EP1838612A1 - Procede et dispositif pour extraire du monoxyde de carbone d'un flux gazeux contenant de l'hydrogene - Google Patents

Procede et dispositif pour extraire du monoxyde de carbone d'un flux gazeux contenant de l'hydrogene

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Publication number
EP1838612A1
EP1838612A1 EP06704259A EP06704259A EP1838612A1 EP 1838612 A1 EP1838612 A1 EP 1838612A1 EP 06704259 A EP06704259 A EP 06704259A EP 06704259 A EP06704259 A EP 06704259A EP 1838612 A1 EP1838612 A1 EP 1838612A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
reactor
hydrogen
carbon monoxide
gas
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.)
Withdrawn
Application number
EP06704259A
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German (de)
English (en)
Inventor
Mathias Haake
Stefan Kotrel
Michael Karcher
Rudi BLÜMMEL
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1838612A1 publication Critical patent/EP1838612A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/586—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/0445—Selective methanation
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a device for removing carbon monoxide from a hydrogen-rich gas stream by reacting the carbon monoxide with hydrogen to methane and water and a method using the device.
  • the cycle gas can be driven through a purification stage, in which the carbon monoxide is reacted with hydrogen to methane and water.
  • the resulting methane and water are harmless to hydrogenation.
  • the removal of carbon monoxide from a hydrogen-rich gas mixture produced by a methanol reforming reaction is known, for example, from DE-C 196 03 222.
  • the removal of carbon monoxide is carried out by selective methanation using a catalyst material containing Ru and TiO 2 and / or by means of selective oxidation using a Pt and TiO 2 -containing catalyst material.
  • the hydrogen thus obtained is then used in fuel cell-powered electric vehicles.
  • a variety of other hydrocarbons can be used to obtain H 2 .
  • the removal of CO from the H 2 -containing gas stream is necessary and can be done for example by methanation.
  • the use of a Methan maschinestress for the operation of a combined heat and power plant with a gas generating system and a fuel cell is known from EP-A 1 246 286.
  • the hydrogen is recovered from natural gas.
  • the conversion of carbon monoxide with hydrogen to methane and water is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, 2000 Electronic Release, Chapters 5.3.2 and 5.3.3.
  • the reaction is carried out in the presence of a nickel oxide-containing and in some cases additionally chromium oxide-containing catalyst. This must be reduced before starting the reaction.
  • the carrier used is alumina or kieselguhr. In comparison with the catalysts known from steam reforming, the metal content must be very high.
  • a disadvantage of the fixed-bed catalysts known from the prior art is their high pressure loss. This large pressure loss makes a large-scale cycle gas compressor required in particular in processes in which the hydrogen-containing gas is driven over the cleaning stage as a recycle gas to compensate for the pressure loss. As the size of the cycle gas compressor increases, both the investment costs and the operating costs increase.
  • a further disadvantage of the solid catalysts is that a catalyst discharge can not be avoided, since the dusting together of the catalyst particles produces catalyst dusts which are entrained by the gas stream and thus can be distributed by the gas flow in the entire gasification stage.
  • the current technical solution provides to use dust, in which the catalyst dusts are separated from the gas stream. However, these dust collectors also lead to an increase in the pressure loss in the circulating gas stream.
  • the object of the invention is to provide a process for the removal of carbon monoxide from a hydrogen-containing gas stream, which has a low pressure loss compared to fixed bed catalysts and in which a catalyst discharge is avoided by the gas stream.
  • the object is achieved by a process for removing carbon monoxide from a hydrogen-containing gas stream by reacting the carbon monoxide with water. hydrogen to methane and water in the presence of a heterogeneous catalyst.
  • the catalyst is present as a thin-film catalyst.
  • a thin-film catalyst is a catalytically coated support material, with the thickness of the catalyst layer being in the range from 0.01 ⁇ m to 100 ⁇ m.
  • the process for removing carbon monoxide is preferably carried out in a methanization reactor.
  • any type of reactor known in the art is suitable.
  • the reactor is preferably a tubular reactor. In the methanation of the thin-film catalyst is added.
  • the methanation reactor may be a standalone reactor or form a reactor zone within a multizone reactor.
  • a hydrogenation and in a subsequent to the first reactor zone second reactor zone the methanization of hydrogenated carbon monoxide are formed in the hydrogenation.
