, the mechanical load-bearing capacity, in particular the abrasion resistance and the bursting or pressure resistance, is also the high-performance adsorber used in accordance with the invention Bentien - in contrast to comparable highly porous activated carbons of the prior art - extremely high, so that the invention used Hochleistungsadsorbentien or activated carbons are also suitable for applications in which they are exposed to high mechanical loads.

at all the above-mentioned and below mentioned parameter details It should be noted that the listed Limit values, in particular upper and lower limits Lower limits, included are, d. H. all values include the respective limits. Furthermore, it goes without saying that it is due to individual cases or, where appropriate, may be required by application deviate from the limits mentioned above without the scope of the present The invention is abandoned.

The aforementioned and in the following still mentioned parameter data for the invention used High performance adsorbents are specified with standardized or explicit Methods of determination or methods of determination familiar to the person skilled in the art certainly. The parameter information concerning the characterization the porosity each result from the nitrogen isotherm of the measured activated carbon.

What As far as the determination of the total pore volume according to Gurvich is concerned, so it is a known to the expert in this field Measuring method of determination. For further details regarding the determination of the total pore volume For Gurvich, for example, reference may be made to L. Gurvich (1915), J. Phys. Chem. Soc. Soot. 47, 805, as well as on S. Lowell et al., Characterization of Porous Solids and Powders: Surface Area Pore Size and Density, Kluwer Academic Publishers, Article Technology Series, pages 111 ff.

The determination of the specific surface according to BET is known in principle as such to a person skilled in the art, so that in this regard no further details need to be carried out. All BET surface area information refers to the determination according to ASTM D6556-04. In the context of the present invention, the so-called MultiPoint BET determination method (MP-BET) is used in a partial pressure range p / p ₀ of 0.05 to 0.1 for determining the BET surface area. For further details on the determination of the BET surface area or the BET method, reference may be made to the abovementioned ASTM D6556-04 and Römpp Chemielexikon, 10th edition, Georg Thieme Verlag, Stuttgart / New York, keyword: "BET method ", Including the literature referenced there, and to Winnacker-Kuchler (3rd edition), Volume 7, pages 93 ff., As well as on Z. Anal. Chem. 238, pages 187 to 193 (1968).

The Determination of the average pore diameter is based on the respective nitrogen isotherms.

The total pore volume according to Gurvich of the high-performance adsorbents used according to the invention is at least 0.7 cm ³ / g, in particular at least 0.8 cm ³ / g, preferably at least 0.9 cm ³ / g, particularly preferably at least 1.0 cm ³ / g, and can reach values of up to 1.5 cm ³ / g, in particular up to 1.6 cm ³ / g, preferably up to 1.8 cm ³ / g. In general, the total pore volume according to Gurvich used in the invention high performance adsorbents in the range of 0.7 to 1.8 cm ³ / g, in particular 0.8 to 1.6 cm ³ / g, preferably 0.9 to 1.5 cm ³ /G.

A Particularity of the invention used Hochleistungsadsorbentien is to be seen, inter alia, that they have a very big Gurvich total pore volume, so that provided a large adsorption capacity with a high proportion of micropores.

in the general are at least 70%, especially at least 75%, preferably at least 80%, more preferably at least 85%, especially preferably at least 90% of the total pore volume, in particular the total pore volume according to Gurvich, the inventively used High performance adsorbents through micropores with pore diameters formed of ≤ 20 Å. Generally, 70% to 95%, especially 75 to 90%, is preferred 75 to 85% of the total pore volume, in particular the total pore volume after Gurvich, the inventively used High performance adsorbents through micropores with pore diameters formed of ≤ 20 Å (In the context of the present invention, the term of the Micropores include such pores with pore diameters up to 20 Å, whereas the term mesopores refers to those pores with pore diameters of> 20 Å to 50 Å inclusive and the term macropores refers to pores with pore diameters> 50 Å.).

Due to their high microporosity, the micropore volume of the high-performance adsorbents used in accordance with the invention is relatively high: this is generally due to micropores with pore diameters Carbon pore volume of ≤ 20 Å after carbon black of the inventively used Hochleistungsadsorbentien in the range of 0.5 to 1.4 cm ³ / g, in particular 0.6 to 1.2 cm ³ / g, preferably 0.7 to 1.1 cm ³ / g. The carbon black determination method is known per se to the person skilled in the art, so that no further details are required in this regard. In addition, for further details of determining the pore surface and pore volume for carbon black, reference may be made, for example, to RW Magee, Evaluation of the External Surface Area of Carbon Black by Nitrogen Adsorption, Presented at the Meeting of the Rubber Division of the American Chem. Soc. , October 1994, z. B. Referenced in: Quantachrome Instruments, AUTOSORB-1, AS1 WinVersion 1.50, Operating Manual, OM, 05061, Quantachrome Instruments 2004, Florida, USA, pages 71 ff.

by virtue of the high microporosity the invention used High performance adsorbents is their average pore diameter relative low: Generally he at most 30 Å, in particular at most 26 Å, preferably at most 25 Å, most preferably at most 24 Å. In general, the mean pore diameter of the invention used High performance adsorbents in the range of 15 to 30 Å, in particular 16 to 26 Å, preferably 17 to 25 Å, more preferably 18 to 24 Å.

As stated above, a peculiarity of the high-performance adsorbents used according to the invention is to be seen in the relatively large BET surface area, which is at least 1,500 m ² / g, preferably at least 1,525 m ² / g, particularly preferably at least 1,550 m ² / g, very particularly preferably at least 1,575 m ² / g. In general, the BET surface area of the high-performance adsorbents used according to the invention is in the range from 1,500 m ² / g to 3,500 m ² / g, in particular 1,500 m ² / g to 2,750 m ² / g, preferably 1,525 to 2,500 m ² / g, particularly preferred 1550 to 2400 m ² / g, most preferably 1575 to 2350 m ² / g.

Also, the weight and volume-related volume V _ads (N ₂ ) of the high-performance _{adsorbents used according to} the invention at different partial pressures p / p ₀ is very large:
Thus, the weight-related adsorbed N ₂ volume V _{ads (wt) of} the high performance _{adsorbents used according to} the invention, determined at a partial pressure p / p ₀ of 0.25, is at least 400 cm ³ / g, in particular at least 420 cm ³ / g, and is in particular in the range of 400 to 800 cm ³ / g, preferably 410 to 750 cm ³ / g, particularly preferably 420 to 700 cm ³ / g. Furthermore, the weight-related adsorbed N ₂ volume V _{ads (wt) of} the high performance _{adsorbents used according to} the invention, determined at a partial pressure p / p ₀ of 0.995, is at least 450 cm ³ / g, in particular at least 460 cm ³ / g, and is in particular Range of 450 to 900 cm ³ / g, preferably 460 to 875 cm ³ / g, particularly preferably 470 to 850 cm ³ / g.

In general, the volume-related adsorbed N ₂ volume V _{ads (vol.) Of} the high-performance _{adsorbents used according to} the invention, determined at a partial pressure p / p ₀ of 0.25, is at least 200 cm ³ / cm ³ , in particular at least 220 cm ³ / cm ³ , and is in particular in the range of 200 to 300 cm ³ / cm ³ , preferably 210 to 275 cm ³ / cm ³ , particularly preferably 225 to 260 cm ³ / cm ³ . Furthermore, the volume-related adsorbed N ₂ volume V _{ads (vol.) Of} the invention used high performance _adsorbents , determined at a partial pressure p / p ₀ of 0.995, at least 250 cm ³ / cm ³ , in particular at least 260 cm ³ / cm ³ , and is in particular in the range of 250 to 400 cm ³ / cm ³ , preferably 260 to 350 cm ³ / cm ³ , particularly preferably 265 to 320 cm ³ / cm ³ .

Another peculiarity of the high-performance adsorbents used according to the invention is the large micropore surface, ie the large surface which is formed by pores with a pore diameter of ≦ 20 Å. In general, the microporous surface formed by pores with pore diameters of ≦ 20 Å is at least 1,400 m ² / g, in particular at least 1,450 m ² / g, preferably at least 1,500 m ² / g, and is generally within the range of carbon blacks of the high-performance adsorbents used according to the invention from 1,400 to 2,500 m ² / g, in particular from 1,450 to 2,400 m ² / g, preferably from 1,500 to 2,300 m ² / g.

