WO2003004405A1 - Dispositif et procede de production d'un gaz de synthese a partir d'un gaz d'hydrocarbures de qualite inferieure - Google Patents

Dispositif et procede de production d'un gaz de synthese a partir d'un gaz d'hydrocarbures de qualite inferieure Download PDF

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Publication number
WO2003004405A1
WO2003004405A1 PCT/JP2002/006813 JP0206813W WO03004405A1 WO 2003004405 A1 WO2003004405 A1 WO 2003004405A1 JP 0206813 W JP0206813 W JP 0206813W WO 03004405 A1 WO03004405 A1 WO 03004405A1
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Prior art keywords
gas
concentric double
jet
catalyst
reactor
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PCT/JP2002/006813
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English (en)
Japanese (ja)
Inventor
Kenichi Imagawa
Yoshimi Shiroto
Jun Hasegawa
Tetsu Shiozaki
Yoshikazu Hozumi
Takaaki Mohri
Mitsunori Shimura
Kenichi Kawazuishi
Takeshi Minami
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Chiyoda Corporation
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Priority claimed from JP2001203627A external-priority patent/JP2003013072A/ja
Priority claimed from JP2001240364A external-priority patent/JP2003054909A/ja
Priority claimed from JP2001296930A external-priority patent/JP2003095613A/ja
Priority claimed from JP2002194966A external-priority patent/JP2004043195A/ja
Application filed by Chiyoda Corporation filed Critical Chiyoda Corporation
Publication of WO2003004405A1 publication Critical patent/WO2003004405A1/fr

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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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
    • 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
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
    • B01F25/3132—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit by using two or more injector devices
    • 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
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
    • B01F25/3132—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit by using two or more injector devices
    • B01F25/31322—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit by using two or more injector devices used simultaneously
    • 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
    • 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
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
    • 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
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the 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
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • 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
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • B01J2208/00221—Plates; Jackets; Cylinders comprising baffles for guiding the flow of the heat exchange medium
    • 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
    • B01J2208/00823—Mixing elements
    • B01J2208/00831—Stationary elements
    • B01J2208/00849—Stationary elements outside the bed, e.g. baffles
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
    • 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
    • C01B2203/1241—Natural gas or methane
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention provides a method for synthesizing carbon monoxide (CO) and hydrogen (H 2 ) by an autothermal reforming (ATR) method that combines a partial oxidation reaction and a reforming reaction of a lower hydrocarbon gas such as methane and natural gas.
  • ATR autothermal reforming
  • the present invention relates to a method and an apparatus for producing gas.
  • the present invention uses an ATR reactor having a burner composed of a plurality of concentric double-tube nozzles arranged on a plane, and uses the concentric double-tube nozzle to supply an oxidizing gas containing oxygen and the lower hydrocarbon from the concentric double-tube nozzle.
  • a method for producing a synthesis gas by partially oxidizing a lower hydrocarbon gas by injecting and mixing the gas into a partial oxidation region of the reactor and reforming a product of the partial oxidation reaction through a catalyst layer.
  • the ATR reactor used therefor Background art
  • the ATR method can produce ammonia, methanol, synthesis gas as a raw material for FT synthesis, or oxo gas from lower hydrocarbon gas such as methane and natural gas.
  • the reaction heat generated by the partial oxidation reaction is generated by sequentially causing both the partial acid reaction (partial combustion) reaction and the reforming reaction in one reactor.
  • This is a gas reforming (reforming) method characterized by being used for a reforming reaction, which is an endothermic reaction.
  • the partial oxidation region 102 provided in the reactor 101 typically contains oxygen having a stoichiometric ratio or less with respect to the complete combustion reaction represented by the following formula (1).
  • a part of methane is partially burned by a flame reaction using a gas, and the partially oxidized reaction product gas passes through the modified catalyst layer 103 of the fixed bed installed at the lower part of the reactor.
  • the steam reforming reaction represented by the following equation (2), the CO shift reaction represented by the following equation (3), and the CO 2 reforming reaction represented by the following equation (4) are caused to cause H 2 and CO (and C ⁇ 2 And H 2 0) are produced.
  • Japanese Patent Application Laid-Open No. 5-256420 and US Pat. No. 5,492,649 disclose the effect of eddy motion in an injection nozzle. Proposed to form a large number of mixing points in the turbulent diffusion flame, thereby suppressing the generation of a large amount of soot in the diffusion flame.
  • Japanese Patent Application Laid-Open No. H11-314901 and U.S. Pat. No. 5,628,931 disclose soot by controlling the operating conditions (operating pressure and steam reforming temperature) of the ATR process. It is proposed to suppress the generation of.
  • it is still difficult to completely suppress peroxidation in a diffusion flame, resulting in thermal damage to injector nozzles and thermal degradation of reforming catalysts. Is left.
  • the improved ATR method using a multi-nozzle burner composed of a plurality of nozzles or orifices is disclosed in Japanese Patent Application Laid-Open No. 2-25615 and Proposed by U.S. Pat. No. 5,980,596.
