EP2640661A1 - Verfahren zur herstellung von synthesegas enthaltend kohlenmonoxid (co) und wasserstoff (h2) - Google Patents
Verfahren zur herstellung von synthesegas enthaltend kohlenmonoxid (co) und wasserstoff (h2)Info
- Publication number
- EP2640661A1 EP2640661A1 EP11793394.5A EP11793394A EP2640661A1 EP 2640661 A1 EP2640661 A1 EP 2640661A1 EP 11793394 A EP11793394 A EP 11793394A EP 2640661 A1 EP2640661 A1 EP 2640661A1
- Authority
- EP
- European Patent Office
- 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.)
- Withdrawn
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
Description
Claims
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) |
PCT/EP2011/071411 WO2012095213A1 (de) | 2011-01-13 | 2011-11-30 | Verfahren zur herstellung von synthesegas enthaltend kohlenmonoxid (co) und wasserstoff (h2) |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2640661A1 true EP2640661A1 (de) | 2013-09-25 |
Family
ID=45217530
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11793394.5A Withdrawn EP2640661A1 (de) | 2011-01-13 | 2011-11-30 | Verfahren zur herstellung von synthesegas enthaltend kohlenmonoxid (co) und wasserstoff (h2) |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2640661A1 (de) |
KR (1) | KR101560266B1 (de) |
DE (1) | DE102011002617A1 (de) |
WO (1) | WO2012095213A1 (de) |
Families Citing this family (9)
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 |
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 |
FR3085370B1 (fr) * | 2018-08-28 | 2020-09-04 | Europlasma | Procede de production d'un gaz de synthese par traitement d'un flux gazeux contenant du co2 et un ou plusieurs hydrocarbures |
KR102195542B1 (ko) * | 2018-11-22 | 2020-12-30 | 한국에너지기술연구원 | 바이오가스 전환용 전기장 부과 촉매반응 시스템 |
BR102018074753B1 (pt) * | 2018-11-29 | 2023-11-21 | Universidade Federal Do Espiríto Santo - Ufes | Processo e reator a plasma para produção de gás de síntese |
WO2020223789A1 (en) * | 2019-05-09 | 2020-11-12 | Pyrogenesis Canada Inc. | Production of syngas using recycled co2 via combined dry and steam reforming of methane |
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 |
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 |
CH720593A1 (de) * | 2023-03-08 | 2024-09-13 | Microwave Solutions Gmbh | Dissoziationsverfahren und system zur dissoziation von kohlendioxid und/oder methan |
Family Cites Families (17)
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 |
US6187226B1 (en) * | 1995-03-14 | 2001-02-13 | Bechtel Bwxt Idaho, Llc | Thermal device and method for production of carbon monoxide and hydrogen by thermal dissociation of hydrocarbon gases |
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 |
DE10162245A1 (de) * | 2001-12-18 | 2003-07-10 | Siemens Ag | Verfahren zur selektiven Erzeugung reaktiver Teilchen |
DE10162244A1 (de) * | 2001-12-18 | 2003-07-10 | Siemens Ag | Verfahren zur selektiven Erzeugung reaktiver Teilchen |
CA2493279A1 (en) * | 2002-07-23 | 2004-01-29 | Ralf Spitzl | Plasma reactor for carrying out gas reactions and method for the plasma-supported reaction of gases |
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 |
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 |
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 |
US20080296294A1 (en) * | 2007-05-30 | 2008-12-04 | Han Sup Uhm | Pure steam torch by microwaves for reforming of hydrocarbon fuels |
DE102009014728A1 (de) * | 2009-03-25 | 2010-09-30 | Siemens Aktiengesellschaft | Verfahren zum Betreiben eines Fossilbrennstoff-Kraftwerks und Fossilbrennstoff-Kraftwerk mit vermindertem Kohlendioxidausstoß |
