EP4247754A1 - Méthode et dispositif pour générer un gaz de synthèse tout en faisant recirculer du dioxyde de carbone - Google Patents

Méthode et dispositif pour générer un gaz de synthèse tout en faisant recirculer du dioxyde de carbone

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Publication number
EP4247754A1
EP4247754A1 EP21798566.2A EP21798566A EP4247754A1 EP 4247754 A1 EP4247754 A1 EP 4247754A1 EP 21798566 A EP21798566 A EP 21798566A EP 4247754 A1 EP4247754 A1 EP 4247754A1
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
oxygen
gas
stripping
reformer
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.)
Pending
Application number
EP21798566.2A
Other languages
German (de)
English (en)
Inventor
Albrecht Heinzel
Thomas Haselsteiner
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.)
Linde GmbH
Original Assignee
Linde GmbH
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 Linde GmbH filed Critical Linde GmbH
Publication of EP4247754A1 publication Critical patent/EP4247754A1/fr
Pending legal-status Critical Current

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    • 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
    • C01B3/36—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 oxygen or mixtures containing oxygen as gasifying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/265—Drying gases or vapours by refrigeration (condensation)
    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • 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
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/005—Carbon dioxide
    • 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
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • 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
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/103—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkali- or earth-alkali- or NH4 salts or inorganic acids derived from sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/20—Carbon monoxide
    • 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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • 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
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1838—Autothermal gasification by injection of oxygen or steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the invention relates to a method for producing a synthesis gas containing carbon monoxide and hydrogen, in which oxygen is made available at an inlet pressure and is then thermochemically converted in a reformer together with a carbon-containing charge and carbon dioxide by partial oxidation or autothermal reforming to form a crude synthesis gas containing carbon dioxide, which is used for Obtaining the synthesis gas is subjected to a gas scrubbing in which a carbon dioxide-laden scrubbing agent is obtained, from which carbon dioxide is separated for recycling into the reformer.
  • the invention relates to a device for carrying out the method according to the invention.
  • pressure level is used below to characterize pressures, which is intended to express the fact that pressures do not have to be used in the form of exact pressure values in order to implement an inventive concept. However, such pressures typically vary within certain ranges, for example ⁇ 1%, 5%, 10%, 20% or even 50% around a mean value. Different pressure levels can be in disjunctive areas or in areas that overlap. In particular, pressure levels include unavoidable or to be expected pressure losses that occur, for example, due to flow effects. The pressure levels given in bar are absolute pressures.
  • a carbonaceous starting material which is natural gas, for example, is processed into a carbonaceous feedstock by desulfurization, heating and compression, and then thermochemically in a reformer with the supply of oxygen, carbon dioxide and possibly water at a pressure of between 5 and 80 bar converted to a crude synthesis gas.
  • the synthesis gas produced in this way which in addition to carbon monoxide and Hydrogen also contains large amounts of carbon dioxide and water as well as other substances that are undesirable in the synthesis gas, is then subjected to a number of separation steps in order to obtain the synthesis gas, which largely consists of hydrogen and carbon monoxide, in the required composition.
  • Carbon dioxide separated from the crude synthesis gas is returned to the reformer, where it is combined with hydrogen
  • CO 2 + H 2 — ⁇ CO + H 2 O reacts to form carbon monoxide and water or with elementary carbon (e.g. soot) according to CO2 + C 2CO to form carbon monoxide, so that the proportion of carbon monoxide in the crude synthesis gas increases and carbon dioxide is released into the atmosphere reduced.
  • elementary carbon e.g. soot