  • the multi-nozzle burners used for these are structures combining special perforated block bodies, and are too complex to be used in large ATR industrial equipment, making their processing and fabrication difficult. At the same time, there is a problem that it is difficult to maintain high-temperature operation. Disclosure of the invention
  • the present invention has been made in view of the above-described problems, and when producing a synthesis gas by the ATR method, the raw material gas and the oxidizing gas are favorably mixed in the partial oxygen region in the reactor, and a uniform partial oxidation reaction proceeds.
  • the formation of soot and the generation of hot spots due to peroxidation are suppressed, and the sintering of the catalyst, which can occur when the high-temperature gas generated by the partial oxidation reaction comes into contact with the catalyst layer, heat damage or partial oxidation products
  • a method that can prevent blockage due to coke deposition in the catalyst layer due to coke precursors (such as unsaturated hydrocarbons such as acetylene and ethylene) present in the catalyst layer, and enable long-term stable operation. And a device therefor.
  • the source gas and the oxidizing gas are separately and uniformly injected into the partial oxidation region.
  • a uniform diffusion flame of the raw material gas and oxidizing gas is realized to form a stable diffusion flame, and the reaction product
  • the present invention provides a method for efficiently producing a synthesis gas by reforming in the presence of a reforming catalyst having excellent heat resistance and high resolution of a coke precursor, and the above-mentioned ATR reactor. It is intended to do so.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, using a multi-nozzle burner equipped with a plurality of concentric double tube nozzles, set the flow velocity of the central jet from the inner nozzle to an appropriate range, Furthermore, by setting the ratio of the velocity of the annular jet from the outer nozzle to the velocity of the center jet in an appropriate range, it is possible to perform a stable and homogeneous partial oxidation reaction with less soot generation and hot spot generation. I found out. At that time, they also found that there was a preferable range for the nozzle interval.
  • a catalyst used in the reforming reaction which is a subsequent process, it shows sufficient heat resistance even at a high temperature of 100 ° C or more, and has excellent resolution of the coke precursor. It was found that there was a catalyst that hardly caused coke deposition.
  • the present invention provides an upper region in which a lower hydrocarbon gas and an oxidizing gas are separately ejected and mixed, a middle region in which a partial oxidation reaction is performed by the mixed lower hydrocarbon gas and the oxidizing gas,
  • a method for producing a synthesis gas by the partial oxidation reaction and the reforming reaction using an auto-summar reforming reactor comprising a lower region in which a reforming reaction is performed in the presence of:
  • the upper region has a burner composed of a plurality of concentric double-tube nozzles that jet the two gases separately from the inner and outer nozzles toward the central region,
  • the present invention provides an upper region in which a lower hydrocarbon gas and an oxidizing gas are separately ejected and mixed, a middle region in which a partial oxidation reaction is performed by the mixed lower hydrocarbon gas and the oxidizing gas, A method for producing a synthesis gas by the above partial oxidation reaction and the above reforming reaction using an autothermal reforming reactor having a lower region in which a reforming reaction is performed in the presence of
  • the upper region has a burner composed of a plurality of concentric double-tube nozzles that eject the two gases separately from the inner and outer nozzles toward the central region,
  • U1 is in the range of 100 to 30 OmZ seconds.
  • U2ZU 1 is in the range of 0.15 to 0.5
  • the lower region is filled with a catalyst in which a metal oxide carrier substantially consisting of magnesium oxide carries a catalyst metal comprising at least one of rhodium and ruthenium to form a catalyst bed, Provides a method characterized in that the specific surface area is 1′.Om 2 / g or less and the amount of the supported catalyst metal is 0.001 to 0.1 mol% based on the metal oxide support. .
  • the present invention provides an upper region in which a lower hydrocarbon gas and an oxidizing gas are separately ejected and mixed, a middle region in which a partial oxidation reaction is performed by the mixed lower hydrocarbon gas and the oxidizing gas,
  • An autothermal reforming reactor for producing a synthesis gas by the partial oxidation reaction and the reforming reaction comprising a lower region in which a reforming reaction is performed in the presence of
  • the upper region is divided into upper and lower parts, one of which is a lower hydrocarbon gas storage chamber and the other is an oxidizing gas storage chamber,
  • the lower end of the lower air storage chamber is formed of a perforated plate having a plurality of holes formed, and a plurality of pipes pass through the lower air storage chamber from the upper air storage chamber to form a plurality of holes.
  • a plurality of concentric double tube nozzles are provided at the lower end of the lower air storage chamber.
  • a lower hydrocarbon gas and an oxidizing gas are separately ejected from the inner and outer nozzles toward the central region.
  • the number of the concentric double tube nozzles is preferably 4 to 300, and more preferably 50 to 100. Further, the distance between the centers of adjacent concentric double tube nozzles is preferably 5 to 20 cm, and more preferably 8 to 15 cm.
  • one of the lower hydrocarbon gas and the oxidizing gas may be a central jet and the other may be an annular jet, and it does not matter which one is the central jet.
