Classifications

• • 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
  • C01B3/46—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 discontinuously preheated non-moving solid materials, e.g. blast and run
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/248—Reactors comprising multiple separated flow channels
  • B01J19/2485—Monolithic reactors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • 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
  • B01J8/04—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 passing successively through two or more beds
  • B01J8/0446—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 passing successively through two or more beds the flow within the beds being predominantly vertical
  • B01J8/0449—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 passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
  • B01J8/0453—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 passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
• • 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
  • B01J8/04—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 passing successively through two or more beds
  • B01J8/0496—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
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21B—MANUFACTURE OF IRON OR STEEL
  • C21B13/00—Making spongy iron or liquid steel, by direct processes
  • C21B13/0073—Selection or treatment of the reducing gases
• • 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
  • B01J2208/00504—Controlling the temperature by means of a burner
• • 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
  • B01J2208/00513—Controlling the temperature using inert heat absorbing solids in the 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00027—Process aspects
  • B01J2219/00038—Processes in parallel
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21B—MANUFACTURE OF IRON OR STEEL
  • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
  • C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
  • C21B2100/22—Increasing the gas reduction potential of recycled exhaust gases by reforming
• • 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
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
  • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
• • 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
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
  • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
• • 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
  • Y02P20/10—Process efficiency
  • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

• the present invention relates to a process for producing a reducing gas comprising: • a step of heating a reactor charged with thermal materials and at least one catalytic mass that is suitable for reforming gases to be reformed, by passing through this reactor by a heating gas, and • a reforming step comprising: • a reactor feed heated to said gas to be reformed and an oxidizing gas, and • a passage of said gas to be reformed and said oxidizing gas through said heated thermal materials and said at least one catalytic mass heated with heating of said gases by direct contact with said thermal materials and reforming said gas to be reformed into said reducing gas by direct contact with said at least one catalytic mass.
• the invention also relates to a device for carrying out the method.
• Various processes have been known for a long time for producing a reducing gas intended, for example, for the reduction of ore. These methods are widely used and generally comprise a catalytic reforming unit, consisting of a set of metal tubes filled with catalysts and carrying out the reforming reaction of natural gas with oxidizing gases such as air or water vapor . Some of these processes include treating the reforming gases to remove CO 2 and I 1 H 2 O from the gas, and heating the gases. treated gases to obtain a sufficient temperature before injection into the ore reduction tank.
• the process advantageously allows the energy supplied to the reforming reaction to be done directly by supplying heat to the catalyst and to the thermal material without heat transfer through metal tubes (a loss of 50 to 50% is avoided). 100 9 C).
• the amount of oxidizing gas required for the reforming reaction is reduced to a strict minimum, ie 1 to 3% (% relative to the total volume of gas), because the traces of soot deposited during the reforming phase (3 to 4%) (% relative to the total volume of gas) are removed immediately during the heating phase in direct contact with the heating gases, which limits to 2 to 3% (% of total gas volume) the amount of non-reducing gas CO 2 + H 2 O in the reducing gas obtained by the reforming.
• the soot traces can also be eliminated during a purge gas purge phase.
• the catalyst used is any suitable catalyst for a gas reforming operation.
• this catalyst allows resorption of deposited carbon traces and reduction of the oxides formed in the catalyst by means of a reducing gas purge. It is also capable of withstanding high temperatures and frequent thermal variations.
• the catalyst offers the possibility of operating in a ratio O / C (oxygen / carbon) very close to unit. It also participates in the accumulation of heat at each heating stage, energy that it yields during the endothermic reforming phase.
• a supported catalyst based on, for example, alumina of more than 90%, preferably greater than 93%, can be used; it may have a specific surface area of between 200 and 400 m 2 / g, preferably 300 m 2 / g, the active element preferably being nickel, the content of which varies from 4 to 6% by weight relative to the mass. of supported catalyst.
• the catalyst may be in spherical or annular form or any similar shape, of a diameter for example of 10-15 mm. It may also be in the form of rectangular wafers with a thickness of eg 15 to 20 mm, grooved wafers by channels and the like.
• the catalyst operates optimally with an O / C ratio close to unity, and according to the invention it is intended to use an oxidizing gas containing in addition to I 1 H 2 O, CO and CO 2 for reforming, the consumption of hydrocarbons and in particular of methane can be considerably reduced.
• the oxidizing gas can come from an industrial process and therefore does not require preheating water vapor which is expensive energy.
• the specific consumption of natural gas is reduced by 5 to 20% compared to competing processes and therefore an equivalent reduction in greenhouse gas (CO 2 ).
• the process has the advantage of considerably reducing the emissions of these greenhouse gases (by a third compared to conventional blast furnace - coking plants), and toxic gases and to improve energy consumption.
• the process further comprises a reduction of ore by said reducing gas with ore formation in the reduced state and a residual gas of which at least a first portion is used as an oxidizing gas for said reforming.
• the oxidizing gases CO 2 and H 2 O required for reforming come from the residual gas of the ore reduction containing CO 2 , H 2 O, H 2 and CO.
