EP4097051A1 - Procédé de synthèse d'ammoniac et installation pour préparation d'ammoniac - Google Patents
Procédé de synthèse d'ammoniac et installation pour préparation d'ammoniacInfo
- Publication number
- EP4097051A1 EP4097051A1 EP21701683.1A EP21701683A EP4097051A1 EP 4097051 A1 EP4097051 A1 EP 4097051A1 EP 21701683 A EP21701683 A EP 21701683A EP 4097051 A1 EP4097051 A1 EP 4097051A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- ammonia
- nitrogen
- synthesis
- converter
- 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
Links
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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- 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 method for ammonia synthesis in a synthesis cycle, wherein a gas mixture comprising nitrogen, hydrogen and ammonia is circulated in the synthesis cycle with a conveying device, nitrogen and hydrogen being at least partially converted to ammonia in a converter and the gas mixture being cooled in this way in a cooling device that ammonia condenses out of the gas mixture.
- the invention relates to a plant for the production of ammonia in a synthesis cycle, with at least one conveying device for circulating a gas mixture comprising nitrogen, hydrogen and ammonia with a converter, with nitrogen and hydrogen being at least partially convertible to ammonia in the converter and with a cooling device in the the gas mixture can be cooled in such a way that ammonia condenses out of the gas mixture.
- Ammonia is one of the most important raw materials.
- the world annual production is currently around 170 million tons.
- Most of the ammonia is used to make fertilizers.
- Large-scale production today largely uses the high-pressure synthesis developed by Haber and Bosch at the beginning of the 20th century in fixed bed reactors with iron as the catalytically active main component, based on a stoichiometrically composed synthesis gas with the main components hydrogen and nitrogen.
- the synthesis gas is mainly generated via the natural gas route.
- the large amounts of carbon dioxide produced are disadvantageous here.
- 10 2017 011 601 A1 shows, for example, a method for ammonia synthesis in which a fresh gas consisting largely of hydrogen and nitrogen is compressed via a compressor and then fed to an ammonia converter for conversion into a converter product containing ammonia and comprising hydrogen and nitrogen.
- Ammonia is then evaporated into the fresh gas upstream of the fresh gas compressor in order to cool the fresh gas and to generate a cold mixture of substances comprising ammonia and fresh gas.
- the mixture of substances is warmed up in a heat exchanger against at least one ammonia synthesis process stream to be cooled and then compressed via the fresh gas compressor in order to obtain a mixture of substances comprising compressed ammonia and fresh gas.
- a stream of substances comprising the fresh gas is fed upstream of a circulation cooler to a gas mixture consisting largely of hydrogen and nitrogen, the components of which are separated from the converter product and the compressed substance mixture comprising ammonia and the fresh gas
- EP 2 589 426 A1 discloses a method for producing ammonia in which hydrogen is obtained from the electrolysis of water.
- nitrogen can be obtained from a cryogenic air separation plant.
- the substances are mixed with one another and compressed to a pressure in the range from 80 to 300 bar.
- the starting materials In ammonia synthesis, the starting materials must be free of oxygen and oxygen-containing compounds such as water, as otherwise they would poison the catalyst in the ammonia converter.
- the hydrogen from the electrolysis is usually saturated with water vapor and also contains up to 0.1% by volume of oxygen.
- hydrogen and nitrogen are mixed in a stoichiometric ratio of 3 to 1 and fed into the synthesis cycle and the water is converted from the starting materials (the so-called make-up gas or fresh gas) through adsorption dryers or through absorption of the water in the liquid ammonia formed (the so-called Make-up gas or fresh gas) removed.
- Adsorption drying is expensive because it requires several adsorbers that are alternately exposed to the fresh gas and have to be thermally regenerated with a flushing gas, which is expensive. This leads to increased investment costs, a time delay when starting up the system (again) and to emissions of the purge gas.
- the absorption has the disadvantage that the fresh gas must be added before the ammonia condenses out.
