Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/755—Nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/20—Carbon compounds
  • B01J27/22—Carbides
  • B01J27/224—Silicon carbide
• • 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
  • C01B3/386—Catalytic partial combustion
• • 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
  • C01B3/40—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 characterised by the catalyst
• • 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1005—Arrangement or shape of catalyst
  • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
• • 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
• • 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
  • C01B2203/1052—Nickel or cobalt catalysts
• • 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
  • C01B2203/1064—Platinum group metal catalysts
• • 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1082—Composition of support materials
• • 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
• • 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 has, on the contrary, a method and a system for detecting an information emergence phenomenon, based on sampled digital data that can be implemented in a discrete manner, per user, an implementation for a group of users, or even a population users, which can simply be reduced to a multiplication of implementation of the method respectively of the system object of the present invention, in order to infer statistical results.
• the catalysts have the advantage of being resistant to double poisoning by coke and metals, since coke is not a problem since the catalyst is easily regenerated and the metals can be recovered due to the chemical resistance of the silicon carbides. used as supports. No advantage of any type relating to the implementation of a controlled oxidation process is however described in EP 313 480 A, in particular as regards the starting of the process and concerning the characteristics necessary for an operation of the process. all security for individuals.
• the Applicant has developed a method for producing synthesis gas with or without a flame, with which the starting operations are facilitated by a better thermal conductivity within the catalytic bed and a much slower gas flow rate in the reactor where the reaction takes place, making it possible to control it both at a temperature above 1000 ° C. and at a temperature of
• the subject of the present invention is therefore a process for obtaining synthesis gas by partial catalytic oxidation with or without a flame, consisting in bringing into contact a hydrocarbon in the gaseous state and an oxidizing gas, as well as possibly a small amount of water vapor, in the presence of a catalyst comprising at least one silicon carbide, at a temperature above 800 ° C., characterized in that the silicon carbide has a specific surface area determined by the BET method of less than or equal to 100 m 2 / g, the contact time between the mixture of the gaseous hydrocarbon, the oxidizing gas and optionally water vapor, and the catalyst is greater than 0.05 second and in that the pressure inside the reactor is above atmospheric pressure.
• reaction temperature a value of between 800 ° C. and 1400 ° C.
• the process according to the present invention has the advantage of operating in non-critical conditions, particularly with regard to the contact time of the gas mixture (hydrocarbon gases , oxidizing gas and water vapor) with the catalyst.
• the catalytic support perfectly conducts the heat produced during the start of the reaction, which makes it possible to avoid the phenomena of runaway observed by applying the prior art.
• This good thermal conductivity of the support makes it possible to maintain a good homogeneity of the catalyst temperature in the bed, and thus to avoid the formation of coke-generating hot spots favoring the sintering phenomena of the active phase observed in the prior art.
• This makes it possible to use a single bed in a conventional reactor, thereby avoiding the use of still-delicate reactor tubes to be uniformly filled with catalyst grains.
• Another advantage is to be able to increase the temperature of the catalytic bed, which allows a better conversion to synthesis gas, the reaction takes place in the presence or absence of water vapor, in the context of an application in catalytic ATR or POx units.
• the oxidizing gas may contain more than 20% by volume of oxygen, preferably between 40 and 100% by volume of oxygen.
• a molar ratio of the carbon of the hydrocarbon (C) to the oxygen will be chosen close to the stoichiometry of the reaction for obtaining the synthesis gas, that is to say say varying more particularly in a range of 1.6 to 2.6.
• the catalyst contains more than 50% by weight of silicon carbides having a BET specific surface area determined by the NF XI 1-621 standard of less than 100 m 2 / g, in particular between 15 and 80 m 2 / g, preferably between 20 and 40 m 2 / g.
• silicon carbides also have a mesoporosity determined by the nitrogen BET method according to the NF XI 1-621 standard of between 20 and 100 nm, a macroporosity determined by the measurement of the mercury porosity between 5 and 100 ⁇ m.
• the silicon carbide used as support is solid and consists of formed grains or not, or solid foam.
• formed grains means grains in the form of carbide balls, extrudates of cylindrical, trilobed or other shape, monoliths in the form of discs or cylinder sections.
• the pressure in the reactor can be maintained at a value between 2 ⁇ 10 5 and 150 ⁇ 10 5 Pa and, preferably, between 5 ⁇ 10 5 and 80 ⁇ 10 5 Pa.
• Silicon catalyst can be used to support Group VIII metals.
