EP3802411A1 - Verfahren zur durchführung stark gas freisetzender reaktionen - Google Patents
Verfahren zur durchführung stark gas freisetzender reaktionenInfo
- Publication number
- EP3802411A1 EP3802411A1 EP19728893.9A EP19728893A EP3802411A1 EP 3802411 A1 EP3802411 A1 EP 3802411A1 EP 19728893 A EP19728893 A EP 19728893A EP 3802411 A1 EP3802411 A1 EP 3802411A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid
- porous structure
- gas
- catalyst
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
- C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
- C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/2485—Monolithic reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J7/00—Apparatus for generating gases
- B01J7/02—Apparatus for generating gases by wet methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/2402—Monolithic-type reactors
- B01J2219/2425—Construction materials
- B01J2219/2427—Catalysts
- B01J2219/2428—Catalysts coated on the surface of the monolith channels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1023—Catalysts in the form of a monolith or honeycomb
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
Definitions
- the present invention relates to a method for carrying out strong gas-releasing reactions by discharging a gas product from a liquid starting material, wherein the liquid starting material flows through a catalyst-loaded porous structure.
- the invention further relates to devices for carrying out the discharge and the use of a catalyst-loaded porous structure for carrying out strong gas-releasing reactions.
- Strong gas-releasing reactions that is strong gas-generating reactions, are e.g. from the dehydrogenation of liquid, organic hydrogen carriers (LOHC: Liquid Organic Hydrogen Carriers) known.
- LOHC Liquid Organic Hydrogen Carriers
- Catalyst pellets are placed the catalytically active nanoparticles. However, this leads to a small amount of catalyst per reactor volume and thus to poor volume utilization. Furthermore occurs in conventional
- US Pat. No. 7,766,986 B2 (or equivalent publication US 2006 0143981 A1) discloses a microchannel reactor with channels. In the microchannels is a catalyst of metal nanoparticles.
- DE 2010 038 491 A1 describes a fuel supply device in which a carrier medium enriched with hydrogen, in particular LOHC, is brought to the dehydrogenation for the provision of hydrogen in a reactor vessel.
- the reactor vessel is a pressure and temperature-resistant outer shell, in which there is a movable, in particular rotating body, wherein the body and / or the outer shell is equipped inside with a catalyst.
- the movable body may be provided on its outer contour with an inside coated with catalyst shroud, the inside being provided with grooves or with porous, in particular sponge-like structures.
- DE 10 2013 214 313 A1 describes a reactor for the release of hydrogen, in a reaction vessel containing at least one body with a metallic support structure, to which a solid, highly porous coating is applied, which contains catalytically active substances.
- the catalytic dehydrogenation is carried out under pressure at high temperatures along the coating, so that hydrogen is released and is discharged ascending upward.
- Another object of the present invention is the use of the method and the corresponding devices in the field of mobility, the so-called.
- On-board generation of hydrogen from LOHC e.g. be in truck.
- a high volumetric gas release rate, in particular hydrogen release rate and a low system weight should be achieved.
- Another object was therefore to provide devices in which the method according to the invention can be carried out. These devices are intended to have a smaller construction volume than the prior art and allow equal or higher levels of discharge of the product.
- the object is achieved by a method for carrying out strong gas-releasing reactions by discharging a gas product from a liquid starting material, characterized in that at least one liquid starting material flows through a catalyst-loaded porous structure.
- the object is achieved by a method for discharging a gas product from a liquid starting material, characterized in that at least one liquid educt flows through a catalyst-loaded porous structure.
- the method is characterized in that Essentially, the entire liquid product flows through the porous structure.
- the term "essentially” is used with reference to an amount of substance to define that at least 80%, preferably 85%, 86, 87, 88, 89%, particularly preferably 90, 91, 92, 93, 94%. , in particular 95, 96, 97, 98, 99 or 100% of this substance are concerned.
- Substantially complete conversion or discharge means for the purposes of the invention that at least 80%, preferably 85%, 86, 87, 88, 89%, particularly preferably 90, 91, 92, 93, 94%, in particular 95, 96, 97, 98, 99 or 100% of the educt are reacted or discharged.
- Discharge in the sense of the present invention means that a gas is liberated as product from a liquid educt.
- the gas product ie the gaseous product, can be bound in an alternative in the educt, in the sense of a solution, absorption, etc., or by partial evaporation of a liquid.
- the gas is formed during the reaction of the liquid starting material on the catalyst, that is synthesized in situ in a chemical reaction.
- mixed forms i. for example both synthesis in combination with desorption, partial evaporation, etc.
- An essential feature of the present invention is that at least one liquid product flows through a porous structure which is loaded (coated or coated) with catalyst.
- flow according to the invention does not mean that the same product, which flows in on one side of the porous structure, flows out on the opposite side of the structure.