• the other two components of the residual gas are already reducing gases that are produced during reforming, and thus promote the reforming efficiency.
• these residual gases are hot at the outlet of the ore reduction tank, which reduces the energy costs of the reforming and the carbon supply in the oxidizing gas reduces the hydrocarbon consumption to be reformed.
• the reduction gas production process according to the invention may not include a CO 2 extraction system or H 2 O or additional heating of the reducing gas, resulting in an investment cost and minimal exploitation.
• the temperature of the reducing gas according to the method of the invention may be set without limitation to the optimum value of 800 to 1300 ⁇ C, preferably from 900 to 1000 ⁇ O thanks to the absence of walls metal heat exchange.
• the method comprises producing, in a first reactor, said heating step and simultaneously, in a second reactor, carrying out said reforming step and, conversely, in a second period of time, the step carried out by the second reactor during the first period of time is carried out by the first reactor and the step carried out in the first reactor during this same first period of time.
• time is performed by the first reactor.
• This purge phase is also advantageously performed after the heating step. Therefore, when for example, the first reactor undergoes the reforming step, the second reactor successively undergoes the heating step and then the purge step and vice versa. This improves the efficiency of the process since the dead time is significantly reduced.
• Other embodiments of the process according to the invention are indicated in the appended claims.
• the invention also relates to a device comprising at least one reactor comprising: • thermal materials and a catalytic mass suitable for reforming gas to be reformed, • a first side of the thermal materials and the catalytic mass, an input heating gas and a second side thereof, opposite the first, a heating gas outlet, • a gas inlet to reform and an oxidizing gas inlet to said second side, and • an output of reducing gas to the aforesaid first side.
• This device is characterized in that it further comprises an ore reduction vessel comprising: an ore inlet, an ore outlet in the reduced state, a reducing gas inlet connected to said reducing gas outlet of said at least one reactor, and a residual gas outlet connected to said oxidizing gas inlet.
• the device according to the invention may advantageously comprise an ore reduction vessel which will advantageously be adapted according to the invention to allow the production of iron sponge or even liquid metal by injecting a reduced amount of oxygen and the presence of a steel-slag separation tank.
• an ore reduction vessel which will advantageously be adapted according to the invention to allow the production of iron sponge or even liquid metal by injecting a reduced amount of oxygen and the presence of a steel-slag separation tank.
• Figure 2 is a schematic view of an advantageous embodiment of the ore tank.
• Figure 3 is a schematic view of an alternative device for producing reducing gas according to the invention.
• FIG. 4 is a perspective view of a refractory thermal element that can be used in the device illustrated in FIG. 1. Briefly, the production of reducing gas is carried out by catalytic reforming of hydrocarbons, natural gas or the like by means of residual gas. from the ore reduction tank and the the production of reducing gas is carried out by catalytic reforming of hydrocarbons, natural gas or the like by means of residual gas. from the ore reduction tank and the the production of reducing gas is carried out by catalytic reforming of hydrocarbons, natural gas or the like by means of residual gas. from the ore reduction tank and the the production of reducing gas is carried out by catalytic reforming of hydrocarbons, natural gas or the like by means of residual gas. from the ore reduction tank and the the production of reducing gas is carried out by catalytic reforming of hydrocarbons, natural gas or the
• the hydrocarbons are selected from the group of methane, ethane, butane, propane, pentane, hexane, heptane, octane, naphtha and gas oil. As can be seen in FIG.
• the reducing gas production unit comprises two reactors 1,1 'refractilized and lined with thermal materials 4,4', 6,6 ', 8,8' and catalytic masses 7 , 7 'suitable, operating alternately in a short cycle, in two phases: in the first reactor 1, there occurs a first phase of reforming and production of reducing gas at high temperature from 800 to 1300O, preferably from 900 to 1000 1 C, in order to send it to a reduction tank 23 and, in the second reactor, a second heating phase is produced, the combustion gases of which are evacuated and cooled in the atmosphere. The combustion gases can also be sent to the atmosphere via an expansion turbine 12.
• the device is in continuous operation.
• the reducing gas produced is sent at high temperature into a reduction tank 23 against the current of the raw ore and calcareous charges.
• the ore is normally reduced in the form of an iron sponge reduced to more than 97%.
• This material can then be treated directly to about 1000 ⁇ C in an electric furnace 30, as the scrap melting furnaces, or be compacted and sent as a feed blast furnace to substantially reduce coke consumption.
• the method according to the invention is advantageously based on a system using two reactors 1 and composed of vertical cylinders (FIG. 1), connected together at 3/4 of the height by a pipe 2.2 'towards a collector 32 connected to a reservoir 20.
