EP3383976A1 - Procédé de production de gaz de synthèse - Google Patents

Procédé de production de gaz de synthèse

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Publication number
EP3383976A1
EP3383976A1 EP16804694.4A EP16804694A EP3383976A1 EP 3383976 A1 EP3383976 A1 EP 3383976A1 EP 16804694 A EP16804694 A EP 16804694A EP 3383976 A1 EP3383976 A1 EP 3383976A1
Authority
EP
European Patent Office
Prior art keywords
gas
reaction zone
hydrogen
hydrocarbon
carbon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16804694.4A
Other languages
German (de)
English (en)
Inventor
Hans-Jürgen MASS
Volker Göke
Otto Machhammer
Andreas Bode
Grigorios Kolios
Karsten BÜKER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
Original Assignee
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ThyssenKrupp AG, ThyssenKrupp Industrial Solutions AG filed Critical ThyssenKrupp AG
Publication of EP3383976A1 publication Critical patent/EP3383976A1/fr
Withdrawn legal-status Critical Current

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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
    • C01B3/344—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 non-catalytic solid particles
    • 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
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/28—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles
    • C01B3/30—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles using the fluidised bed technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • 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
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
    • 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
    • C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
    • 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
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0272—Processes for making hydrogen or synthesis gas containing a decomposition step containing a non-catalytic decomposition step
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • 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
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • 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
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • 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
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1252—Cyclic or aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • 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

