EP3818009A1 - Method for avoiding voc and hap emissions from synthesis gas-processing systems - Google Patents

Method for avoiding voc and hap emissions from synthesis gas-processing systems

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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)
French (fr)
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
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Filing date
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Application filed by ThyssenKrupp AG, ThyssenKrupp Industrial Solutions AG filed Critical ThyssenKrupp AG
Publication of EP3818009A1 publication Critical patent/EP3818009A1/en
Pending legal-status Critical Current

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    • 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).

Abstract

The invention relates to a system for the synthesis of ammonia, comprising at least: a) a reformer (1); b) a carbon monoxide (CO) converter (2); c) a carbon dioxide (CO2) scrubber unit with recovery (3); d) a methanation unit (4); and e) an ammonia synthesis unit (5); characterized in that the carbon dioxide (CO2) scrubber unit with recovery (3) is connected to at least one fired auxiliary steam boiler (6). The invention furthermore relates to an ammonia synthesis method.

Description

Verfahren zur Vermeidung von VOC und HAP Emissionen aus Synthesegas verarbeitenden Anlagen  Process to avoid VOC and HAP emissions from plants processing synthetic gas
Die Erfindung betrifft eine Anlage zur Ammoniak-Synthese, ein Verfahren zur Ammoniak- Synthese und die Verwendung der erfindungsgemäßen Anlage zur Ammoniak-Synthese zur Herstellung von Ammoniak und Reduktion von flüchtigen Kohlenwasserstoffen (VOC und HAP). 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).
Im Hinblick auf das weltweite Bevölkerungswachstum kommt der Entwicklung von flexiblen und effizienten Düngern eine große und wachsende Bedeutung zu. Einen sehr großen Anteil an der weltweiten Düngerproduktion entfällt auf harnstoffhaltige Dünger. Diese wasserlöslichen Dünger zerfallen im Boden zu Ammoniumsalzen bzw. Nitraten und stellen einen wichtigen Basisdünger dar. Diese harnstoffhaltigen Dünger können mit weiteren Elementen wie Kalium, Mangan, Phosphaten, Schwefel, Schwefelverbindungen, Selen, Kalzium kombiniert werden. With regard to global population growth, the development of flexible and efficient fertilizers is of great and growing importance. 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.
Harnstoff kann gemäß den vereinfachten Gleichungen [1] und [2] hergestellt werden: Urea can be produced according to the simplified equations [1] and [2]:
2 NH3 + C02 ^ H2N-COONH4 [1] 2 NH 3 + C0 2 ^ H 2 N-COONH 4 [1]
H2N-COONH4 ^ (NH2)2CO + H20 [2] H 2 N-COONH 4 ^ (NH 2 ) 2 CO + H 2 0 [2]
Die beiden Ausgangsstoffe Ammoniak und Kohlendioxid können dabei in der Ammoniaksynthese basierend auf dem Haber-Bosch Verfahren bereitgestellt werden. Ammoniak ist dabei die weltweit zweitmeist produzierte synthetische Chemikalie (Ullmannn’s Encyclopedia of Industrial Chemistry, 2012, Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim, DOI :10.1002/14356007. o02_o1 1 , im folgenden„Ullmann’s“). The two starting materials ammonia and carbon dioxide can be made available in the ammonia synthesis based on the Haber-Bosch process. 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”).
Die Herstellung von Ammoniak erfolgt dabei im Wesentlichen aus den Elementen Wasserstoff und Stickstoff und einen Eisenkatalysator. Die Temperaturen bewegen sich häufig im Bereich zwischen 400 °C und 500 °C und bei einem Druck über 100 bar. Der wesentliche Faktor für die Prozesskosten liegen dabei in der Bereitstellung von Wasserstoff aus der Synthesegas Herstellung (Ullmann’s, Seite 139). 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).
Eine Erzeugung von Ammoniak erfolgt dementsprechend bevorzugt im Grundsatz wie beispielsweise bei Holleman, Wiberg, Lehrbuch der Anorganischen Chemie, 102 Auflage, 2007, Seiten 662-665 (ISBN 978-3-1 1 -017770-1 ) beschrieben, basierend auf dem„Haber- Bosch-Verfahren“ aus den Elementen gemäß Gleichung [3]: Accordingly, 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]:
3 H2 + N2 ^ 2 NH3 + 92.28 kJ [3] 3 H 2 + N 2 ^ 2 NH 3 + 92.28 kJ [3]
Das Edukt Stickstoff (N2) kann beispielsweise durch Tieftemperaturluftzerlegung oder durch Reduktion von Sauerstoff in der Luft durch Verbrennung gewonnen werden. Der Wasserstoff wird bevorzugt über den„Steam-Reforming-Prozess“ gemäß Gleichung [4] erhalten: 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]:
CnH2m + nH20 ^ (n+m) H2 + nCO [4] C n H 2 m + nH 2 0 ^ (n + m) H 2 + nCO [4]
In der anschließenden„Kohlendioxid-Konvertierung“ erfolgt eine weitere Umsetzung gemäß Gleichung (5): In the subsequent "carbon dioxide conversion" there is a further conversion according to equation (5):
CO + H20 ^ C02 + H2 [5] CO + H 2 0 ^ C0 2 + H 2 [5]
Das gemäß Gleichung [5] entstehende Kohlendioxid (C02) dient bevorzugt Kohlendioxidquelle zur Harnstoffsynthese gemäß den Gleichungen [1] und [2] 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]
