Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/02—Inorganic material
  • B01D71/024—Oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/02—Inorganic material
  • B01D71/024—Oxides
  • B01D71/0271—Perovskites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
  • B01D63/02—Hollow fibre modules
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
  • B01D63/08—Flat membrane modules
  • B01D63/087—Single membrane modules
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
  • C01B13/02—Preparation of oxygen
  • C01B13/0229—Purification or separation processes
  • C01B13/0248—Physical processing only
  • C01B13/0251—Physical processing only by making use of membranes
• • 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
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
• • 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
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
  • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
  • C01B3/382—Multi-step processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/102—Nitrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2317/00—Membrane module arrangements within a plant or an apparatus
  • B01D2317/04—Elements in parallel
• • 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
  • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
  • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
  • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• • 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
  • C01B2203/06—Integration with other chemical processes
  • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
• • 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
  • C01B2203/06—Integration with other chemical processes
  • C01B2203/068—Ammonia synthesis
• • 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
  • C01B2203/08—Methods of heating or cooling
  • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
  • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
  • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
• • 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
  • C01B2203/14—Details of the flowsheet
  • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
• • 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
  • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
  • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2210/00—Purification or separation of specific gases
  • C01B2210/0043—Impurity removed
  • C01B2210/0046—Nitrogen

Definitions

• the present invention relates to an improved process for oxygenation and an improved plant therefor.
• Oxygen transfer membranes are ceramics of particular composition and lattice structure which exhibit the ability to conduct oxygen at higher temperatures, thus allowing oxygen to be selectively separated from air, for example Transition of the oxygen from one side to the other on the membrane is the different oxygen partial pressure on the two sides.
• Oxygen permeation increases exponentially with increasing temperature and, in the case of an exothermic reaction, there is the danger of a "runaway" reaction.
• a fundamental circumvention of the safety problems set out above and a simplification of the reaction technique results from the separation of mass transport through the membrane and the actual oxidation reaction.
• the separation takes place the oxygen from the permeate side of the membrane by a purge gas (sweep gas), which receives the oxygen and in a further, physically separate reactor (part) in contact with the medium to be oxidized.
• Another object of the present invention was to provide an improved process for recovering oxygen from oxygen Gases that can be operated for a long time without replacing the membrane and which has a high fault tolerance in terms of leaks in the membrane or the composite metal seal / ceramic.
• the present invention relates to a method for enriching the content of oxygen in oxygen and nitrogen-containing gases in a separator having an internal space divided by an oxygen-conducting ceramic membrane into a substrate chamber and a permeate chamber, comprising the steps of: a) Compressing and heating an oxygen-containing gas to a
• Feed gas b) introducing the compressed and heated feed gas into the substrate chamber of the separator, c) introducing a purge gas containing oxygen and nitrogen into the permeate chamber of the separator, d) adjusting such a pressure in the substrate chamber, the oxygen partial pressure of the feed gas transporting causing oxygen to pass through the oxygen-conducting ceramic membrane into the permeate chamber; e) discharging the oxygen-depleted feed gas from the substrate chamber; and f) discharging the oxygen-enriched purge gas from the permeate chamber.
• nitrogen in the sweep gas may well be used, giving the opportunity to purge the permeate side with oxygen and nitrogen-containing gas, preferably air, and thereby generate the driving force of oxygen permeation in that the gas pressure on the feed side of the membrane is higher than on the permeate side of the membrane Membrane.
• oxygen and nitrogen-containing gas preferably air
• This method has a number of advantages over the previously proposed systems.
• the system has intrinsic security. If a membrane breaks, oxygen-containing gas mixes with oxygen-containing gas.
• the degree of enrichment of the oxygen-containing gas can be very elegantly regulated. For example, it would be possible to tolerate individual broken membrane pieces. Although nitrogen would then flow through these break points on the permeate side, and reduce the accumulation. However, this could be compensated for by simply increasing the pressure on the oxygen-providing side. This would increase the flow of oxygen through the undamaged parts of the membrane and achieve the same total enrichment as before. Defects occurring during operation of the membrane could therefore be tolerated to a limited extent.
• any oxygen-containing gases can be used. These preferably additionally contain nitrogen and in particular no oxidizable components. Air is particularly preferably used as feed gas.
• the Oxygen content of the feed gas is typically at least 5 vol.%, Preferably at least 10 vol.%, Particularly preferably 10-30 vol.%.
• any oxygen and nitrogen-containing gases can be used. These preferably contain no oxidizable components.
• the oxygen content of the purge gas is typically at least 5% by volume, preferably at least 10% by volume, particularly preferably 10-30% by volume.
• the nitrogen content of the purge gas is typically at least 15% by volume, preferably at least 35% by volume, more preferably 35-80% by volume.
• the purge gas may optionally contain other inert components, such as water vapor and / or carbon dioxide. Air is particularly preferably used as purge gas.
• Any oxygen-conducting ceramic membranes which are selective for oxygen can be used in the process according to the invention.
• the oxygen-transporting ceramic materials used according to the invention are known per se.
• These ceramics may consist of oxygen anions and electron-conducting materials.