In addition, the high-performance adsorbents used according to the invention have extremely high butane adsorption and at the same time an extremely high iodine value, which characterizes their property of exhibiting excellent adsorption properties with regard to a wide variety of substances to be adsorbed. Thus, according to ASTM D5742-95 / 00 determined butane adsorption of the inventively used Hochleistungsadsorbentien is generally at least 25%, in particular at least 30%, preferably at least 40%; In general, the high-performance adsorbents used according to the invention have a butane adsorption determined in accordance with ASTM D5742-95 / 00 in the range from 25% to 80%, in particular from 30 to 70%, preferably from 35 to 65%. The determined according to ASTM D4607-94 / 99 iodine number of the invention used Hochleistungsadsorbentien is generally at least 1350 mg / g, in particular at least at least 1,450 mg / g, preferably at least 1,500 mg / g; The high-performance adsorbents used according to the invention preferably have an iodine value determined in accordance with ASTM D4607-94 / 99 in the range from 1,350 to 2,100 mg / g, in particular 1,450 to 2,050 mg / g, preferably 1,500 to 2,000 mg / g.

In spite of the high porosity, especially microporosity, have the high performance Adsorbentien used in the invention a high pressure or bursting strength (weight capacity) and an extremely high abrasion resistance. So lies the printing or Bursting strength (weight load capacity) per charcoal grain, in particular per activated carbon beads, at least 10 newton, especially at least 15 newton, preferably at least 20 Newtons. In general, the pressure or bursting strength varies (Weight loadability) per charcoal grain, in particular per activated carbon bead, in the range of 10 to 50 Newton, in particular 12 to 45 Newton, preferably 15 to 40 Newtons.

As previously stated is also the abrasion hardness the invention used High-performance adsorbents extremely high: that's how the abrasion resistance lies according to the method according to CEFIC (Conseil Européen of the Fédérations of the I'Industry Chimique, Avenue Louise 250, Bte 71, B-1050 Brussels, November 1986, European Council of Chemical Manufacturers' Federations, Test methods for Activated carbon, number 1.6 "Mechanical Hardness, "pages 18/19) always at 100%. Abrasion resistance also meets ASTM D3802 the invention used High performance adsorbents always 100% obtained. Therefore, one became developed a modified test method based on this CEFIC method, more meaningful To obtain values. The modified determination method simulated better the resistance of the sample or the high-performance adsorbents across from Abrasion or grinding under practical conditions. To this end the sample is vibrated horizontally for a defined time, Grinding bowls charged with a tungsten carbide ball under standardized conditions Conditions claimed. For this purpose, the procedure is as follows: 200 g of a sample are kept for one hour at (120 ± 2) ° C in a convection oven (Type: Heraeus UT 6060 from Kendro GmbH, Hanau) dried and subsequently in a desiccator over Desiccant cooled to room temperature. 50 g of the dried Sample are removed and by means of a screening machine with test sieve (Type: AS 200 control from Retsch GmbH, Hanau) at a swing height of 1.2 mm over for ten minutes a test sieve (mesh sieve: 0.315 mm, diameter: 200 mm, height: 50 mm) sieved; the undersize is discarded. 5 ml of the nominal grain are placed in a 10 ml graduated cylinder according to DIN ISO 384 (volume: 10 ml, height: 90 mm) and filled the weight by means of a weighing glass with ground glass lid (volume: 15 ml, diameter: 35 mm, height: 30 mm) to an accuracy of 0.1 mg by means of analytical balance (type: BP121S Sartorius AG, Göttingen, Weighing range: 120 g, accuracy class: E2, readability: 0.1 mg). The weighed Sample is combined with a 20 mm diameter tungsten carbide milling ball into a 25 ml screw-top grinding bowl (volume: 25 ml, diameter: 30 mm, length: 65 mm, material: stainless steel) and then the abrasion test by means of vibratory mill (Type: MM301 from Retsch GmbH, Haan, vibrating mill with grinding bowl) carried out; there The grinding bowl vibrates in a horizontal position for one minute a frequency of 10 Hz in the vibratory mill, which causes the grinding ball hits the test and thus generates abrasion. Subsequently, the sample by means of a screening machine with a swing height of 1.2 mm five minutes long over screened the aforementioned test sieve, the undersize again Discarded and the nominal grain greater than 0.315 mm to 0.1 mg exactly in the weighing glass weighed back with lid becomes. The calculation of the abrasion hardness as% by mass according to the following formula: Abrasion hardness [%] = (100 × back weighing [g]) / weight [g]. According to this modified determination method in a modification of the aforementioned CEFIC standard the abrasion resistance of the high performance adsorbents used according to the invention at least 95%, in particular at least 96%, preferably at least 97%, more preferably at least 98%, most preferably at least 99%.

The used according to the invention High-performance adsorbents are based on granular, in particular spherical activated carbon formed, the average particle diameter, determined according to ASTM D2862-97 / 04, in the range of 0.01 to 1.0 mm, especially 0.1 to 0.8 mm, preferably 0.2 to 0.7 mm, particularly preferably 0.4 up to 0.55 mm, varies.

Of the Ash content of the invention used High performance adsorbents as determined by ASTM D2866-94 / 04 are at most 1%, in particular at most 0.8%, preferably at most 0.6%, more preferably at most 0.5%.

Of the according to ASTM D2867-04 / 04 determined moisture content of the invention used Hochleistungsadsorbentien is at the most 1%, in particular at most 0.5%, preferably at most 0.2%.

The high-performance adsorbents used according to the invention generally have a bulk density (bulk density), determined according to ASTM B527-93 / 00, in the range of 250 to 750 g / l, in particular 300 to 700 g / l, preferably 300 to 650 g / l, particularly preferably 350 to 600 g / l, on.

As far as the outer pore volume after carbon black of the high-performance adsorbents used according to the invention is concerned, this is generally in the range from 0.05 to 0.5 cm ³ / g, in particular from 0.1 to 0.45 cm ³ / g. In general, the outer pore volume after carbon black of the high-performance adsorbents used according to the invention forms at most 35%, preferably at most 30%, of the total pore volume, in particular 10% to 35%, preferably 14 to 30%, of the total pore volume.

As far as the outer pore surface according to carbon black of the high-performance adsorbents used according to the invention is concerned, this is generally in the range from 50 to 300 m ² / g, in particular 60 to 250 m ² / g, preferably 70 to 200 m ² / g. In general, the outer pore surface after carbon black of the high-performance adsorbents used according to the invention forms at most 15%, preferably at most 10%, of the total pore surface area, in particular 4% to 15%, preferably 4 to 12%, of the total pore surface area.

What the production of the high performance adsorbents used according to the invention As far as they are concerned, these are by carbonation and subsequent activation of gelatinous sulfonated styrene / divinylbenzene copolymers, especially sulfonated divinylbenzene-crosslinked polystyrenes, in granular form, preferably in spherical form, available. The divinylbenzene content of as starting materials for the preparation the invention used Hochleistungsadsorbentien used sulfonated styrene / divinylbenzene Copoly mers should in particular in the range of 1 to 15 wt .-%, preferably 2 to 10 wt .-%, based on the styrene / divinylbenzene copolymers lie. The starting copolymers must selected by type of gel to be a microporous Structure can form. When from unsulfonated starting materials is expected, the sulfonation can be carried out in situ, in particular with methods known per se to those skilled in the art, preferably by means of sulfuric acid and / or oleum. This is familiar to the person skilled in the art. As starting materials especially proven have become gel-like Types of the corresponding ion exchange resins or the corresponding Precursors of ion exchange resins, which are still sulfonated have to. In the carbonization (synonymous as pyrolysis, burn-off or Called carbonization), the conversion of the carbonaceous takes place Starting polymers to carbon, d. H. in other words that will charred carbonaceous feedstock. At the carbonization the aforementioned gel-like organic polymer granules, in particular polymer beads, based on styrene and divinylbenzene, the sulfonic acid groups contain leads the cleavage of the sulfonic acid groups while the carbonization to free radicals and thus to crosslinks, without which there is no pyrolysis residue (= Carbon). in the In general, carbonation under an inert atmosphere (e.g. Nitrogen) or possibly slightly oxidizing atmosphere. Likewise it be beneficial while the carbonization, especially at higher temperatures (eg Range of about 500 to 650 ° C), to the inert atmosphere a smaller amount of oxygen, especially in the form of air (eg 1 to 5%), add to an oxidation of the carbonated To effect polymer skeleton and in this way the subsequent Activation easier. In general, the carbonation at temperatures of 100 to 950 ° C, in particular 150 to 900 ° C, preferably 300 to 850 ° C, carried out. The total duration of carbonation is about 30 minutes up to 6 hours. In connection to the carbonation becomes the carbonated intermediate of activation subjected at the end of which the inventively used Hochleistungsadsorbentien based on activated carbon in grain form, in particular spherical shape, result. The basic principle of activation is to be a part of Carbonization generated carbon selectively and selectively degrade under suitable conditions. This creates numerous Pores, crevices and cracks, and related to the mass unit surface increases significantly. The activation becomes more targeted Burning of the coal made. Because when activated carbon is degraded, occurs in this process, a loss of substance, which - under optimal conditions - synonymous with an increase the porosity and increase of the inner surface and the pore volume is. The activation therefore takes place under selective or controlled oxidizing conditions. The activation will in general at temperatures of 700 to 1300 ° C, in particular 800 to 1,200 ° C, preferably 900 to 1100 ° C, carried out.

