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EP3818009A1 - Procédé pour éviter les émissions de cov et de pad d'installations de traitement de gaz de synthèse - Google Patents

Procédé pour éviter les émissions de cov et de pad d'installations de traitement de gaz de synthèse

Info

Publication number
EP3818009A1
EP3818009A1 EP19733724.9A EP19733724A EP3818009A1 EP 3818009 A1 EP3818009 A1 EP 3818009A1 EP 19733724 A EP19733724 A EP 19733724A EP 3818009 A1 EP3818009 A1 EP 3818009A1
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
reformer
unit
ammonia
synthesis
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
EP19733724.9A
Other languages
German (de)
English (en)
Inventor
Bernd Mielke
Klaus NÖLKER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
Original Assignee
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ThyssenKrupp AG, ThyssenKrupp Industrial Solutions AG filed Critical ThyssenKrupp AG
Publication of EP3818009A1 publication Critical patent/EP3818009A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • 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
    • B01D53/005—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 heat treatment
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • 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
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • 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
    • 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
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/586—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • 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
    • 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
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
    • 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
    • C01B2203/0435—Catalytic purification
    • C01B2203/0445—Selective methanation
    • 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
    • C01B2203/047—Composition of the impurity the impurity being 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
    • C01B2203/04—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
    • C01B2203/04—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
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/068—Ammonia synthesis
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00—Methods of steam generation characterised by form of heating method
    • F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
    • F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a plant for ammonia synthesis, a process for ammonia synthesis and the use of the plant for ammonia synthesis according to the invention for the production of ammonia and reduction of volatile hydrocarbons (VOC and HAP).
  • Urea-based fertilizers account for a very large share of global fertilizer production. These water-soluble fertilizers break down into ammonium salts or nitrates in the soil and represent an important basic fertilizer. These urea-containing fertilizers can be combined with other elements such as potassium, manganese, phosphates, sulfur, sulfur compounds, selenium, calcium.
  • ammonia is the second most widely produced synthetic chemical worldwide (Ullmannn’s Encyclopedia of Industrial Chemistry, 2012, Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim, DOI: 10.1002 / 14356007. O02_o1 1, hereinafter referred to as “Ullmann’s”).
  • Ammonia is mainly produced from the elements hydrogen and nitrogen and an iron catalyst.
  • the temperatures are often in the range between 400 ° C and 500 ° C and at a pressure above 100 bar.
  • the main factor for the process costs is the supply of hydrogen from the synthesis gas production (Ullmann’s, page 139).
  • ammonia is preferably produced in principle, for example in Holleman, Wiberg, Textbook of Inorganic Chemistry, 102 edition, 2007, pages 662-665 (ISBN 978-3-1 1 -017770-1), based on the "Haber-Bosch method" from the elements according to equation [3]:
  • the starting material nitrogen (N 2 ) can be obtained, for example, by cryogenic air separation or by reduction of oxygen in the air by combustion.
  • the hydrogen is preferably obtained via the “steam reforming process” according to equation [4]:
  • the carbon dioxide (C0 2 ) produced according to equation [5] is preferably used as a carbon dioxide source for urea synthesis according to equations [1] and [2]
  • VOCs and HAPs are increasingly becoming a problem.
  • methanol is classified as VOC and is therefore subject to strict emission limits.
  • methanol and other VOCs and HAPs are produced as by-products of synthesis gas production in the front end of an ammonia plant, for example. They then get into the environment at various points via various detours.
  • One possibility is, for example, the blow-off line of the excess C0 2 , which has so far often not been subject to any cleaning.
  • Methanol and other VOC and HAP are absorbed into the wash solution of the C0 2 wash in the C0 2 wash cycle, accumulate there and are released via the C0 2 gas.
  • the C0 2 gas is usually not completely consumed in downstream process plants, for example in urea synthesis. This leaves an excess C0 2 stream loaded with methanol and other VOCs and HAPs, which is released into the environment untreated.
  • EP 0 345 504 A1 discloses a device for carrying out exothermic, catalytic gas reactions for ammonia or methanol synthesis.
