[go: up one dir, main page]

WO2012095213A1 - Procédé de production de gaz de synthèse contenant du monoxyde de carbone (co) et de l'hydrogène (h2) - Google Patents

Procédé de production de gaz de synthèse contenant du monoxyde de carbone (co) et de l'hydrogène (h2) Download PDF

Info

Publication number
WO2012095213A1
WO2012095213A1 PCT/EP2011/071411 EP2011071411W WO2012095213A1 WO 2012095213 A1 WO2012095213 A1 WO 2012095213A1 EP 2011071411 W EP2011071411 W EP 2011071411W WO 2012095213 A1 WO2012095213 A1 WO 2012095213A1
Authority
WO
WIPO (PCT)
Prior art keywords
plasma
carbon dioxide
reaction
reaction chamber
synthesis gas
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.)
Ceased
Application number
PCT/EP2011/071411
Other languages
German (de)
English (en)
Inventor
Thomas Hammer
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Priority to EP11793394.5A priority Critical patent/EP2640661A1/fr
Priority to KR1020137021268A priority patent/KR101560266B1/ko
Publication of WO2012095213A1 publication Critical patent/WO2012095213A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C01B3/342—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 with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations
    • 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
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • 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
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • 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
    • 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
    • B01J2219/0004—Processes in series
    • 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
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0875—Gas
    • 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
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894—Processes carried out in the presence of a plasma
    • 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
    • C01B2203/0205—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
    • C01B2203/0222—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic carbon dioxide 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
    • C01B2203/0205—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
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a 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
    • C01B2203/0205—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
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide 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
    • C01B2203/06—Integration with other chemical 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • 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
    • C01B2203/0861—Methods of heating the process for making hydrogen or synthesis gas by plasma
    • 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
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C01B2203/0894—Generation of steam
    • 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
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • 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
    • 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
    • Y02P20/141—Feedstock