Der vorliegende Prozess ist wie viele andere großtechnische Synthesegasprozesse auch mit der Bildung von VOC- (Volatible Organic Compounds) und HAP-Emissionen (Hazardous Air Polutants) verbunden. VOCs und HAPs stellen zunehmend ein Problem dar. In den USA ist z.B. Methanol als VOC eingestuft und unterliegt damit strengen Emissionsgrenzwerten. Methanol und andere VOCs und HAPs entstehen beispielsweise als Nebenprodukte einer Synthesegasherstellung im Frontend z.B. einer Ammoniakanlage. Über diverse Umwege gelangen diese dann an verschiedenen Stellen in die Umwelt. Eine Möglichkeit ist beispielsweise die Abblaseleitung des Überschuss-C02, die bislang häufig keinerlei Reinigung unterliegt. Methanol und andere VOC und HAP gelangen über die Absorption in die Waschlösung der C02-Wäsche in den C02-Wäsche-Kreislauf, reichern sich dort an und werden über das C02 Gas abgegeben. Das C02 Gas wird üblicherweise nicht vollständig in nachgeschalteten Prozessanlagen, beispielsweise in der Harnstoffsynthese, verbraucht. Es bleibt daher ein mit Methanol und anderen VOCs und HAPs beladener Überschuss-C02- Strom, der unbehandelt an die Umgebung abgegeben wird. Like many other large-scale synthesis gas processes, the present process is also associated with the formation of VOC (Volatile Organic Compounds) and HAP (Hazardous Air Polutants) emissions. VOCs and HAPs are increasingly becoming a problem. In the USA, for example, methanol is classified as VOC and is therefore subject to strict emission limits. For example, 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 offenbart eine Vorrichtung zur Durchführung exothermer, katalytischer Gasreaktionen für die Ammoniak- oder Methanol-Synthese. DE 10 2010 035 885 A1 offenbart ein Verfahren zur Herstellung von Synthesegas aus kohlenwasserstoffhaltigen Einsatzgasen, wobei eine autotherme Reformierung bei einem geringen Dampf/Kohlenstoffverhältnis durchgeführt wird. 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 offenbart ein Verfahren zur kombinierten Abgasbehandlung von Ammoniak- und Stickoxid-haltiger Abgasströme in Industrieanlagen. 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 offenbart ein Verfahren zur Verminderung des NH3-Methanol-Ausstoßes einer Ammoniak-Syntheseanlage unter Strippung der Ammoniak und Methanol gelöst enthaltenden Kondensaten. 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 offenbart ein Verfahren zur Verminderung von VOC Emissionen indem der Kohelndioxid-Abluftstrom in den Primär-Reformer der Ammoniaksynthese-Anlage zurückgeführt wird. 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 offenbart ein Verfahren zur Herstellung einer Ammoniak Synthese Mischung und Kohlenmonoxid. US 6,178,774 B1 discloses a method for producing an ammonia synthesis mixture and carbon monoxide.
US 4,198,378 A offenbart ein Verfahren zur Entfernung gasförmiger Verunreinigungen wie H2S und C02. Die Verunreinigungen werden in einer Absorbtionssäule entfernt. 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 offenbart eine Vorrichtung und ein Verfahren zur Herstellung von Synthesegas mit Hilfe von zwei autothermen Reformern. 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 offenbart ein Verfahren zur Gewinnung von Wasserstoff aus einem methanhalltigen Gas. DE 103 34 590 A1 discloses a process for the production of hydrogen from a methane-resonant gas.
EP 0 604 554 B1 offenbart ein Verfahren zur Herstellung eines Stickstoff enthaltenden Gasstromes, der mehr als 21 Mol-% Sauerstoff enthält, mit einer Gasturbine, die eine Luftkompressoreinheit und eine Energieproduktionseinheit aufweist. 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 offenbart ein Verfahren zur Kapazitätserhöhung eines Harnstoffsynthesekomplexes. US 2017/0166518 A1 discloses a method for increasing the capacity of a urea synthesis complex.
Weitere Verfahren zur Herstellung von Ammoniak finden sich in der WO 90/06281 A1 und US 2008/0228321 A1. Verfahren zur Bereitstellung von Wasserstoff finden sich in der US 2017/0158504 A1 , US 3,441 ,393 A und WO 2010/109184 A1. Die vorliegende Erfindung hat die Aufgabe eine Anlage zur Ammoniak-Synthese bereitzustellen, welche eine deutlich verringerte Emission von flüchtigen, umweit- und gesundheitsschädlichen Kohlenwasserstoffen (VOCs und HAPs) aufweist. Further processes for the production of ammonia can be found in WO 90/06281 A1 and US 2008/0228321 A1. Methods for providing hydrogen can be found in US 2017/0158504 A1, US 3,441, 393 A and WO 2010/109184 A1. The object of the present invention is to provide a plant for ammonia synthesis which has a significantly reduced emission of volatile hydrocarbons (VOCs and HAPs) which are harmful to the environment and to health.
Die Aufgabe der Erfindung wird überraschenderweise durch eine Anlage zur Ammoniak- Synthese gemäß Anspruch 1 gelöst. Weitere vorteilhafte Ausgestaltungen finden sich in den abhängigen Ansprüchen. The object of the invention is surprisingly achieved by a plant for ammonia synthesis according to claim 1. Further advantageous refinements can be found in the dependent claims.
Die Erfindung umfasst des Weiteren ein Verfahren zur Ammoniak-Synthese. Weitere vorteilhafte Ausgestaltungen finden sich in den jeweiligen abhängigen Ansprüchen. The invention further comprises a method for ammonia synthesis. Further advantageous refinements can be found in the respective dependent claims.