The peculiarity in the production of the high-performance adsorbents used according to the invention is - in addition to the selection of the above-described starting material - to be seen in the special procedure of activation, in particular in the duration of activation in combination with the selected activation atmosphere. Surprisingly, if the activation is carried out for an extremely long time, in particular for 12 to 30 hours, preferably for 19 to 23 hours, using a weakly oxidizing atmosphere which contains only small amounts of water vapor in an otherwise nitrogen-containing atmosphere, and in amounts of only about 0.1 to 5 vol .-%, in particular 0.5 to 4 vol .-%, water vapor-based on the selected starting materials, the high-performance adsorbents of high microporosity and high mechanical stability used according to the invention result with the other properties described above. In particular, it is surprising that, on the one hand, the extremely long activation duration does not lead to harmful, excessive burnup with considerable loss of substance and, on the other hand, despite the high porosity and, at the same time, high micro-porosity results in extremely high abrasion resistance and mechanical compressive strength. It was not to be expected that such long activation periods would not lead to a disadvantageous result and that, with such long activation periods, the microporosity or microporous volume is generated predominantly selectively, as long as the gel-type starting materials, as defined above, are used. By varying the activation periods, in particular in the range of 12 to 30 hours, preferably 19 to 23 hours, the microporosity can then be adjusted in a targeted manner. In this way, the high-performance adsorbents used according to the invention can be tailor-made, so to speak.

For example can usable according to the invention High performance adsorbents are each prepared as follows: commercial Gel-type ion exchange precursors based on divinylbenzene crosslinked Polystyrene copolymers with a divinylbenzene content of about 4% be first pre-dried to remove the approximately 50% water content, and subsequently at temperatures of 100 ° C to 150 ° C with a sulfuric acid / oleum mixture sulfonated in a conventional manner. Then in known per se Way at temperatures up to 950 ° C Carbonated under nitrogen atmosphere for four hours and then the Activation initiated by the nitrogen atmosphere low Amounts of water vapor (about 1 to 3 vol .-%) are added; the Steam supply is maintained to reduce the water vapor content in to regulate this way. The activation will last for 19 hours ( "Activated carbon I ") or For 23 hours ("activated charcoal II ") operated. After cooling At room temperature, sorbents which can be used according to the invention are obtained. The parameters of the corresponding activated carbons ("activated carbon I "or" activated carbon II ") are shown in Table 1.

• * Mikroporen: Poren mit Porendurchmessern ≤ 20 Å
• ** p/p₀ = Partialdruck oder Partialdruckbereich

For further details on the high performance adsorbents which can be used according to the invention, it is possible to refer to the DE 10 2006 048 790 A1 as well as the DE 20 2006 016 898 U1 to get expelled. Table 1: Comparison of physico-chemical parameters of two high-performance adsorbents based on spherical activated carbon which can be used according to the invention on the one hand and commercially available microporous activated carbon in spherical form from Kureha on the other hand Activated carbon I Activated carbon II Commercially available activated carbon of the company Kureha Total pore volume (Gurvich) (p / p ₀ = 0.995) [cm ³ / g] ** .7336 1.3550 .5891 Mean pore diameter [Å] 18.57 24.67 17,89 BET (multipoint, MP) (p / p ₀ = 0.05-0.1) (ASTM D6556-04) [m ² / g] ** 1580 2197 1317 Micro pore volume (carbon black) [cm ³ / g] * .6276 .9673 .5240 Percentage of micropores in total pore volume [%] * 85.55 71.39 88.95 Adsorbed volume N ₂ (p / p ₀ = 0.25) by weight [cm ³ / g] ** 423 650 349 Adsorbed volume N ₂ (p / p ₀ = 0.25) by volume [cm ³ / cm ³ ] ** 236 235 206 Adsorbed volume N ₂ (p / p ₀ = 0.995) by weight [cm ³ / g] ** 473 770 380 Adsorbed volume N ₂ (p / p ₀ = 0.995) by volume [cm ³ / cm ³ ] ** 264 279 224 Microporous surface (carbon black) [cm ² / g] * 1509 1995 1271 Outer pore volume (carbon black) [cm ³ / g] 0.11 0.39 0.07 Proportion of outer pore volume in relation to total pore volume [%] 14.4 28.6 11.1 Outer pore surface (carbon black) [cm ² / g] 71 202 46 Percentage of outer pore surface area based on BET surface area (MP) [%] 4.5 9.2 3.5 adsorbate N ₂ N ₂ N ₂ Butane adsorption (ASTM D542-95 / 00) [%] 33.5 59.6 29.2 Iodine Number (ASTM D4607-94 / 99) [mg / g] 1470 1840 1343 Pressure or bursting strength (weight load capacity) [kg / activated carbon beads] 3.75 1.4 0.45 Average diameter (ASTM D2862-97 / 04) [mm] 0.52 0.44 0.44 Ash content (ASTM D2866-94 / 04) [%] 0.50 0.45 0.04 Moisture content (ASTM D2867-04 / 04) [%] 0.04 0.1 0.37

• * Micropores: Pores with pore diameters ≤ 20 Å
• ** p / p ₀ = partial pressure or partial pressure range

As the Applicants surprisingly and unexpectedly found, the aforementioned sorbents based on the above-described microporous active carbon-based high performance adsorbents in the present invention, in particular when used in the storage container according to the invention, provide the best values for use with gaseous fuels, in particular hydrogen with regard to storage of the gaseous fuels, in particular hydrogen, in comparison to commercially available microporous activated carbon and activated carbon of lesser microporosity. Thus, at 20 bar and 77 K with the active carbon-based microporous high performance adsorbents of the type described above, at least 30 g of hydrogen per kg of activated carbon, in particular at least 35 g of hydrogen per kg of activated carbon, preferably at least 40 g of hydrogen per kg of activated carbon, more preferably at least Store 70 g of hydrogen per kg of activated carbon, adsorptive only; In addition there is still non-adsorptive storage capacity, in particular as a result of storage of gaseous hydrogen in interspaces, cavities, cavities, macro- and mesopores or the like, which - in addition to the adsorptive storage capacity - at least 5 g of hydrogen per kg of activated carbon, in particular at least 10 g of hydrogen per kg Activated carbon, preferably at least 15 g of hydrogen per kg of activated carbon, more preferably at least 30 g of hydrogen per kg of activated carbon is, so that a total storage capacity with respect to hydrogen at 20 bar and 77 K for the inventively used, active carbon-based microporous Hochleistungsadsorbentien of the type described above at least 35 g of hydrogen per kg of activated carbon, in particular at least 40 g of hydrogen per kg of activated carbon, preferably at least 45 g of hydrogen per kg of activated carbon, more preferably at least 50 g of hydrogen per kg of activated carbon, most preferably at least 55 g Hydrogen per kg of activated carbon, more preferably at least 100 g of hydrogen per kg of activated carbon, results (by adjusting the pressure and / or temperature, the relevant amounts of storage can be specifically controlled.). As the investigations of the applicants have shown, the analog storage capacities of commercially available microporous activated carbon and activated carbon of lower microporosity (micropore volume fraction <70%), in particular of meso- and / or macroporous activated carbon, are at least 20% to 30% below that of the prior art aforementioned values. As the Applicants have surprisingly found out, an optimal storage capacity is thus achieved only with the previously described microporous activated carbon-based high-performance adsorbents.

in the According to the present invention, the storage container component a tank system, in particular mobile tank system, for providing a gaseous one Fuel for be a drive unit. The tank system is thus characterized from that it at least one storage container as described above. That's why first to the above statements to the storage tank fully incorporated by reference and referenced.