-
2011
- 2011-01-13 DE DE102011002617A patent/DE102011002617A1/de not_active Ceased
- 2011-11-30 WO PCT/EP2011/071411 patent/WO2012095213A1/de active Application Filing
- 2011-11-30 KR KR1020137021268A patent/KR101560266B1/ko active IP Right Grant
- 2011-11-30 EP EP11793394.5A patent/EP2640661A1/de not_active Withdrawn
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2012095213A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102011002617A1 (de) | 2012-07-19 |
WO2012095213A1 (de) | 2012-07-19 |
KR20130112940A (ko) | 2013-10-14 |
KR101560266B1 (ko) | 2015-10-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2640661A1 (de) | Verfahren zur herstellung von synthesegas enthaltend kohlenmonoxid (co) und wasserstoff (h2) | |
CN109200969B (zh) | 低温等离子双电场辅助处理含二氧化碳和/或一氧化碳气体合成化合物的方法 | |
DE69731767T2 (de) | Verfahren und vorrichtungen zur herstellung von wasserstoff durch plasmareforming | |
DE19739181A1 (de) | Entladungsreaktor und Verwendung desselben | |
EP2720788B1 (de) | Verfahren zur modifizierung eines methanhaltigen gasvolumenstroms | |
DE112013004853T5 (de) | Wasserstofferzeugungsvorrichtung und Brennstoffzellensystem mit Wasserstofferzeugungsvorrichtung | |
CN104071747A (zh) | 一种等离子体甲烷重整制备合成气的方法 | |
EP2834208A1 (de) | Verfahren und vorrichtung zur plasmatechnischen herstellung von acetylen | |
EP2915869A1 (de) | Flugstromvergaser mit integriertem Mitteltemperaturplasma | |
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 | |
EP3526315B1 (de) | Verfahren zur herstellung von methan | |
EP1456119B1 (de) | Verfahren und vorrichtung zur umwandlung eines brennstoffes | |
EP3898505B1 (de) | Verfahren zur kohlenwasserstoffpyrolyse mit räumlich getrennter beheizungs- und reaktionszone innerhalb des reaktorraums | |
WO2021094464A1 (de) | Verfahren und vorrichtung zur herstellung von wasserstoff und pyrolysekohlenstoff aus kohlenwasserstoffen | |
DE202022002211U1 (de) | Metall- & kohlenstoffbasierte katalytische Vorrichtung zur Durchführung von Methanpyrolyse | |
Deutschmann | High temperature catalysis: efficient way for chemical conversion of logistic fuels | |
DE10163474A1 (de) | Verfahren und Vorrichtung zur Behandlung und/oder Reformierung von gasförmigen Brennstoffen und zugehörige Anwendung | |
WO2021078517A1 (de) | Herstellung eines synthesegases umfassend kohlenmonoxid und wasserstoff | |
EP1456118B1 (de) | Verfahren und vorrichtung zur umwandlung eines brennstoffes | |
EP3143102A1 (de) | Verfahren und vorrichtung zur herstellung von synthetischen kohlenwasserstoffen | |
EP3898504B1 (de) | Verfahren zur herstellung von wasserstoff, kohlenmonoxid und einem kohlenstoffhaltigen produkt | |
WO2024133866A1 (de) | Verfahren zur verwertung von kohlenwasserstoff-haltigen produkten durch plasmaunterstützte pyrolyse unter erzeugung von wasserstoff und festem kohlenstoff | |
CH720593A1 (de) | Dissoziationsverfahren und system zur dissoziation von kohlendioxid und/oder methan | |
WO2023025759A1 (de) | Ammoniaksynthese mit co2-neutralem wasserstoff | |
EP4454747A1 (de) | Vorrichtung und verfahren zur plasma-induzierten zersetzung von alkanen, insbesondere von methan, in kohlenstoff und wasserstoff |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20130618 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20160119 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SIEMENS AKTIENGESELLSCHAFT |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20190716 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20191127 |