  • FIG. 1 schematically shows a typical structure of a conventional ATR reactor.
  • FIG. 2 schematically shows a preferred structure of the ATR reactor of the present invention.
  • FIG. 3 shows a preferred arrangement of concentric double tube nozzles in the burner nozzle sheet in the ATR reactor of the present invention.
  • FIG. 4 is a schematic diagram of the partial oxidation reaction apparatus used in Example 5. Embodiment of the Invention
  • FIG. 2 shows a schematic structure of the ATR reactor used in the method of the present invention.
  • the most significant feature of the ATR reactor used in the method of the present invention is that the ATR reactor is provided with a plurality of concentric double tube nozzles for separately and evenly ejecting the source gas and the oxidizing gas.
  • the structure of the nozzle burner is the same as that of the conventional single-nozzle ATR reactor shown in Fig. 1.
  • the reactor 1 shown in Fig. 2 has three functional areas: a burner section (upper area) 2, a gas phase partial oxidation reaction section (middle area) 3, and a catalytic reforming reaction section (lower area) 4 using a catalyst. Consists of Although FIG.
  • FIG. 2 shows the case where the source gas is the central jet and the oxygen gas is the annular jet, the oxidizing gas may be the central jet and the raw material may be the annular jet.
  • the positions of the gas storage chambers for the source gas and the oxidizing gas are opposite to those in FIG. The following description is based on FIG.
  • the burner section 2 that forms the upper region of the reactor is divided into upper and lower chambers.
  • the upper side is a source gas storage chamber 5 to which the source gas is supplied
  • the lower side is an oxidizing gas storage chamber 6 to which the oxygen gas is supplied. It has become.
  • a tube sheet 7 having a plurality of holes to which gas introduction tubes 9 are connected. I have.
  • the lower part of the oxidizing gas storage chamber 6 and the gas-phase partial oxidation reaction part 3 are separated by a burner nozzle sheet 8 having a plurality of openings.
  • Each gas introduction tube 9 connected to the plurality of holes of the tube sheet 7 passes through the inside of the oxidizing gas storage chamber 6 and extends to a position penetrating through each center of the plurality of openings of the burner nozzle sheet 8 to form an annular opening.
  • a multi-nozzle burner having a plurality of concentric double tube nozzles arranged on the surface of the burner nozzle sheet 8 is formed.
  • the structure of the nozzle in the burner nozzle sheet 8 is a concentric annular arrangement in which a narrow-diameter tube (center opening) is concentrically surrounded by a wide-diameter opening to form an annular opening.
  • Source gas is ejected from one opening (center opening in Fig. 2), and oxidizing gas is ejected from the other opening (annular opening in Fig. 2).
  • Figure 3 shows a typical arrangement of concentric double tube nozzles as viewed from the middle region.
  • a square-pitch type nozzle arrangement as shown in Fig. 3 is very effective for achieving sufficient mixing of the source gas and the oxidizing gas, and is also effective for performing a uniform partial oxidation reaction.
  • the gas-phase partial oxidation reaction section 3, which forms the middle region of the reactor, is located below the multi-nozzle burner, and performs a partial oxidation reaction by mixing the raw material gas ejected from the concentric double tube nozzle with the oxidizing gas.
  • a catalytic reforming reaction section 4 consisting of a catalyst bed 13 filled with a reforming catalyst, and there is no partition between them, so the gas generated in the partial oxidation zone 12 Passes through the catalyst bed 13 as it is, during which a reforming reaction takes place.
  • a lower hydrocarbon gas such as methane and natural gas is used as a raw material gas, and oxygen, air, or oxygen-enriched air is used as an oxidizing gas depending on the use of the synthesis gas.
  • carbon dioxide for controlling the temperature of the steam and partial oxidation zone required for reforming steam also has a temperature controlling action, and these gases are generally referred to as a moderator gas
  • oxidizing gas is the source gas described above.
  • the carbon dioxide may be supplied after adjusting the carbon dioxide concentration according to the desired composition of the synthesis gas.
  • the raw material gas is mixed with, for example, carbon dioxide as a moderator gas, preheated, and then supplied to the raw material gas storage chamber 5 on the upper side of the burner, where it is ejected to the partial oxidation zone 12 through the gas introduction tube 9. I do.
  • the oxidizing gas is mixed with, for example, steam as a moderator gas, preheated, and then supplied to the oxygen gas storage chamber 6 below the burner, where the gas is supplied between the burner tube sheet 8 and the gas introduction tube 9. It gushes from the annular opening 10 to the partial oxidation zone 12.
  • a high-temperature combustion (partial oxidation) gas is generated by the oxidation reaction of the raw material gas.
  • the jet velocity of the central jet (source gas in Fig. 2) and the annular jet (oxidizing gas in Fig. 2) are very important for the rapid mixing of the two gases after jetting and the formation of a stable diffusion flame. It is preferable that the flow velocity U1 of the central jet jetted from the gas introduction tube 9 be in the range of 100 to 30 OmZ seconds. Also, a ring spouting from the ring opening The ratio of the flow velocity U2 of the turbulent jet to the flow velocity U1 of the central jet is an important factor governing the mixing of the source gas and the oxidizing gas.To maximize the mixing efficiency, U2ZU1 is 0.15 to It is preferably in the range of 0.5, more preferably in the range of 0.2 to 0.4.