Advantageous the storage tank can have a Guide, preferably the transport guide and / or the gas guide, with a heat exchanger device be connected.

Also the tank system can have at least one interface for transmission from at least one sensor element for measuring operation-specific Properties of the storage tank and / or the sorbent and / or sorbent values, advantageously have a data interface.

Of the Construction and operation of the tank system are described below using an example closer explains where the stored gas is hydrogen. Of course the following also for others Types of gas.

There are several options for removing hydrogen from the mobile tank system. The amount of hydrogen stored in the mobile tank system is composed of the adsorbed phase (H _ads ), that is, the hydrogen adsorbed on the sorbent, and the gas phase (H _gas ), that is, the hydrogen gas present in the free volume of the tank. For any state (temperature and pressure), a state of equilibrium which depends on the adsorption properties of the sorption material is established. Directly after refueling, for example of a vehicle (pressure in the tank system 40 bar, temperature 77 K), hydrogen required by the drive unit of the vehicle can be taken directly from the gas phase. This hydrogen is available almost immediately, in a by the pressure prevailing in the tank system be tunable amount available. By removing hydrogen from the gas phase, the equilibrium between adsorbed phase and gas phase in the tank is disturbed. As the pressure falls, part of the adsorbed hydrogen is desorbed to partially compensate for the loss in the gas phase. However, the lowering of the temperature caused by the desorption again slows down the desorption process. For example, with short removal of hydrogen from the gas phase of the mobile tank system, the pressure drops from 40 bar to 38 bar, the temperature falling from 77 K to 65 K due to the negligible heat flow from the environment through the insulation Lowering ultimately depends on the adsorption enthalpies and properties of the sorbent.). The hydrogen is thus continuously withdrawn from the gas phase to supply the drive unit of the vehicle. However, as soon as the pressure in the tank system falls below the pressure requested by the customer, a volume flow of hydrogen required by the drive unit of the vehicle can no longer be maintained (for example Pressure 2 bar) (values depending on sorbent and consumer).

By a connected feed pump (Disadvantage: electrical consumers!) Or preferably by targeted increase the temperature in the tank system can supply hydrogen be ensured.

This can be advantageously realized by already removed, cold Hydrogen over a heat exchanger, which prefers the ambient heat uses, warms and back again is directed into the tank system, where stored in the gas heat capacity on the Transferred sorbent will (recycle). The control of the heat input can by means of suitable Valves, for example by means of two positioned on the tank system Solenoid valves, which interrupt the line to unwanted Heat input, for example when not using the vehicle, avoid. By means of the featured Recycling system can change the temperature in the tank system without use an electric heater increases and thus also the hydrogen present in the adsorbed phase Deshorbed and used if necessary.

For further details in this regard may also on the WO 2005/044454 A2 and 20 2004 017 036 U1 to get expelled.

in the Framework of the method according to the invention can for filling and / or unloading the storage container, a filling / discharge nozzle be used, wherein the filling / discharge nozzle a first guide for passing a sorbent and an adsorbate adsorbed thereon, in particular a gaseous Fuel, preferably hydrogen, comprising sorbent material, being the first guide with a transport guide a storage container can be brought into connection, and a second guide, in particular for passing a Gases, which with a gas guide a storage tank in Connection can be brought has.

The Task of supply and discharge of sorbent material and carrier gas the nozzle, which is characterized in that the length of the nozzle in the storage tank readjusted can be used to stir up the sorbent material as close as possible and dissipate to be able to. Possible is through the readjustable, spatial Near the removal to the sorption also the integration of a suction effect in the Exhaustion, so that for emptying of the storage container not necessarily the recirculation of gas, for example hydrogen, necessary is. Could be advantageous for example, the Bernoulli principle described above, but outside the storage container, used to unload the material.

Of the Nozzle has first over one execution (Transport guide) for particles of the sorbent material, which are transported by a gas stream. The compound preferably has a round cross-section, wherein the diameter advantageously a multiple of the transported Particle size corresponds.

Farther is a second implementation (Gas guide) for gas intended. This implementation is only for provided the gas transport and advantageous by means of filters against the penetration of particles of the sorbent material protected.

alternative could also both executions for the Transport of sorbent be suitable. Thus, when filling and Unloading the storage tank always chilled Transport medium with one of the two bushings, preferably insulated Execution, be transported. Because with can Losses are avoided, resulting in the use of a warm execution for a give cold medium (medium warms on / desorbs gas when heated).

For example can / can the first implementation and / or the second implementation be thermally insulated. This can cause a heat input into the cold gases and the cold sorbent material (preferably 77K) can be prevented.

Prefers can the first guide and the second guide spaced next to each other. In a further embodiment can the first guide and the second guide be arranged concentrically around each other. This is the feeder and the exhaustion concentric with each other or arranged around each other.

Advantageous can the nozzle in its end, which in contact with a Storage container brought or insertable in these is, at least partially flexible. Thereby becomes the filling and discharge further simplified.

Preferably the nozzle can be an interface for receiving data and / or to transfer of data. Preference is given to a particular electrical Data connection, which is an information exchange between the following described system, such as a gas station, and the storage container, for example in a tank system of a vehicle - or the vehicle itself - allowed. Transfer can be For example, type of sorbent material, load condition, pressure, temperature and the same.

The inventive method can be performed using a system wherein a feeder is provided, which is a device for unloading befindlichem in a storage container spent sorbent material and means for filling a Storage container with unused sorbent material, and wherein a storage device for storing sorbent material to be delivered to a storage container is provided, which at least temporarily with the charging device connected is.

at such a system may preferably be a kind of gas station act. At this gas station can such as mobile tank systems, which are components of a vehicle, be refueled. Those described in connection with the prior art Problems can be avoided if that for the gas storage provided sorbent outside the tank system, preferably at a gas station with the adsorbate (for example hydrogen) is loaded. The resulting heat of sorption can without time pressure and be dissipated with lower cost and energy expenditure.

Advantageous the charging device of the system for filling a storage container with sorption material at elevated pressure compared to the ambient pressure, preferably at a pressure of greater than or equal to 40 bar, for example 40 bar, be trained.

Farther For example, the feeder of the system may be one as above described filling / discharge nozzle have, so that in this regard the corresponding versions is fully incorporated by reference and referenced.

In In another embodiment, the system can have at least one interface for receiving data and / or transmitting data, already explained above has been particularly preferred, a data interface.

Advantageous The system can provide a means of controlling the quality of a storage tank have discharged sorbent material. Backed, completely discharged Sorbent or partially discharged sorbent material could be first through a quality control judged and possibly damaged or unusable particles are sorted out.

In In another embodiment, the system may include means for regenerating from a storage tank have discharged sorbent material. The completely discharged Sorbent or the partially discharged Sorptionsma material could be regenerated (heat treated / annealed) to remove gaseous contaminants Example of minor components of the gas used to remove. Thus, with regular regeneration for example, without significant disadvantages the use of hydrogen with lower quality / purity possible (for example, substance purity class 3.0 instead of class 5.0).

Preferably has the system over a device for loading a sorbent, in particular a sorbent described above, and / or a sorbent material, in particular a sorption material as described above, with a gas, preferably with hydrogen. This loading device can have different components.

For example the loading device can be a cooling device for cooling the Sorbent and / or sorption material to a predetermined temperature exhibit. The sorbent or sorption material can be cooled (77 K) and newly loaded with hydrogen and again - for example, at a gas pump - provided become.