  • the raw synthesis gas is usually cooled to remove water before it is brought into contact with a scrubber in a scrubber absorber column, which is capable of absorbing carbon dioxide at a first pressure much more efficiently than hydrogen and carbon monoxide.
  • the absorbed substances are separated from the loaded scrubbing agent in the regeneration section of the gas scrubber in order to obtain a regenerated scrubbing agent for reuse in the absorber.
  • the loaded detergent is expanded to a second pressure in a desorber, with part of the absorbed carbon dioxide being released into the gas phase.
  • a gas atmosphere is also generated by the partial evaporation of the loaded detergent, which acts as a stripping gas due to its low carbon dioxide partial pressure.
  • the carbon dioxide separated from the loaded detergent in this way is obtained at a pressure level that is well below the pressure at which the thermochemical conversion takes place.
  • the patent application CA2634302A1 proposes, in addition to scrubbing vapor, to use at least part of the natural gas used to generate synthesis gas as stripping gas, which is available at a pressure higher than that at which carbon dioxide can be obtained from the loaded scrubbing agent simply by expansion and stripping with scrubbing agent vapor.
  • the loaded scrubbing agent cannot be completely freed from carbon dioxide because of the carbon dioxide usually already contained in the natural gas. which is why, regardless of the amount of natural gas available for stripping, it is always necessary to expand the scrubbing agent so that part of the carbon dioxide is at a pressure level that is significantly lower than that of the natural gas and can therefore only be returned with a significantly greater energy input than the remaining carbon dioxide.
  • the object of the present invention is therefore to provide a method of the generic type and a device for carrying it out, by means of which the carbon dioxide contained in the loaded detergent can be supplied to the thermochemical conversion with less energy than is possible according to the prior art.
  • this object is achieved according to the invention in that at least part of the oxygen provided is used as stripping gas upstream of the reformer during the separation of carbon dioxide from the scrubbing agent laden with carbon dioxide.
  • the inlet pressure of the oxygen intended for use in the thermochemical conversion is usually higher than the pressure at which carbon dioxide can be obtained from the loaded detergent simply by expansion and stripping with detergent vapor. Since the carbon dioxide separated from the loaded scrubbing agent during stripping can be recovered using the oxygen pressure, it is possible to save on compression work when recycling the carbon dioxide.
  • the stripping according to the invention is preferably carried out at the inlet pressure level of the oxygen made available. If the oxygen is available free of carbon dioxide, as is usually the case, the carbon dioxide content of the detergent can also be reduced by the stripping according to the invention to the lowest value required for regeneration without partially evaporating the loaded detergent or below the input pressure level of the available having to relax oxygen.
  • the stripping of the loaded detergent is preferably carried out in a first desorber designed as a stripping column, from the bottom of which at least substantially carbon dioxide-free detergent is collected.
  • the oxygen enriched with carbon dioxide during stripping is drawn off from the top of the first desorber, possibly compressed and fed to the reformer.
  • detergent vapor can be used, which is expediently generated by evaporating part of the bottom fraction. Since detergent vapor is discharged from the first desorber with the top fraction in this process variant, it makes sense to cool the top fraction in order to condense out detergent and return it to the first desorber.
  • the synthesis gas is to be obtained at a very low pressure level and the raw synthesis gas is scrubbed at a pressure that is lower than the inlet pressure of the oxygen, it may be useful to reduce the pressure of the scrubbing agent loaded during the gas scrubbing before the stripping according to the invention Oxygen to the input pressure level of the oxygen made available or - to raise to the pressure level at which the thermochemical conversion is carried out - if this is lower.
  • the treated detergent can become enriched with oxygen.
  • the nitrogen enriched with oxygen and possibly carbon dioxide is preferably discarded.
  • a further embodiment of the method according to the invention provides that the temperature of the oxygen is adjusted to a defined value before it is used as stripping gas.