Die Erfindung umfasst des Weiteren die Verwendung der erfindungsgemäßen Anlage zur Ammoniak-Synthese zur Herstellung von Ammoniak und Reduktion von flüchtigen Kohlenwasserstoffen (VOC und HAP). 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).
Die erfindungsgemäße Anlage zur Ammoniak-Synthese umfasst mindestens die nachfolgend beschriebenen Komponenten. Zur Bereitstellung von Wasserstoff dient ein Reformer, bevorzugt ein Primär- und ein Sekundärreformer und/oder ein autothermer Reformer. Die Bildung von Wasserstoff erfolgt dabei bevorzugt im Grundsatz nach obiger Gleichung 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
CnH2m + nH20 ^ (n+m) H2 + nCO [4] C n H 2 m + nH 2 0 ^ (n + m) H 2 + nCO [4]
Eine Darstellung zur Funktionsweise des Reformers findet sich in Ullmann’s, Kapitel 6.1.1 Seiten 174 bis 179. Des Weiteren umfasst die erfindungsgemäße Anlage einen Kohlenmonoxid (CO) - Konverter. In diesem wird das in Gleichung [4] gebildete und für die eigentliche Ammoniaksynthese nicht benötigte Kohlenmonoxid (CO) unter weiterer Wasserstoffbildung in Kohlendioxid bevorzugt gemäß Gleichung [5] umgesetzt. A description of the functioning of the reformer can be found in Ullmann’s, chapter 6.1.1, pages 174 to 179. Furthermore, the system according to the invention comprises a carbon monoxide (CO) converter. In this, 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 + H20 ^ C02 + H2 [5] CO + H 2 0 ^ C0 2 + H 2 [5]
Eine Beschreibung zur Funktionsweise und Aufbau von möglichen Kohlenmonoxid (CO) - Konvertern („Carbon Monoxide Shift Conversion) findet sich unter Ullmann’s, Kapitel 6.1.2, Seiten 179 bis 182. An den Kohlenmonoxid (CO) - Konverter schließt sich eine Kohlendioxid (CO 2)- Wäschereinheit mit Regeneration an. Der Ausdruck ,,-einheit“ umfasst im Sinne der Erfindung dem Fachmann für den genannten Zweck bekannte Vorrichtungen und Apparate, in diesem Fall typischerweise/beispielsweise einen Absorber, einen Desorber, eine oder mehrere Zirkulationspumpen sowie Wärmeübertrager zum Aufwärmen/Abkühlen des Lösungsmittels. Eine Kohlendioxid (C02)- Wäschereinheit mit Regeneration kann beispielsweise als bekannte Vorrichtung/Anordnung ausgeführt sein, bei der Kohlendioxid in einem Absorber unter Druck in einem geeigneten Lösungsmittel - beispielsweise Kaliumkarbonat oder Amine - gelöst wird und anschließend getrennt vom übrigen Synthesegas (das in der Kohlendioxid (C02)- Wäschereinheit mit Regeneration an Kohlendioxid abgereicherte bzw. von Kohlendioxid befreite Synthesegas) entspannt („flash“) wird. Das Lösungsmittel kann anschließend wieder erwärmt und in einer Stripping Säule (Desorber) regeneriert werden. Eine detaillierte Beschreibung findet sich beispielsweise unter Ullmann’s, Kapitel 6.1.3, Seiten 182 bis 184. Eine Kohlendioxid (C02)- Wäschereinheit mit Regeneration unterscheidet sich von einem Adsorptionsverfahren (beispielsweise Druckwechseladsorption PSA) dadurch, dass erstgenannte die für die nachfolgende Ammoniaksynthese essentielle Komponente Stickstoff (N2) nicht aus dem Synthesegasstrom entfernt und insgesamt über eine dem Verwendungszweck entsprechende Selektivität bei der Entfernung von Gaskomponenten verfügt. A description of the functioning and structure of possible carbon monoxide (CO) converters ("Carbon Monoxide Shift Conversion) can be found in Ullmann's, Chapter 6.1.2, pages 179 to 182. A carbon dioxide (CO 2 ) - Washer unit with regeneration on. For the purposes of the invention, the term “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 detailed description can be found, for example, in Ullmann's, Chapter 6.1.3, pages 182 to 184. 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.
Eine Methanisierungseinheit ermöglicht die weitere Reduzierung von Kohlenstoffoxiden (COx). Dies erfolgt beispielsweise gemäß den Gleichungen [6] und [7]: A methanation unit enables the further reduction of carbon oxides (CO x ). This is done, for example, according to equations [6] and [7]:
CO + 3 H2 ^ CH4 + H20 [6] CO + 3 H 2 ^ CH 4 + H 2 0 [6]
C02 + 4 H2 ^ CH4 + 2 H20 [7] C0 2 + 4 H 2 ^ CH 4 + 2 H 2 0 [7]
Die Methanisierungseinheit umfasst bevorzugt im Sinne der Erfindung noch weitere Anlagenelemente zur Aufreinigung, beispielsweise über den Selectoxo-Prozess, Methanolation, Trockner, Cryogene Verfahren, Waschen mit flüssigen Stickstoff und/oder Druckwechseladsorption. Der Ausdruck ,,-einheit“ umfasst im Sinne der Erfindung dem Fachmann für den genannten Zweck bekannte Vorrichtungen und Apparate. Eine detaillierte Beschreibung findet sich unter Ullmann’s, Kapitel 6.1.3, Seiten 184 bis 186. Prozessbedingungen für die Gleichungen [6] und [7] sind beispielsweise 25 bar bis 35 bar und 250 °C bis 350 °C über einem Nickelkatalysator. According to the invention, 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. For the purposes of the invention, the term “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.