  • the distance between the concentric double-pipe nozzles is also important. This is to prevent the formation of a stable flame and the high temperature near the nozzles. It is preferably in the range of ⁇ 20 cm, and 8 ⁇ : I more preferably in the case of 5 cm.
  • the equivalent diameter D of the formed coaxial double jet should be in the range of 10 to 6 Omm, more preferably in the range of 30 to 50 mm.
  • ⁇ is the combustion gas density (kg / m 3 ) and is defined as the value at the temperature under the condition that the center jet and the annular jet are mixed.
  • the temperature of partial oxidation depends on the type and amount of moderator gas mixed with oxygen.
  • the desired ratio of hydrocarbon gas to oxygen is always carried out in excess hydrocarbon conditions to avoid overheating and soot formation due to peroxidation.
  • a porous dispersion plate 1 la is provided in the source gas storage chamber to promote uniform dispersion of the source gas.
  • a porous dispersion plate 11b is provided in the oxidizing gas storage chamber.
  • the pressure loss in each of these porous dispersion plates is preferably about 800 to 100 kg Zm 2 .
  • the inner wall of the ATR reactor is covered with refractory material (brick) 14 so that it can be kept hot.
  • the burner nozzle sheet 8 Since the burner nozzle sheet 8 is directly exposed to a high-temperature flame, there is a possibility of damage such as melting and cracking.Use a heat-resistant and corrosion-resistant metal material, and install a cooling pipe in the burner nozzle sheet. It is customary to employ forced cooling means to remove heat by embedding and flowing cooling water through this. Typically, one or more grooves for cooling pipes may be provided on the inner surface of the burner nozzle sheet, and cooling pipes may be embedded therein. Considering the arrangement of the cooling pipes around the concentric double pipe nozzle, it is preferable that the concentric double pipe nozzles are arranged at a square pitch.
  • the number of nozzles is determined by the amount of gas to be processed and the specified linear velocity at the time of gas ejection. To take advantage of the characteristics of the multi-burner, four or more nozzles, preferably one
  • the number is usually 300 or less, preferably 100 or less.
  • the reforming catalyst Since the gas oxidized (combusted) in the partial oxidation zone passes at a high temperature through the fixed bed catalyst layer provided in the lower region of the ATR reactor, the reforming catalyst constantly contacts the hot gas. Although heated, the method of the present invention suppresses the generation of so-called hot spots, which are extremely high temperatures, and preferably withstands high temperatures of 100 ° C. or more. Since a reforming catalyst with excellent heat resistance is used, sintering rarely causes thermal damage.
  • combustion takes place in the presence of substoichiometric oxygen.
  • acetylene a precursor to soot formation
  • the method of the present invention a state in which the raw material gas and the oxidizing gas are sufficiently mixed and there is almost no extreme lack of oxygen hardly occurs.
  • the preferably used reforming catalyst decomposes and removes soot and its precursor, it is difficult for the soot to block the catalyst layer.
  • it has the property of suppressing the coke precipitation reaction represented by the following formulas (6) and (7), so that it is possible to exhibit stable performance for a long period of time without hindering driving operation due to these problems. .
  • the C + C0 2 (7) reforming catalyst is generally chosen, one or more metals selected from Group VI or the Periodic Table Groups, in particular a ring group of noble metals or nickel A catalyst in which one or more metals are supported on a carrier is preferably used. These catalytic metals can also be used in combination with other metals such as lanthanum and cerium.
  • the metal component is usually supported on a support made of a refractory inorganic acid having high thermal stability.
  • Such catalyst supports include Group III metal oxides, rare earth metal oxides, alumina, alumina-containing oxides, hexaaluminates, calcium aluminates, magnesium, magnesium monoalumina spinel, cement, etc. .
  • the catalyst particles may be of various shapes, but are generally cylindrical (Raschig rings), saddles, stars, and the like.
  • a particularly preferred reforming catalyst uses magnesium oxide (MgO) having a specific surface area of 1.0 m 2 / g or less as a catalyst carrier, and further contains a catalyst metal containing at least one of rhodium and ruthenium with respect to magnesium oxide. It is supported at a rate of 001 to 0.1 mol%.
  • the MgO purity of this catalyst support is 98% by weight or more
  • the total content of iron, nickel and silica is 1.0 weight in total. / 0 or less is preferable.
  • MgO is generally obtained by calcining magnesium hydroxide, magnesium carbonate, basic magnesium carbonate, etc. at a temperature of at least 1,000 ° C, preferably at a temperature of 1,000 to 1,500 ° C, more preferably at a temperature of 1,050 to 1,300 ° C.