  • reaction temperature is preferably in the range from 80 0 C to 500 0 C, more preferably in the range of 100 ° C to 300 ° C and particularly preferably in the range from 100 0 C to 200 0 C.
  • the reaction temperature may be e.g. be achieved in that the wall of the methanation reactor is designed as a double jacket, in which flows a heat transfer medium. Suitable heat carriers are e.g. Steam or thermal oils.
  • the reaction temperature can also be achieved by flowing through the methanization reactor before adding the hydrogen-containing gas stream of a hot inert gas stream.
  • an inert gas stream e.g. Nitrogen.
  • the heat produced during the reaction of the carbon monoxide with hydrogen to form methane and water does not have to be dissipated via the reactor walls.
  • the application of the catalytically active component to the carrier material can be carried out in vacuo by sputtering or by electron beam evaporation. Another possibility is the impregnation of the catalytically active component on the support material.
  • the vapor deposition of the catalytically active component in vacuo can e.g. as described in DE-A 199 63 443 for Raney alloys.
  • the catalytically active component is evaporated in vacuo and condensed uniformly on the support.
  • the evaporation takes place with the usual, known to a person skilled in the art, for example thermally, by electron beam evaporation, by sputtering or combination of these methods.
  • the layers of the vapor-deposited catalytically active component obtained by the condensation are generally extremely thin and are in the range from 0.01 ⁇ m to 100 ⁇ m.
  • the support material is impregnated with an impregnation medium which contains the catalytically active component, its constituents, precursors of the catalytically active component and / or precursors of its constituents. If the impregnation medium contains precursor compounds, these are converted in the course of further processing to the actual catalytically active component.
  • the catalytically active component, its constituents, the precursors of the catalytically active component or the precursors of their constituents or mixtures thereof are dissolved or suspended in a solvent or suspending agent. If one of the substances with which the carrier material is soaked, is liquid, can be dispensed with the solvent or suspending agent.
  • this is preferably pretreated before the application of the catalytically active component.
  • a pretreatment are the coating of the carrier with adhesion promoters or a roughening with mechanical or thermal processes. Mechanical methods are e.g. Grinding or sandblasting, thermal methods include heating, plasma etching or glowing.
  • the impregnation method as described in EP-A 0 965 384, is preferably carried out with an impregnation medium whose surface tension is at most 50 mN / m.
  • the impregnated carrier material After soaking, the impregnated carrier material is usually dried in a known manner to rid it of the solvent or suspending agent. For this purpose, the impregnated carrier material is preferably heated. At the same time or instead also a vacuum can be applied. When applying precursor compounds which can be thermally decomposed into active composition, they are thermally decomposed in a known manner to give active composition. For this purpose, the impregnated and optionally already dried carrier material is heated to the appropriate temperature. The required temperature depends on the catalytically active component.
  • impregnation can also take place in any other manner known to those skilled in the art.
  • the preferred method of applying the catalytically active component to the support material is by soaking.
  • Thin-film catalysts in which the catalytically active component is applied to a carrier material designed as a woven or knitted fabric are characterized by the fact that the gas permeability of the catalyst can be optimally adjusted due to the flexibility of the fabric or knitted fabric with simultaneous high carbon monoxide conversion.
  • the adjustability of the gas permeability it is possible to set a minimal pressure loss compared to fixed-bed catalysts. Also, the mechanical and static load of the system is lower than in a fixed bed catalyst system.
  • the catalyst layer is characterized by a particular abrasion stability. This avoids that catalyst particles from the thin-layer catalyst reach the gas stream and are discharged therefrom out of the reactor.
  • a variety of films and fabrics, as well as knitted fabrics, such as knitted fabrics can be used. Particularly suitable are woven or knitted fabrics. According to the invention, it is possible to use fabrics of different weaves, such as smooth fabrics, twill fabrics, weave fabrics, five-shaft atlas fabrics or other special weave fabrics.
  • wire mesh come according to an embodiment of the invention tissue made of weavable metal wires, such as iron, spring steel, brass, phosphor bronze, pure nickel, monel, aluminum, silver, nickel silver, nickel, chrome nickel, chromium steel, stainless, acid-resistant and highly heat-resistant chromium nickel steels and titanium into consideration. The same applies to knitted fabrics, e.g. Knits.
  • woven or knitted fabrics of inorganic materials may be used, such as Al 2 O 3 and / or SiO 2 .