Definitions

  • the invention relates to a process for the production of synthesis gas containing carbon monoxide (CO) and hydrogen (H 2 ) from carbon dioxide (CO2).
  • synthesis gas ie a hydrogen-containing gas mixture, in particular a gas mixture of carbon monoxide and hydrogen, or for the production of fuels.
  • synthesis gas ie a hydrogen-containing gas mixture, in particular a gas mixture of carbon monoxide and hydrogen
  • the problem arises that the catalysts used do not show sufficient service life. This is based on the one hand by thermodynamic phenomena, on the other hand by material properties of the catalyst materials used. For example, takes place at temperatures below 400 Christstem ⁇ ° C no chemical conversion.
  • the invention is therefore the problem of providing an improved process for the production of synthesis gas starting from carbon dioxide.
  • the problem is solved according to the invention by a method of the initially mentioned type, which is characterized in that the carbon dioxide flows through a plasma, wherein a decomposition of the carbon dioxide is carried out in decomposition products, after which the decomposition products flow through a kohlenwasserstoff term gas, wherein by reaction of the Zertechnischeproduk te with the gaseous hydrocarbon synthesis gas Herge ⁇ provides.
  • the inventive method provides a two-stage Pro ⁇ process sequence for the preparation of synthesis gas, that is, in front of a gas mixture of carbon monoxide and hydrogen, wherein the used in a first step, preferably gaseous carbon dioxide, which may be in pure form or as part of a Gasge ⁇ premixture, by a plasma generated by a plasma generating device flows, through which plasma it is advantageously decomposed completely into decomposition products.
  • a first step preferably gaseous carbon dioxide, which may be in pure form or as part of a Gasge ⁇ premixture
  • a plasma generated by a plasma generating device flows, through which plasma it is advantageously decomposed completely into decomposition products.
  • temperatures of several thousand degrees Celsius are reached.
  • the decomposition products among which, for example, elemental carbon or oxygen, carbon or Sauerstoffra ⁇ cals but also various molecular fragments fall will supplied in a second step, a hydrocarbon-containing gas and flow through this, wherein a mixing of the decomposition products with the gaseous hydrocarbon he follows.
  • a hydrocarbon-containing gas and flow through this, wherein a mixing of the decomposition products with the gaseous hydrocarbon he follows.
  • the use of pure gaseous hydrocarbon is preferred here. Due to the high temperature of the gaseous decomposition products, an endothermic reaction with the hydrocarbon takes place during the mixing to syn ⁇ thesegas.
  • the Vermischdauer is relatively short, that is, the mixing preferably takes place within we ⁇ few milliseconds.
  • the invention proposes a thermodynamically favored process route for the production of synthesis gas, which leads to fast, efficient chemical conversions.
  • the übli ⁇ ch ensure used heating a gas mixture of carbon ⁇ hydrogen and carbon dioxide is prevented by high mixing and reaction rates of decomposition products of carbon dioxide to the hydrocarbon in which the temperature range of the thermodynamically favored formation of soot would inevitably go through.
  • the carbon dioxide and / or the decomposition products flow or flow at a flow rate of 10 to 100 m / s.
  • such high flow velocities shorten the residence time of the carbon dioxide in the plasma , so that no thermodynamic equilibrium of the decomposition reaction (s) of the carbon dioxide can be established here.
  • a higher proportion of the electrical energy of the Plas ⁇ mas is used for the decomposition of carbon dioxide molecules ⁇ re spective be obtained concerning the second process step, high mixing rates of the decomposition products with the gaseous hydrocarbon.
  • the Ausbeu ⁇ te of synthesis gas and thus the efficiency of the method according ⁇ invention is increased as a whole or
  • the required technical ⁇ th products carbon monoxide and hydrogen with high Selekti ⁇ tivity can be generated.
  • the flow rates may also be higher or lower.
  • an apparatus for producing plasmas which in the operating gas has an amplitude of the reduced electrical energy, can be used to generate the plasma.
  • see field strength in the range of about 100 V / mm bar to about 10 kV / mm bar provides.
  • reduced electric fields generate high-energy electrons in the plasma, which promote or accelerate the decomposition of the carbon dioxide.
  • the plasma is not completely thermalized, so it is not in a thermodynamic equilibrium. At atmospheric pressure and an operating voltage of 10 kV, this means that the electrodes used for plasma generation can have distances of 1 mm to 100 mm. At higher pressures, either higher operating voltages or shorter electrode distances are required.
  • the plasma generation is not limited to this range of design parameters and operating conditions.
  • the mixing of the decomposition products is carried out with the hydrocarbon-containing gas so that the temperature of the synthesis gas produced is less than or equal to 1100 ° C, in particular ⁇ sondere between 700 and 1000 ° C. Consequently, the tem ⁇ temperature of the synthesis gas is after completion of the process in the Be ⁇ rich to 1000 ° C or below.
  • the process should advantageously be operated so that this criterion is Lucashal ⁇ th, which is due equally with thermodynamically favored equilibrium conditions.
  • AC voltage in particular low-frequency AC voltage, or pulsperiodische voltage
  • pulsed voltage has the advantage that a thermalization, that is, the setting of a thermodynamic equilibrium is suppressed, however, is this requires an increased effort to provide the electrical energy necessary.
  • the electrodes may be in direct contact with the plasma, in which case graphite electrodes are preferred.
  • electrodes for generating plasma can not be used in direct contact with the flowing carbon dioxide and pulse-periodic voltage, in particular high-frequency pulsperiodische voltage, AC voltage, in particular high-frequency AC voltage, or electromagnetic Wel ⁇ len, especially microwaves.