  • the molding aid is selected from i) carbon, ii) fatty acid having 12 to 22 carbon atoms or its magnesium salt, iii) carboxymethylcellulose (CMC) or its magnesium salt, and i) polyvinyl alcohol. It is preferred to use at least one compound.
  • carbon graphite, carbon black, activated carbon and the like are used.
  • fatty acid lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and the like are used.
  • molding aids are usually used in powder form.
  • the powdered molding aid is added to the powdered MgO, and after uniform mixing, the mixture is formed into a desired shape.
  • the amount of the molding aid added is preferably from 0 :! to 5% by weight, preferably from 1.0 to 4.0% by weight, based on the total amount of MgO and the molding aid. / 0 is more preferable.
  • a molding method a press molding method is generally used, but a tableting method or the like may be employed.
  • the size of the molded body formed into a desired shape such as a tablet, a column, a ring, or a hollow cylinder is usually 3 to 30 mm, preferably 5 to 25 mm in its major axis length. However, appropriate dimensions may be adopted according to the catalyst bed.
  • a conventional method such as an impregnation method, an immersion method, or an ion exchange method can be used.
  • the catalyst metal is prepared in the form of a water-soluble compound such as a halide, a nitrate, a sulfate, an organic acid salt (for example, an acetate), a complex salt (a chelate), etc., and is applied to the MgO carrier as an aqueous solution.
  • the MgO support supporting the water-soluble compound of the catalytic metal may then be dried at a temperature of about 35 to 200 ° C and fired at a temperature of about 200 to 1500 ° C.
  • MgO powder having a purity of 99.2% by weight or more, 3.5% by weight of carbon (based on the total amount of MgO and carbon) was added and mixed as a sliding material (binder), and this was formed into a tablet to form 1Z8.
  • the inch pellets were fired in air at 1060 ° C. for 3 hours to obtain a Mg 2 O carrier.
  • this MgO support was impregnated with an aqueous solution of rhodium () acetate, dried in air at 35 ° C for 52 hours, and calcined in air at 850 ° C for 3 hours to obtain a RhZMgO catalyst.
  • This catalyst contains rhodium (Rh) as Rh metal at 600 wt ppm relative to the support MgO, and has a surface area of 0. Met.
  • the performance of the reforming catalyst prepared above was confirmed using a simulated gas that assumed a gas generated in the partial oxidation region of the ATR reactor.
  • Three annular electric furnaces are arranged vertically, and a tubular reaction tube with a length of 700 mm and an inner diameter of 16 mm is installed vertically so as to penetrate them, so that the upper, middle and lower parts of the reactor can be independently temperature controlled. I made it.
  • the reactor was charged with 20 cc of the reforming catalyst prepared above. Prior to the experiment, hydrogen was passed through the reactor, and the catalyst was reduced at 900 ° C for 1 hour.
  • the composition of the generated gas is methane 0.2% by volume on a dry basis, Carbon dioxide was 11 to 12% by volume, hydrogen was 57 to 58% by volume, and carbon monoxide was 29 to 30% by volume. This composition was almost constant over 100 hours after the start of the reaction. The equilibrium attainment rate was maintained at 95-100%. During operation, the condensed water extracted from the product separator in a timely manner was colorless and transparent, and no solids such as soot were observed. After the experiment was completed, the reactor was opened to extract the catalyst, and the state was examined. No damage was found to the catalyst and no deposition of coke was observed.
  • a reforming reaction was continuously performed using the same raw material gas and reaction conditions as in Example 1 except that the reactor was charged with the RuZMgO catalyst prepared above.
  • the composition of the generated gas is, on a dry basis, 0.1 to 0.2% by volume of methane, 11 to 12% by volume of carbon dioxide, 57 to 58% by volume of hydrogen, and 29 to 30% by volume of carbon monoxide. This composition was almost constant for 100 hours after the start of the reaction. The equilibrium attainment ratio was maintained at 95-100%.
  • the condensed water extracted from the product separator at appropriate times was colorless and transparent, and no solids such as soot were observed.
  • the reactor was opened, the catalyst was extracted, and the state was examined. No catalyst damage or coke deposition was observed. Comparative example
  • a nickel-supported alumina (NiZAlsOg) catalyst usually used as a reforming catalyst was prepared as follows. Aluminum hydroxide (Nippon Ketjen) was fired in air at 650 for 1.5 hours, and this was granulated into 18-inch pellets to obtain an alumina carrier. Next, this alumina carrier was immersed in an aqueous nickel nitrate solution (Ni content: 5.5 wt.) For 26 hours to allow equilibrium adsorption of Ni on the carrier, and then the Ni-adsorbed alumina carrier was filtered. This was dried in air at 35 ° C. for 52 hours, and further calcined in air at 800 ° C. for 3 hours to obtain a Ni-supported alumina catalyst. The catalyst, the N i support A 1 2 0 3 with respect to 1 0 contained wt% N i metal, its surface area was 1 8. 6m 2 / g.