  • the temperature of the stripping gas is preferably adjusted to the temperature of the scrubbing agent to be regenerated.
  • the invention provides for the oxygen provided as stripping gas to be heated or cooled against one or more process streams to be cooled.
  • the method according to the invention can be used with particular preference when the gas scrubbing is operated with an inorganic and non-flammable scrubbing agent.
  • An example of such a wash is the potash wash, in which an aqueous potassium carbonate solution, which can be enriched with catalysts, is used as the washing agent.
  • the invention relates to a device for generating a carbon monoxide and hydrogen-containing synthesis gas, with a reformer, a gas washing device connected to the reformer with an absorber and a regeneration part, and feed lines via which a carbon-containing charge, oxygen and carbon dioxide can be introduced into the reformer.
  • a reformer a gas washing device connected to the reformer with an absorber and a regeneration part, and feed lines via which a carbon-containing charge, oxygen and carbon dioxide can be introduced into the reformer.
  • a gas washing device connected to the reformer with an absorber and a regeneration part, and feed lines via which a carbon-containing charge, oxygen and carbon dioxide can be introduced into the reformer.
  • the stated object is achieved according to the invention in that the regeneration part of the gas scrubbing device comprises a first desorber connected to the supply line for the oxygen, in which at least part of the oxygen to be supplied to the reformer can be used as stripping gas in the regeneration of the scrubbing agent laden with carbon dioxide.
  • the first desorber is connected to the reformer via a line and possibly a compressor in such a way that the desorber enriched with carbon dioxide during stripping Oxygen can be fed to the reformer.
  • the first desorber is preferably designed as a stripping column in the bottom of which scrubbing agent that is at least largely free of carbon dioxide can collect.
  • the bottom space of the stripping column can have a heating device, by means of which part of the bottom fraction can be vaporized to support the stripping action of the oxygen.
  • the device according to the invention has a condenser for condensing detergent vapor, which is discharged with the oxygen stream from the first desorber. It makes sense for the condenser to be connected to the first desorber in such a way that detergent that has condensed out can be returned to the first desorber.
  • An expedient embodiment of the invention provides a second desorber connected to the first desorber and the absorber of the gas scrubbing device, in which the scrubbing agent treated in the first desorber by stripping with oxygen can be subjected to further stripping with nitrogen in order to remove dissolved oxygen before being passed on to the absorber removed from the detergent.
  • An exhaust pipe is preferably attached to the head of the second desorber, via which the nitrogen enriched with oxygen and possibly carbon dioxide during the stripping can be drawn off and disposed of, e.g. by releasing it into the atmosphere.
  • the supply line for the oxygen preferably comprises a temperature control device arranged upstream of the first desorber for setting the temperature of the part of the oxygen provided as stripping gas.
  • Heat can expediently be supplied to or withdrawn from the oxygen in a targeted manner by the temperature control device in order to adjust its temperature to the temperature of the loaded detergent to be treated in the first desorber.
  • the temperature control device is preferably designed as a heat exchanger, through which heat can be transferred indirectly from a heat carrier, which is, for example, a process flow, to the oxygen or from the oxygen to the heat carrier.
  • FIG. 1 shows a preferred embodiment of the invention with a device for removing oxygen from detergent to be regenerated.
  • a hydrocarbon-containing feed 1 such as natural gas and carbon dioxide 2 are introduced into the reformer R, which is a POX reactor, for example, for conversion into a carbon monoxide-rich crude synthesis gas 3 .
  • the oxygen required for the reforming reaction enters the reformer R via line 4.
  • the crude synthesis gas 6, which now largely consists of hydrogen, carbon monoxide and carbon dioxide is fed to the lower end of the absorber column A of the gas washing device G, where it flows upwards and is brought into intensive contact with a detergent 7 .
  • the scrubbing agent 9 which collects in the sump space of the absorber column A and is laden with carbon dioxide, is expanded via the throttle element a in the first separator D1 in order to convert the co-absorbed hydrogen and co-absorbed carbon monoxide into the gas phase and to increase the synthesis gas yield Line 10 and the compressor V1 returned to the crude synthesis gas 6.
