Classifications

• • 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
  • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
  • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
  • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
• • 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
  • B01J19/0006—Controlling or regulating processes
  • B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
  • B01J19/0026—Avoiding carbon deposits
• • 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
  • B01J4/00—Feed or outlet devices; Feed or outlet control devices
  • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
• • 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
  • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
  • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
  • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
  • C01B3/382—Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
  • B01F2025/91—Direction of flow or arrangement of feed and discharge openings
  • B01F2025/913—Vortex flow, i.e. flow spiraling in a tangential direction and moving in an axial direction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/10—Mixing gases with gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
  • B01F25/70—Spray-mixers, e.g. for mixing intersecting sheets of material
  • B01F25/72—Spray-mixers, e.g. for mixing intersecting sheets of material with nozzles
• • 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
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00245—Avoiding undesirable reactions or side-effects
  • B01J2219/00259—Preventing runaway of the chemical reaction
  • B01J2219/00265—Preventing flame propagation
• • 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
  • C01B2203/08—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
  • C01B2203/12—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
  • C01B2203/1235—Hydrocarbons
  • C01B2203/1247—Higher hydrocarbons
• • 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
  • C01B2203/1276—Mixing of different feed components
• • 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
• • 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 an effective mixing chamber for a reformer, in particular for a reformer for the production of middle distillates, and a method for operating this mixing chamber.
• the oxygen is usually provided by means of air.
• the heat which is necessary for the steam reforming is made available by the partial oxidation of the hydrocarbon.
• the process can thus be run in an autothermal operating mode. In principle, a higher efficiency is possible because system-related Enthalpy losses are only possible by the warm product gas flow.
• the autothermal reforming seems very promising. This can be explained by the high reaction temperature (about 800 ° C.) and good reaction kinetics.
• a poor quality of the reactant mixture regularly has a negative effect on the sales of the fuel.
• the mixing chamber of a reformer therefore has the following functions: Supply of the fuel
• a direct injection of the fuel is usually carried out by a single-substance or a multi-substance nozzle.
• the fuel is atomized at high pressure.
• suitable single-substance nozzles are the continuous spin-pressure atomizing nozzle, as is customary in smaller boilers for heating oil, or the high-pressure injector, as used in today's gasoline and diesel engines.
• the Venturi tube which serves to suck in and atomize a liquid.
• the fuel When using a multi-fuel nozzle, the fuel is usually atomized together with a gas stream. Such nozzles produce very fine droplets with a diameter of about 10 to 30 microns.
• a three-component nozzle is also known, in which, in addition to the liquid fuel and air, additionally superheated steam is passed through the nozzle.
• the required heat can also be achieved by a partial combustion of the fuel, or the mixing chamber can be heated by an external heater.
• the object of the invention is to provide a particularly effective mixing chamber for a reformer, which enables a particularly uniform distribution of the educts and homogenization of the flow distribution, and thus can be operated particularly effectively. Furthermore, it is the object of the invention to provide a mixing chamber which largely avoids undesired formation of soot and deposition on the reforming catalyst and as completely as possible converts the fuel in the subsequent reformer. In this case, the mixing chamber should be used in particular for low-sulfur diesel and kerosene.
• the invention describes a mixing chamber in which a fuel and an oxidizing agent are mixed, this mixture subsequently being provided for feeding to a reforming catalyst.
• a mixing chamber could for example be part of an autothermal reformer (ATR).
• ATR autothermal reformer
• the mixing chamber for a reformer according to the invention consists of metal or ceramic.
• Ceramics are advantageous since generally lower thermal insulation is required, and above all, however, when using stainless steel, the nickel present can cause some unwanted reactions as a catalyst. Such disadvantages can be prevented when using ceramics.