  • Example 3 Except that the reactor was filled with N i / A 1 2 0 3 catalyst prepared as described above was performed continuously reforming reaction using the same raw material gas and reaction conditions as in Example 1. 24 hours after the start of the reaction, the equilibrium attainment rate of the raw material methane rapidly decreased to 80%. Also, during operation, it was confirmed that soot was mixed in the condensed water that was extracted from the product separator in a timely manner.After the experiment was completed, the reactor was opened, and the catalyst was extracted and examined. Deposits of black were observed.
  • Example 3 Example 3
  • a synthesis gas production test was performed using an ATR reactor having the same configuration as that shown in FIG.
  • the ATR reactor was supplied with natural gas, the raw material gas, and steam and oxygen gas to react with the natural gas. Each gas was compressed to operating pressure and supplied preheated to operating temperature. There are two flows of these ATR supply gases These were separately sent to the multi-burner in the ATR reactor, from which they were simultaneously injected into the reaction system.
  • the multiburner has seven concentric double tube nozzles. As shown in Fig. 2, the burner nozzle sheet is fastened and fixed with flanges provided respectively in the lower part of the gaseous oxide storage chamber and the upper part of the partial oxidation zone.
  • the inner tube of the concentric double tube nozzle (source gas introduction tube) has an inner diameter of 7 mm and a wall thickness of 3 mm, and the inner diameter of the outer oxidizing gas nozzle surrounding it is 19 mm.
  • the ATR reactor bottom was 0. 488m 3 filled with reforming catalyst was prepared in the same manner (RhZMgO catalyst) as in Example 1.
  • Natural gas was desulfurized before entering the ATR reactor.
  • Table 1 shows the composition of the raw natural gas after desulfurization. Natural gas composition (mol%)
  • natural gas contained 20% CO 2 .
  • This natural gas was pressurized to 27 kg / cm 2 G, heated to 500 ° C., and supplied from the raw gas supply line to the ATR reactor at a supply flow rate of 1385 Nm 3 / hour.
  • oxygen gas (99.5% purity) and steam were mixed and supplied to the ATR reactor from the oxidizing gas supply line. Pressure and temperature at this time, oxygen gas pressure 27 k gZc m 2 G and a temperature of 300 ° C, steam and pressure 30 kg / cm 2 G and a temperature of 300 ° C, 728 Nm 3 / time, respectively, 1 296 Nm It was supplied to the ATR reactor at the supply flow rate at 3 o'clock. Under the test conditions, the flow rate (U 1) of the source gas-containing fluid injected from the inner pipe of the concentric double pipe nozzle of the multi-burner was 144 seconds, and the flow rate of the oxidizing gas-containing fluid injected from the outer annular opening was 144 seconds. The ratio between the flow rate (U2) and U1 (U2 / U1) was 0.28. In addition, the equivalent diameter (D) of the double jet calculated by equation (1) is 13 mm and is 7 mm.
  • the temperature of the gas at the outlet of the catalyst layer was about 1,050 ° (:, the pressure was about 25 kg / cm2 G.
  • the composition of the product gas when it reached almost equilibrium is shown in Table 2.
  • reaction product gas was cooled downstream of the ATR reactor, and most of the steam in the product gas was condensed and separated.However, there was almost no soot in the condensed water, and the reactor after operation was inspected internally. However, no thermal damage to the multi-burner or any abnormality in the refractory or catalyst on the inner wall of the reactor was observed.
  • Example 4
  • a synthesis gas production test was performed using an ATR reactor having the same configuration as that shown in FIG. However, the positions of the source gas storage chamber and the oxidizing gas storage chamber are reversed, natural gas is supplied as raw material gas to the lower storage chamber, and water vapor and oxygen gas react with the natural gas as the upper storage chamber.
  • the central jet was acid gas and the annular jet was source gas.
  • Each gas is compressed to operating pressure, preheated to operating temperature and supplied, and injected from the multi-burner into the partial oxidation reaction system. I shot it.
  • the multi-burner has seven concentric double tube nozzles. As shown in Fig.
  • the burner nozzle sheet is fixed by tightening flanges provided at the lower part of the lower gas storage chamber (in this example, the raw material gas storage chamber) and the upper part of the partial oxidation zone.
  • the center inner tube (oxidizing gas inlet tube) of the concentric double tube nozzle has an inner diameter of 7 mm and a wall thickness of 3 mm, and the outer gas gas nozzle surrounding it has an inner diameter of 19 mm.
  • the ATR reactor bottom was 0. 488m 3 filled with reforming catalyst made of tone in the same manner (RhZMgO catalyst) as in Example 1.
  • Natural gas was desulfurized before entering the ATR reactor.
  • Table 3 shows the composition of the raw natural gas after desulfurization.
  • the natural gas contains 20% C_ ⁇ 2. This natural gas was pressurized to 27 kg / cm 2 G, heated to 500 ° C., and supplied from the raw gas supply line to the ATR reactor at a supply flow rate of 1385 Nm 3 .
  • oxygen gas 99.5% purity
  • steam were mixed and supplied to the ATR reactor from the oxidizing gas supply line.
