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  • 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
  • C01B3/386—Catalytic partial combustion
• • 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
  • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
  • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/005—Separating solid material from the gas/liquid stream
  • B01J8/0065—Separating solid material from the gas/liquid stream by impingement against stationary members
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
  • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/1872—Details of the fluidised bed reactor
• • 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
• • 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
  • C01B3/42—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 using moving solid particles, e.g. fluidised bed technique
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
  • B01J2208/00398—Controlling the temperature using electric heating or cooling elements inside the reactor bed
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
  • B01J2208/00415—Controlling the temperature using electric heating or cooling elements electric resistance heaters
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00796—Details of the reactor or of the particulate material
  • B01J2208/00893—Feeding means for the reactants
• • 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
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
  • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
• • 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
  • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
• • 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
  • C01B2203/1282—Mixing of different feed components using static mixers
• • 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
  • C01B2203/16—Controlling the process
  • C01B2203/1628—Controlling the pressure

Definitions

• the invention relates to a catalytic process for natural gas reforming
• Hydrocarbons in particular natural gas, with the aid of
• oxygen-containing gases which is the catalyst
• the invention relates to a device for carrying out the method.
• Synthesis gas in particular for the operation of decentralized
• Fuel cells to distinguish. The latter are not large-scale installations. Instead, they are small, compact units, some of which are mobile. Therefore, and because these along with costly devices, such as
• Fuel cells are operated, which make high demands on the purity of the produced synthesis gas, come for such reformers sometimes quite expensive structures in question.
• Hydrocarbons is an endothermic process that requires heat.
• the heating of the tubular catalyst chambers takes place from the outside by air-driven
• the invention is therefore based on the object, such a method and an apparatus of the type mentioned in such a way to further develop and design that the described disadvantages are avoided.
• Oxygen also means oxygen-containing gases, such as air.
• the device according to the invention consists of a reactor which is divided by gas-permeable walls into an oxygen space and a catalyst space.
• the gas-permeable walls are preferably formed as tubes
• the pressure difference is adjusted so that the oxygen flows into the catalyst space, the fuel gas becomes instantaneous at least partially oxidized on the tubes. This gives an autothermal process with increased CO 2 content in the
• gas-permeable pipes there are all types of gas-permeable pipes available that withstand the usual temperatures of 500 ° C to 1100 ° C, so metal pipes with small holes, formed of sheet metal discs tubes with inner supports, sintered tubes made of metal or ceramic and fiber tube. Ceramic pipes should preferably be constructed of short cylinder sections because of the risk of breakage, which are centered with a metal structure from the inside and biased. The openings and pores should be smaller than the catalyst particles.
• Such a structure can also be created by concentric tubes.
• the less gas-permeable structure serves primarily the gas metering by a differential pressure, a coarser structure with a high pore content serves the
• Ceramic tubes have a high compressive strength. Therefore, these tubes should preferably be externally loaded with a higher pressure and not inside. Advantageous in this sense are tubes with a small diameter.
• the oxidation takes place directly on or in the tube wall. Because of the short distance of the oxidation zone to the
• Heat transfer from a fluidized bed to a tube are fully utilized, which has a very high power density in the reactor result.
• the catalyst space can be arranged both in the tubes and around the tubes. Gas speed and size of the
• Catalyst particles can be chosen so that the
• Catalyst particles a fixed bed, a stationary bed,
• Fluidized bed or partially predominantly held in suspension It is particularly advantageous if the
• Catalyst particles are deposited at the top of the catalyst space by a separator and flow back into the catalyst space.
• the separator may consist of devices that use gravity, use centrifugal force or work as a filter.
• Separators that work with gravity are, for example, lamella separators, which are formed from sheets and form oblique channels, which are inclined to the vertical.
• the sheets preferably have a corrugated or honeycomb structure so that the catalyst particles in the grooves can more easily flow back into the catalyst space.
• the lamella separators can also be made of ceramic be shaped, as is usual in exhaust or flue gas catalysts. Lamella separators are particularly suitable because of their low overall height and gentle separation. With lamellar separators a gentle classification is possible. For example, carbon particles and soot that may form in the process can pass through the fin separators, while the larger and heavier catalyst particles are returned to the catalyst space. Therefore are
• centrifugal separators are also known fins. These have a curved shape and are preferably flowed through horizontally. The curved shape ensures that the catalyst particles collect on the walls and are thus deposited.