In a further embodiment, the loading device may have a device for setting a predetermined loading pressure. It is energetically advantageous to cool and load the sorbent or sorption material successively in discrete processes or continuously. For example, staggering could be 0 ° C / -40 ° C / -80 ° C / -120 ° C / -160 ° C / -196 ° C. If appropriate, it is also sensible to couple the temperatures to known phase transitions, for example CO ₂ → CO _{2 gas} (sublimation). Also a Va riation of the loading pressure may help to save energy depending on the adsorption behavior of the materials.

A different possibility is to get back, partially discharged sorption material or completely discharged Sorbent without quality control or to cool regeneration and to load again - for example at a gas pump - provided to be able to. Optionally, over a tank system integrated, readable and writable Chip be assured that in a meaningful cycle (for example, every fifth refueling operation) a quality control independently from the loading condition is made.

The Invention will now be described by way of embodiments with reference explained in more detail in the accompanying drawings. Show it:

1 to 4 a first embodiment of an inventively usable storage container;

5 to 8th a second embodiment of an inventively usable storage container;

9 to 12 a third embodiment of an inventively usable storage container;

13 a schematic view of an inventively usable tank system, which cooperates with an inventively employable system for providing a sorption material; and

14 a schematic cross-sectional view through an inventively applicable filling / discharge nozzle.

In the embodiments, a situation is described in which in a storage container 10 a sorbent material is added to which hydrogen is adsorbed. The storage tank is part of a mobile tank system, which is installed in a vehicle. The storage container is filled at a delivery system, which represents a gas station.

In the 1 to 12 First, various embodiments of a storage container 10 shown - as well as their filling and discharging processes.

The in the 1 to 4 illustrated storage container 10 is designed in the form of a pressure vessel. The storage tank 10 initially has an inner container 12 in which is a sorption material 11 located. The sorbent material 11 consists of a sorbent on which hydrogen is adsorbed. The inner container 12 is from an outer container 13 surrounded, being between the two containers 12 . 13 an isolation area 14 is provided. The storage tank 10 furthermore has a connecting element 15 For example, a flange through which it can be connected to an external delivery system. In addition, the Speicherbe has container 10 performing on a first guide 16 , which serves as a transport guide for the sorption material and subsequently as a transport guide 16 is designated. In addition, a second guide is performing 17 provided, which serves as a gas guide and subsequently as a gas guide 17 is designated. This gas guide 17 is in the present example as a nozzle 18 educated.

The aim of this embodiment is a mechanically simple as possible filling and discharging system, complex structures and moving parts within the storage container 10 to avoid. The basic idea is the granular sorption material 11 via a gas stream at virtually any pressure up to about 40 bar to transport. The tank system should basically have two openings / passages. The first implementation 16 (Transport guide) is equipped with a relatively large in relation to the particle size of the sorbent material diameter (for example, diameter equal to 50 times the particle size). The implementation 16 serves to transport the sorption material 11 from the gas station to the tank system as well as from the tank system to the gas station. The second implementation 17 (Gas guide) is in the form of a nozzle 18 executed and has a filter which retains penetrating Sorptionsmaterialpartikel. This nozzle 18 serves as a gas outlet when filling the tank system. When loading the tank system ( 3 ) with fresh sorption material 11 this is via a volume flow over the first passage 16 in the storage tank 10 brought in. The hydrogen carrier gas required for this leaves the storage tank 10 over the gas guide 17 , During a discharge ( 2 ) of the tank system, hydrogen gas flows over the nozzle 18 executed implementation 17 in the storage tank 10 , By the high Flow rate at the outlet and the position of the nozzle 18 in the storage tank 10 is in the storage tank 10 existing sorbent material 11 whirled up and about the transport guide 16 by the gas flow from the storage tank 10 transported. Thus, the tank system can be loaded and unloaded. While driving ( 4 ) is desorbed hydrogen via the gas guide 17 removed and fed to the drive unit. In order to control the desorption optimally, heated hydrogen can be transported via the transport guide 16 in the storage tank 10 be introduced.

The in the 5 to 8th illustrated storage container 10 is also formed in the form of a pressure vessel. The storage tank 10 As in turn has an inner container 12 in which the sorption material 11 located. The sorbent material 11 consists of a sorbent on which hydrogen is adsorbed. The inner container 12 is from an outer container 13 surrounded, being between the two containers 12 . 13 an isolation area 14 is provided. The storage tank 10 furthermore has a connecting element 15 For example, a flange through which it can be connected to an external delivery system. In addition, the storage tank features 10 about a first guide 16 , which serves as a transport guide for the sorption material 11 serves. In addition, a second guide 17 provided, which serves as a gas guide. In the present example, the two guides 16 . 17 tubular and form a pipe loop 19 , In the pipe loop 19 are two hinged flaps 20 arranged the flow inside the pipe loop 19 to influence.

The in the 5 to 8th illustrated embodiment of the storage container 10 makes the dynamic pressure drop in places with increased flow velocity according to the Bernoullig equation 1 2 pv 2 + ρgh + p = const. use (Venturi tube). The storage tank 10 characterized by a closed pipe loop 19 with the lowest possible internal flow resistance, which in two places by 90 ° rotatable, flow-driven flaps 20 is interrupted. Goal of these flaps 20 is the deflection of the flow (sorption + carrier gas) during the filling process. The first flap closes the passage through the piping system and thereby causes the introduction of the sorbent material 11 into the storage tank ( 7 ). The carrier gas is conveyed via the second flap back into the pipe system and can be returned to the pump. A filter in front of the flap 20 prevents the discharge of sorbent material 11 , When emptying the storage tank 10 ( 6 ) the carrier gas flows through the pipe loop 19 in the opposite direction. A narrowing 21 The pipe loop (see the Venturi principle described above) leads to the reduction of the static pressure in the pipe section and thereby to a suction of sorbent material 11 from the storage tank 10 , The sorbent material 11 is dispersed in the carrier stream and from the storage tank 10 worn out. A slight inclination 22 of the storage container 10 and a favorable positioning of the constriction of the Venturteililstücks 21 near the lowest point, by using gravity on the inclined plane, the task is to take over the sorption material 11 into the reach of the intake. The inclination is in relation to a reference plane 23 , which is formed in the present example as a horizontal plane. Whether the reference plane is a horizontal or vertical plane depends on the general orientation of the storage container 10 from. While driving ( 8th ) is desorbed hydrogen via the gas guide 17 from the storage tank 10 taken.

Also in the 9 to 12 illustrated storage container 10 is designed in the form of a pressure vessel. The storage tank 10 again has an inner container 12 in which the sorption material 11 located. The sorbent material 11 consists of a sorbent on which hydrogen is adsorbed. The inner container 12 is from an outer container 13 surrounded, being between the two containers 12 . 13 an isolation area 14 is provided. The storage tank 10 furthermore has a connecting element 15 For example, a flange through which it can be connected to an external delivery system.

Advantage of in the 9 to 12 illustrated embodiment, the decoupling of the components required for the filling and discharge from the storage container 10 and thus a significant saving in weight and heat capacity. The task of supplying and removing sorption material 11 and carrier gas takes over through the filler neck 15 introduced filling / discharge nozzle 30 in his end area 34 which is in the storage tank 10 protrudes, can also be designed flexibly and which is characterized in that the length of the nozzle 30 in the storage tank 10 can be readjusted to the sorbent material 11 to be able to whirl up and remove as close as possible to the place. This Nachjustierbarkeit is in the 9 to 12 in the form of an arrow 33 shown.

It is advantageous in this context, the particular suitability of this embodiment for a concentric arrangement of transport guide 31 and gas routing 32 , The storage tank 10 then has a single guide 24 on, through which the other two guides 31 . 32 of the neck 10 can be passed. It is possible by the nachjustierbare, spatial proximity of the guides 31 . 32 to the sorption material 11 also the integration of a suction effect in the guides 31 . 32 , so that for the emptying of the storage container 10 not necessarily the recirculation of hydrogen is necessary. Advantageously, for example, in connection with the 5 to 8th described Bernoulli principle, but outside the storage container 10 , used to unload the material.