  • pulse-periodic voltage in particular high-frequency pulsperiodische voltage
  • AC voltage in particular high-frequency AC voltage
  • electromagnetic Wel ⁇ len especially microwaves.
  • the resulting process thermal energy can be used ⁇ tech nically, wherein the generated steam, that is, in particular, the water vapor produced, more preferably the decomposition products of carbon dioxide and / or hydrocarbon-containing gas is supplied.
  • the unwanted formation of soot during the cooling of the synthesis gas can be thermodynamically suppressed and the chemical equilibrium of the products shifted in the direction of the hydrogen.
  • the synthesis gas to a post-reaction catalyst in particular based on nickel (Ni) or zir ⁇ konium (Zr), is supplied. So while the herstel ⁇ regulatory procedure incompletely reacted materials catalytically supported given the opportunity to synthesis gas to react.
  • the catalyst may, for. B. in the form of a solid, for example with a honeycomb or in powder form.
  • nickel or zirconium catalysts the use of other catalyst materials is conceivable.
  • the synthesis gas a Synthesere ⁇ action, particularly the methanol or dimethyl ether synthesis.
  • the thermal energy of the synthesis gas produced is used for subsequent processes, thus the process heat is used efficiently.
  • the subsequent dimethyl ether synthesis it is possible to improve the customary catalytic preparation process consisting essentially of elimination of water from methanol to dimethyl ether, since the customarily necessary use of hydrogen is reduced.
  • the efficiency of the dimethyl ether synthesis can slide che cakes ⁇ be increased.
  • the invention relates to an apparatus for producing synthesis gas containing carbon monoxide and hydrogen from carbon dioxide, which is designed for carrying out the method described.
  • the apparatus comprises at least a first reaction chamber, comprising at least a pre ⁇ device for generating plasma for decomposing the supplied via at least one supply line into the first reaction chamber, flowing through this carbon dioxide into decomposition products, and at least one of the first Conceptskam ⁇ mer via at least one line downstream or directly connected to the first reaction chamber second reaction ⁇ chamber containing via a feed line containing hydrocarbon-containing gas or is flowed through by this, wherein in flowing through the decomposition products produced by the gaseous hydrocarbon by reaction of the decomposition ⁇ products with the gaseous hydrocarbon synthesis gas and is discharged via a discharge line, on.
  • the two-stage production process according to the invention for the synthesis of synthesis gas can be carried out using the process according to the invention.
  • SEN device are designed such that the decomposition of supplied carbon dioxide in the or the first reaction chamber (s) via the in this or these plasma generated is carried out, and the subsequent mixing of the Zerlegungspro ⁇ products of the carbon dioxide with the hydrocarbon-containing gas in the or the second reaction chamber (s) takes place.
  • All reaction chambers are equipped with suitable supply and discharge lines, so that the gaseous substances used for the production process according to the invention can flow between them. It is equally conceivable that one or more second reaction chamber (s) are directly connected to one or more first reaction chamber (s) or are in direct contact with them.
  • the inventive device comprises at least two separate, in particular parallel Before ⁇ directional units for synthesis gas production, which in each case has at least a first and to form at least comprise a second reaction ⁇ chamber, individually or in groups at respective device units at a plurality ,
  • the device for generating plasma has a plurality of plasma sources.
  • the mixing of the decomposition products can be improved with the gaseous Kohlenwas ⁇ serstoff, which is particularly characterized grounded be ⁇ that is obtained by the use of several small plasma sources for the separation of carbon dioxide greater Ver ⁇ ratio of contact surface area to volume.
  • the plasma sources can be electrically excited differently.
  • the reduced electric field strength of the plasma sources is preferably in the range of about 100 V / mm bar to about 10 kV / mm bar.
  • the at least one line between the first and the second reaction chamber and / or the second reaction chamber at least one opening for coupling of steam, in particular water vapor on.
  • the soot formation can be achieved by feeding small amounts of water vapor during the cooling of Synthesis gas thermodynamically suppressed and continue to move the product range in favor of hydrogen.
  • the second reaction chamber may be followed by a catalyst, in particular based on nickel (Ni) or zirconium (Zr), for the after-reaction of the synthesis gas. Accordingly, it is possible to catalytically convert materials or compounds that are not completely converted to synthesis gas into synthesis gas, thereby increasing the efficiency of syngas production.
  • a catalyst in particular based on nickel (Ni) or zirconium (Zr), for the after-reaction of the synthesis gas. Accordingly, it is possible to catalytically convert materials or compounds that are not completely converted to synthesis gas into synthesis gas, thereby increasing the efficiency of syngas production.
  • the second reaction chamber optionally downstream of the catalyst or the second reaction chamber, a further reaction chamber for carrying out a synthesis reaction, in particular the methanol or dimethyl ether synthesis, is connected downstream. So the thermal energy of the synthesis gas for Vietnamese ⁇ processes can be efficiently utilized.
  • FIG. 1 shows a device for carrying out the method according to the invention according to a first embodiment
  • FIG. 2 shows a device for carrying out the method according to the invention according to a second embodiment
  • FIG. 3 shows a device for carrying out the method according to the invention according to a third embodiment
  • FIG. 4 shows a device for carrying out the method according to the invention in accordance with a fourth embodiment
  • 5 shows a device for carrying out the method according to the invention in accordance with a fifth embodiment