• the Group VIII metal content is between 0.5 and 20% by weight of the catalyst and preferably between 1 and 10% by weight of the catalyst.
• the preferred metal of Group VIII is nickel.
• the catalyst can be obtained by any method known to those skilled in the art. In particular, it can be prepared by impregnating the silicon carbide with a solution containing a salt of at least one Group VIII metal, the impregnated metal salt being subsequently decomposed by calcining in air at 300 to 400.degree. impregnated support.
• the catalyst can be used as such or reduced in situ in the reactor under a stream of hydrogen, at a temperature between 200 and 400 ° C, before starting the unit.
• the contact time between the mixture of the gaseous hydrocarbon, the oxidizing gas and, if appropriate, the steam will be regulated. water, at a value between 0.5 and 5 seconds.
• it will limit the amount of steam introduced at a water vapor / carbon molar ratio of the hydrocarbon (H 2 0 / C) less than or equal to 0.2.
• the temperature of the catalyst bed is maintained between 900 and 1300 ° C.
• synthesis such as Fischer Tropsch conversion or methanol production.
• the gases are preheated between 400 and 650 ° C before entering the catalyst bed.
• hydrocarbons that make it possible to form synthesis gas are chosen from gasoline, reservoir gas condensates, and hydrocarbons comprising from 1 to 3 carbon atoms, methane being preferred.
• the method according to the invention can be implemented in existing ATR units.
• FIG. 1 represents two partial oxidation curves of the methane on the catalyst based on alumina ⁇ (Ci) under the conditions of Example 3 for two contact times, respectively of 0.6 and 3 seconds;
• FIG. 2 represents a partial oxidation curve of the methane on the SiC (C 2 ) -based catalyst under the conditions of Example 3 for two contact times, respectively of 0.6 and 3 seconds.
• FIG. 3 represents a partial oxidation curve of the methane on the ⁇ -alumina catalyst under the conditions of Example 3 for a contact time of 3 seconds.
• EXAMPLE 1 The present example aims to show the effectiveness of catalytic supports based on silicon carbides having a BET specific surface area of less than 100 m 2 / g and, more particularly, between 15 and 80 m 2 / g.
• a sample of 10 g of silicon carbide (SiC) in the form of 0.4 to 1 mm grains with a BET specific surface area of 40 m 2 / g is used in the present example. It was previously impregnated with a solution of nickel nitrate allowing the deposition of 2.6 g of salt on SiC to obtain a final nickel content of 5% by weight relative to the final catalyst. The impregnated catalyst is dried under air at 100 ° C and then calcined at 300 ° C in dry air.
• a microreactor 2 g of catalyst supported on SiC are introduced, and the atmosphere of the reactor is then flushed under a stream of air at room temperature.
• the reactor pressure is then raised to 5 ⁇ 10 5 Pa under a mixture of methane and air with a carbon / oxygen molar ratio equal to 2.6, while the temperature of the catalytic bed is 900 ° C.
• the circulation rate of the gaseous mixture is adjusted for a contact time of 3 seconds, the mixture at the outlet of the reactor being analyzed online by gas chromatography.
• the purpose of this example is to show the ability of the silicon carbide carrier to rapidly diffuse the heat generated during the methane oxidation reaction out of the reaction zone, thereby preventing the temperature rise of the system.
• thermodynamics thermodynamics
• the excess temperature produced during the first hours of testing on alumina exceeds a few hundred degrees. In this situation, it is likely that methane breaks down essentially into carbon and hydrogen. Then, as the amount of carbon deposited on the catalyst increases, the catalyst becomes more and more conductive and the total conversion returns to that expected for a reaction temperature of 900 ° C.
• the used catalysts Ci and C 2 have been subjected to oxidative regeneration under air. This consists of increasing the temperature of the reactor from room temperature to a temperature of 900 ° C, with a growth of 10 ° C / min, and then to maintain this temperature for 30 minutes, in order to burn the carbon. After cooling, it was found that the alumina-based catalyst Ci did not resist the oxidative regeneration treatment and was completely destroyed, while the SiC-based catalyst C 2 retained its original texture.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• General Health & Medical Sciences (AREA)
• Inorganic Chemistry (AREA)
• Catalysts (AREA)
• Silicon Compounds (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Carbon And Carbon Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2001
  • 2001-06-21 FR FR0108170A patent/FR2826293B1/fr not_active Expired - Fee Related
• 2002
  • 2002-06-18 EP EP02751263A patent/EP1399249A2/fr not_active Withdrawn
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• 2003
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