• it is also possible to use combinations of very different ceramics or of ceramic and non-ceramic materials for example combinations of oxygen anions-conducting ceramics and electron-conducting ceramics or combinations of different ceramics, which each conduct oxygen anions and electrons or not all components of which have an oxygen conduction or combinations of oxygen-conducting ceramic materials with non-ceramic materials, such as metals.
• Examples of preferred multiphase membrane systems are mixtures of ceramics with ion conductivity and another material with electron conductivity, in particular a metal. These include in particular combinations of materials with fluorite structures or fluorite-related structures with electron-conducting Materials, for example combinations of ZrO 2 or CeO 2 , which are optionally doped with CaO or Y 2 O 3 with metals, such as palladium.
• preferred multiphase membrane systems are mixed structures having a partial perovskite structure, i. Mixed systems, of which there are different crystal structures in the solid, and at least one of them is a perovskite structure or a perovskite-related structure.
• porous ceramic membranes which preferably conduct oxygen on account of the pore morphology, for example porous Al 2 O 3 and / or porous SiO 2 .
• oxygen-transporting materials are oxide ceramics, of which those with perovskite structure or with Brownmillerit Jardin or Aurivillius Kunststoff are particularly preferred.
• Perovskites used according to the present invention typically have the structure ABO 3-5 , wherein A represents bivalent cations and B represents trivalent or higher valent cations, the ionic radius of A is greater than the ionic radius of B, and ⁇ is a number between 0.001 and 1.5 is between 0.01 and 0.9, and more preferably between 0.01 and 0.5, to produce the electroneutrality of the material.
• A represents bivalent cations
• B represents trivalent or higher valent cations
• ⁇ is a number between 0.001 and 1.5 is between 0.01 and 0.9, and more preferably between 0.01 and 0.5, to produce the electroneutrality of the material.
• the perovskites used according to the invention it is also possible for mixtures of different cations A and / or cations B to be present.
• Brownmillerites used according to the invention typically have the structure
• Cations B can preferably occur in several oxidation states. However, a part or all of the cations of type B can also be trivalent or higher cations with a constant oxidation state.
• Particularly preferably used oxide ceramics contain type A cations which are selected from cations of the second main group, the first subgroup, the second subgroup, the lanthanides or mixtures of these cations, preferably of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2 + , Cu 2+ , Ag 2+ , Zn 2+ , Cd 2+ and / or the lanthanides.
• Particularly preferably used oxide ceramics contain type B cations which are selected from cations of the groups HIB to VIIIB of the Periodic Table and / or the lanthanide group, the metals of the third to fifth main group or mixtures of these cations, preferably Fe 3+ , Fe 4+ 1 Ti 3+ , Ti 4+ , Zr 3+ , Zr 4+ , Ce 3+ , Ce 4+ , Mn 3+ , Mn 4+ , Co 2+ , Co 3+ , Nd 3+ , Nd 4+ , Gd 3+ , Gd 4+ , Sm 3+ , Sm 4+ , Dy 3+ , Dy 4+ , Ga 3+ , Yb 3+ , Al 3+ , Bi 4+ or mixtures of these cations.
• type B cations which are selected from cations of the groups HIB to VIIIB of the Periodic Table and / or the lanthanide group, the metals of the third to fifth main group
• Still further particularly preferably used oxide ceramics contain type B cations which are selected from Sn 2+ , Pb 2+ , Ni 2+ , Pd 2+ , lanthanides or mixtures of these cations.
• Aurivillites used according to the invention typically have the structural element (Bi 2 O 2 ) 2 "1" (VO 3,5 [] o, 5 ) 2 * or related structural elements, where [] denotes an oxygen vacancy.
• the pressure of the feed gas in the substrate chamber can vary within wide ranges.
• the pressure is chosen in a particular case so that the oxygen partial pressure on the feed side of the membrane is greater than on the permeate side.
• Typical pressures in the substrate chamber are in the range between 10 "2 and 100 bar, preferably between 1 and 80 bar, and in particular between 2 and 10 bar.
• the gas pressure in the permeate chamber may also vary within wide limits and is in each individual case by Typical pressures in the permeate chamber are in the range between 10 '3 and 100 bar, preferably between 0.5 and 80 bar, and in particular between 0.8 and 10 bar.
• the temperature in the separator is to be chosen so that the highest possible separation efficiency can be achieved.
• the temperature to be selected in the individual case depends on the type of membrane and can be determined by the expert by routine experimentation. For ceramic membranes are typical operating temperatures in the range of 300 to 1500 0 C, preferably from 650 to 1200 0 C.
• the oxygen-enriched purge gas derived from the permeate chamber is used to produce synthesis gas.
• a hydrocarbon mixture preferably natural gas, or a pure hydrocarbon, preferably methane
• the oxygen-enriched purge gas optionally converted together with water vapor in a reformer in a conventional manner into hydrogen and carbon oxides.
• This synthesis gas can optionally be used after further treatment steps to remove the carbon oxides in the Fischer-Tropsch synthesis or in particular in the ammonia synthesis.