• centrifugal separator A popular type of centrifugal separator are cyclones. These can be arranged both inside and outside the reactor.
• filter elements such as candle filters. By shaking or by brief pressure surges from the clean gas side, the catalyst particles can be returned to the catalyst space
• the device according to the invention is suitable not only for the reformer, which is operated at a typical temperature of 850 ° C, but also for the pre-reformer, which is operated at much lower temperatures.
• Fig. 1 shows an allothermal reactor with a stationary fluidized bed.
• Fig. 2 shows an allothermal reactor with a stationary fluidized bed and a separator.
• 3 shows an allothermal reactor with a
• FIG. 4 shows a lamella separator from the side.
• FIGS. 5 and 6 show lamellar separators in cross section.
• Fig. 7 shows an autothermal reactor with a stationary fluidized bed.
• Fig. 8 shows an autothermal reactor with a stationary fluidized bed and a separator.
• Fig. 9 shows an autothermal reactor with a highly fluidized fluidized bed and a separator.
• Fig. 10 shows an allothermic reactor with a fixed bed.
• Fig. 11 shows the section of a fixed bed in the tube in allothermal operation.
• FIG. 12 shows a multi-layered porous tube with fine pores inside and coarse pores outside.
• FIG. 13 shows a detail of FIG. 12.
• Fig. 14 shows an arrangement of porous pipes
• Fig. 15 shows a pipe cross-section in which the surface of the pipe wall is enlarged by a rib structure in the oxygen space.
• Fig. 16 shows a tube cross-section in which the surface of the tube wall is enlarged to oxygen space by increased porosity. 17 shows an arrangement of porous tubes with internal oxygen space.
• Fig. 1 shows an allothermic reactor 1 in which the
• Catalyst space 6 is formed as a stationary fluidized bed 6a.
• the reactor 1 also has a gas space 7 above the fluidized bed.
• a plurality of porous tubes 11 are arranged, which form the oxygen space 4a.
• the oxygen 4 passes through the tubesheet 9 into the porous tubes 11 and leaves the reactor 1 via the tubesheet 10 as a flue gas 5, which consists essentially of CO 2, O 2, H 2 O and optionally N 2.
• the tube feeds 12 and 13 outside the fluidized bed 6a are non-porous.
• connection to the porous tubes 11 can be performed as a plug connection with labyrinth seal, as it does not depend on an absolute tightness.
• the raw gas to be reformed 2 is between the tube sheet 9 and the nozzle plate. 8
• Oxygen space 4a is now adjusted so that a portion of the fuel gas 21 flows into the oxygen space 4a, and just enough so that the energy for this endothermic
• the fuel gas 21 largely corresponds to the synthesis gas 3 at the outlet of the reactor 1 in a fluidized bed. Further details on the porous tubes 11 are described below with reference to FIGS. 15 to 17.
• Fig. 2 corresponds largely to Fig. 1. Instead of a
• Catalyst particles are conveyed by the separating device 15 back into the free space 7. That's symbolic
• FIG. 3 largely corresponds to FIG. 2.
• the catalyst particles 18 are so small and the fluidization speed is so high that no recognizable upper limit of the fluidized bed is formed. Part of the catalyst particles 18 are suspended and excess catalyst particles 18 are separated by the separation device 15 and returned to the reactor 1. The small catalyst particles 18 are due to their small pulse only slightly mechanical
• the usual ceramic protective cover around the catalyst particles 18 can therefore be dispensed with.
• FIGS. 4 to 6 show details of a separating device 15.
• the separating device 15 is here as
• Catalyst particles 18 are deposited by gravity.
• Fig. 4 shows a vertical section through such a lamella. It consists of a plurality of inclined plates 16. As the arrows indicate 17, the synthesis gas 3 flows through these narrow channels. entrained
• Fig. 5 and Fig. 6 shows a view in the direction of the channel axis of a lamella. It is particularly advantageous to form the sheets 16 so that the catalyst particles 18 can collect in grooves 18, where the flow velocity of the gas is smaller than in the middle and therefore the return transport of the gas
• Catalyst particle 18 is facilitated.