Die erfindungsgemäße Anlage umfasst des Weiteren eine Ammoniaksyntheseeinheit. Der Ausdruck ,,-einheit“ umfasst im Sinne der Erfindung dem Fachmann für den genannten Zweck bekannte Vorrichtungen und Apparate. Die Ammoniaksyntheseeinheit umfasst den eigentlichen Ammoniaksynthesereaktor zur Umsetzung von Wasserstoff und Stickstoff gemäß Gleichung [3]. Die Bereitstellung von Stickstoff kann bevorzugt in einer angeschlossenen Luftzerlegungsanlage erfolgen oder aus der im Sekundärreformer verarbeiteten (-‘verbrannten“) Prozessluft. Beispiele für geeignete Reaktoren finden sich auch in der EP 0 345 504 A1 und der DE 35 22 308 A1 , Beispiele 1 bis 7 und der Beschreibung. Bevorzugt ist die Ammoniaksyntheseeinheit mit Vorrichtungen zur Aufreinigung, Komprimierung und/oder Verflüssigung verbunden. The system according to the invention further comprises an ammonia synthesis unit. For the purposes of the invention, the term “unit” includes devices and apparatus known to the person skilled in the art for the stated purpose. 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.
Die erfindungsgemäße Anlage ist dadurch gekennzeichnet, dass die Kohlendioxid (C02)- Wäschereinheit mit Regeneration mit mindestens einem befeuerten Hilfsdampfkessel verbunden ist. In dem befeuerten Hilfsdampfkessel wird das nicht in weiteren Prozessschritten benötigte Kohlendioxid vor Abgabe an die Atmosphäre verbrannt. Die in diesem Kohlendioxidstrom aus der Kohlendioxid (C02)- Wäschereinheit mit Regeneration enthaltenden flüchtigen Kohlenwasserstoffe (VOCs und HAPs), beispielsweise Methanol, werden somit in dem befeuerten Hilfsdampfkessel zu Kohlendioxid und Wasser umgesetzt. Der Ausdruck „befeuerter Hilfsdampfkessel“ umfasst bevorzugt im Sinne der Erfindung thermisch befeuerte (Erwärmung durch Erzeugung thermischer Energie) Elemente zur (Prozess-)Dampf- und Wärmeerzeugung. 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. In the 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. The expression “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.
Bevorzugt sind in Prozessrichtung und in Reihe der Reformer der Kohlenmonoxid (CO) - Konverter, die Kohlendioxid (C02)- Wäschereinheit mit Regeneration, die Methanisierungseinheit und Ammoniaksyntheseeinheit verbunden. Der Ausdruck „verbunden“ umfasst im Sinne der Erfindung geeignete Rohre, Verbindungsstücke, Pumpen, Kompressoren, usw. welche für den Transport von Flüssigkeiten und Gasen auch bei Unterdrück (kleiner 1 bar) und Überdruck (größer als 1 bar) geeignet sind. Zwischen den voranstehend genannten Elementen können weitere Elemente wie Wärmetauscher, Pumpen, Kompressoren, Heizungen usw. angeordnet sein. Die Kohlendioxid (C02)- Wäschereinheit mit Regeneration weist eine zusätzliche Verbindung zu mindestens einem befeuerten Hilfsdampfkessel auf. Der gefeuerte Hilfsdampfkessel gehört üblicherweise zu der Synthesegas verarbeitenden Anlage dazu. Der Ausdruck„Hilfsdampfkessel“ umfasst bevorzugt im Sinne der Erfindung Vorrichtungen zur Dampferzeugung, welche über einen Verbrennungsvorgang Wärme/Energie zur Dampferzeugung bereitstellen. Grundsätzlich ist die Vorgehensweise bei allen Chemieanlagen anwendbar, die Methanol-, VOC und HAP- Emissionen an einem vergleichsweise kleinen Prozessvent (Prozessentlüftung) aufweisen und über einen gefeuerten Hilfsdampfkessel verfügen. 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. In the context of the invention, 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. For the purposes of the invention, the expression “auxiliary steam boiler” preferably includes devices for generating steam which provide heat / energy for generating steam via a combustion process. In principle, 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.
Bevorzugt ist der befeuerte Hilfsdampfkessel mit einer Abluftvorrichtung verbunden und ermöglicht somit die Abgabe des nicht weiter, beispielsweise in anderen Prozessschritten, genutzten Kohlendioxidstroms. Dieser Kohlendioxidstrom ist im Bezug auf VOCs und HAPs gereinigt bzw. abgereichert. 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.
In einer bevorzugten Ausführungsform umfasst der Reformer einen (Primär)-Dampfreformer mit oder ohne Sekundärreformer und/oder einen autothermen Reformer. Insbesondere bei einer hohen Ammoniaktagesproduktion kann der Reformer auch nur aus einem oder mehreren autothermen Reformern bestehen. In a preferred embodiment, the reformer comprises a (primary) steam reformer with or without a secondary reformer and / or an autothermal reformer. In particular with a high ammonia production per day, the reformer can also consist of only one or more autothermal reformers.
Bevorzugt ist in Prozessrichtung und in Reihe der Reformer, der Kohlenmonoxid (CO) - Konverter, die Kohlendioxid (C02)- Wäschereinheit mit Regeneration, die Methanisierungseinheit und die Ammoniaksyntheseeinheit verbunden. Die Kohlendioxid (CO 2)- Wäschereinheit mit Regeneration weist eine zusätzliche Verbindung zu mindestens einem befeuerten Hilfsdampfkessel auf. 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.