In the 13 a scheme is presented, which is initially a mobile tank system 40 shows which is to be arranged in a vehicle. The tank system 40 initially has a storage tank 10 , for example, in one of the in the 1 to 12 illustrated variants may be formed. About appropriate guides 42 is the storage tank 10 with a heat exchanger device 43 connected, which via a line 45 again with a drive unit 41 of the vehicle is connected.

For removing hydrogen from the mobile tank system 40 There are several options. The amount of in the storage tank 10 stored hydrogen is made up of the adsorbed phase (R _ads ), ie the hydrogen adsorbed on the sorbent, as well as the gas phase (H _gas ), ie the tanks in the free volume of the storage tank 10 present hydrogen gas, together. For any state (temperature and pressure), a state of equilibrium which depends on the adsorption properties of the sorbent is established. Immediately after refueling the vehicle (pressure in the tank system 40 bar, temperature 77 K), can from the drive unit 41 the vehicle required hydrogen are taken directly from the gas phase. This hydrogen is almost immediately in a through the storage container 10 prevailing pressure determinable amount available. The removal of hydrogen from the gas phase, which is in the tank 10 disturbed equilibrium between adsorbed phase and gas phase. As the pressure falls, part of the adsorbed hydrogen is desorbed to partially compensate for the loss in the gas phase. However, the lowering of the temperature caused by the desorption again slows down the desorption process. With short removal of hydrogen from the gas phase of the storage container 10 For example, the pressure drops from 40 bar to 38 bar, with the temperature dropping from 77 K to 65 K, for example, due to the negligible heat flow from the environment through the insulation. (The size of the sag is ultimately due to the adsorption enthalpies and properties of the sorbent dependent.). The hydrogen is thus constantly withdrawn from the gas phase to the drive unit 41 to supply the vehicle. However, as soon as the pressure in the storage tank 10 falls below the pressure requested by the customer, one of the drive unit 41 The vehicle required volume flow of hydrogen are no longer maintained (for example, pressure 2 bar). The corresponding values depend on the sorbent used.

By a connected pump (disadvantage: electrical consumers!) Or preferably by targeted increase in the temperature in the storage tank 10 the supply of hydrogen can be ensured. This can be advantageously realized by already removed, cold hydrogen through a heat exchanger 43 , which preferably uses the ambient heat, heated and back into the storage tank 10 is passed, where the stored in the gas heat capacity is transferred to the sorbent material (recycle). The control of the heat input, for example, by means of two on the storage container 10 positioned solenoid valves that interrupt the line to prevent unwanted heat input, for example, when not using the vehicle. By means of the presented recycle system, the temperature in the tank system can 40 increases without the use of an electric heater, and thus also desorbs the hydrogen present in the adsorbed phase and used if necessary.

The storage tank 10 can about a system 50 for providing a sorbent material 11 , in the present case a gas station, with sorption material 11 be supplied. This can be done by the storage tank 10 during the filling process and unloading with a charging device 51 be connected, what by the arrows 54 and 55 is shown. The charging device may be a kind of dispenser of the filling station system 50 act. Furthermore, between the mobile tank system 40 and the delivery system 50 a data line 53 be present in the form of suitable interfaces, via which in particular measured values can be exchanged, which can advantageously support the filling process and unloading process. The feeder 51 is via a connection line 63 with a storage device 52 connected, is stored in the already loaded sorption material.

The about the feeder 41 discharged sorbent material may, for example, via a device 56 for quality control and a facility 57 for the regeneration of a facility 58 to Be loading a sorbent and / or sorbent supplied and then, after loading, until further use in the storage container 52 be cached. This transport path of the sorbent material is in 13 through the arrows 59 . 60 . 61 and 62 shown.

With the mobile tank system 40 Recovered, completely discharged sorbent or partially discharged sorbent material could be in the system 50 be handled in two ways.

Recovered, completely discharged sorbent or partially discharged sorbent material could be first checked by a quality control facility 56 be assessed. It could possibly be sorted out damaged or unusable particles.

The sorbent and / or sorbent material could be in the facility 57 regenerated (heat treated / baked) to remove gaseous contaminants, for example from minor constituents of the gas used. Thus, with regular regeneration, for example, without significant disadvantages, the use of hydrogen of lower quality / purity is possible (for example, class purity class 3.0 instead of class 5.0).

The sorbent / sorbent material can be cooled (77 K) and recharged with hydrogen and made available again at the pump. This happens in the facility 58 , It is energetically advantageous to cool and load the sorbent / sorption material successively in discrete processes or continuously. For example, staggering could be as follows: 0 ° C / -40 ° C / -80 ° C / -120 ° C / -160 ° C / -196 ° C. If appropriate, a coupling of the temperatures to known phase transitions, for. B. CO _{2 solid} → CO _{2 gas} (sublimation). Also, a variation of the loading pressure may help energy saving depending on the adsorption behavior of the materials.

Another possibility is that recycled, partially discharged sorbent / sorbent material can be cooled and loaded without quality control or regeneration in order to be made available again at the pump. If necessary, you can have one in the tank system 40 integrated, readable and writable chip to ensure that in a meaningful cycle (for example, every fifth refueling operation), a quality control is performed regardless of the load condition.

An example of a suitable filling / discharging nozzle 30 who is in the system 50 can be used to connect to the storage tank 10 of the tank system 40 is related to 14 described. A tap suitable for the system advantageously has the following properties:
He has a thermal insulation 35 to prevent unwanted heat input into the cold gases and cold sorbent material (preferably 77K). Furthermore, a first implementation, namely a transport guide 31 , intended. This transport guide 31 serves as a passage for Sorptionsmaterialpartikel which are transported by a gas stream. The transport guide 31 preferably has a round cross-section, wherein the diameter advantageously corresponds to a multiple of the particle size to be transported. Furthermore, a second passage for gas, namely a gas guide 32 , intended. This implementation 32 is intended only for gas transport and protected by filters against the ingress of Sorptionsmaterialpartikeln. Alternatively, both bushings could be used 31 . 32 be suitable for the transport of sorbent material. Thus, when filling and discharging the storage container always cooled transport medium with one of the two feedthroughs 31 . 32 , preferably insulated bushings, are transported. This can be avoided losses that would otherwise arise when using a warm passage for a cold medium. (Medium warms up / sorbent desorbs gas when heated).

An interface can also be advantageous 36 be provided for an electrical data connection, an information exchange between the gas station 50 and the tank system 40 of the vehicle or the vehicle itself allowed. For example, the type of sorbent material, the loading state, the pressure, the temperature and the like could be transmitted.

The following describes, by way of example, the process occurring during a refueling operation. It should be assumed from the following starting position:
A vehicle reaches the gas station, for example, in the following state:
Residual pressure in the tank system less than 5 bar
Temperature in the tank system greater than 0 ° C

That means in the tank system 40 of the vehicle are granular or pre-compacted, loose sorption material, which is partially loaded with hydrogen (the amount of adsorbed hydrogen is dependent on temperature and pressure in the tank system 40 as well as the amount and the adsorption properties of the sorption material used.), as well as nichtadsorbierter, gaseous hydrogen (The amount of gaseous hydrogen is determined by pressure, temperature and / or present in the tank free volume.).

To begin the refueling process, first the filling nozzle 30 at the connecting flange 15 of the storage container 10 appropriate. Subsequently, a determination of the residual amount of stored hydrogen by pressure and temperature measurement within the tank system 40 of the vehicle.

Now the discharge takes place in the tank 10 of the vehicle sorption by blowing in hydrogen. Due to the special shape and position of the nozzle 18 ( 1 ) becomes the powdery sorbent material 11 whirled up and by the gas flow over the outlet (gas guidance 17 ). The pressure of this discharge circuit need not necessarily be 40 bar, but can, for example, the residual pressure in the tank 10 be adapted to adsorption or further desorption of the sorbent material 11 during the discharge process.

After removal of an advantageous portion of the sorbent material 11 (For example, about 98%) is the tank system (ie the empty storage tank 10 ) of the vehicle by blowing cold (77 K) hydrogen cooled. It is cold (77 K) hydrogen gas with adjusted flow rate and volume flow from the gas station 50 on the intended for the gas inlet implementation 16 in the storage tank 10 blown by the heat flow dQ / dt from the pressure vessel (inner tank 12 of the storage container 10 ) is derived to the cold hydrogen gas heat, which by the discharge of the now warmed up hydrogen gas through the intended implementation 17 from the storage tank 10 of the vehicle is transported.