• Fig. 7 shows an autothermal reactor 1 which is similar
• Oxygen space 4a and the catalyst space 6 is selected so that the oxygen 4 flows into the catalyst space 6.
• the catalyst space 6 is formed here as a stationary fluidized bed 6a. The oxidation of the fuel gases 21 takes place
• Fuel gas 21 largely corresponds to the synthesis gas 3 in a fluidized bed.
• the large surface area of the porous tubes 11 and the high turbulences in fluidized-bed reactors ensure that the catalyst particles 18 do not overheat.
• FIGS. 8 and 9 show autothermal reactors 1
• Catalyst particles are at least partially levitated.
• the oxygen 4 flows from the oxygen space 4a into the catalyst space 6, as in the case of FIGS.
• FIGS. 2 and 3 are in Figs. 8 and 9 in the upper part of
• FIG. 10 shows an allothermal reactor 1, wherein the
• Catalyst space 6 is formed as a fixed bed 6c.
• Catalyst particles 18 are located here in the catalyst space 6 in the porous tubes 11.
• the oxygen space 4a is arranged around the tubes. The pressure difference is here so
• the porous tubes 11 are prevented from falling out of the tubesheet 19 by a sieve. At the upper end are the porous tubes of one
• Head plate 20 is attached.
• the raw gas 2 flows from below into the reactor 1 and leaves the reactor 1 as synthesis gas 3.
• Oxygen 4 is introduced into the oxygen space 4a and leaves the reactor 1 as a flue gas 5. The strength of
• Energy input in the course of the longitudinal axis can be adjusted by a different gas resistance of the porous tubes 11 along its axis. This advantage does not exist in the heating of massive pipes with flue gases,
• Fig. 11 shows the cross section of the porous tube 11 of Fig. 10.
• the fuel gas 21 flows out of the catalyst space 6 to the outside in the oxygen space 4a.
• the fuel gas 21 is now oxidized by the oxygen 4.
• the flue gas 5 mixes here with the oxygen. As with all combustion processes, it is beneficial to work with a small excess of oxygen.
• the porous tube 11 has a higher porosity at the oxidation zone.
• Fig. 13 shows an enlarged detail of Fig. 12.
• Fuel gas 21 is already in the pore space IIb on the oxygen 4 and oxidizes the fuel gas to flue gas 5. Thus, similar conditions are produced as in a pore burner. The heat is transmitted to the pipe so well and transported by heat conduction to the inner wall. The hot tube IIa heats the catalyst space 6.
• Fig. 14 the arrangement of Fig. 10 is shown in cross section.
• the reactor can be so synonymous
• Figs. 15 to 17 show such a case.
• the oxygen space 4a In Fig. 16, the oxygen space 4a and thus the
• the coarser structure IIb is on the inside and the finer metering structure IIa on the outside.
• the fuel gas 21 flows from the catalyst space 6, which is arranged around the tubes, in the Pipe interior and is oxidized there directly to the inner wall or in the inner wall.
• the coarser structure also by
• Rib structure is shown in Fig. 15. A bigger one
• Oxidation surface has been created here by a rib structure on tube IIb.
• the grooves can also be arranged helically.
• Heat transfer to the catalyst particles 18 may be arranged a rib structure inside and outside of the tube wall 11.
• Fig. 17 shows a reactor cross section in which the
• Catalyst space 6 is arranged around the porous tubes 11.
• the catalyst space may be designed as a stationary fluidized bed 6a, as a circulating fluidized bed 6b or as a fixed bed 6c.
• the catalyst space can also as
• Be formed fluidized bed which improves the heat transfer to the catalyst particles and for a
• the oxidation in the porous structure of the tubes is similar to a pore burner, in which the temperatures are also significantly lower than in a free flame.
• Temperature difference between the combustion chamber in the pores and the catalyst particles is also much smaller. As a result, fewer pollutants are formed.

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• General Health & Medical Sciences (AREA)
• Inorganic Chemistry (AREA)
• Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
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• 2011
  • 2011-12-20 EP EP11194439.3A patent/EP2607301A1/de not_active Withdrawn
• 2012
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  • 2012-12-18 WO PCT/EP2012/075961 patent/WO2013092593A1/de not_active Ceased
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