Bevorzugt weist der befeuerte Hilfsdampfkessel Zuleitungen für Luft (oder ein sauerstoffhaltiges Gas und/oder Gasgemische) sowie Zuleitungen für Brennmittel, beispielsweise Erdgas, Wasserstoff, Synthesegas, Sauerstoff und/oder Gemische davon auf. 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.
Besonders bevorzugt ist die Zuleitungen für Luft mit der Kohlendioxid (C02)- Wäschereinheit mit Regeneration verbunden. Diese Verbindungsanordnung ermöglicht ein direktes Vormischen der Abluft aus der Kohlendioxid (C02)- Wäschereinheit mit der Luftzufuhr des befeuerten Hilfsdampfkessel. Diese voranstehend beschriebene Vormischung ermöglicht eine nahezu vollständige Verbrennung der VOCs und HAPs in der Abluft aus der Kohlendioxid (C02)- Wäschereinheit. 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.
In einer weiteren bevorzugten Ausführungsform weist der befeuerte Hilfsdampfkessel eine Kapazität von 10 Tonnen bis 200 Tonnen Dampf pro Stunde auf. In a further preferred embodiment, the fired auxiliary steam boiler has a capacity of 10 tons to 200 tons of steam per hour.
Die Erfindung umfasst des Weiteren ein Verfahren zur Ammoniak-Synthese mindestens umfassend die folgenden Schritte. The invention further comprises a method for ammonia synthesis at least comprising the following steps.
In einem ersten Schritt wird ein alkanhaltiges (insbesondere Methan enthaltenes) Gas in einen Reformer eingeleitet und wie voranstehend gemäß Gleichung [4] beschrieben ein erstes Synthesegasgemisches mit Wasserstoff, Kohlenmonoxid und Kohlendioxid erhalten. Anschließend wird das erste Synthesegasgemisch in einen Kohlenmonoxid (CO) - Konverter überführt. In dem Kohlenmonoxid (CO) - Konverter wird das in Gleichung [4] gebildete und für die eigentliche Ammoniaksynthese nicht benötigte und für viele Katalysatoren problematische Kohlenmonoxid (CO) unter weiterer Wasserstoffbildung in Kohlendioxid gemäß Gleichung (5) umgesetzt und eines zweites Synthesegasgemisch erhalten. Das zweite Synthesegasgemisches wird anschließend in eine Kohlendioxid (C02)- Wäschereinheit mit Regeneration eingeleitet und überführt. Die Wäschereinheit kann beispielsweise als Vorrichtung/Anordnung ausgeführt sein, bei der Kohlendioxid in einem Absorber unter Druck in einem geeigneten Lösungsmittel - beispielsweise Kaliumkarbonat oder Amine - gelöst wird und anschließend getrennt vom übrigen (nahezu kohlendioxidfreien) Synthesegas entspannt („flash“) wird. Das Lösungsmittel kann beispielsweise anschließend wieder erwärmt und in einer Stripping Säule (Desorber) regeneriert werden. Anschließend werden ein drittes (nahezu Kohlendioxid freies oder abgereichertes) Synthesegasgemisch und ein Kohlendioxid (C02) haltigen Abgas erhalten. Das dritte Synthesegasgemisch wird in eine Methanisierungseinheit überführt. Die Methanisierungseinheit ermöglicht, beispielsweise gemäß den Gleichungen [6] und [7], die weitere Reduzierung von Kohlenstoffoxiden (COx). Anschließend wird ein viertes Synthesegasgemisch erhalten und das vierte Synthesegasgemisch in eine Ammoniaksyntheseeinheit eingeleitet. Die Ammoniaksyntheseeinheit umfasst den eigentlichen Ammoniaksynthesereaktor zur Umsetzung von Wasserstoff und Stickstoff bevorzugt gemäß Gleichung [3]. In der Ammoniaksyntheseeinheit wird Ammoniak erhalten. Dieser wird anschließend bevorzugt durch eine oder mehrere Druckabsenkungen aufbereitet, komprimiert und/oder verflüssigt. Der erfindungsgemäße, kontinuierliche Prozess ist dadurch gekennzeichnet, dass das Kohlendioxid (C02) haltige Abgas (aus der Kohlendioxid (C02)- Wäschereinheit mit Regeneration) ganz oder anteilig in einen befeuerten Hilfsdampfkessel eingeleitet wird und durch Oxidation (Verbrennung) im Hilfsdampfkessel ein an flüchtigen Kohlenwasserstoffen (VOC und HAP) armes oder freies Abgas erhalten wird. Die nicht in den Hilfsdampfkessel eingeleiteten Anteile des Kohlendioxids haltigen Abgases können bevorzugt in anderen Prozessschritten, beispielsweise zur Harnstoffsynthese verwendet werden. In a first step, 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. In the carbon monoxide (CO) converter that is formed in equation [4] and not required for the actual ammonia synthesis and for many catalysts problematic carbon monoxide (CO) reacted with further hydrogen formation in carbon dioxide according to equation (5) and obtained a second synthesis gas mixture. 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.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens umfasst der Reformer einen (Primär)-Dampfreformer mit oder ohne Sekundärreformer und/oder einen autothermen Reformer. Insbesondere bei einer hohen Ammoniaktagesproduktion kann der Reformer auch nur aus einem oder mehreren autothermen Reformern bestehen. In a preferred embodiment of the method according to the invention, the reformer comprises a (primary) steam reformer with or without a secondary reformer and / or an autothermal reformer. In particular with a high ammonia production per day, the reformer can also consist of only one or more autothermal reformers.