Definitions

  • the invention relates to a process for the production of synthesis gas, in which a hydrocarbon-containing coke gas and a carbon dioxide-containing converter gas are introduced into a first reaction zone and hydrogen, contained in
  • hydrocarbon-containing coke gas at least partially with carbon dioxide to water and that water with the hydrocarbon thermally to synthesis gas containing carbon monoxide and hydrogen are reacted. Furthermore, in a second reaction zone, an oxygen-containing gas is introduced and generates thermal energy with this and part of the hydrogen from the first reaction zone.
  • Synthesis gas is to be understood as meaning a substance mixture containing hydrogen and carbon monoxide, which can be used as a basic chemical in a large number of industrial processes. For example, synthesis gas is used to produce
  • a method of the generic type is known from the patent application WO2014097142.
  • it is proposed to pass the hydrogen formed in the first reaction zone into the second reaction zone at a temperature between 800 and 1400 ° C. in order to utilize its heat content for the conversion of hydrogen to carbon dioxide.
  • this technology is not suitable for the use of coke gas and converter gas, since the reverse water gas shift reaction takes place in a reactor with a catalyst. However, this would have only a short life due to the impurities of the coke gas and the converter gas.
  • the heat integration is not optimal.
  • Coke gas is to be understood as meaning a hydrogen and / or methane-rich mixture of substances which is produced, inter alia, during the operation of a coking plant.
  • Converter gas is a carbon monoxide and / or carbon dioxide rich
  • Contain impurities such as sulfur compounds
  • these gases before their use, apart from the simple use as a fuel, previously had to be cleaned consuming and separated into their components. This is usually done in catalytic and / or adsorptive processes.
  • the object of the present invention is a process for the production of
  • the object is achieved in that the thermal energy generated in the second reaction zone is supplied to the first reaction zone.
  • the effective use of heat involves both the supply of heat from the second reaction zone into the first reaction zone in order to provide the necessary energy for the endothermic reactions taking place there, as well as the heat exchange through special heat exchange zones at the inlet and outlet of the reactor.
  • the incoming and outgoing gases are in direct heat exchange with a solid.
  • an additional advantage of this method is that the smelter gases can be recovered without complete purification or separation.
  • Impurities in the coke and / or converter gas in particular longer-chain and / or cyclic hydrocarbons, such as benzene, toluene, ethylbenzene, xylene, naphthalene or tar, which occur mainly in the coke gas, are due to the prevailing reaction conditions in the reaction zones inter alia to carbon and Hydrogen decomposes.
  • the reaction temperatures are preferably from 1000 to 1800 ° C and in particular from 1200 to 1400 ° C.
  • sulfur-containing impurities are removed from the gas mixture for the introduction of the coke gas into the reactor. Suitable methods for this are known to the person skilled in the art. As a result, particularly pure carbon, which is discharged through the solid, would arise. However, separation of the sulfur-containing compounds from the gaseous product stream is also possible. The hydrocarbons or carbon dioxide need not be separated and purified before being introduced into the reactor.
  • Thermal decomposition of the hydrocarbons from the hydrocarbonaceous coke gas and the carbon dioxide-containing converter gas may also occur. That means that
  • Hydrocarbons especially methane
  • Hydrocarbons are decomposed to hydrogen and carbon.
  • the process according to the invention makes it possible to carry out the reactions taking place in the first reaction zone largely independently of other reactions and thus to control them comparatively easily and well. For example, the amount of reacted over the temperature, for example
  • Hydrocarbon set and thus especially the amount of hydrogen generated in the first reaction zone can be controlled. If there is no full turnover, the temperature can be reduced and the used
  • Hydrocarbons in the hydrocarbon-containing gas are in the first
  • Reaction zone only partially decomposed. The reactions are both parallel and sequential.
  • the hydrogen, carbon monoxide and unreacted gases, if present, are then passed into the second reaction zone.
  • the second reaction zone is advantageously carried out, an oxidation or at least partial oxidation of hydrogen from the first reaction zone, with oxygen.
  • the heat produced by the combustion is transferred via the
  • Reaction zone supplied.
  • a solid in granular form is used.
  • the solid can be passed through the reactor as a moving fixed bed, ie as a moving bed. If by pyrolytic decomposition of
  • Hydrocarbons also produces carbon, this is on the granular Solid deposited.
  • the moving bed preferably moves from the second to the first reaction zone.
  • the granular solid is advantageously circulated.
  • the first reaction zone is preferably supplied with the entire energy required for the thermal hydrocarbon decomposition from the second reaction zone.
  • the resulting synthesis gas at the outlet of the reactor preferably contains hydrogen and carbon monoxide. However, it can not be implemented
  • Gas components in particular carbon dioxide or water formed be included.
  • the necessary purification procedures depend on the later use of the synthesis gas and are known to the person skilled in the art.
  • the effective use of heat also takes place in that at the upper end of the reactor, in a second heat exchange zone, cold granular solid entering the reactor is heated and the outgoing gas stream is cooled. At the lower end of the reactor, in a first heat exchange zone, the granular solid emerging from the reactor is cooled by the incoming gas mixture and this is thus preheated.
  • reaction zones and heat exchange zones are expediently arranged in a reaction chamber designed as a vertical shaft, so that the movement of the moving bed occurs solely under the action of gravity.
  • Operation may be continuous or quasi-continuous. It is conceivable, instead of a traveling fixed bed and a fluidized bed.
  • a moving bed differs from a fluidized bed by the preferred direction of movement or by the flow rate of the particles and the particle size. In a moving bed, the particles are in direct contact with each other, whereas in a fluidized bed, the particles should as far as possible not come into contact with each other.
  • the granular solid has almost at reactor inlet and outlet
  • the gas leaving the second reaction zone is passed in countercurrent to the moving bed and thereby cooled in direct heat exchange, in particular in a second heat exchange zone.
  • the hydrocarbon-containing coke gas is preferably conducted in countercurrent to the moving bed in the first reaction zone and thereby heated in direct heat exchange, in particular in a first heat exchange zone with this.
  • the gases can be withdrawn from the reaction space at a temperature of between 50 and 500.degree.
  • carbon may form, which deposits on the granular solid of the fixed bed.
  • carbon deposited on the granular solid becomes the first downstream
  • the granular solid acts as a filter, so that in particular resulting hydrogen, but also other gases, largely free of