• reactors 1, 1 'refractorized each comprise successively from a first side to a second side: - a burner 3 or 3' - Ceramic thermal materials 4,4 'located under the combustion chambers 5 and 5' in the case of vertical cylinders, and placed above the pipes 2 and 2 'of reducing gas evacuation whose temperature reaches 800 to 1300 9 C, preferably from 900 to 1000 0 C optionally, these thermal materials being formed of packing elements capable of capturing the heat of a hot gas and of retroceding it to a cold gas, for example balls , plates or other corpuscles of refractory or ceramic materials, the size and nature of which depend on the temperature chosen for the reducing gas, - thermal materials 6,6 'located below the pipes 2 and 2', - catalytic masses 7 , 7 'promoting the reforming reaction between the natural gas or other hydrocarbon and oxidizing gas while also ensuring the thermal load due to the endothermic reaction.
• the process according to the invention operates advantageously in a cyclic manner:
• the reactor 1 receives at its base the reactants, that is to say natural gas or hydrocarbons to be reformed by the pipe 18 and the oxidizing gas through the pipe 10, which is from the reduction tank 23 after cooling.
• the gases are heated gradually up to about 580-600 9 C in the thermal substance 8, then pass through the catalytic mass 7 where they undergo the reforming reaction. Further heating of the reducing gas formed takes place in the thermal material 6 to the temperature predicted between 900 and 130O 4 C.
• This reducing gas leaves the reactor 1 via the pipe 2 and from there is directed to the reduction vessel of the ore 23 via tube 19 and injection nozzles.
• This reforming step has a duration of 2 to 4 minutes.
• the reactor is in the ignition heating phase of the burner 3 'supplied with superheated combustion air via the tube 13' and the valve 130 and the heating gas via the pipe 16 'and the valve 160'.
• the heating gas is also derived from the reduction tank and is formed, like the oxidizing gas of the reactor 1, residual gas that escapes from this tank.
• the burned heating gas passes through the combustion chamber 5 ', the thermal materials 4' and 6 'as well as the catalytic mass 7'.
• This purge phase is limited to 3 to 5 seconds, which has the result of not causing loss since the reducing gas injected through the pipe 31 , 31 'remains, after passing through the catalyst 7.7', therein and starts again in the next cycle in the storage tank 20.
• the reducing gas containing from 95 to 97%) (% relative to the total volume of gas) CO + H2 is injected at the base of the reduction vessel 23 through the pipe 19.
• the ore is introduced via the airlock (raw ore feed input) 22. It is heated up gradually and the
• the oxide gradually converts to FeO and then to pure iron.
• the latter generally remains in the solid phase in the form of an iron sponge, as in the other previous processes, at 900-1000 ° C., mixed with the ore waste and reaction products with the added limestone. From there, the iron sponge is discharged to an electric furnace via the control device where it is compacted and delivered for other uses such as blast furnace feeding.
• a variant of the reduction tank 23 is illustrated in FIG. 2. This variant requires the production of a reducing gas at a higher temperature, as allowed by the process according to the invention.
• the reduction tank 23 comprises several levels of reducing gas injection, and it is completed by a tank 23 'with a liquid phase.
• This cooling takes place in a heat exchanger 24 which can be used for example to heat the residual gas leaving the tank 23 via the pipe 41.
• the material is of the iron sponge in the solid state and not agglomerated.
• the iron sponge is introduced into the the tank 23 'further comprises a second level of nozzles 25 which injects a portion of the uncooled hot reducing gas (1300 ° C.) and nozzles 26 for the oxygen injection, This ensures a high temperature rise above 1500 ° C resulting in the liquefaction of the iron sponge.
• the bottom of the tank is provided with outlet openings for slag and liquid steel. from the tank 23 'are reinjected into the tank 23 at the mo Yen of nozzles 34. This version ensures the direct production of steel without resorting to additional operations.
• the 3 represents two reactors 1, arranged end to end in a single enclosure 35.
• the two The reactors comprise a common reducing gas outlet 2 and a common combustion chamber 5,5 'divided in two by a central wall provided with orifices 36.
• the two reactors function as the device illustrated in FIG. 1, except that, when the burned heating gases are evacuated via the pipe 11, 11 'via the valve 110, 110', a flow rate slightly greater than the gas flow rate at the inlet is imposed so that a vacuum is generated and the direction of the Gas flow is controlled and forced from the combustion chamber 5,5 'to the outlet 9,9', 10,10 ', 11,11'.
• FIG. 4 illustrates a particular form of thermal material that can be used according to the invention. It is understood that many different refractory materials, and different shapes can also be used in the reducing gas production device according to the invention.
• the following table gives the characteristics of the gases obtained at different points of the process according to the invention in the iron sponge production mode as illustrated in FIG. 1. For 1 mole of natural gas considered as CH 4

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• Chemical & Material Sciences (AREA)
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• General Health & Medical Sciences (AREA)
• Combustion & Propulsion (AREA)
• Inorganic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Manufacture Of Iron (AREA)

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• 2004
  • 2004-06-25 BE BE2004/0318A patent/BE1016102A3/fr not_active IP Right Cessation
• 2005
  • 2005-06-24 WO PCT/EP2005/052975 patent/WO2006000579A1/fr active Application Filing
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