  • DE 10 2010 035 885 A1 discloses a process for producing synthesis gas from hydrocarbon-containing feed gases, an autothermal reforming being carried out at a low steam / carbon ratio.
  • DE 10 2009 013 691 A1 discloses a method for the combined exhaust gas treatment of exhaust gas streams containing ammonia and nitrogen oxide in industrial plants.
  • EP 0 294 564 A1 discloses a method for reducing the NH3-methanol output of an ammonia synthesis plant by stripping the condensates containing ammonia and methanol in solution.
  • US 2017/0320728 A1 discloses a method for reducing VOC emissions by returning the carbon dioxide exhaust air stream to the primary reformer of the ammonia synthesis plant.
  • US 6,178,774 B1 discloses a method for producing an ammonia synthesis mixture and carbon monoxide.
  • US 4,198,378 A discloses a process for removing gaseous contaminants such as H 2 S and C0 2 .
  • the impurities are removed in an absorption column.
  • DE 10 2014 209 635 A1 discloses an apparatus and a method for producing synthesis gas with the aid of two autothermal reformers.
  • DE 103 34 590 A1 discloses a process for the production of hydrogen from a methane-resonant gas.
  • EP 0 604 554 B1 discloses a method for producing a nitrogen-containing gas stream which contains more than 21 mol% oxygen, with a gas turbine which has an air compressor unit and an energy production unit.
  • US 2017/0166518 A1 discloses a method for increasing the capacity of a urea synthesis complex.
  • the invention further comprises a method for ammonia synthesis. Further advantageous refinements can be found in the respective dependent claims.
  • the invention further comprises the use of the plant according to the invention for ammonia synthesis for the production of ammonia and reduction of volatile hydrocarbons (VOC and HAP).
  • the ammonia synthesis plant according to the invention comprises at least the components described below.
  • a reformer is used to provide hydrogen, preferably a primary and a secondary reformer and / or an autothermal reformer.
  • the formation of hydrogen preferably takes place in principle according to the above equation
  • the system according to the invention comprises a carbon monoxide (CO) converter.
  • CO carbon monoxide
  • the carbon monoxide (CO) formed in equation [4] and not required for the actual ammonia synthesis is converted into carbon dioxide with further hydrogen formation, preferably according to equation [5].
  • CO carbon monoxide
  • unit includes devices and apparatus known to the person skilled in the art, in this case typically / for example an absorber, a desorber, a or several circulation pumps and heat exchangers for heating / cooling the solvent.
  • a carbon dioxide (C0 2 ) scrubber unit with regeneration can, for example, be designed as a known device / arrangement in which carbon dioxide is dissolved in an absorber under pressure in a suitable solvent - for example potassium carbonate or amines - and then separated from the rest of the synthesis gas (which in the Carbon dioxide (C0 2 ) - scrubber unit with regeneration of synthesis gas depleted or freed of carbon dioxide) is released ("flash").
  • the solvent can then be reheated and regenerated in a stripping column (desorber).
  • a carbon dioxide (C0 2 ) scrubber unit with regeneration differs from an adsorption process (for example pressure swing adsorption PSA) in that the former is the essential component for the subsequent ammonia synthesis Nitrogen (N 2 ) is not removed from the synthesis gas stream and overall has a selectivity for the removal of gas components that is appropriate for the intended use.
  • an adsorption process for example pressure swing adsorption PSA
  • Nitrogen (N 2 ) is not removed from the synthesis gas stream and overall has a selectivity for the removal of gas components that is appropriate for the intended use.
  • a methanation unit enables the further reduction of carbon oxides (CO x ). This is done, for example, according to equations [6] and [7]:
  • the methanation unit preferably comprises further plant elements for purification, for example via the Selectoxo process, methanolation, dryer, cryogenic process, washing with liquid nitrogen and / or pressure swing adsorption.
  • unit includes devices and apparatus known to the person skilled in the art for the stated purpose. A detailed description can be found in Ullmann’s, chapter 6.1.3, pages 184 to 186. Process conditions for equations [6] and [7] are, for example, 25 bar to 35 bar and 250 ° C to 350 ° C over a nickel catalyst.
  • the system according to the invention further comprises an ammonia synthesis unit.