  • the pressure and temperature at this time were as follows: oxygen gas at a pressure of 27 kgZcm 2 G and a temperature of 300 ° C, and steam at a pressure of 30 kg / cm 2 G and a temperature of 300 ° C. At 728 Nm 3 and 1 296 Nm 3 Z, respectively. It was supplied to the ATR reactor at the supply flow rate at the time.
  • the temperature of the gas at the outlet of the catalyst layer was about 1050 ° C, and the pressure was about 25 kg cm 2 G.
  • Table 4 shows the composition of the product gas when the equilibrium is reached.
  • reaction product gas was cooled downstream of the ATR reactor, and most of the steam in the product gas was condensed and separated.However, there was almost no soot in the condensed water and the reactor after operation was inspected internally. However, no thermal damage to the multi-burner or any abnormality in the refractory or catalyst on the inner wall of the reactor was observed.
  • Natural gas was desulfurized before entering the partial oxidation reactor.
  • Table 5 shows the composition of the raw natural gas after desulfurization.
  • the natural gas contains 20% C_ ⁇ 2. This natural gas was supplied to the partial oxidation reactor from the raw material gas supply line at 500 ° C and 25 kg / cm 2 G, 735 Nm 3 / h.
  • oxygen gas purity 99.5%
  • steam were mixed and supplied to the partial oxidation reactor from the oxidizing gas supply line.
  • the pressure and temperature were set to 25 kg gcm 2 G and 300 ° C for oxygen gas and steam, respectively, with the supply amount of 386 NmVh for oxygen gas and 688 ⁇ 3 , !! for steam. It was fed to the oxidation reactor.
  • the flow rate (U 1) of the source gas-containing fluid injected from the inner pipe of the concentric double pipe nozzle of the multi-burner is 144 s
  • the flow rate of the oxygen gas-containing fluid injected from the outer annular opening The ratio between (U2) and U1 (U2 U1) was 0.28.
  • the equivalent diameter (D) of the double jet expressed by equation (1) was 11 mm.
  • the gas temperature at the outlet of the partial oxidation reactor was about 1300 ° C and the pressure was 25 kg / cm 2 G. Table 6 shows the composition of the outlet gas.
  • a multi-burner in which a plurality of concentric double pipe nozzles are arranged at appropriate intervals is used, and the distance between the concentric double pipe nozzles and the flow velocity or flow velocity ratio of the central jet and the annular jet are appropriately adjusted.
  • the gas mixture can be uniformly supplied to the partial oxidation zone. Thermal damage is suppressed.
  • long-term stable ATR operation without soot generation is achieved.
  • the upper region is divided into an upper gas storage chamber and a lower gas storage chamber, and a gas introduction tube communicating from the upper gas storage chamber to the partial oxidation reaction zone is provided in the lower gas storage tube.
  • It has a structure that penetrates the air chamber, and a concentric double tube nozzle is formed by the opening of the burner tube sheet at the lower end of the lower air storage chamber and the tip of the gas introduction tube from the upper air storage chamber.
  • a concentric double tube nozzle is formed by the opening of the burner tube sheet at the lower end of the lower air storage chamber and the tip of the gas introduction tube from the upper air storage chamber.
  • such a structure has high energy efficiency, can be operated at a high pressure, has a simple apparatus configuration, and can be easily scaled up. Therefore, the technical significance when considering application to a very large synthesis gas production system is extremely large.
  • the reforming catalyst preferably used in the present invention has extremely high heat resistance and has a property of decomposing a coke precursor, so that heat damage to the catalyst and clogging of the catalyst layer due to coke deposition are further suppressed, Stable continuous operation can be performed over a long period.

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Abstract

L'invention concerne un dispositif de production d'hydrogène et de monoxyde de carbone à partir d'un gaz d'hydrocarbures de qualité inférieure au moyen d'un procédé de reformage autothermique, ainsi qu'un procédé de production d'hydrogène et de monoxyde de carbone à partir d'un gaz d'hydrocarbures. Le dispositif, à savoir un réacteur, comprend une zone supérieure destinée à souffler séparément un gaz de matière et un gaz d'oxyde en vue d'un mélange, une zone intermédiaire servant à réaliser une réaction d'oxydation partielle au moyen du mélange de gaz de matière et de gaz d'oxyde, ainsi qu'une zone inférieure permettant la réalisation d'une réaction de reformage à la vapeur en présence de catalyseurs. Deux types de gaz sont soufflés à partir de la zone supérieure vers la zone intermédiaire au moyen d'un brûleur constitué d'une pluralité de buses à doubles tubes concentriques, la vitesse d'écoulement U1 du gaz soufflé à partir d'une buse interne étant maintenue entre 100 et 300 m/s, le rapport U2/U1 entre la vitesse d'écoulement du gaz soufflé à partir d'une buse externe et la vitesse d'écoulement U1 étant compris entre 0,15 et 0,5. Si nécessaire, le nombre de buses à doubles tubes est compris entre 4 et 300, les intervalles entre les buses à doubles tubes concentriques étant compris entre 5 et 20 cm. Ainsi, étant donné que le gaz de matière est mélangé uniformément au gaz d'oxyde, on supprime la génération de suies et de points chauds.