- the circulating gas is diluted in terms of its ammonia content by the reactants introduced, so that the condensation temperature remains the same less ammonia is separated from the circulating gas and the ammonia content at the inlet of the converter is increased compared to adsorption drying.
- the high pressure volume of the apparatus in the synthesis cycle is increased and thus the investment costs also increase.
- nitrogen is introduced into the synthesis cycle in the flow direction upstream of the converter and / or directly into the converter. At the entrance to the converter, there is then a lower entrance concentration of ammonia. More ammonia can therefore be formed per pass through the converter, so that a smaller amount of catalyst and a smaller amount of recycle gas are required.
- the nitrogen is thus fed to the synthesis circuit upstream of the conveying device and before the cooling device.
- the circulating gas containing ammonia is not diluted with nitrogen prior to the condensation of the ammonia, so that the ammonia condenses out at higher partial pressures and there is a lower concentration of ammonia at the inlet to the converter. It can therefore per pass through the converter More ammonia can be formed, so that a smaller amount of catalyst and a smaller amount of recycle gas is required than if the nitrogen is added together with the hydrogen before the ammonia separation.
- the conveying device which can be a circulator, for example, therefore circulates a smaller amount of gas.
- the outlet temperature of the individual catalyst bed can be controlled not only by admixing cold quench gas, but also by adjusting the ratio of hydrogen and nitrogen to one another at each bed inlet.
- the speed of the reaction can also be controlled in this way.
- hydrogen can be provided by means of electrolysis of water.
- the electrolysis of water does not produce high-purity hydrogen. Rather, what remains is water or water vapor that has to be separated from the hydrogen.
- the water By introducing the hydrogen downstream of the converter and upstream of the cooling device, the water can be absorbed by the ammonia and condense out with the ammonia in the cooling device. In this way, it is possible to dispense with an expensive apparatus for adsorption.
- the energy required for the electrolysis is obtained from renewable energies.
- Renewable energies or regenerative energies are understood to mean energy carriers that are practically inexhaustible within the human timeframe or that are renewed relatively quickly. This includes, for example, solar energy, geothermal energy or energy from biomass.
- the stoichiometric ratio of introduced hydrogen and nitrogen is 3 to 1.
- the ratio of hydrogen to nitrogen is regulated when the hydrogen supply decreases, the ratio of hydrogen and nitrogen in the range of 0 , 95 and 1 lies. This means that the process can continue to operate even if hydrogen production declines. When hydrogen production rises again, the hydrogen to nitrogen ratio can slowly be brought back to normal, i.e. to a stoichiometric ratio of hydrogen to nitrogen of 3 to 1, by increasing the hydrogen feed into the synthesis cycle. This method prevents frequent starting or stopping of the plant in which the process is operated, with fluctuating or non-existent hydrogen production by electrolysis, should the renewable energy sources fluctuate.
- hydrogen is compressed before it is introduced into the synthesis cycle.
- the hydrogen from the electrolysis is compressed separately, so that the end stages of the corresponding compressor have to compress a lower volume flow than if hydrogen and nitrogen are compressed together and fed into the synthesis cycle.
- the compressor therefore also requires less drive power.
- a plant for the production of ammonia in a synthesis cycle with at least one conveying device for circulating a gas mixture comprising nitrogen, hydrogen and ammonia with a converter, with nitrogen and hydrogen being at least partially convertible to ammonia in the converter and with a Cooling device in which the gas mixture can be cooled in such a way that ammonia condenses out of the gas mixture.
- the system is characterized in that hydrogen and nitrogen can be introduced into the synthesis cycle at sections that are different from one another.
- nitrogen in the flow direction in front of and / or in the flow direction behind the converter in the synthesis cycle can be introduced.
- the entrance to the converter there is then a lower entrance concentration of ammonia. More ammonia can therefore be formed per pass through the converter, so that a smaller amount of catalyst and a smaller amount of recycle gas are required.