  • Carbon particles can be withdrawn from the first reaction zone and, for example, in the second reaction zone can be performed. Carbon, which enters the second reaction zone despite the described filter action, reacts with the oxygen present there to form a carbon dioxide which forms a part of the synthesis gas directly or after the reverse water gas shift reaction. The water formed in the first reaction zone reacts with the predominant one
  • the process according to the invention is not negative because the carbon is not the main product.
  • the reaction also produces no impurities but only carbon monoxide and hydrogen, thus forming part of the
  • Product composition of the first reaction zone is fed to water or steam.
  • the hydrocarbonaceous coke gas used is a methane-rich gas, which is produced in particular during operation of a coking plant and uses carbon dioxide-containing converter gas, as occurs in particular during operation of a steelworks. Both gases are often available at identical locations in large quantities.
  • a hydrogen to carbon monoxide ratio in the synthesis gas at the outlet of the reactor between 0.8 and 2.5, the ratio of the amount of gas from the hydrocarbon-containing coke gas to the carbon dioxide-containing
  • Hydrogen to carbon monoxide depends on how the synthesis gas
  • hydrocarbons particularly methane or natural gas, or carbon dioxide may be added to the second reaction zone to adjust a hydrogen to carbon monoxide ratio in the synthesis gas at the exit of the reactor between 0.8 and 2.5, more preferably in the first reaction zone.
  • one or more electrically conductive heating elements may be arranged in a reaction zone in such a way that they enter into thermal connection with the substances to be reacted directly or indirectly.
  • An electrically conductive heating element is either fixed or movable within the reaction zone.
  • the heating element may be part of a moving bed of a granular, electrically conductive solid, which may be, for example, carbon, which is moved through the reaction zone.
  • an electrically conductive heating element is connected to a power source through which electrical current is passed through the heating element.
  • an induction coil is arranged outside the two reaction zones, which supplies a magnetic alternating field as soon as an electrical alternating voltage is applied to it.
  • Heating element which is electrically isolated from the induction coil, is arranged so that eddy currents can be induced in him by the magnetic alternating field, which lead to heating of the heating element due to the ohmic losses.
  • the heating element of a ferromagnetic material, such as an iron-silicon or iron-nickel alloy or ⁇ -metal,
  • magnetization losses contribute to the heating of the
  • Heating element and thus to form a temperature gradient between a heating element and its environment.
  • a granular solid is preferably corundum (Al 2 0 3 ) or quartz glass (Si0 2 ) or mullite (Al 2 0 3 Si0 2 ) or cordierite ((Mg, Fe) 2 (Al 2 Si) [Al 2 Si 4 0 18 ] ) or steatite
  • Hydrocarbon decomposition generated carbon used.
  • a carbon-rich granules which is formed of solid, wholly or predominantly made of carbon grains, which are present in a grain size of 0.5 to 80 mm, but preferably from 1 to 50 mm.
  • such granules may consist entirely or partially of coke breeze, which due to its small grain size is not suitable for use in blast furnaces.
  • the granules of carbon which is generated in the process by thermal hydrocarbon decomposition and recycled.
  • the synthesis gas production according to the invention can be carried out without pressure or under pressure. Preferably, it is carried out at pressures between 10 and 25 bar, more preferably - except for pressure losses - at the highest pressure at which the hydrocarbon-containing coke gas is available for the production of carbon.
  • the advantages of the method according to the invention lie in the fact that the metallurgical gases do not have to be subjected to expensive purification or separation before utilization.
  • the already high H 2 content in the coke gas and the high CO content in the converter gas reduce the required energy input for the
  • Solid can be achieved.
  • Another advantage is the effective use of heat.
  • the energy required for the endothermic reactions is produced directly within the reactor, ie in situ, and passed on between the reaction zones.
  • the incoming gas is heated directly by heat exchange zones and cooled the exiting gas. Due to the direct cooling of the product stream in the second heat exchange zone also side reactions, eg. B. suppresses the Boudouard reaction of two carbon monoxide to carbon and carbon dioxide.
  • the process runs purely thermally and without catalyst.
  • FIG. 1 shows a preferred embodiment of the method according to the invention, in which a reactor is used, through whose reaction space a moving bed is guided out of a granular solid which comprises a first and a second reaction zone and a first and second heat exchange zone. Via line 1 is granular solid, with ambient temperature in the
  • the granular solid is, for example, in the process by the thermal
  • Hydrocarbon decomposition produced carbon.
  • the granular solid is guided under the action of gravity in a moving bed W down.
  • hydrocarbon-containing gas 2 is passed together with a carbon dioxide-containing gas 4 from below into the reaction space R and in countercurrent through the
  • the gases can also be brought together in advance of the reactor and introduced together in a supply line.
  • the first reaction zone Z1 takes place at the onset of gases, a reaction of the carbon dioxide with the hydrogen to carbon monoxide and water via a thermal reverse water-gas shift reaction.
  • the water from this reaction is converted together with the hydrocarbon, in the preferred case methane, in an endothermic thermal decomposition reaction to hydrogen and carbon dioxide.
  • the carbon dioxide can then turn with hydrogen to carbon monoxide be implemented.
  • Both reactions, the reverse water gas shift reaction and the thermal steam reforming, are both sequential and parallel. Together with no or only partially reacted hydrocarbon, the hot hydrogen formed flows into the second one arranged above the first
  • Reaction zone Z2 In the second reaction zone Z2, an oxygen-containing gas 3 is supplied.
  • the hydrogen is burned together with the oxygen, at least partially, and thus provides the required for the production of synthesis gas
  • the heat of reaction can also be introduced via electrical current into the second reaction zone Z2.
  • the water formed in the hydrogen combustion is at least partially transferred together into the first reaction zone and can be reacted there. Not completely reacted products of the first reaction zone Z1 can in the second
  • Reaction zone Z2 be further implemented. From the second reaction zone Z2, the synthesis gas 5 is removed, which is cooled in countercurrent to the moving bed W, in a second heat exchange zone WT2.
  • the synthesis gas 5 has at the upper end of the reactor K, the outlet of the reactor, a temperature between 50 and 500 ° C.
  • granular solid is removed via a discharge line 6 at a temperature close to the ambient temperature, or at least between 50 and 300 ° C., and fed to a treatment device A in which this is removed, for example by removing the deposited carbon or by comminuting, Sifting and classifying is processed to be recycled as recycled solid 7 back into the reaction space R.
  • hydrocarbon-containing gas 2 at the lower end of the reactor in the moving bed, so that first takes place a partial pyrolytic decomposition of the hydrocarbon, in particular the methane to carbon and hydrogen.
  • the carbon accumulates on the fixed bed, so the amount of circulating granular fixed bed can be kept constant. Only shortly before entering the first reaction zone Z1, separated from the addition point of the hydrocarbon-containing gas 2, the