Bevorzugt werden der erhaltene Ammoniak und ein Großteil des Kohlendioxids (C02) haltigen Abgases in einer Harnstoffanlage, bevorzugt verbundenen Harnstoffanlage, zu Harnstoff umgesetzt. Die Weiternutzung ermöglicht eine effektive Nutzung des Ammoniaks und insbesondere des bevorzugt zur Erzeugung des Synthesegases verwendeten Erdgases. Die gennannte Ausführung umfasst auch die bevorzugte direkte Nutzung eines Teils des Kohlendioxids (C02) haltigen Abgases ohne eine Verbrennung in dem erfindungsgemäßen Hilfsdampfkessel. 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.
Besonders bevorzugt wird der befeuerten Hilfsdampfkessel bei 170 °C bis 550 °C und/oder 5 bar bis 150 bar auf der Seite der Dampferzeugung betrieben. 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.
Die Erfindung umfasst des Weiteren die Verwendung der erfindungsgemäßen Anlage zur Ammoniak-Synthese zur Herstellung von Ammoniak und gleichzeitiger Reduktion von flüchtigen Kohlenwasserstoffen (VOC und HAP). 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).
Des Weiteren wird die Erfindung anhand der folgenden Figuren näher erläutert. Die Figuren beschränken dabei nicht den Schutzumfang der Erfindung, sondern dienen nur der beispielhaften Erläuterung. Die Figuren sind nicht maßstabsgetreu. Furthermore, the invention is explained in more detail with reference to the following figures. The figures do not limit the scope of protection of the invention, but only serve as an example. The figures are not to scale.
Es zeigen: Show it:
Figur 1 ein schematisches Fließbild einer Anlage zur Ammoniaksynthese und Figure 1 is a schematic flow diagram of a plant for ammonia synthesis and
Figur 2 ein schematisches Fließbild einer erfindungsgemäßen Anlage zur Ammoniaksynthese. Figure 2 is a schematic flow diagram of a plant for ammonia synthesis according to the invention.
Figur 1 zeigt ein schematisches Fließbild einer Anlage zur Ammoniaksynthese. Zur Bereitstellung von Wasserstoff dient ein Reformer (1 ), bevorzugt ein Primär- und ein Sekundärreformer und/oder ein autothermer Reformer. Die Bildung von Wasserstoff erfolgt dabei im Grundsatz nach Gleichung [4] Des Weiteren umfasst die Anlage einen Kohlenmonoxid (CO) - Konverter (2). In diesem wird das in Gleichung [4] gebildete und in der eigentlichen Ammoniaksynthese nicht benötigte Kohlenmonoxid (CO) unter weiterer Wasserstoffbildung in Kohlendioxid gemäß Gleichung [5] umgesetzt. An den Kohlenmonoxid (CO) - Konverter (2) schließt sich eine Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) an. Die Kohlendioxid (C02)- Wäschereinheit kann beispielsweise als bekannte Vorrichtung/Anordnung ausgeführt sein, bei der Kohlendioxid in einem Absorber unter Druck in einem geeigneten Lösungsmittel - beispielsweise Kaliumkarbonat oder Amine - gelöst wird und anschließend wieder getrennt vom Synthesegas entspannt („flash“) wird. Das Lösungsmittel kann anschließend wieder erwärmt und in einer Stripping Säule (Desorber) regeneriert werden. Eine Methanisierungseinheit (4) ermöglicht die weitere Reduzierung von Kohlenstoffoxiden (COx). Dies erfolgt beispielsweise gemäß den Gleichungen [6] und [7]. Die Anlage umfasst des Weiteren eine mit der Methanisierungseinheit (4) verbundene Ammoniaksyntheseeinheit (5). Die Ammoniaksyntheseeinheit (5) umfasst den eigentlichen Ammoniaksynthesereaktor zur Umsetzung von Wasserstoff und Stickstoff gemäß Gleichung [3]. Die Bereitstellung von Stickstoff kann bevorzugt aus der im Sekundärreformer verarbeiteten (=verbrannten) Prozessluft erfolgen. Die Ammoniaksyntheseeinheit (5) ist mit Vorrichtungen zur Aufreinigung, Komprimierung und/oder Verflüssigung (9) verbunden. In Prozessrichtung und in Reihe sind der Reformer (1 ) der Kohlenmonoxid (CO) - Konverter (2), die Kohlendioxid (CO 2)- Wäschereinheit mit Regeneration (3), die Methanisierungseinheit (4), die Ammoniaksyntheseeinheit (5) und die Vorrichtungen zur Aufreinigung, Komprimierung und/oder Verflüssigung (9) verbunden. Die Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) weist eine zusätzliche Ableitung (8c) für die nicht weiter benötigten Abgase (6a) (hauptsächlich C02) zu einer Abluftanlage (7) auf. In der Abluftanlage (7) werden die in der Kohlendioxid (C02)- Wäschereinheit anfallenden Abgase (hauptsächlich C02) und flüchtigen organischen Kohlenwasserstoffe als Abgas (6a) an die Umgebung abgegeben. Der Ausdruck „verbunden“ umfasst im Sinne der Erfindung geeignete Rohre, Verbindungsstücke, Pumpen, Kompressoren, usw. welche für den Transport von Flüssigkeiten und Gasen auch bei Unterdrück (kleiner 1 bar) und Überdruck (größer als 1 bar) geeignet sind. Zwischen den voranstehend genannten Elementen können weitere Elemente wie Wärmetauscher, Pumpen, Kompressoren, Heizungen usw. angeordnet sein. 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]. Nitrogen can preferably be provided from the process air processed (= burned) in the secondary reformer. The ammonia synthesis unit (5) is connected to devices for purification, compression and / or liquefaction (9). In the process direction and in series are 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). In the exhaust air system (7), the exhaust gases (mainly C0 2 ) and volatile organic hydrocarbons produced in the carbon dioxide (C0 2 ) scrubber unit are released to the environment as exhaust gas (6 a). For the purposes of the invention, 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.