• the purge gas is typically enriched to about 35% to 45% oxygen content, and fed directly into a preferably autothermal reformer ("ATR").
• ATR autothermal reformer
• the nitrogen-containing oxygen-enriched purge gas derived from the permeate chamber is used to carry out oxidation reactions, in particular in the production of nitric acid or in the oxidative dehydrogenation of hydrocarbons, such as propane.
• the nitrogen-containing oxygen-depleted feed gas derived from the substrate chamber is used to carry out oxidation reactions, in particular for the regeneration of coke-laden catalysts.
• the invention also relates to specially designed plants for the enrichment of oxygen in gases.
• a separation device in the interior of which a plurality of mutually parallel hollow fibers of oxygen-conducting ceramic material are arranged, wherein the interiors of the hollow fibers form a permeate chamber of the separation device and the outer environment of the hollow fibers forms a substrate chamber of the separation device,
• Discharge for diverting the oxygen depleted feed gas from the substrate chamber.
• a " separation device in the interior of which a plurality of mutually parallel hollow fibers of oxygen-conducting ceramic material are arranged, wherein the interiors of the hollow fibers form a substrate chamber of the separation device and the outer environment of the hollow fibers a
• Permeate chamber of the separator forms, B 1 ) at least one component which consists of a plurality of hollow fibers, which at the
• End faces are connected to a supply line for an oxygen-containing feed gas and with a discharge for an oxygen-depleted feed gas, wherein supply and discharge for the feed gas and the depleted feed gas are not connected to the permeate chamber, C ' ) at least one opening into the permeate chamber of the separator
• the individual hollow fibers in the components B) and B ' ) can be spatially separated from each other or even touch each other.
• the hollow fibers are connected via a distributor unit and a collector purity with the inlet and outlet for the gas to be transported through the hollow fibers.
• the separation devices A) and A ' ) can be passively heated by the temperature of the gas to be introduced.
• the separators A) and A " ) may be equipped with a heater.
• F represent a part of the spaces Permeatkammem and forms the other part of the spaces substrate chambers, and at least one dimension of the spaces in the range of less than 10 mm, preferably less than 2 mm moves, wherein the oxygen transport between the substrate and Permeatkammem by at least one common room wall is made, which is characterized by a common plate
• Oxygen conductive ceramic material is formed
• Substrate chambers which are connected to at least one collector unit, wherein the collector unit communicates with a discharge for the oxygen depleted feed gas
• Permeatkammem which are connected to at least one collector unit, wherein the collector unit is connected to a discharge for the oxygen-enriched purge gas, and wherein K) Permeatkammem and substrate chambers are not in communication.
• spacer elements are provided in all rooms.
• the supply lines to the substrate chamber and / or the permeate chamber are connected to compressors, by means of which the gas pressure in the chambers can be adjusted independently.
• the supply line to the permeate chamber is connected to a container, from which the system oxygen and nitrogen-containing purge gas is supplied.
• Another object of the invention is the use of oxygen-enriched and from a separator with oxygen-conducting membrane originating gas for the production of synthesis gas, preferably for use in the Fischer Tropsch synthesis or in the ammonia synthesis.
• Yet another object of the invention is the use of oxygen-enriched gas derived from an oxygen-conducting membrane separator in nitric acid production.
• Figure 1 shows the experimental apparatus.
• a hollow fiber (4) made of oxygen-conducting ceramic material is clamped in a heatable apparatus.
• the ends of the hollow fiber (4) are sealed with silicone gaskets (5).
• the inside and the outside of the hollow fiber (4) can be exposed to different gases and / or experimental conditions.
• the purge gas (“sweep gas") introduced into the apparatus through the supply line (1) and flowing in the permeate chamber (3) absorbs oxygen at appropriate partial pressures from the inside of the hollow fiber (4) ("substrate chamber”).
• the oxygen-enriched gas can then be analyzed by gas chromatography.
• the permeated amount of oxygen can then be determined.
• the ceramic hollow fiber was supplied with air as sweep gas and as oxygen-lean gas.
• air as sweep gas
• oxygen-lean gas oxygen-lean gas
• the inside (core-side) the hollow fiber was subjected to an increased air pressure, while the air pressure on the outside (shell-side) was each left at 1.2 bar.

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• 2005
  • 2005-02-11 DE DE102005006571A patent/DE102005006571A1/de not_active Withdrawn
• 2006
  • 2006-01-23 WO PCT/EP2006/000545 patent/WO2006084563A2/de active Application Filing
  • 2006-01-23 US US11/815,794 patent/US20090272266A1/en not_active Abandoned
  • 2006-01-23 CN CNA2006800046140A patent/CN101115678A/zh active Pending
  • 2006-01-23 AU AU2006212562A patent/AU2006212562A1/en not_active Abandoned
  • 2006-01-23 EP EP06722979A patent/EP1851168A2/de not_active Withdrawn
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  • 2006-01-23 JP JP2007554461A patent/JP2008529944A/ja active Pending
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  • 2006-01-23 BR BRPI0608232-7A patent/BRPI0608232A2/pt not_active Application Discontinuation
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