This is followed by injection of fresh, fully hydrogenated sorbent material 11 at for example 40 or 100 bar pressure, via the intended for the filling implementation (transport guide 16 ). The sorbent material 11 was already in the gas station 50 pre-cooled to 77 K and loaded with hydrogen at 40 bar. Therefore, a transport of the sorbent material 11 from the gas station 50 in the tank system 40 at 40 bar needed to avoid desorption of hydrogen. Otherwise, re-adsorption processes could occur in the tank system 40 lead to an increase in the temperature and consequently to a shorter service life or smaller load density and thus to a lower range of the vehicle. Also conceivable would be a load at the gas station 50 at pressures greater than 40 bar, the pressure during refueling of the tank system 40 could be lowered to 40 bar. Consequently, a portion of the adsorbed hydrogen would desorb from the sorbent material and the temperature in the storage tank 10 sink below 77K. At a lower temperature in the storage tank 10 At the same pressure (40 bar), a larger amount of hydrogen could be stored or the service life of the tank system 40 increase.

After complete filling of the storage tank 10 with sorption material 11 At 40 bar the refueling process is finished. The vehicle can be decoupled from the gas station and continue its journey. Further embodiments, modifications and variations of the present invention will be readily apparent to and realizable by those skilled in the art upon reading the description without departing from the scope of the present invention.

10

storage container

11

sorption

12

inner container

13

Outer isolation tank

14

Quarantine

15

connecting element

16

First guide Transport guide, execution

17

Second guide (Gas guide) execution

18

jet

19

pipe loop

20

rotatable flap

21

Venturi section

22

inclination

23

horizontal level

24

guide

30

Filling / discharge nozzle

31

transport guide

32

gas guide

33

positioning dependent from the level

34

end of the filling / discharging outlet

35

thermal isolation

36

interface (Data Connection)

40

tank system

41

power unit

42

guide

43

heat exchanger device

45

management

46

vehicle

50

system for providing a sorption material (gas station)

51

loader

52

memory device

53

Data Interface

54

unloading

55

filling process

56

Facility for quality control

57

Facility to regenerate

58

Facility for loading a sorbent and / or sorbent material

59

transport of the sorbent material

60

transport of the sorbent material

61

transport of the sorbent material

62

transport of the sorbent material

63

connection between the charging device and the storage device

Claims (42)