  • the ammonia synthesis unit comprises the actual ammonia synthesis reactor for the conversion of hydrogen and nitrogen according to equation [3].
  • the provision of nitrogen can preferably be in a connected air separation plant or from the process air processed (burned) in the secondary reformer. Examples of suitable reactors can also be found in EP 0 345 504 A1 and DE 35 22 308 A1, Examples 1 to 7 and the description.
  • the ammonia synthesis unit is preferably connected to devices for purification, compression and / or liquefaction.
  • the plant according to the invention is characterized in that the carbon dioxide (C0 2 ) scrubber unit is connected to regeneration with at least one fired auxiliary steam boiler.
  • the carbon dioxide that is not required in further process steps is burned before being released into the atmosphere.
  • the volatile hydrocarbons (VOCs and HAPs) in this carbon dioxide stream from the carbon dioxide (C0 2 ) scrubber unit with regeneration, for example methanol, are thus converted to carbon dioxide and water in the fired auxiliary steam boiler.
  • fired auxiliary steam boiler preferably includes, in the sense of the invention, thermally fired (heating by generating thermal energy) elements for (process) steam and heat generation.
  • the carbon monoxide (CO) converter, the carbon dioxide (C0 2 ) scrubber unit with regeneration, the methanation unit and ammonia synthesis unit are preferably connected in the process direction and in the row of the reformers.
  • the term “connected” includes suitable pipes, connecting pieces, pumps, compressors, etc., which are suitable for the transport of liquids and gases even under negative pressure (less than 1 bar) and overpressure (greater than 1 bar). Additional elements such as heat exchangers, pumps, compressors, heaters, etc. can be arranged between the elements mentioned above.
  • the carbon dioxide (C0 2 ) scrubber unit with regeneration has an additional connection to at least one fired auxiliary steam boiler.
  • the fired auxiliary steam boiler is usually part of the synthesis gas processing plant.
  • auxiliary steam boiler preferably includes devices for generating steam which provide heat / energy for generating steam via a combustion process.
  • the procedure can be applied to all chemical plants that have methanol, VOC and HAP emissions on a comparatively small process vent (process ventilation) and have a fired auxiliary steam boiler.
  • the fired auxiliary steam boiler is preferably connected to an exhaust air device and thus does not allow the discharge of the further, for example in other process steps, used carbon dioxide flow.
  • This carbon dioxide stream is cleaned or depleted in relation to VOCs and HAPs.
  • the reformer comprises a (primary) steam reformer with or without a secondary reformer and / or an autothermal reformer.
  • the reformer can also consist of only one or more autothermal reformers.
  • the reformer, the carbon monoxide (CO) converter, the carbon dioxide (C0 2 ) scrubber unit with regeneration, the methanation unit and the ammonia synthesis unit are preferably connected in the process direction and in the row.
  • the carbon dioxide (CO 2 ) scrubber unit with regeneration has an additional connection to at least one fired auxiliary steam boiler.
  • the fired auxiliary steam boiler preferably has supply lines for air (or an oxygen-containing gas and / or gas mixtures) and supply lines for fuel, for example natural gas, hydrogen, synthesis gas, oxygen and / or mixtures thereof.
  • the supply lines for air are particularly preferably connected to the carbon dioxide (C0 2 ) scrubber unit with regeneration.
  • This connection arrangement enables a direct premixing of the exhaust air from the carbon dioxide (C0 2 ) scrubber unit with the air supply of the fired auxiliary steam boiler.
  • This premix described above enables almost complete combustion of the VOCs and HAPs in the exhaust air from the carbon dioxide (C0 2 ) scrubber unit.
  • the fired auxiliary steam boiler has a capacity of 10 tons to 200 tons of steam per hour.
  • the invention further comprises a method for ammonia synthesis at least comprising the following steps.
  • an alkane-containing (in particular methane-containing) gas is introduced into a reformer and, as described above in accordance with equation [4], a first synthesis gas mixture with hydrogen, carbon monoxide and carbon dioxide is obtained.
  • the first synthesis gas mixture is then transferred to a carbon monoxide (CO) converter.