  • Synthetic wires and woven or knitted plastics can also be used according to an embodiment of the invention. Examples are polyamides, polyesters, polyvinyls, polyolefins such as polyethylene, polypropylene, polytetrafluoroethylene and other plastics which can be processed into woven or knitted fabrics.
  • Preferred support materials are metal foils or metal mesh, such as stainless steels with the material numbers 1.4767, 1.4401, 2.4610, 1.4765, 1.4847, 1.4301, etc.
  • the designation of these materials with the mentioned material numbers follows the information of the material numbers in the "Stahleisenliste", published by the Association of German Ironworkers , 8th edition, pages 87, 89 and 106, Verlag Stahleisen mbH, Dusseldorf, 1990.
  • the well-known under the name Kanthai material of the material number 1.4767 is particularly preferred.
  • the metal foils and metal meshes are particularly well suited because they can be roughened by surface annealing prior to coating with catalytic active compounds or promoters.
  • the metallic supports are heated at temperatures of 400 to 1100 0 C, preferably 800 to 1000 0 C for 0.5 to 24 hours, preferably 1 to 10 hours in an oxygen-containing atmosphere such as air.
  • the activity of the catalyst can be controlled or increased.
  • Thin-film catalysts are characterized by the fact that, given a high conversion, only a small amount of the catalytically active component is required due to the small layer thickness.
  • the surface loading of the support material with catalyst is preferably ⁇ 5,000 mg catalyst per m 2 surface, more preferably ⁇ 3,000 mg catalyst per square meter surface and in particular ⁇ 2,000 mg catalyst / m 2 surface.
  • Suitable catalytically active materials for the conversion of carbon monoxide and hydrogen to methane and water are ruthenium, nickel, platinum, palladium, rhodium, copper or mixtures of these elements. In addition, these materials can also be doped with alkali metals, alkaline earth metals or their oxides. Particularly suitable as the catalytically active component is ruthenium.
  • the abrasion stability of the thin-film catalyst also offers economic advantages, since due to the thin layers only small amounts of the catalytically active component are needed. Since a large proportion of the suitable catalytically active components are precious metals with a high purchase price, the small amount of investment required by the catalyst makes it possible to keep the investment cost share low.
  • the catalysts produced by vapor deposition, sputtering or impregnation according to the invention, in particular catalyst wovens, catalyst knits and catalyst foils have a very good adhesive strength of the catalytically active compounds or promoters. Therefore, they can be deformed, cut and processed, for example, to monolithic catalyst elements, without the catalytically active compounds or promoters detach.
  • catalyst knits and catalyst films according to the invention it is possible to produce any desired shaped catalyst packings for a reactor, for example a flow reactor, plate reactor or reactor designed as a spiral heat exchanger. It is possible to produce catalyst packing elements with different geometries, as known from the distillation and extraction technology. Examples of advantageous catalyst packing geometries according to the invention which offer the advantage of low pressure loss in operation are those of the Montz A 3 and Sulzer BX, DX and EX type. An example of a catalyst geometry according to the invention, of catalyst foils or catalyst expanded metal foils, are those of the Montz BSH type.
  • the amount of catalyst processed per unit volume in particular amount of catalyst tissue, amount of catalyst or catalyst film can be controlled in a wide range, resulting in a different size of the openings or channel widths in the catalyst fabric, catalyst knit or in the catalyst film.
  • the maximum pressure drop in the reactor e.g. Flow or distillation reactor can be adjusted and thus the catalyst can be adapted to experimental specifications.
  • the catalyst used according to the invention has a monolithic form, as described, for example, in EP-AO 564 830. Further suitable catalysts are described in EP-AO 218 124 and EP-A-0 412 415.
  • Another advantage of the monolithic catalysts used according to the invention is the good fixability in the reactor bed, so that they can be used very well for example in hydrogenation in the liquid phase in the upflow mode at high cross-sectional loading. In contrast, there is the risk of turbulence in the catalyst bed in conventional supported catalysts, which can lead to possible abrasion or disintegration of the molding. In gas phase hydrogenation, the catalyst pack is resistant to shock or vibration.
  • the thin-film catalyst is packaged as a pack.
  • Suitable low-pressure tissue packs are e.g. in WO-A 97/02890.