Method for providing a sorption material ( 11 ) for a storage container ( 10 ), the sorption material ( 11 ) a sorbent and an adsorbate adsorbed thereto in the form of a gaseous fuel, preferably hydrogen, wherein in the storage container ( 10 ), spent sorption material from the storage container ( 10 ), wherein the spent sorbent material outside the storage container ( 10 ) is reloaded with the gaseous fuel and then the loaded with the gaseous fuel sorption material ( 11 ) for the storage container ( 10 ), the discharge of the storage container ( 10 ) of the spent sorbent material by blowing in the gaseous fuel. Process according to Claim 1, characterized in that the sorption material ( 11 ) is temporarily stored in a storage device until further use and / or that from the storage container ( 10 ) is subjected to a quality control prior to reloading spent sorbent material. Method according to claim 1 or 2, characterized in that the from the storage container ( 10 ) is subjected to a regeneration process before reloading and / or that the sorption material ( 11 ) is cooled to a predetermined temperature before reloading. Method according to one of the preceding claims, characterized in that before the discharge of the storage container ( 10 ) of the spent sorbent the remaining amount of in the storage container ( 10 ), on the sorption material ( 11 ) Adsorbed adsorbate and / or unadsorbed, gaseous fuel is determined. Method according to one of the preceding claims, characterized in that the Speicherbe container ( 10 ) is brought to a predetermined temperature or cooled between the discharge and the refilling. Method according to one of the preceding claims, characterized in that the refilling of the storage container ( 10 ) with unconsumed sorption material ( 11 ) at a higher pressure compared to the ambient pressure, preferably a pressure of at least 40 bar. Process according to Claim 6, characterized in that the unused sorption material ( 11 ) at an elevated pressure of at least 40 bar to the storage tank ( 10 ) is transported and filled in this. Method according to one of the preceding claims, characterized in that the storage container ( 10 ) for storing the sorption material ( 11 ) with a pressure vessel ( 12 ), a connecting element ( 15 ) to an external delivery system, at least one sorbent material ( 11 ), which at least during the operational use of the storage container ( 10 ) is stored in this, and with a transport guide ( 16 ) for loading and / or unloading the storage container ( 10 ) with sorption material ( 11 ), the sorbent material ( 11 ) comprises the sorbent and the adsorbate adsorbed thereto, wherein at least one second guide for supplying and / or removing a gas as a gas guide ( 17 and wherein the sorbent is formed on the basis of activated carbon activated carbon sorbents in the form of discrete activated charcoal grains, preferably in spherical form, wherein at least 70% of the total pore volume of the high performance adsorbents is formed by micropores having pore diameters of ≤ 20 Å. Process according to claim 8, characterized in that the high-performance adsorbents have a mean pore diameter of at most 30 Å and / or the high-performance adsorbents have a BET surface area of at least 1500 m ² / g and / or the high-performance adsorbents have a total pore volume of at least 0 , 7 cm ³ / g, in particular wherein at least 70% of this total pore volume are formed by micropores with pore diameters of ≤ 20 Å. Process according to Claim 8 or 9, characterized in that the total pore volume according to Gurvich of the high-performance adsorbents is at least 0.7 cm ³ / g, in particular at least 0.8 cm ³ / g, preferably at least 0.9 cm ³ / g, particularly preferably at least 1 , 0 cm ³ / g, and / or values up to 1.5 cm ³ / g, in particular up to 1.6 cm ³ / g, preferably reached up to 1.8 cm ³ / g, and / or that the Gurvich total pore volume of the high-performance adsorbents ranges from 0.7 to 1.8 cm ³ / g, in particular from 0.8 to 1.6 cm ³ / g, preferably from 0.9 to 1.5 cm ³ / g. Method according to one of claims 8 to 10, characterized that at least 75%, especially at least 80%, preferably at least 85%, especially preferably at least 90% of the total pore volume, in particular of the total pore volume after Gurvich, the high-performance adsorbents by Micropores are formed with pore diameters of ≤ 20 Å and / or that 70% to 95%, in particular 75% to 90%, preferably 75% to 85%, of Total pore volume, in particular the total pore volume according to Gurvich, high-performance adsorbents through micropores with pore diameters formed of ≤ 20 Å become. Process according to one of Claims 8 to 11, characterized in that the microporous volume to carbon black of the high-performance adsorbents formed by micropores with pore diameters of ≤ 20 Å is in the range from 0.5 to 1.4 cm ³ / g, in particular from 0.6 to 1 , 2 cm ³ / g, preferably 0.7 to 1.1 cm ³ / g. Method according to one of claims 8 to 12, characterized that the mean pore diameters of high performance adsorbents at most 26 Å, in particular at most 25 Å, preferably at most 24 Å, and / or that the mean pore diameter of the high-performance adsorbents in the range from 15 to 30 Å, in particular 16 to 26 Å, preferably 17 to 25 Å, more preferably 18 to 24 Å, lies. Process according to one of Claims 8 to 13, characterized in that the BET surface area of the high-performance adsorbents is in the range from 1,500 m ² / g to 3,500 m ² / g, in particular 1,500 m ² / g to 2,750 m ² / g, preferably 1,525 to 2,500 m ² / g, more preferably 1,550 to 2,400 m ² / g, very particularly preferably 1,575 to 2,350 m ² / g. Process according to one of Claims 8 to 14, characterized in that the weight-related adsorbed N ₂ volume V _{ads (w / w) of} the high-performance _adsorbents , determined at a partial pressure p / p ₀ of 0.25, at least 400 cm ³ / g, in particular at least 420 cm ³ / g, and in particular in the range of 400 to 800 cm ³ / g, preferably 410 to 750 cm ³ / g, particularly preferably 420 to 700 cm ³ / g, is and / or that the volume-related adsorbed N ₂ volume V _{ads (vol.) Of} high performance _adsorbents , determined at a partial pressure p / p ₀ of 0.25, at least 200 cm ³ / cm ³ , in particular at least 220 cm ³ / cm ³ , and in particular in the range of 200 to 300 cm ³ / cm ³ , preferably 210 to 275 cm ³ / cm ³ , particularly preferably 225 to 260 cm ³ / cm ³ , is located. Process according to one of Claims 8 to 15, characterized in that the weight-related adsorbed N ₂ volume V _{ads (w / w) of} the high-performance _adsorbents , determined at a partial pressure p / p ₀ of 0.995, is at least 450 cm ³ / g, in particular at least 460 cm ³ / g, and in particular in the range of 450 to 900 cm ³ / g, preferably 460 to 875 cm ³ / g, particularly preferably 470 to 850 cm ³ / g, and / or that the volume-related adsorbed N ₂ volume V _{ads (vol.) Of} high performance _adsorbents , determined at a partial pressure p / p ₀ of 0.995, at least 250 cm ³ / cm ³ , in particular at least 260 cm ³ / cm ³ , and in particular in the range of 250 to 400 cm ³ / cm ³ , preferably 260 to 350 cm ³ / cm ³ , particularly preferably 265 to 320 cm ³ / cm ³ , is located. Method according to one of claims 8 to 16, characterized in that the micro pore surface formed by pores with pore diameters of ≤ 20 Å after carbon black of the high performance adsorbents at least 1,400 m ² / g, in particular at least 1,450 m ² / g, preferably at least 1,500 m ² / g, is and / or that the micro pore surface formed by pores with pore diameters of ≦ 20 Å after carbon black of the high-performance adsorbents in the range of 1400 to 2500 m ² / g, in particular 1450 to 2400 m ² / g, preferably 1,500 to 2,300 m ² / g, lies. Method according to one of claims 8 to 17, characterized that the High-performance adsorbents have a butane adsorption of at least 25%, in particular at least 30%, preferably at least 40% and / or that the High performance adsorbents have a butane adsorption in the range of 25 to 80%, in particular 30 to 70%, preferably 35 to 65%. Method according to one of claims 8 to 18, characterized that the High-performance adsorbents have an iodine value of at least 1,350 mg / g, in particular at least 1,450 mg / g, preferably at least 1,500 mg / g, and / or that the High performance adsorbents have an iodine value in the range of 1,350 to 2,100 mg / g, in particular 1,450 to 2,050 mg / g, preferably 1,500 to 2,000 mg / g. Method according to one of claims 8 to 19, characterized in that the storage container ( 10 ) an inner container ( 12 ) for receiving the sorption material ( 11 ) and one the inner container ( 12 ) surrounding outer insulation container ( 13 ), in particular between the inner container ( 12 ) and the outer container ( 13 ) an isolation area ( 14 ) is provided. Method according to one of claims 8 to 20, characterized in that a transport guide ( 16 ) and / or a gas guide ( 17 ) tubular or in the form of a nozzle ( 18 ) is / are trained. Process according to claim 21, characterized in that in the gas duct ( 17 ) at least one filter element for filtering sorption material ( 11 ) and / or sorbent is provided. Method according to one of claims 21 or 22, characterized in that the transport guide ( 16 ) and the gas guide ( 17 ) in the storage container ( 10 ) are connected to each other and a pipe loop ( 19 ), in particular wherein in the pipe loop ( 19 ) at least one rotatable flap ( 20 ), preferably two flaps, for changing the flow rate within the pipe loop ( 19 ) is / are and / or in particular wherein in the pipe loop ( 19 ) at least one filter element for filtering sorption material ( 11 ) and / or sorbent is provided and or the filter element in the region of the rotatable flap ( 20 ) is arranged. Method according to one of Claims 21 to 23, characterized in that the storage container ( 10 ) at least during the loading and / or unloading operation in a (skew) position ( 22 ), relative to a horizontal or vertical reference plane ( 23 ), be brought or aligned. Method according to one of claims 21 to 24, characterized in that the transport guide ( 16 ) and the gas guide ( 17 ) in a single guide ( 24 ) and that the leadership ( 24 ) as a receptacle for a filling / discharge nozzle ( 30 ) is formed. Method according to one of claims 21 to 25, characterized in that at least one sensor element for measuring operation-specific properties of the storage container ( 10 ) and / or the sorbent material ( 11 ) and / or the sorbent is provided, in particular wherein the storage container ( 10 ) has at least one interface for transmitting values detected via the at least one sensor element. Method according to one of Claims 1 to 26, characterized in that the storage container ( 10 ) is formed as a storage tank for the gaseous fuel. Method according to one of Claims 1 to 27, characterized in that the storage container ( 10 ) as part of a tank system ( 40 ), in particular mobile tank system, for providing the gaseous fuel for a drive unit ( 41 ) is provided. Method according to claim 28, characterized in that the storage container ( 10 ) about a guided tour ( 42 ), preferably the transport guide ( 16 ) and / or the gas guide ( 17 ), with a heat exchanger device ( 43 ) is connected. A method according to claim 28 or 29, characterized in that at least one interface for the transmission of at least one sensor element for measuring operation-specific properties of the storage container ( 10 ) and / or the sorbent material ( 11 ) and / or sorbent values. Method according to one of the preceding claims, characterized in that for filling and / or discharging the storage container ( 10 ) a filling / discharge nozzle ( 30 ) is used, wherein the filling / discharge nozzle ( 30 ) - a first tour ( 31 ) for passing the sorbent material comprising the sorbent and the adsorbate adsorbed therewith ( 11 ), the first guide ( 31 ) with a transport guide of the storage container ( 10 ), and - a second tour ( 32 ) for passing the gaseous fuel, which with a gas guide of the storage container ( 10 ) is connectable. Method according to claim 31, characterized in that the first guide ( 31 ) and / or the second guide ( 32 ) are thermally isolated. Method according to claim 31 or 32, characterized in that the first guide ( 31 ) and the second guide ( 32 ) spaced adjacent to each other or that the first guide ( 31 ) and the second guide ( 32 ) are arranged concentrically around each other. Method according to one of claims 31 to 33, characterized in that the filling / discharge nozzle ( 30 ) in its end region ( 34 ) which is in contact with a storage container ( 10 ) Can be brought or introduced into this, at least partially flexible. Process according to Claim 34, characterized in that the filling / discharging nozzle ( 30 ) an interface ( 36 ) for receiving data and / or transmitting data. Method according to one of the preceding claims, characterized in that the method using a system ( 50 ), wherein a charging device ( 51 ) is provided, which comprises a device for unloading from that in the storage container ( 10 ) spent sorbent material and means for filling the storage container ( 10 ) with unconsumed sorbent material, and wherein a memory device ( 52 ) for storing it to the storage container ( 10 ) sorbent material to be delivered ( 11 ) provided at least temporarily with the charging device ( 51 ) is connected. Process according to claim 36, characterized in that the charging device ( 51 ) for filling the storage container ( 10 ) with the sorption material ( 11 ) is formed when compared to the ambient pressure increased pressure, preferably a pressure of at least 40 bar. Method according to claim 36 or 37, characterized in that the charging device ( 51 ) the filling / discharge nozzle ( 30 ) having. Method according to one of Claims 36 to 38, characterized in that the system ( 50 ) at least one interface ( 53 ) for receiving data and / or transmitting data. Method according to one of Claims 36 to 39, characterized in that the system ( 50 ) An institution ( 56 ) to control the quality of the storage container ( 10 ) discharged sorption material ( 11 ) having. Method according to one of Claims 36 to 40, characterized in that the system ( 50 ) An institution ( 57 ) for regenerating from the storage container ( 10 ) discharged sorption material ( 11 ) having. Method according to one of Claims 36 to 41, characterized in that the system ( 50 ) a loading device ( 58 ) for loading the sorbent and / or the sorption material ( 11 ) with the gaseous fuel, in particular wherein the loading device ( 58 ) a cooling device for cooling the sorbent and / or the sorption material ( 11 ) to a predetermined temperature and / or in particular wherein the loading device ( 58 ) has means for setting a predetermined loading pressure.