PCT/JP2002/006813 2001-07-04 2002-07-04 Dispositif et procede de production d'un gaz de synthese a partir d'un gaz d'hydrocarbures de qualite inferieure WO2003004405A1 (fr)

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JP2001203627A JP2003013072A (ja) 2001-07-04 2001-07-04 低級炭化水素ガスから合成ガスを製造する方法とその装置
JP2001-203627 2001-07-04
JP2001240364A JP2003054909A (ja) 2001-08-08 2001-08-08 低級炭化水素ガスから合成ガスを製造する方法
JP2001-240364 2001-08-08
JP2001296930A JP2003095613A (ja) 2001-09-27 2001-09-27 低級炭化水素ガスから合成ガスを製造する方法および装置
JP2001-296930 2001-09-27
JP2002194966A JP2004043195A (ja) 2002-07-03 2002-07-03 低級炭化水素ガスから合成ガスを製造する方法および装置
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Publication number Priority date Publication date Assignee Title
WO2007045457A1 (fr) * 2005-10-21 2007-04-26 Eni S.P.A. Dispositif de mélange de fluide inséré dans ou combiné avec un réacteur
DE102006054415A1 (de) * 2006-11-16 2008-05-21 Uhde Gmbh Verfahren und Vorrichtung zum Eindüsen von Sauerstoff in ein einen Synthesereaktor durchströmendes Reaktionsgas

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JPS5815469Y2 (ja) * 1975-12-19 1983-03-29 カブシキガイシヤ イシイテツコウシヨ ナフサガス発生装置における騒音防止板付ナフサスチ−ムスプレヤ−
EP0291111A1 (fr) * 1987-05-12 1988-11-17 Shell Internationale Researchmaatschappij B.V. Procédé d'oxydation partielle d'un combustible gaseux hyrdrocarboné
JPH04331704A (ja) * 1991-04-26 1992-11-19 Ube Ind Ltd 一酸化炭素および水素を含有する合成ガスの製造方法
JPH10273302A (ja) * 1997-03-28 1998-10-13 Sekiyu Sangyo Kasseika Center 合成ガス製造装置
WO1998046525A1 (fr) * 1997-04-11 1998-10-22 Chiyoda Corporation Procede de preparation d'un gaz de synthese par reformage autothermique
JP2000103604A (ja) * 1998-07-28 2000-04-11 Chiyoda Corp 炭化水素の改質用触媒の調製方法及びその触媒担体形成用酸化マグネシウム成形体

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JPS5246192B2 (fr) * 1972-10-31 1977-11-22
JPS5525122B2 (fr) * 1973-05-18 1980-07-03
JPS5815469Y2 (ja) * 1975-12-19 1983-03-29 カブシキガイシヤ イシイテツコウシヨ ナフサガス発生装置における騒音防止板付ナフサスチ−ムスプレヤ−
EP0291111A1 (fr) * 1987-05-12 1988-11-17 Shell Internationale Researchmaatschappij B.V. Procédé d'oxydation partielle d'un combustible gaseux hyrdrocarboné
JPH04331704A (ja) * 1991-04-26 1992-11-19 Ube Ind Ltd 一酸化炭素および水素を含有する合成ガスの製造方法
JPH10273302A (ja) * 1997-03-28 1998-10-13 Sekiyu Sangyo Kasseika Center 合成ガス製造装置
WO1998046525A1 (fr) * 1997-04-11 1998-10-22 Chiyoda Corporation Procede de preparation d'un gaz de synthese par reformage autothermique
JP2000103604A (ja) * 1998-07-28 2000-04-11 Chiyoda Corp 炭化水素の改質用触媒の調製方法及びその触媒担体形成用酸化マグネシウム成形体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007045457A1 (fr) * 2005-10-21 2007-04-26 Eni S.P.A. Dispositif de mélange de fluide inséré dans ou combiné avec un réacteur
EA013043B1 (ru) * 2005-10-21 2010-02-26 Эни С.П.А. Устройство для смешивания текучих сред, вставленное в реактор или объединенное с реактором
US7815700B2 (en) 2005-10-21 2010-10-19 Eni S.P.A. Fluid mixing device inserted in or combined with a reactor
DE102006054415A1 (de) * 2006-11-16 2008-05-21 Uhde Gmbh Verfahren und Vorrichtung zum Eindüsen von Sauerstoff in ein einen Synthesereaktor durchströmendes Reaktionsgas
WO2008058646A1 (fr) 2006-11-16 2008-05-22 Uhde Gmbh Procédé et dispositif d'injection d'oxygène dans un gaz de réaction qui traverse un réacteur de synthèse
JP2010510046A (ja) * 2006-11-16 2010-04-02 ウーデ ゲゼルシャフト ミット ベシュレンクテル ハフツング 合成反応器を通流する反応ガス中に酸素を噴射するための方法および装置

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