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Procédé de production de gaz de synthèse (5), un gaz de cokéfaction (2) contenant de l'hydrocarbure et un gaz de convertisseur (4) contenant du dioxyde de carbone étant introduits dans une première zone réactionnelle (Z1) et de l'hydrogène, contenu dans le gaz de cokéfaction (2) contenant de l'hydrocarbure, étant converti au moins partiellement avec du dioxyde de carbone en eau et l'eau avec l'hydrocarbure thermiquement en gaz de synthèse contenant du monoxyde de carbone et de l'hydrogène. Par ailleurs, un gaz (3) contenant de l'oxygène est introduit dans une seconde zone réactionnelle (Z2) , et de l'énergie thermique est produite à partir de celui-ci et d'une partie de l'hydrogène issu de la première zone réactionnelle (Z1), l'énergie thermique produite dans la seconde zone réactionnelle (Z2) alimentant la première zone réactionnelle (Z1).
EP16804694.4A 2015-12-01 2016-11-28 Procédé de production de gaz de synthèse Withdrawn EP3383976A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015015531.8A DE102015015531A1 (de) 2015-12-01 2015-12-01 Verfahren zur Erzeugung von Synthesegas
PCT/EP2016/025155 WO2017092873A1 (fr) 2015-12-01 2016-11-28 Procédé de production de gaz de synthèse

Publications (1)

Publication Number Publication Date
EP3383976A1 true EP3383976A1 (fr) 2018-10-10

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EP16804694.4A Withdrawn EP3383976A1 (fr) 2015-12-01 2016-11-28 Procédé de production de gaz de synthèse

Country Status (5)

Country Link
US (1) US11078077B2 (fr)
EP (1) EP3383976A1 (fr)
CN (1) CN108779404B (fr)
DE (1) DE102015015531A1 (fr)
WO (1) WO2017092873A1 (fr)

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CN108779404A (zh) 2018-11-09

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