  • CO carbon monoxide
  • the second synthesis gas mixture is then introduced into a carbon dioxide (C0 2 ) scrubber unit with regeneration and transferred.
  • the scrubber unit can be designed, for example, as a device / arrangement in which carbon dioxide is dissolved in an absorber under pressure in a suitable solvent - for example potassium carbonate or amines - and then expanded (flash) separately from the rest of the (virtually carbon dioxide-free) synthesis gas.
  • the solvent can then, for example, be reheated and regenerated in a stripping column (desorber).
  • a third (almost carbon dioxide-free or depleted) synthesis gas mixture and a carbon dioxide (C0 2 ) -containing exhaust gas are then obtained.
  • the third synthesis gas mixture is transferred to a methanation unit.
  • the methanation unit enables, for example according to equations [6] and [7], the further reduction of carbon oxides (CO x ).
  • a fourth synthesis gas mixture is then obtained and the fourth synthesis gas mixture is introduced into an ammonia synthesis unit.
  • the ammonia synthesis unit comprises the actual ammonia synthesis reactor for the conversion of hydrogen and nitrogen, preferably according to equation [3].
  • Ammonia is obtained in the ammonia synthesis unit. This is then preferably processed, compressed and / or liquefied by one or more pressure drops.
  • the continuous process according to the invention is characterized in that the carbon dioxide (C0 2 ) -containing exhaust gas (from the carbon dioxide (C0 2 ) scrubber unit with regeneration) is introduced in whole or in part into a fired auxiliary steam boiler and by oxidation (combustion) in the auxiliary steam boiler volatile hydrocarbons (VOC and HAP) poor or free exhaust gas is obtained.
  • the portions of the exhaust gas containing carbon dioxide which are not introduced into the auxiliary steam boiler can preferably be used in other process steps, for example for urea synthesis.
  • the reformer comprises a (primary) steam reformer with or without a secondary reformer and / or an autothermal reformer.
  • the reformer can also consist of only one or more autothermal reformers.
  • the ammonia obtained and a large part of the carbon dioxide (C0 2 ) -containing exhaust gas are preferably converted to urea in a urea plant, preferably a connected urea plant.
  • the continued use enables an effective use of the ammonia and in particular the natural gas that is preferably used for the production of the synthesis gas.
  • the aforementioned embodiment also includes the preferred direct use of part of the carbon dioxide (C0 2 ) -containing exhaust gas without combustion in the auxiliary steam boiler according to the invention.
  • the fired auxiliary steam boiler is particularly preferably operated at 170 ° C. to 550 ° C. and / or 5 bar to 150 bar on the side of the steam generation.
  • the invention further comprises the use of the ammonia synthesis plant according to the invention for the production of ammonia and simultaneous reduction of volatile hydrocarbons (VOC and HAP).
  • Figure 1 is a schematic flow diagram of a plant for ammonia synthesis
  • Figure 2 is a schematic flow diagram of a plant for ammonia synthesis according to the invention.
  • Figure 1 shows a schematic flow diagram of a plant for ammonia synthesis.
  • a reformer (1) preferably a primary and a secondary reformer and / or an autothermal reformer, is used to provide hydrogen. The formation of hydrogen takes place in principle according to equation [4].
  • the system also includes a carbon monoxide (CO) converter (2). In this, the carbon monoxide (CO) formed in equation [4] and not required in the actual ammonia synthesis is converted with further hydrogen formation into carbon dioxide according to equation [5].
  • a carbon dioxide (C0 2 ) scrubber unit with regeneration (3) connects to the carbon monoxide (CO) converter (2).
  • the carbon dioxide (C0 2 ) scrubber unit can be designed, for example, as a known device / arrangement in which carbon dioxide is dissolved in an absorber under pressure in a suitable solvent - for example potassium carbonate or amines - and then expanded again separately from the synthesis gas (“flash”) becomes. The solvent can then be reheated and regenerated in a stripping column (desorber).
  • a methanation unit (4) enables the further reduction of carbon oxides (CO x ). This is done, for example, according to the Equations [6] and [7].
  • the system also includes an ammonia synthesis unit (5) connected to the methanation unit (4).