  • 6 shows a device for carrying out the method according to the invention in accordance with a sixth embodiment
  • FIG. 7 shows a part of an apparatus for carrying out the method according to the invention in accordance with a seventh embodiment
  • Fig. 8 shows a device for performing the method according to the invention according to an eighth execution ⁇ form.
  • Fig. 1 shows a device 1 for performing the method according to the invention for producing synthesis gas showing containing carbon monoxide (CO) and hydrogen (H 2) from Kohlendi ⁇ oxide (CO 2) according to a first disclosed embodiment.
  • the Vorrich ⁇ device 1 essentially comprises a first and a second re ⁇ action chamber 2, 3, which are connected to each other via a line. 4 Furthermore, the reaction chambers 2, 3 own supply lines 5, 6 and the second reaction chamber 3, a discharge line 7 assigned.
  • the first reaction chamber 2 comprises at least one Vorrich ⁇ device for generating plasma 8, which is advantageous as shown in Fig. 7, a plurality of plasma sources 8 'has.
  • the plasma sources 8, 8 ' are connected by electrical energy supply lines 17 to electrical power supplies 16.
  • the first reaction chamber 2 is used for the decomposition of the supplied via the supply line 5, through the first reaction chamber 2 at a flow rate of, for example, about 50 m / s flowing carbon dioxide in decomposition products. This takes place at temperatures of a few 1000 ° C.
  • the device for generating plasma 8 is z. B. operated with a reduced electric field strength of 1 kV / mm bar, taking care that the generated plasma is not fully thermalized, that is, is not in a thermodynamic equilibrium state. To generate the plasma, it is preferable to use high-frequency alternating voltage in the used diofrequency range, since so no contact of electrodes of the apparatus for generating plasma 8 with the plasma and further no use of shielding gases is necessary.
  • the use of a surface acoustic wave plasma is advantageous at the desired high flow rates.
  • the plasma power is focused in a small volume through which the carbon dioxide with which he ⁇ mentioned high flow rate flows.
  • the residence time in the zone of electrical energy dissipation is so short that the setting of a thermodynamic equilibrium is prevented or a high proportion of the electrical energy is used to decompose the carbon dioxide.
  • the decomposition products flow via the line 4 into the second reaction chamber 3, in which a thorough mixing with the gaseous hydrocarbon fed via the line 6 and, subsequently, a conversion to synthesis gas, wel ⁇ ches as the final product at a temperature of about 800 to 900 ° C. is discharged via the line 7 from the second reaction chamber 3.
  • a thorough mixing with the gaseous hydrocarbon fed via the line 6 and, subsequently, a conversion to synthesis gas, wel ⁇ ches as the final product at a temperature of about 800 to 900 ° C. is discharged via the line 7 from the second reaction chamber 3.
  • too high Strömungsgeschwindigkei ⁇ th both the decomposition products as well as of the gaseous hydrocarbon are advantageous because such high speeds Mi ⁇ research result.
  • the mixing time is, for example, only a few milliseconds.
  • the line 4 is kept short to avoid unnecessary heat losses and Nachreaktio ⁇ NEN during the transfer of the decomposition products of the carbon dioxide
  • the second reaction chamber 3 for reforming can be associated with a plurality of first reaction chambers 2 with corresponding devices for generating plasma 8 or plasma reactors. This will achieved the desired large contact area between plasma gas and hydrocarbon.
  • the inventive method is a thermodynamically favored process route, which leads to fast, efficien ⁇ th chemical conversions of the substances used to synthesis gas. It is characterized by in essentially two
  • Steps split process avoided heating the Gasge ⁇ mixture of carbon dioxide and hydrocarbon, so that the temperature range of the thermodynamically preferred
  • FIG. 3 shows a device 1 for carrying out the method according to the invention according to a third embodiment.
  • the essential difference from the embodiment according to FIGS. 1 and 2 is that the second reaction chamber 3 is connected via an additional supply line 9 from a heat exchanger 10 steam is supplied, whereby the soot formation thermodynamically suppressed during the cooling of the synthesis gas and the product spectrum of the synthesized synthesis gas is shifted in favor of the hydrogen.
  • the heat exchanger 10 can advantageously be operated via the process heat produced in the method according to the invention.
  • Fig. 4 shows a variant, wherein the water vapor is not blown into the second reaction chamber 3, but in the two reaction chambers 2, 3 connecting line 4, whereby a premixing of the decomposition products with the steam is possible.
  • 5 shows a device 1 for carrying out the method according to the invention according to a fifth embodiment.
  • the second reaction chamber 3 is followed by a catalytic converter 11, which does not completely complete the after-reaction converted substances is used to achieve such a full imple ⁇ tion of the materials used.
  • the catalyst 11 may be formed, for example, as a solid-state catalyst based on a perovskite structure with zirconium as the active element.
  • Fig. 6 shows based on the imple mentation form shown in FIG. 5, the possibility of the synthesis gas after passing through the catalyst ⁇ sators 11 a follow-up process, that is z.
  • the catalyst 11 is connected to the reaction chamber 12 via the line 13.
  • the hydrogen can ⁇ example, be generated via electrolysis processes.
  • FIG. 8 shows a further possibility of scaling the method according to the invention.
  • a large second reaction chamber 3 for the reforming to assign a plurality of first reaction chambers 2 for the plasma decomposition of carbon dioxide here are several units of the device 1, 1 ' , each consisting of first and second reaction chambers 2, 3 and optionally catalysts 11 and catalytic reactors connected in parallel. This ensures that the contact surface between the Decomposition products of the carbon dioxide-containing plasma gas and the hydrocarbon grows with the plant size.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