Figur 2 ein schematisches Fließbild der erfindungsgemäßen Anlage zur Ammoniaksynthese. Der grundsätzliche Aufbau entspricht dem in Figur 1 beschriebenen Aufbau. Die erfindungsgemäße Anlage ist dadurch gekennzeichnet, dass die Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) mit einem befeuerten Hilfsdampfkessel (6) verbunden ist. Die in der Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) mit dem Kohlendioxid in dem kohlendioxidhaltigen Abgasen (6a) anfallenden flüchtigen Kohlenwasserstoffe (VOCs und HAPs), beispielsweise Methanol, werden in dem befeuerten Hilfsdampfkessel verbrannt und zu Kohlendioxid und Wasser umgesetzt. Der Hilfsdampfkessel (6) wird über eine erste Zuleitung (8a) mit Luft und eine zweite Zuleitung (8b) mit Brenngas versorgt. Die erste Zuleitung (8a) ist dabei mit der Ableitung (8c) aus der Wäschereinheit mit Regeneration (3) verbunden, so dass eine Vormischung der in der Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) mit dem C02 anfallenden flüchtigen Kohlenwasserstoffe mit Luftsauerstoff erfolgt. Über die Abluftvorrichtung (7) gelangt an flüchtigen Kohlenwasserstoffen (VOC und HAP) armes oder freies Abgas (6b) in die Atmosphäre. Bezuqszeichen Figure 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). REFERENCE CHARACTERS
(1 ) Reformer (1) reformer
(2) Kohlenmonoxid (CO) - Konverter  (2) Carbon monoxide (CO) converter
(3) Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) Carbon dioxide (C0 2 ) - scrubber unit with regeneration
(4) Methanisierungseinheit  (4) methanation unit
(5) Ammoniaksyntheseeinheit  (5) ammonia synthesis unit
(6) befeuerten Hilfsdampfkessel  (6) fired auxiliary steam boiler
(6a) das Kohlendioxid (C02) haltige Abgas (6a) the carbon dioxide (C0 2 ) -containing exhaust gas
(6b) an flüchtigen Kohlenwasserstoffen (VOC und HAP) armes oder freies Abgas (6b) Low or free exhaust gas of volatile hydrocarbons (VOC and HAP)
(7) Abluftanlage (7) Exhaust system
(8a) erste Zuleitung  (8a) first supply line
(8b) zweite Zuleitung  (8b) second supply line
(9) Vorrichtungen zur Aufreinigung, Komprimierung und/oder Verflüssigung  (9) Purification, compression and / or liquefaction devices

Claims

Patentansprüche claims
1. Anlage zur Ammoniak-Synthese mindestens umfassend: 1. Plant for ammonia synthesis at least comprising:
a.) einen Reformer (1 );  a.) a reformer (1);
b.) einen Kohlenmonoxid (CO) - Konverter (2);  b.) a carbon monoxide (CO) converter (2);
c.) eine Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3); c.) a carbon dioxide (C0 2 ) scrubber unit with regeneration (3);
d.) eine Methanisierungseinheit (4);  d.) a methanation unit (4);
e.) eine Ammoniaksyntheseeinheit (5);  e.) an ammonia synthesis unit (5);
dadurch gekennzeichnet, dass die Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) mit mindestens einem befeuerten Hilfsdampfkessel (6) verbunden ist. characterized in that the carbon dioxide (C0 2 ) scrubber unit with regeneration (3) is connected to at least one fired auxiliary steam boiler (6).
2. Anlage nach Anspruch 1 , dadurch gekennzeichnet, dass der befeuerte Hilfsdampfkessel (6) mit einer Abluftvorrichtung (7) verbunden ist. 2. Installation according to claim 1, characterized in that the fired auxiliary steam boiler (6) is connected to an exhaust air device (7).
3. Anlage nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Reformer (1 ) einen Dampfreformer mit oder ohne Sekundärreformer und/oder einen autothermen Reformer umfasst. 3. Plant according to claim 1 or 2, characterized in that the reformer (1) comprises a steam reformer with or without a secondary reformer and / or an autothermal reformer.
4. Anlage nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass eine Luftzerlegungsanlage enthalten ist und/oder der Stickstoff aus der in einem Sekundärreformer beaufschlagten (=verbrannten) Prozessluft bereitgestellt wird. 4. Plant according to one of claims 1 to 3, characterized in that an air separation plant is included and / or the nitrogen is provided from the process air charged (= burned) in a secondary reformer.
5. Anlage nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass in Prozessrichtung und in Reihe der Reformer (1 ), der Kohlenmonoxid (CO) - Konverter (2), die Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3), die Methanisierungseinheit (4) und Ammoniaksyntheseeinheit (5) verbunden sind und die Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) eine zusätzliche Verbindung zu mindestens einem befeuerten Hilfsdampfkessel (6) aufweist. 5. Plant according to one of claims 1 to 4, characterized in that in the process direction and in series the reformer (1), the carbon monoxide (CO) converter (2), the carbon dioxide (C0 2 ) - scrubber unit with regeneration (3) , The methanation unit (4) and ammonia synthesis unit (5) are connected and the carbon dioxide (C0 2 ) scrubber unit with regeneration (3) has an additional connection to at least one fired auxiliary steam boiler (6).