• the mixing chamber according to the invention has a Zu accommodationsslei ⁇ device with a nozzle for a liquid fuel, a supply line for water vapor and a supply line for an oxidizing agent, in particular for air.
• the mixing chamber may be subdivided into two zones in which the vaporization of the fuel and the uniform distribution takes place in the first zone, while in the second zone the uniformly vaporized fuel is intensively and uniformly mixed with an oxidizing agent.
• the feed line and the nozzle for the fuel and the feed for the water vapor are arranged within the first zone such that the nozzle for the fuel is arranged adjacent to the feed of the water vapor, so that the injected into the interior of the mixing chamber and atomized fuel evaporates immediately in hot steam.
• Downstream of the fuel introduced and the water vapor is at the boundary to the second zone of the mixing chamber at least one feed for the oxidizing agent, preferably for air.
• the supply can advantageously have a plurality of outlets, for example in the form of a nozzle ring. It has been found that in order to achieve a fast mixture and a good mixture quality a pronounced vortex structure is necessary. In order for the gases to be mixed at the highest possible speeds, a narrowing of the mixing chamber in the area of the feed is recommended.
• the oxidizing agent is advantageously supplied radially from a plurality of narrow openings. However, it is explicitly not the principle of a Venturi tube.
• the water is thermally pretreated, ie evaporated and superheated.
• the water vapor is insbe ⁇ sondere introduced at a temperature in the range of 350 0 C to 500 0 C in the first zone of the mixing chamber.
• the steam atmosphere in the first zone advantageously prevents carbon formation.
• the temperature of the first zone of the mixing chamber is at least 50 K higher than the boiling point of the fuel.
• this is in the form of a cylinder which has a taper in the direction of the nozzle for the fuel and in the direction of the second zone.
• the first zones of the mixing chamber are present as cyclone separators.
• the fuel used has a certain amount of low-boiling hydrocarbons and minerals. With these fuels, complete vaporization under the given conditions is not physically possible.
• the catalyst surface of the monolith that is to say the honeycomb ceramic carrier coated with precious metals, where it would lead to poisoning and thus to a reduction in activity, it is important to remove these from the gas stream. It would be desirable to remove these particles before the oxidation agent is introduced into the second zone.
• the dynamic principle is exploited, by means of which centrifuged force, for example in a cyclone separator, can be used to separate non-evaporated liquid from a gas stream.
• centrifuged force for example in a cyclone separator
• it has been found that it is not effective to design the first zone as a classic cyclone to which the fuel and water vapor are both fed tangentially.
• At least 3 to 4 cm free space should remain in front of the atomizer nozzle in order to allow evaporation first, before the fuel droplets reach the wall of the mixing chamber or cyclone.
• the evaporator would have to be designed to be relatively large, especially if the thermal insulation is also taken into consideration.
• the opening which represents the outlet from the evaporator, or the transition between the first and second zone, kon ⁇ structurally placed in the direction of the atomizer, that forms an annular gap between the wall of the evaporator and the second zone.
• the non-evaporated particles are regularly directed into the gap by the centrifugal force, while the gas phase flows centrally out of the evaporator into the second zone.
• the low-volatility particles and deposits collected in the gap can thus not enter the catalyst and do not lead to an impairment of the rest of the flow control.
• the nozzle for the fuel feed points in the direction of the second zone of the mixing chamber.
• an oxidizing agent is supplied to the fully vaporized and evenly distributed fuel.
• the oxidizing agent is advantageously also fed in the cold state.
• the supply line for the oxidizing agent regularly has a plurality of openings.
• a nozzle ring has proven to be very effective.
• the supply of the oxidizing agent takes place shortly before Ein ⁇ enters the reforming catalyst.
• the time duration before entry into the reforming catalyst can be reduced, in which the gaseous fuel is exposed to the oxidizing agent.
• the risk of premature burning or ignition of the fuel-air mixture is regularly reduced, or can be completely prevented.
• the flow guidance in the mixing chamber is such that there is no recirculation of the oxidant mixed fuel from the second zone can come back to the first zone. As a result, it is ensured in the first zone due to the lack of oxygen that there is no ignition, and further that soot formation is prevented.
• Figure 1 Scheme of the mixing chamber according to the invention with the first
• Zone I evaporator
• second zone II evaporator
• catalyst device K evaporator
• FIG. 2 Principle of the effective supply of oxidant within the second zone.
• FIG. 3 exemplary embodiment of the air feed in the form of a nozzle ring