  • the metal fabric is formed into packing elements, wherein the packing elements of dimensionally stable, ordered structured and contacting layers of fabric material or fabric-like material.
  • the contacting deformed layers of fabric material or fabric-like material are arranged to form a plurality of narrow flow channels, preferably nearly triangular, nearly rectangular quadrangular or nearly equilateral hexagonal flow channels, with each angle of inclination of the teeth of the individual fabric layers of the package against the column axis is inclined.
  • the fabric layers may be firmly joined together at some points of contact.
  • Disc-shaped reactor internals are preferably formed from individual packing elements.
  • the individual contacting deformed layers of fabric material are preferably arranged both in the packing elements and the disc-shaped reactor internals formed therefrom so that the forming flow channels run alternately in opposite directions when the angle of inclination of the teeth of the individual fabric layers against the reactor axis is greater than zero.
  • the reactor internals In the formation of disk-shaped reactor internals from the packing elements, the reactor internals preferably have the respective inner diameter of the methanization reactor and a height of 40 to 300 mm.
  • a plurality of reactor internals, each having the internal diameter of the methanation reactor can be arranged one above the other, wherein the disk-shaped reactor internals are preferably rotated in each case by about 90 ° to each other in the stacked reactor internals.
  • the lowest possible pressure loss is achieved in that the angle of inclination of the teeth of the individual fabric layers of the package against the reactor axis in Range of 0 to 25 °, preferably in the range of 3 to 14 ° and in particular in the range of 4 to 6 °.
  • the process is used to remove carbon monoxide from a hydrogen-containing gas stream for purifying recycle gas from a chemical plant.
  • a hydrogen-containing gas stream for purifying recycle gas from a chemical plant.
  • recycle gas As circulating gas while the gas is called, which is driven within the chemical plant in the circuit.
  • the inventive method for removing carbon monoxide from a hydrogen-containing gas stream for cleaning the hydrogen-containing gas supplied to a fuel cell is used.
  • the inventive method for removing carbon monoxide from the cycle gas of a hydrogenation is used. Since many hydrogenations are performed on noble metal-containing catalysts, such as platinum or palladium, which are prone to poisoning and reversible deactivation in carbon monoxide-containing gases due to their high carbon monoxide absorption energy, high catalyst life requires the removal of carbon monoxide from the gas stream.
  • the carbon monoxide feed may be introduced either through the feed, i. the component to be hydrogenated to be hydrogenated, or by the fresh gas, i. the hydrogen supplied from outside to the process. Furthermore, the carbon monoxide can also arise within the hydrogenation plant.
  • the substance to be hydrogenated and hydrogen are fed to the hydrogenation reactor.
  • the component to be hydrogenated reacts with the hydrogen in the presence of the hydrogenation catalyst.
  • the reaction is carried out with a hydrogen excess.
  • the product and the unreacted hydrogen and reaction by-products are removed from the hydrogenation reactor and fed to a separator in which the product is separated.
  • a hydrogen-containing gas stream is withdrawn from the separator.
  • the gas stream contains impurities which were fed either with the fresh gas or the feed to the hydrogenation reactor or which are formed by the reaction in the hydrogenation reactor. To remove the impurities from the gas stream, a portion of the gas stream is removed as exhaust gas from the process.
  • the carbon monoxide produced within the plant may e.g. be formed in the hydrogenation reactor, in the separator or in the lines between the individual parts of the reaction mixture.
  • the entry of carbon monoxide via the feed is possible in particular when the cycle gas stage is a synthesis stage downstream of another stage.
  • the carbon monoxide is formed in the upstream stage and entered with the reaction stream in the Kreisgaslab.
  • the upstream stage is also hydrogenation, the carbon monoxide may be intentionally added to the reactant stream to moderate the activity of the upstream stage catalyst. This is e.g. then the case when in the upstream stage, the selective hydrogenation of a triple bond to a double bond to palladium is to be carried out while the selectivity is increased via the controlled addition of carbon monoxide.
  • carbon monoxide can pass through the carbon monoxide-saturated reactant stream into the subsequent to the selective hydrogenation stage and cause an undesirable attenuation of the noble metal catalyst used there.
  • Carbon monoxide formation within the chemical plant in which the hydrogen-containing gas stream is circulated is always present when, in addition to the intended reaction, e.g. the hydrogenation, under the operating conditions, a carbon monoxide is split off as a side reaction.