L'invention concerne un procédé de production de gaz de synthèse contenant du monoxyde de carbone (CO) et de l'hydrogène (H2) sur la base de dioxyde de carbone (CO2), le dioxyde de carbone (CO2) s'écoulant à travers un plasma, une décomposition du dioxyde de carbone (CO2) en produits de décomposition ayant lieu, après quoi les produits de décomposition s'écoulent à travers un gaz contenant des hydrocarbures, le gaz de synthèse étant produit par la réaction des produits de décomposition avec l'hydrocarbure gazeux.
PCT/EP2011/071411 2011-01-13 2011-11-30 Procédé de production de gaz de synthèse contenant du monoxyde de carbone (co) et de l'hydrogène (h2) Ceased WO2012095213A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP11793394.5A EP2640661A1 (fr) 2011-01-13 2011-11-30 Procédé de production de gaz de synthèse contenant du monoxyde de carbone (co) et de l'hydrogène (h2)
KR1020137021268A KR101560266B1 (ko) 2011-01-13 2011-11-30 일산화탄소(co) 및 수소(h2)를 함유하는 합성 가스를 생산하는 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011002617A DE102011002617A1 (de) 2011-01-13 2011-01-13 Verfahren zur Herstellung von Synthesegas enthaltend Kohlenmonoxid (CO) und Wasserstoff (H2)
DE102011002617.7 2011-01-13