- Flow through in the sense of the invention vodiegenden means that the product in the porous structure flows in, reacted in contact with the catalyst, that is discharged, and the gaseous product, possibly unreacted liquid starting material and optionally at least one further product, preferably a further liquid, discharged product flow out.
- the invention relates to a method characterized in that the porous structure is a material, preferably a monolith, which has three-dimensionally fluidically connected cavities.
- Three-dimensionally fluidically connected cavities in the sense of the present invention means that a large number of individual pores, also referred to as cavities, are present in the porous structure and linked to one another, so that a flow through the porous structure is ensured by a fluid.
- the porous structure has a common solids-free space that extends across the porous structure, that is, from one edge to the opposite edge.
- the solids-free space is formed by pores, cavities, which are fluidically linked together.
- the process is characterized in an alternative in that the porous structure is loaded (coated or treated as equivalent termini) with catalyst particles.
- the porous structure is loaded in one embodiment with catalyst particles.
- the catalyst is fixed to the walls of the pores or cavities of the porous structure.
- nanoscale catalyst particles that is to say catalyst particles having an average diameter of 1 to 1000 nm, preferably 1 to 100 nm, more preferably 1 to 10 nm.
- the porous structure has pores or cavities with a nominal pore size of 1 nm-20 ⁇ m.
- the porous structure is a monolithic body.
- Alternative contains or consists of at least one monolith of the following materials: Al 2 O 3, ZrO 2, TiO 2, Al-Si mixed oxides, cordierite, stainless steels or High-temperature steels.
- the porous structure is a ceramic sponge, preferably a ceramic sponge monolith.
- the porous structure is formed of a plurality of monoliths.
- Monoliths to be used according to the invention are catalyst-functionalized monoliths.
- the term monolith also includes others
- the one or more materials preferably monoliths of the porous structure, have pores, cavities with a cell density of 200 to 1000 cpsi, preferably 250 to 800, particularly preferably 200 to 700, 350 to 650, in particular 400 to 600.
- the monolith (s) is / are functionalized with catalyst, ie there is at least one catalyst in the pores.
- the catalysts used are catalysts comprising metals, preferably noble metals, more preferably ruthenium, platinum, palladium and / or gold and / or
- Transition metals preferably nickel, copper, cobalt, iron, etc. used.
- microporous support materials are used to increase the surface area of the catalytically active material (metals).
- the support material typically Al 2 O 3, ZrO 2, TiO 2, SIO 2 is applied to the monolith by conventional methods such as sol-gel technique, washcoat or the like, alternatively on an otherwise coated body such as a polyester. a microstructured system.
- the catalyst located in the porous structure ie in the pores of the material, preferably a monolith, shows a
- Volume unit Monolith or cell can change axially or radially.
- the porous structure is preferably a sintered material containing or consisting of metal, glass, ceramic or temperature-stable plastic or any combination thereof.
- the walls of the pores have an (additional) microporous layer which is loaded with catalyst nanoparticles.
- One embodiment relates to a method characterized in that at least one liquid gas-laden product flows pressure-driven into the porous structure or flows through it.
- the process according to the invention can be carried out continuously.
- a strong gas-releasing reaction according to the invention is characterized by liberation of at least 2 moles of a gaseous product from one mole of liquid starting material or at least 100 ml of a gaseous product from 1 ml of a liquid product.
- Reactions in which from one mole of a liquid educt optionally one mole of a liquid product and at least two moles of a gaseous product, preferably 3, 4, 5 moles of a gaseous product, more preferably 6, 7 moles of a gaseous product, in particular 8, 9 or more moles are released.
- such reactions are defined via volumes as reactions from which at least 100 ml of a gaseous product are formed from 1 ml of a liquid educt, preferably 200, 300, particularly preferably 400, in particular 500 ml or more of a gaseous product being formed or synthesized.
- another fluid product may be formed.
- Hydrogen carrier liquid organic hydrogen carrier
- the range of eligible as LOHC substances is extremely large.
- Such systems can be used for energy-efficient transport of hydrogen from a central source to decentralized consumption or for hydrogen-powered mobility with fuel cells or
- Essential for the present invention is the release of gas in a flow-through of the liquid starting material pore in which a catalyst, preferably in Particle shape is arranged.
- the wall of the cavity, ie the pore, is preferably loaded or loaded with nanosize catalyst particles.
- Such a porous structure corresponds to a three-dimensional clamped shell catalytic converter.
- the liquid educt is introduced from one side by means of pressure in the porous structure. Upon contact with the catalyst, the gas discharge takes place.
- the three-dimensional fluid isch linked cavities allow trouble-free removal of the resulting glass bubbles in the flow direction, in other words there is a convective transport of the discharged gas, so the transport of the gas bubbles with the flowing liquid.