• FIG. 4 Principle of the separation of the non-evaporated force
• FIG. 5 shows three embodiments of the mixing chamber according to the invention, in which the first zone I is designed in each case as a cyclone.
• C means fuel H 2 O water vapor O oxidizing agent K catalyst
• the ⁇ dukte a reformer should by means of exact Dosie ⁇ tion, mixture formation, possibly evaporation and homoge- ner flow distribution in the direction of the catalyst for Will be provided. This is realized in the mixing chamber according to the invention.
• the mixing chamber As an example, for an ATR with a power of 3 kW egg 3.6 kg / h of air, 1.73 kg / h Was ⁇ ser and 800 g / h of fuel introduced into the mixing chamber.
• the mixing chamber according to the invention has two zones, wherein a catalyst device K regularly connects to the second zone II, for example, in ATR.
• the first zone is intended for the vaporization of the fuel and the mixing with the steam required for this purpose.
• the evaporator zone I (first zone) has a feed for liquid fuel C with a nozzle. This is arranged centrally on an end face of the mixing chamber, so that the jet emerging from the nozzle can be distributed uniformly and almost parallel to the axis in the mixing chamber.
• An advantageous nozzle is in particular a single-substance nozzle with a spray angle of about 60 °.
• the fuel droplets C produced regularly have a droplet size of approximately 30 ⁇ m.
• the temperature in the evaporator section is adjusted regularly by 400 0 C.
• the use of a two-fluid nozzle has proven to be less advantageous or unsuitable, although it produces a spray pattern with very fine droplets. Apart from the relatively high pressure and energy loss of about 1 to 2 bar or more on the gas side, the biggest drawback in the temperature sensitivity is close to 300 0 C. Added to the strong connection between the liquid and the gas flow, which Scheme designed more difficult.
• Adjacent to the nozzle for the fuel (atomizer nozzle) Adjacent to the nozzle for the fuel (atomizer nozzle), the supply for the water vapor H 2 O is arranged. The supply takes place via at least one pipe, with a typical diameter of about 3 mm to 10 mm, which is oriented such that the water vapor escaping from it is directed directly into the fuel leaving the nozzle.
• the nozzle is aligned tangentially, so that the emerging water vapor offset the escaping fuel for better mixing in a rotational movement.
• the oxidizing agent O is then fed to the vaporized steam stream H 2 O / C mixed with steam.
• This is done by at least one feeder.
• the oxidizing agent is supplied by a plurality of feeds, for example in the form of a nozzle ring.
• the feeds can advantageously also be arranged deviating from the radial direction (up to approximately 15 °).
• the supply of the oxidant O takes place at a taper between zone I and zone II, as shown in FIG.
• the distance between the oxidation supply and the nozzle for the fuel is for example 75 mm.
• FIG. 3 shows an advantageous embodiment of the oxidant supply. This provides for the supply of air through a pipe. At the tapered point, a slot in the form of a ring is rotated from the inside into the outer wall, which acts as an air distributor, and is connected to the supply pipe. By an inner sleeve, the annular air distribution is shielded against the interior. Only through several small holes that extend through the cuff into the annular air distributor, is a feeder of the oxidant radially into the interior of the mixing chamber possible.
• a further embodiment provides that the holes in the sleeve have a small deviation of about 5 to 15 ° from the radial direction.
• the oxidizing agent flowing out of it also contains a tangential component, which leads to a stronger turbulence and thus, as a rule, to an effective mixing.
• FIG. 4 shows the principle of the evaporator zone I designed as a cyclone.
• the unevaporated fuel droplets pass through the flow to the outer edge of the chamber and are collected in the gap SP so that they do not enter the second zone.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• General Health & Medical Sciences (AREA)
• Health & Medical Sciences (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Sustainable Development (AREA)
• Sustainable Energy (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Hydrogen, Water And Hydrids (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

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Cited By (6)

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Citations (3)

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• 2004
  • 2004-11-17 DE DE102004055425A patent/DE102004055425B4/de not_active Expired - Lifetime
• 2005
  • 2005-11-12 US US11/791,011 patent/US7461618B2/en not_active Expired - Lifetime
  • 2005-11-12 JP JP2007541666A patent/JP4898695B2/ja not_active Expired - Fee Related
  • 2005-11-12 EP EP05806947.7A patent/EP1812154B1/de not_active Expired - Lifetime
  • 2005-11-12 WO PCT/DE2005/002041 patent/WO2006053534A1/de not_active Ceased
  • 2005-11-12 CA CA2587326A patent/CA2587326C/en not_active Expired - Lifetime

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