Publications (1)

Publication Number Publication Date
WO2012095213A1 true WO2012095213A1 (fr) 2012-07-19

Family

ID=45217530

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/071411 Ceased WO2012095213A1 (fr) 2011-01-13 2011-11-30 Procédé de production de gaz de synthèse contenant du monoxyde de carbone (co) et de l'hydrogène (h2)

Country Status (4)

Country Link
EP (1) EP2640661A1 (fr)
KR (1) KR101560266B1 (fr)
DE (1) DE102011002617A1 (fr)
WO (1) WO2012095213A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101401423B1 (ko) 2013-08-16 2014-06-02 한국에너지기술연구원 마이크로웨이브 플라즈마­촉매 하이브리드 공정을 이용한 이산화탄소로부터 가연성 합성가스 제조 장치 및 방법
WO2020043985A1 (fr) * 2018-08-28 2020-03-05 Europlasma Procédé de production d'un gaz de synthèse par traitement d'un flux gazeux contenant du co2 et un ou plusieurs hydrocarbures
WO2020107090A1 (fr) * 2018-11-29 2020-06-04 Petróleo Brasileiro S.A. - Petrobras Procédé et réacteur à plasma pour la production d'un gaz de synthèse
CN113233416A (zh) * 2021-05-13 2021-08-10 内蒙古工业大学 一种制备富氢合成气的方法
EP3966160A4 (fr) * 2019-05-09 2023-07-05 Pyrogenesis Canada Inc. <sup2/>? <sub2/>?2?production de gaz de synthèse à l'aide de corecyclé par reformage combiné à la vapeur et à sec de méthane
WO2024184026A1 (fr) * 2023-03-08 2024-09-12 Microwave Solutions Gmbh Procédé et système de dissociation pour dissocier du dioxyde de carbone et/ou du méthane

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109187730B (zh) * 2018-08-27 2020-10-20 河南大学 一种基于摩擦纳米发电机气体放电的自驱动co2传感器
KR102195542B1 (ko) * 2018-11-22 2020-12-30 한국에너지기술연구원 바이오가스 전환용 전기장 부과 촉매반응 시스템
KR102372537B1 (ko) * 2021-10-26 2022-03-08 순천대학교 산학협력단 액상 플라즈마 반응을 이용하여 탄화수소로부터 수소 및 나노탄소를 동시에 생성시키는 장치 그리고 이를 이용한 수소 및 나노탄소를 동시에 생성시키는 방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000073247A1 (fr) * 1999-05-27 2000-12-07 Bechtel Bwxt Idaho, Llc Dispositif thermique et procede de production de monoxyde de carbone et d'hydrogene par dissociation tthermique de gaz d'hydrocarbures
WO2003051767A2 (fr) * 2001-12-18 2003-06-26 Siemens Aktiengesellschaft Procede et dispositif de transformation d'un combustible
FR2873306A1 (fr) * 2004-07-26 2006-01-27 Physiques Sarl Et Chimiques Generateur electrique et son application a l'oxydation totale ou partielle de carburants
US20080296294A1 (en) * 2007-05-30 2008-12-04 Han Sup Uhm Pure steam torch by microwaves for reforming of hydrocarbon fuels
WO2010108936A1 (fr) * 2009-03-25 2010-09-30 Siemens Aktiengesellschaft Procédé d'exploitation d'une centrale électrique à combustibles fossiles et centrale électrique à combustibles fossiles avec réduction des émissions de dioxyde de carbone