- This liquid may on the one hand be the liquid starting material, but on the other hand also the discharged, liquid product. In the flow direction loaded laden educt is tracked. Due to the trouble-free removal of the discharged gas, this does not hinder the access of fresh educt to the catalyst. Schematically, this is shown in Fig. 1.
- FIG. 1 shows schematically the method according to the invention.
- the number 1 denotes the gas-loaded, liquid educt.
- Numeral 2 represents the catalysed cavity walls.
- the released gas is number 3 and the discharging product is number 4.
- FIG. 2 shows a device for carrying out the method according to the invention.
- the numeral 5 denotes the porous tube membrane.
- the loaded, liquid educt 1 is entered from two sides. On one side, the discharged liquid product 4 is discharged from the porous tube membrane 5. On the other hand, the discharging gas 3 is discharged.
- FIG 3 shows another variant of the invention, in which rotating filter discs 6 are used.
- the liquid reactant is fed.
- the liquid educt is introduced into the filter disks 6 due to the centrifugal force.
- the filter discs 6 are acted upon by a catalyst 2.
- the discharged gas 3 and the discharged liquid product 4 are separated from each other and discharged.
- FIG. 4 illustrates a component used for fluidic heating.
- Such components have a dense, metallic structure for the fluidic heating 8. Furthermore, a porous, metallic structure 9 is used as material.
- the basic principle of the invention is that the contact between the liquid educt and the catalyst is not by diffusion into a porous
- Catalyst pellet counter to the direction of transport of the gaseous product takes place, but by a pressure-driven flow through a porous
- Catalyst body having pores in the range of less than 1 nm to about 20 nm from the inside out in the simplest case, a sintered tube consisting of metal, glass, ceramic, or a temperature-stable plastic, in the three-dimensional pore system, the catalyst nanoparticles are deposited and fixed to the walls.
- a microporous layer can be previously applied to the walls inside the tube, which then in turn absorbs the catalyst nanoparticles, but does not makes the pores of the tube impassable for the liquid.
- tubes almost any shape, such as capillaries, hollow fibers,
- Filter disks or other, even 3D-printed porous structures with a large outer surface per volume are used.
- Channel structures for a heating fluid can also be integrated directly into the components by means of 3D printing.
- the forming gas can escape easily through the three-dimensional pore network to the outside and does not block the access of the internally tracked laden liquid.
- the forming gas Upon exiting the pores, in the surrounding housing, e.g. by gravity or in execution as a rotating disc filter also by centrifugal forces additionally assisted separation of gas and liquid.
- the present invention also relates to devices for carrying out the method according to the invention.
- the basic principle of such a device is shown in Fig. 2 using the example of the use of a raw membrane as a porous structure. It is a tubular or tubular structure whose walls have a porous structure. In this tube is preferably introduced from both ends loaded liquid educt at elevated pressure and or temperature.
- a temperature increase can generally be carried out before the starting material is poured into the device or porous structure or first or additionally in the device and / or porous structure.
- elevated conditions such as e.g. an elevated pressure or temperature conditions above the standard conditions of 25 ° C and 1 atmospheric pressure.
- An increased pressure or a pressure difference between the supply and the discharge side of the porous structure according to the invention can be achieved by a pump or e.g. be generated by centrifugal forces.
- the loaded liquid educt is introduced into the porous structure.
- gas is discharged and a discharged, liquid product remains. Both are displaced in the flow direction from the porous structure by nach Wegendes liquid educt.
- the discharged gas has a lower pressure on the outside of the porous structure than the supplied liquid.
- the discharged liquid product has a lower pressure than the introduced liquid product.
- An apparatus according to the invention for the discharge of gases from liquid substances, in particular from highly gas-releasing educts thus contains a porous structure, the pores are loaded with catalyst or acted upon and a device for increasing the pressure of the liquid educt or for generating a pressure difference between the Supply side of the educt and the discharge side of the products in order to achieve an inflow into the porous structure.
- a device for increasing the pressure is in one alternative, a pump.
- this is a device which sets one or more porous structures shaped as round filter pockets into rotation and generates a pressure difference between the inside and outside by the centrifugal force.
- an electrical resistance heating For heating, ie for increasing the temperature of the liquid starting material and / or for introducing the heat energy required for the gas formation or for the gas release from the liquid, e.g. an electrical resistance heating are used, which preferably couples the heat required for the discharge of the gas directly into the porous structure, whereby a particularly efficient heat transfer is achieved.
- a device according to the invention of rotating filter discs is constructed on a hollow shaft, as shown in Fig. 3.
- Dargestelit Loaded liquid educt is fed into the hollow shaft. Due to the rotation, the liquid educt is introduced into the filter discs due to the centrifugal force.
- the filter discs are the porous structures that are exposed to catalyst. The gas product present after the passage of the porous structure can easily be separated from an optionally liquid product by means of centrifugal force. Such a device is very compact.