  • the ammonia synthesis unit (5) comprises the actual ammonia synthesis reactor for converting hydrogen and nitrogen according to equation [3].
  • the ammonia synthesis unit (5) is connected to devices for purification, compression and / or liquefaction (9).
  • the reformer (1) the carbon monoxide (CO) converter (2), the carbon dioxide (CO 2 ) scrubber unit with regeneration (3), the methanation unit (4), the ammonia synthesis unit (5) and the devices connected for purification, compression and / or liquefaction (9).
  • the carbon dioxide (C0 2 ) scrubber unit with regeneration (3) has an additional discharge line (8c) for the exhaust gases (6a) (mainly C0 2 ) that are no longer required to an exhaust air system (7).
  • the exhaust gases mainly C0 2
  • volatile organic hydrocarbons produced in the carbon dioxide (C0 2 ) scrubber unit are released to the environment as exhaust gas (6 a).
  • the term “connected” includes suitable pipes, connecting pieces, pumps, compressors, etc., which are suitable for the transport of liquids and gases even under negative pressure (less than 1 bar) and overpressure (greater than 1 bar). Additional elements such as heat exchangers, pumps, compressors, heaters, etc. can be arranged between the elements mentioned above.
  • FIG. 2 is a schematic flow diagram of the ammonia synthesis plant according to the invention.
  • the basic structure corresponds to the structure described in FIG. 1.
  • the system according to the invention is characterized in that the carbon dioxide (C0 2 ) scrubber unit with regeneration (3) is connected to a fired auxiliary steam boiler (6).
  • the volatile hydrocarbons (VOCs and HAPs) accumulating in the carbon dioxide (C0 2 ) scrubber unit with regeneration (3) with the carbon dioxide in the carbon dioxide-containing exhaust gases (6a), for example methanol, are burned in the fired auxiliary steam boiler and converted to carbon dioxide and water.
  • the auxiliary steam boiler (6) is supplied with air via a first supply line (8a) and with fuel gas via a second supply line (8b).
  • the first feed line (8a) is connected to the discharge line (8c) from the scrubber unit with regeneration (3), so that a premixing of the volatile hydrocarbons obtained in the carbon dioxide (C0 2 ) scrubber unit with regeneration (3) with the C0 2 done with atmospheric oxygen.
  • Low or free exhaust gas (6b) of volatile hydrocarbons (VOC and HAP) enters the atmosphere via the exhaust air device (7).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
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Abstract

L'invention concerne une installation pour la synthèse d'ammoniac comprenant au moins : a) un reformeur (1) ; b) un convertisseur de monoxyde de carbone (CO) (2) ; c) une unité de lavage de dioxyde de carbone (CO2) avec régénération (3) ; d) une unité de méthanation (4) ; e) une unité de synthèse d'ammoniac (5) ; caractérisée en ce que l'unité de lavage de dioxyde de carbone (CO2) avec rgénération (3) est connectée à au moins un générateur de vapeur d'appoint à combustible (6). L'invention concerne en outre un procédé pour la synthèse d'ammoniac.
EP19733724.9A 2018-07-03 2019-06-24 Procédé pour éviter les émissions de cov et de pad d'installations de traitement de gaz de synthèse Pending EP3818009A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018210910.9A DE102018210910A1 (de) 2018-07-03 2018-07-03 Verfahren zur Vermeidung von VOC und HAP Emissionen aus Synthesegas verarbeitenden Anlagen
PCT/EP2019/066573 WO2020007627A1 (fr) 2018-07-03 2019-06-24 Procédé pour éviter les émissions de cov et de pad d'installations de traitement de gaz de synthèse

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EP3818009A1 true EP3818009A1 (fr) 2021-05-12

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US (1) US20210261424A1 (fr)
EP (1) EP3818009A1 (fr)
DE (1) DE102018210910A1 (fr)
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CN114076321B (zh) * 2021-11-15 2024-04-30 镇海石化工程股份有限公司 利用硫磺回收装置焚烧炉治理石化VOCs废气的方法

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DE102018210910A1 (de) 2020-01-09
WO2020007627A1 (fr) 2020-01-09

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