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL169299C (nl) * 1976-12-15 1982-07-01 Energiagazdalkodasi Intezet Werkwijze en inrichting voor het oxyderen van een koolwaterstoffen bevattend gas.
AT384007B (de) * 1984-04-02 1987-09-25 Voest Alpine Ag Verfahren zur herstellung von synthesegasen sowie vorrichtung zur durchfuehrung des verfahrens
DD244076A1 (de) * 1985-12-23 1987-03-25 Tech Hochschule C Schorlemmer Plasmachemischer reaktor fuer disperse materialien
FR2758317B1 (fr) * 1997-01-13 1999-09-17 Piotr Czernichowski Conversion d'hydrocarbures assistee par les arcs electriques glissants en presence de la vapeur d'eau et/ou de gaz carbonique
FR2768424B1 (fr) * 1997-09-01 1999-10-29 Albin Czernichowski Assistance electrique d'oxydation partielle d'hydrocarbures legers par l'oxygene
JP3834614B2 (ja) * 2001-10-29 2006-10-18 独立行政法人産業技術総合研究所 低温プラズマによる合成ガスの製造方法
DE10162244A1 (de) * 2001-12-18 2003-07-10 Siemens Ag Verfahren zur selektiven Erzeugung reaktiver Teilchen
DE50303853D1 (de) * 2002-07-23 2006-07-27 Iplas Gmbh Plasmareaktor zur durchführung von gasreaktionen und verfahren zur plasmagestützten umsetzung von gasen
US7381382B2 (en) * 2004-03-29 2008-06-03 Massachusetts Institute Of Technology Wide dynamic range multistage plasmatron reformer system
US20090100752A1 (en) * 2004-06-26 2009-04-23 Sessa John P Device for converting carbonaceous matter into synthesis gas and associated methods
US7595031B2 (en) * 2006-01-12 2009-09-29 Nanoenergy Group (Uk) Plasma reformer with extended volume discharge
JP5120923B2 (ja) 2007-03-30 2013-01-16 島根県 水素および一酸化炭素の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000073247A1 (fr) * 1999-05-27 2000-12-07 Bechtel Bwxt Idaho, Llc Dispositif thermique et procede de production de monoxyde de carbone et d'hydrogene par dissociation tthermique de gaz d'hydrocarbures
WO2003051767A2 (fr) * 2001-12-18 2003-06-26 Siemens Aktiengesellschaft Procede et dispositif de transformation d'un combustible
FR2873306A1 (fr) * 2004-07-26 2006-01-27 Physiques Sarl Et Chimiques Generateur electrique et son application a l'oxydation totale ou partielle de carburants
US20080296294A1 (en) * 2007-05-30 2008-12-04 Han Sup Uhm Pure steam torch by microwaves for reforming of hydrocarbon fuels
WO2010108936A1 (fr) * 2009-03-25 2010-09-30 Siemens Aktiengesellschaft Procédé d'exploitation d'une centrale électrique à combustibles fossiles et centrale électrique à combustibles fossiles avec réduction des émissions de dioxyde de carbone

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101401423B1 (ko) 2013-08-16 2014-06-02 한국에너지기술연구원 마이크로웨이브 플라즈마­촉매 하이브리드 공정을 이용한 이산화탄소로부터 가연성 합성가스 제조 장치 및 방법
WO2020043985A1 (fr) * 2018-08-28 2020-03-05 Europlasma Procédé de production d'un gaz de synthèse par traitement d'un flux gazeux contenant du co2 et un ou plusieurs hydrocarbures
FR3085370A1 (fr) * 2018-08-28 2020-03-06 Europlasma Procede de production d'un gaz de synthese par traitement d'un flux gazeux contenant du co2 et un ou plusieurs hydrocarbures
WO2020107090A1 (fr) * 2018-11-29 2020-06-04 Petróleo Brasileiro S.A. - Petrobras Procédé et réacteur à plasma pour la production d'un gaz de synthèse
GB2595067A (en) * 2018-11-29 2021-11-17 Petroleo Brasileiro Sa Petrobras Process and plasma reactor for the production of synthesis gas
GB2595067B (en) * 2018-11-29 2022-09-07 Petroleo Brasileiro Sa Petrobras Plasma process and reactor for producing synthesis gas
EP3966160A4 (fr) * 2019-05-09 2023-07-05 Pyrogenesis Canada Inc. <sup2/>? <sub2/>?2?production de gaz de synthèse à l'aide de corecyclé par reformage combiné à la vapeur et à sec de méthane
CN113233416A (zh) * 2021-05-13 2021-08-10 内蒙古工业大学 一种制备富氢合成气的方法
CN113233416B (zh) * 2021-05-13 2023-05-12 内蒙古工业大学 一种制备富氢合成气的方法
WO2024184026A1 (fr) * 2023-03-08 2024-09-12 Microwave Solutions Gmbh Procédé et système de dissociation pour dissocier du dioxyde de carbone et/ou du méthane
CH720593A1 (de) * 2023-03-08 2024-09-13 Microwave Solutions Gmbh Dissoziationsverfahren und system zur dissoziation von kohlendioxid und/oder methan