- a further embodiment relates to integrated components with a dense metallic structure, which are used for a fluidic heating.
- integrated Components can be manufactured eg by means of 3D printing, eg 3D printing of metals by selective laser melting (SLM).
- SLM selective laser melting
- An example is shown in FIG.
- Further alternatives relate to material variants for the porous structures, the materials being selected from the group consisting of or consisting of ceramic filters, metallic filters, polymer filters and composite materials.
- electrically conductive materials metal, conductive ceramics or polymers or composites
- the walls of the cavities of the porous structure are not uniformly exposed to catalyst particles, there is an asymmetric arrangement of the catalyst particles.
- Such an asymmetrical arrangement can e.g. according to EP 1, 599 613 A are produced.
- the evolution of gas in the cavities of the porous structure can be additionally controlled.
- the method according to the invention is repeated or alternatively carried out in successively connected devices. Such cascading according to the second alternative, i.
- the liquid phase both liquid starting material and possibly liquid product, flows successively through several devices according to the invention, leading to an increase in sales per element, ie per device, as well as to an optimization of the overall conversion.
- the inventive method for the discharge of gas from liquid educts and the devices derived therefrom allow a much higher effective amount of catalyst per volume, avoid at the same time
- Mass transport resistances allows a high catalyst concentration per volume, an integrated phase separation and also a direct electrical or fluidic heating.
- the principle is generalizable to all reactions that release large quantities of gas from a liquid and produce one or more liquid products in addition to the gas.
- porous carrier layers mounted inside the pore system With regard to the configuration of the geometry of the porous structure through which it flows, possible porous carrier layers mounted inside the pore system, the materials for the flow-through structure and the active catalyst phase as well as the geometry of the reactor housing, numerous variations are possible. Also, the gas / liquid separation can be additionally supported by execution of the structure as a rotating disc filter.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102018112463.5A DE102018112463A1 (de) | 2018-05-24 | 2018-05-24 | Verfahren zur Durchführung stark Gas freisetzender Reaktionen |
| PCT/EP2019/062859 WO2019224126A1 (de) | 2018-05-24 | 2019-05-17 | Verfahren zur durchführung stark gas freisetzender reaktionen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3802411A1 true EP3802411A1 (de) | 2021-04-14 |
Family
ID=66776298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19728893.9A Pending EP3802411A1 (de) | 2018-05-24 | 2019-05-17 | Verfahren zur durchführung stark gas freisetzender reaktionen |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3802411A1 (de) |
| DE (1) | DE102018112463A1 (de) |
| WO (1) | WO2019224126A1 (de) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1599613B1 (de) | 2003-03-03 | 2006-06-28 | DECHEMA Gesellschaft für Chemische Technologie und Biotechnologie e.V. | Verfahren zur beschichtung eines substrates |
| US7351395B1 (en) * | 2003-05-06 | 2008-04-01 | Air Products And Chemicals, Inc. | Hydrogen storage by reversible hydrogenation of pi-conjugated substrates |
| US7485161B2 (en) * | 2005-01-04 | 2009-02-03 | Air Products And Chemicals, Inc. | Dehydrogenation of liquid fuel in microchannel catalytic reactor |
| DE102005010213A1 (de) | 2005-03-05 | 2006-09-07 | Bayer Technology Services Gmbh | Katalytisch aktiver Membranporendurchflussreaktor zur Umsetzung von organischen Verbindungen |
| DE102010038491A1 (de) | 2010-07-27 | 2012-02-02 | Bayerische Motoren Werke Aktiengesellschaft | Kraftstoffversorgungseinrichtung für Wasserstoff-Kraftfahrzeuge |
| DE102011079858A1 (de) * | 2011-07-26 | 2013-01-31 | Bayerische Motoren Werke Aktiengesellschaft | Reaktor zur Freisetzung von Wasserstoff aus flüssigen Verbindungen |
| US20140378700A1 (en) * | 2013-06-21 | 2014-12-25 | Uop Llc | Liquid phase dehydrogenation of heavy paraffins |
| DE102013214313A1 (de) | 2013-07-22 | 2015-01-22 | Bayerische Motoren Werke Aktiengesellschaft | Reaktor zur Freisetzung von Wasserstoff aus flüssiger Verbindung |
-
2018
- 2018-05-24 DE DE102018112463.5A patent/DE102018112463A1/de active Pending
-
2019
- 2019-05-17 EP EP19728893.9A patent/EP3802411A1/de active Pending
- 2019-05-17 WO PCT/EP2019/062859 patent/WO2019224126A1/de not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019224126A1 (de) | 2019-11-28 |
| DE102018112463A1 (de) | 2019-11-28 |
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Owner name: KARLSRUHER INSTITUT FUER TECHNOLOGIE |