6. Anlage nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der befeuerte Hilfsdampfkessel (6) Zuleitungen für Luft (8a) und Zuleitungen für Brennmittel (8b) aufweist. 6. Installation according to one of claims 1 to 5, characterized in that the fired auxiliary steam boiler (6) has supply lines for air (8a) and supply lines for fuel (8b).
7. Anlage nach Anspruch 6, dadurch gekennzeichnet, dass die Zuleitungen für Luft (8a) mit der Kohlendioxid (C02)- Wäschereinheit mit Regeneration (3) verbunden ist. 7. Plant according to claim 6, characterized in that the supply lines for air (8a) with the carbon dioxide (C0 2 ) - scrubber unit with regeneration (3) is connected.
8. Anlage nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der befeuerter Hilfsdampfkessel (6) eine Kapazität von 10 Tonnen bis 200 Tonnen Dampf pro Stunde aufweist. 8. Installation according to one of claims 1 to 7, characterized in that the fired auxiliary steam boiler (6) has a capacity of 10 tons to 200 tons of steam per hour.
9. Verfahren zur Ammoniak-Synthese mindestens umfassend die Schritte: 9. A method for ammonia synthesis at least comprising the steps:
a.) einleiten eines alkanhaltigen Gases in einen Reformer (1 ) und erhalten eines ersten Synthesegasgemisches,  a.) introducing an alkane-containing gas into a reformer (1) and receiving a first synthesis gas mixture,
b.) einleiten des ersten Synthesegasgemisches in einen Kohlenmonoxid (CO) - b.) introducing the first synthesis gas mixture into a carbon monoxide (CO) -
Konverter (2) und erhalten eines zweiten Synthesegasgemisches; Converter (2) and receive a second synthesis gas mixture;
c.) einleiten des zweiten Synthesegasgemisches in eine Kohlendioxid (C02)-c.) introduce the second synthesis gas mixture into a carbon dioxide (C0 2 ) -
Wäschereinheit mit Regeneration (3) und erhalten eines dritten Synthesegasgemisches und einem Kohlendioxid (C02) haltigen Abgases (6a); d.) einleiten des dritten Synthesegasgemisches in eine Methanisierungseinheit (4) und erhalten eines vierten Synthesegasgemisches; Scrubber unit with regeneration (3) and receive a third synthesis gas mixture and a carbon dioxide (C0 2 ) containing exhaust gas (6a); d.) introducing the third synthesis gas mixture into a methanation unit (4) and obtaining a fourth synthesis gas mixture;
e.) einleiten des vierten Synthesegasgemisches in eine Ammoniaksyntheseeinheit e.) introduce the fourth synthesis gas mixture into an ammonia synthesis unit
(5) und erhalten von Ammoniak; (5) and obtained from ammonia;
wobei das Kohlendioxid (C02) haltige Abgas (6a) aus Schritt c.) ganz oder anteilig in einen befeuerten Hilfsdampfkessel (6) eingeleitet wird und ein an flüchtigen Kohlenwasserstoffen (VOC und HAP) armes oder freies Abgas (6b) erhalten wird. wherein the carbon dioxide (C0 2 ) -containing exhaust gas (6a) from step c.) is introduced in whole or in part into a fired auxiliary steam boiler (6) and an exhaust gas (6b) low or free of volatile hydrocarbons (VOC and HAP) is obtained.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass der Reformer (1 ) einen Dampfreformer mit oder ohne Sekundärreformer und/oder einen autothermen Reformer umfasst. 10. The method according to claim 9, characterized in that the reformer (1) comprises a steam reformer with or without a secondary reformer and / or an autothermal reformer.
1 1. Verfahren nach Anspruch 9 oder 10, dadurch gekennzeichnet, dass das der Ammoniak (1 e) und ein Großteil des Kohlendioxid (C02) haltigen Abgases (6a) oder an flüchtigen Kohlenwasserstoffen (VOC und HAP) armes oder freies Abgas (6b) in einer Harnstoffanlage zu Harnstoff umgesetzt werden. 1 1. The method according to claim 9 or 10, characterized in that the ammonia (1 e) and a large part of the carbon dioxide (C0 2 ) containing exhaust gas (6a) or volatile hydrocarbons (VOC and HAP) poor or free exhaust gas (6b ) are converted to urea in a urea plant.
12. Verfahren nach einem der Ansprüchen 9 bis 1 1 , dadurch gekennzeichnet, dass der befeuerten Hilfsdampfkessel (6) bei 170 °C bis 550 °C auf der Seite der Dampferzeugung betrieben wird. 12. The method according to any one of claims 9 to 1 1, characterized in that the fired auxiliary steam boiler (6) is operated at 170 ° C to 550 ° C on the side of the steam generation.
13. Verfahren nach einem der Ansprüchen 9 bis 12, dadurch gekennzeichnet, dass der befeuerten Hilfsdampfkessel (6) bei 5 bar bis 150 bar auf der Seite der Dampferzeugung betrieben wird. 13. The method according to any one of claims 9 to 12, characterized in that the fired auxiliary steam boiler (6) is operated at 5 bar to 150 bar on the side of the steam generation.
14. Verwendung der Anlage zur Ammoniak-Synthese nach einem der Ansprüche 1 bis 8 zur Herstellung von Ammoniak und Reduktion von flüchtigen Kohlenwasserstoffen (VOC und HAP). 14. Use of the plant for ammonia synthesis according to one of claims 1 to 8 for the production of ammonia and reduction of volatile hydrocarbons (VOC and HAP).
EP19733724.9A 2018-07-03 2019-06-24 Method for avoiding voc and hap emissions from synthesis gas-processing systems Pending EP3818009A1 (en)

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