Also Published As

Publication number Publication date
EP2640661A1 (fr) 2013-09-25
KR101560266B1 (ko) 2015-10-14
KR20130112940A (ko) 2013-10-14
DE102011002617A1 (de) 2012-07-19

Similar Documents

Publication Publication Date Title
WO2012095213A1 (fr) Procédé de production de gaz de synthèse contenant du monoxyde de carbone (co) et de l&#39;hydrogène (h2)
Taylan et al. Dissociation of carbon dioxide using a microhollow cathode discharge plasma reactor: effects of applied voltage, flow rate and concentration
DE19739181A1 (de) Entladungsreaktor und Verwendung desselben
EP2720788B1 (fr) Procédé de modification d&#39;un flux gazeux contenant du méthane
DE102007013219A1 (de) Plasmagestützte Synthese
DE102013226126A1 (de) Allotherme Methan-Reformierung mit physikalischer Energierückgewinnung
CN104071747A (zh) 一种等离子体甲烷重整制备合成气的方法
WO2013149723A1 (fr) Procédé et dispositif pour la fabrication d&#39;acétylène par une technique de plasma
CN102993053A (zh) 负电性等离子体辅助的二氧化碳减排加工方法与设备
EP3898505B1 (fr) Procédé de pyrolyse d&#39;hydrocarbures avec zones de chauffage et de réaction spatialement séparées à l&#39;intérieur de la chambre du réacteur
EP4048827B1 (fr) Méthode et dispositif de production d&#39;un gaz de synthèse contenant du monoxyde de carbone et de l&#39;hydrogène
EP1456119B1 (fr) Procede et dispositif de transformation d&#39;un combustible
DE202022002211U1 (de) Metall- &amp; kohlenstoffbasierte katalytische Vorrichtung zur Durchführung von Methanpyrolyse
WO2021094464A1 (fr) Procédé et dispositif de production d&#39;hydrogène et de carbone pyrolytique à partir d&#39;hydrocarbures
Lim et al. Carbon dioxide destruction with methane reforming by a novel plasma-catalytic converter
EP3898504A2 (fr) Procédé et dispositif de fabrication d&#39;hydrogène, de monoxyde de carbone et d&#39;un produit contenant du carbone
DE10163474A1 (de) Verfahren und Vorrichtung zur Behandlung und/oder Reformierung von gasförmigen Brennstoffen und zugehörige Anwendung
EP3143102B1 (fr) Procédé et dispositif pour la fabrication d&#39;hydrocarbures synthétiques
EP1456118B1 (fr) Procede et dispositif pour convertir un carburant
WO2024133866A1 (fr) Procédé d&#39;utilisation de produits contenant des hydrocarbures par pyrolyse assistée par plasma avec génération d&#39;hydrogène et de carbone solide
EP4392361B1 (fr) Synthèse d&#39;ammoniac avec de l&#39;hydrogène neutre de co2
CH720593A1 (de) Dissoziationsverfahren und system zur dissoziation von kohlendioxid und/oder methan
Deutschmann High temperature catalysis: efficient way for chemical conversion of logistic fuels
DE102013213528A1 (de) Reformersystem zur Verbrennung von Restgas in einem Dampfreformer
BE1029714B1 (de) Ammoniaksynthese mit CO2-neutralem Wasserstoff

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11793394

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011793394

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137021268

Country of ref document: KR

Kind code of ref document: A