  • the loaded scrubbing agent 11 After being heated in the heat exchanger W1, is expanded via the throttle element b in the first desorber D1 arranged in the regeneration part T of the gas washing device G to the pressure level of the oxygen made available via line 12, with a first part of the carbon dioxide contained is released.
  • Carbon dioxide-free oxygen 12 is fed as stripping gas to the first desorber D1, which is designed as a stripping column, via its bottom space, and on its way up further carbon dioxide is separated from the scrubbing agent conveyed in countercurrent. From a portion of the largely carbon dioxide-free detergent collecting in the sump space, detergent vapor is generated with the aid of the heating device H, which also rises and supports the stripping effect of the oxygen 12 .
  • a gas mixture 13 can be drawn off at the pressure level of the oxygen 12, which also contains vaporous detergent in addition to oxygen and carbon dioxide.
  • the detergent is condensed and then separated in the second separator E2 from the gas phase 4 consisting largely of oxygen and carbon dioxide. While the liquid detergent flows back into the first desorber D1, the gas phase 4 containing oxygen and carbon dioxide passes through the second compressor V2 as a feedstock into the reformer R.
  • the largely carbon dioxide-free scrubbing agent 15 is drawn off from the bottom of the first desorber D1, cooled in the first heat exchanger W1 and sent to a second desorber D2 gave up his head.
  • nitrogen 16 is fed in as stripping gas, with the aid of which the oxygen is removed from the scrubbing agent conveyed in countercurrent.
  • the oxygen-laden stripping nitrogen 17 drawn off from the top of the second desorber is discarded, while the regenerated scrubbing agent 7, which is free of oxygen and carbon dioxide, is drawn off from the sump space of the second desorber D2 with the aid of the pump P and, after cooling, is used again in the third heat exchanger W3 for gas scrubbing is used in absorber A.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Gas Separation By Absorption (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne une méthode et un dispositif pour générer un gaz de synthèse (8) contenant du monoxyde de carbone et de l'hydrogène. De l'oxygène (12) est fourni à une pression d'entrée et l'oxygène, conjointement avec un insert contenant du carbone (1) et du dioxyde de carbone (2), est ensuite converti thermochimiquement en un gaz de synthèse brut contenant du dioxyde de carbone (3) par un reformeur (R) au moyen d'une oxydation partielle ou d'un reformage autothermique, ledit gaz de synthèse brut subissant un procédé de lavage de gaz (A) pour obtenir le gaz de synthèse (8), un agent de lavage chargé en dioxyde de carbone (11) étant accumulé, le dioxyde de carbone étant séparé de celui-ci pour être remis en circulation dans le reformeur (R). L'invention est caractérisée en ce qu'au moins une partie de l'oxygène fourni (12) est utilisée comme gaz de stripage pour séparer le dioxyde de carbone de l'agent de lavage chargé en dioxyde de carbone (11) en amont du reformeur (R).
EP21798566.2A 2020-11-18 2021-10-20 Méthode et dispositif pour générer un gaz de synthèse tout en faisant recirculer du dioxyde de carbone Pending EP4247754A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020007035.3A DE102020007035A1 (de) 2020-11-18 2020-11-18 Verfahren und Vorrichtung zur Erzeugung von Synthesegas unter Rückführung von Kohlendioxid
PCT/EP2021/025415 WO2022106051A1 (fr) 2020-11-18 2021-10-20 Méthode et dispositif pour générer un gaz de synthèse tout en faisant recirculer du dioxyde de carbone

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EP4247754A1 true EP4247754A1 (fr) 2023-09-27

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EP21798566.2A Pending EP4247754A1 (fr) 2020-11-18 2021-10-20 Méthode et dispositif pour générer un gaz de synthèse tout en faisant recirculer du dioxyde de carbone

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3401779A1 (de) * 1984-01-19 1985-08-01 Linde Ag, 6200 Wiesbaden Verfahren zur kombinierten herstellung von ammoniak und harnstoff
US7083662B2 (en) 2003-12-18 2006-08-01 Air Products And Chemicals, Inc. Generation of elevated pressure gas mixtures by absorption and stripping
DE102015015310A1 (de) * 2015-11-26 2017-06-14 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Kohlendioxidabtrennung aus Synthesegas
DE102018210910A1 (de) * 2018-07-03 2020-01-09 Thyssenkrupp Ag Verfahren zur Vermeidung von VOC und HAP Emissionen aus Synthesegas verarbeitenden Anlagen

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