  • Reactants prone to such a side reaction are e.g. Aldehydes, especially when they are unsaturated in ⁇ -, ß-position or have an aromatic radical.
  • aldehydes which are unsaturated in the ⁇ -, ⁇ -position are crotonaldehyde, citral, dehydro-lysmeral, myrtenal or cinnamaldehyde.
  • saturated aldehydes are citronellal or phenylpropionaldehyde.
  • Aldehydes with an aromatic radical are e.g. Benzaldehydes, pyridine carbaldehydes, furaldehydes and thiophene carbaldehydes.
  • acyl halides, .alpha.-ketophosphonates or acyl cyanides can also occur as carbon monoxide source in the reactant stream.
  • Carbon monoxide cleavage can be acid catalyzed, base catalyzed, or radical catalyzed. Catalytic carbon monoxide removal on homogeneous metal complexes is just as possible as carbon monoxide elimination on metal-containing heterogeneous catalysts.
  • the inventive method for removing CO from the H 2 -containing gas stream is used to operate a fuel cell.
  • the methanation reactor is part of a stationary fuel cell system.
  • H 2 is recovered in a reforming reactor.
  • the H 2 -containing product gas stream is passed through the methanation reactor after reforming, with the CO contained in the gas stream reacting to methane and water.
  • the gas released from CO by this method is suitable for the operation of a fuel cell.
  • the pressure loss in the gas generation system of the fuel cell can be kept low at high space velocity of the gas stream. As a result, the power loss of the fuel cell system is reduced because less work has to be done for the introduction and compression of the fuel stream to be reformed. The lower power loss improves the overall efficiency of the fuel cell system.
  • methanol is also present as an impurity in the hydrogen-containing gas stream
  • the removal of the methanol is necessary because otherwise the methanol is split in the methanation reactor in the presence of the heterogeneous catalyst to carbon monoxide and hydrogen.
  • the proportion of carbon monoxide in the gas stream increases and it is necessary to dimension the reactor much larger for complete conversion of the carbon monoxide. This leads to additional investment and operating costs. Examples
  • Example 1 Preparation of a thin-film catalyst
  • a pre-calcined at 900 ° C Kanthaigewebe is impregnated with a Ru-nitrosyl nitrate solution and then dried at 120 0 C for one hour in the air.
  • an aqueous 20.3 wt% Ru (NO) (NO 3 ) 3 solution was diluted with distilled water to 0.7 wt% Ru.
  • the impregnation was carried out in a hand impregnation system, in which first the metal fabric tape is pulled through a shallow dish which is filled with the impregnation solution. The metal mesh was wetted with the Ru-containing impregnation solution.
  • the still wet, wetted metal fabric tape was then predried in a drying zone with the aid of IR lamps and then dried in a drying oven at 120 ° C in the presence of ambient air. The drying time was 1 h.
  • the Ru-impregnated shawl is rolled into a fabric packing.
  • the finished kon Stammioneirte Ru-impregnated Kanthal is at 120 0 C in the methanization reactor is reduced for 4 hours at ambient pressure under a H 2 atmosphere.
  • the surface loading with ruthenium corresponds to 580 mg Ru / m 2 Kanthaigewebe.
  • a prepared according to Example 1 Ru- / Kanthal catalyst was in an oil-heated double jacket tube, which was applied at ambient pressure with a CO-containing hydrogen Ström tested.
  • the CO residual concentration in the exhaust gas stream downstream of the reactor was measured by means of a CO analyzer from Uras.
  • the maximum catalyst load as a function of the temperature and CO concentration at which complete degradation of the carbon monoxide could be observed in the methanation experiment is shown in Table 1.
  • the first column shows the temperature at which the methanation was carried out.
  • the second column shows the GHSV (gaseous hourly space velocity), at which CO was completely decomposed with an input concentration of 25 ppm.
  • the GHSV is plotted, in which CO was completely degraded with an input concentration of 100 ppm.
  • Lysmeral was boiled under reflux in the presence of a Pd / C catalyst and the resulting gases were driven out of the reaction mixture with H 2 and passed through a Ru-Kanthal tissue packing, which was housed in an oil-heated jacketed tube.
  • the CO load of the supplied gas was in the range of 150 to 250 ppm.
  • the temperature was 140 0 C within the first 15 hours in the further course of the experiment 180 0 C.
  • the analysis of the carbon monoxide the reactor verlas- send gas flow resulted in a complete removal of the supplied Kohlenmonoxi- of.
  • the GHSV was 2600 h ⁇
  • the ready-made catalyst was gradually reduced h at 80 0 C, 120 ° C, 180 ° C and 200 0 C in the methanization reactor immediately before the actual experiment for each case. 1
  • the surface loading with Ru was 2075 mg Ru / m 2 Kanthaigewebe.
  • Example 5 Methanation of CO
  • the Ru / Kanthal catalyst prepared according to Example 4 was charged in an oil-heated jacketed tube at 2013 mbara with a CO-containing H2 stream of known concentration. The entire reactor was charged with 6 individual packs, 5 packs each 8 cm and 1 pack 5 cm long.
  • Table 2 shows the gas composition before and after the reactor.
  • the set GHSV amounted to about 1 to 800 h '1.
  • the reactor temperature was 200 0 C. While the reaction was measured by the package, no pressure loss, the pressure loss must ie, less during measurement than 100 have been mbar be (sensitivity of the measuring apparatus). The CO was almost completely degraded in this experiment.
  • Table 2 Gas composition before and after the methanization reactor.
  • the gas fractions refer to the dry gas.
  • the H 2 O content of the undried gas was 25% by volume.

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Abstract

L'invention concerne un procédé pour extraire du monoxyde de carbone d'un flux gazeux contenant de l'hydrogène par transformation du monoxyde de carbone avec l'hydrogène en méthane et en eau, en présence d'un catalyseur hétérogène, lequel se trouve sur un support sous forme de catalyseur en couche mince. La présente invention porte également sur un dispositif pour réaliser ce procédé.
EP06704259A 2005-01-11 2006-01-09 Procede et dispositif pour extraire du monoxyde de carbone d'un flux gazeux contenant de l'hydrogene Withdrawn EP1838612A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005001290A DE102005001290A1 (de) 2005-01-11 2005-01-11 Vorrichtung und Verfahren zur Entfernung von Kohlenmonoxid aus einem wasserstoffhaltigen Gasstrom
PCT/EP2006/050100 WO2006074988A1 (fr) 2005-01-11 2006-01-09 Procede et dispositif pour extraire du monoxyde de carbone d'un flux gazeux contenant de l'hydrogene

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DE102005049568A1 (de) 2005-10-17 2007-04-19 Basf Ag Verfahren zur kontinuierlichen Hydrierung oder hydrierenden Aminierung
DE102005055632A1 (de) * 2005-11-22 2007-05-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verbundsystem und dessen Verwendung sowie Verfahren zum sauerstofffreien Verpacken von oxidationsempfindlichen Verpackungsgütern
DE102008002535A1 (de) 2007-06-25 2009-01-02 Basf Se Verfahren zur Herstellung vicinaler Dioxoverbindungen durch Oxidation vicinaler Dihydroxyverbindungen an Silber enthaltenden Dünnschichtkatalysatoren
KR101329082B1 (ko) * 2011-11-25 2013-11-14 한국원자력연구원 광섬유 레이저를 이용한 탄소 및 산소 동위원소 분리 방법 및 장치
SG11201901571RA (en) * 2016-09-23 2019-04-29 Basf Se Process for providing a catalytically active fixed bed for the hydrogenation of organic compounds

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GB8607268D0 (en) * 1986-03-24 1986-04-30 Atomic Energy Authority Uk Methanation & steam reforming catalyst
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EP1246286A1 (fr) 2001-03-31 2002-10-02 OMG AG & Co. KG Appareil combiné pour la production de chaleur et de courant avec système de production de gaz et piles à combustible et procédé de fonctionnement
EP1246287B1 (fr) 2001-03-31 2011-05-11 Viessmann Werke GmbH & Co KG Appareil combiné pour la production de chaleur et de courant avec système de production de gaz et piles à combustible et procédé de fonctionnement
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EP1435672A1 (fr) * 2002-12-30 2004-07-07 Umicore AG & Co. KG Couche de diffusion de gaz contenant un catalyseur pour une pile à combustible

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WO2006074988A1 (fr) 2006-07-20
JP2008526676A (ja) 2008-07-24
US20100119423A1 (en) 2010-05-13
DE102005001290A1 (de) 2006-07-20
US7678837B2 (en) 2010-03-16

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