- the nitrogen is thus fed to the synthesis circuit upstream of the conveying device and before the cooling device.
- hydrogen can be introduced into the synthesis circuit in the flow direction upstream of the cooling device. Before the cooling device also means behind the converter. Thus, any water containing hydrogen can be dissolved in the ammonia formed and is condensed out together with the ammonia in the cooling device.
- At least one electrolysis cell is provided for producing the hydrogen.
- the required hydrogen is provided accordingly through the electrolysis of water.
- Fig. 3 is a schematic representation of a method according to the invention for
- the anhydrous fresh gas introduced is mixed with the cycle gas by means of a conveyor 2 in the synthesis cycle 1.
- a converter 3 is provided for converting hydrogen H2 and nitrogen N2.
- hydrogen H2 and nitrogen N2 react to form ammonia NH3.
- the gas mixture consisting of hydrogen H2, nitrogen N2 and ammonia NH3 is passed into a cooling device 4.
- the cooling device 4 the gas mixture is cooled down to such an extent that ammonia NH3 condenses and can be separated out in liquid form.
- the converted starting materials hydrogen H2 and nitrogen N2 as well as the uncondensed ammonia NH3 are returned in the synthesis circuit 1 to the conveying device 2.
- the delivery device can be a pump or a circulator.
- the nitrogen N2 required for the ammonia synthesis is supplied in highly pure gaseous form by a nitrogen supply 5.
- the hydrogen H2 which is also necessary, is generated by electrolysis 6 of water.
- the electricity required for this is obtained from fluctuating, renewable energies.
- the power consumption of the electrolyzer can be reduced to 20% of the nominal power.
- Hydrogen H2 and nitrogen N2 are mixed and compressed together to the pressure of the synthesis in a compressor 7.
- the water present is removed in an adsorption dryer 8 with the aid of molecular sieves.
- Adsorption drying is expensive, since several adsorbers are required for the adsorption dryer, which are alternately acted upon with the gas mixture and which have to be thermally regenerated with a flushing gas, which is expensive.
- the circulating gas is diluted in terms of its ammonia content by the reactants introduced, so that less ammonia is separated from the circulating gas at the same condensation temperature and the ammonia content at the inlet of the converter 3 is increased compared to the adsorption drying.
- FIG. 3 shows a schematic representation of the method according to the invention or the plant according to the invention for the production of ammonia NH3.
- the nitrogen N2 is supplied in high purity, free of oxygen and oxygen-containing compounds, from the nitrogen supply 5.
- the nitrogen N2 is directed both upstream and directly into the converter 3 in the direction of flow.
- More ammonia NH3 can therefore be formed per pass through the converter 3, so that a smaller amount of catalyst and a smaller amount of circulating gas are required compared with the simultaneous addition of hydrogen H2 and nitrogen N2.
- the hydrogen H2 from the electrolysis 6 is compressed separately with a compressor 7, so that the end stages of the compressor 6 have to compress a lower volume flow than if hydrogen H2 and nitrogen N2 are compressed together and fed to the synthesis circuit 1.
- the hydrogen H2 which has been compressed to approximately 261 bara, is added to the cycle gas upstream of the cooling device 4. This has the advantage that the water contained in the hydrogen H2 dissolves in the condensing ammonia NH3 and is removed from the synthesis circuit 1 with the liquid ammonia NH3. A separate drying of the fresh gas with the associated financial and equipment expenditure as well as the time-consuming and emission-prone regeneration of the adsorption dryer 8 are therefore no longer necessary.
- the minimum hydrogen H2 to nitrogen N2 ratio for the feed to the converter is set at approximately 1, so that the partial load range of the converter 3 can be further reduced without the reaction coming to a standstill. This is particularly advantageous because, with a low hydrogen supply, it enables the reaction to behave autothermally without external heating.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Analytical Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
- Drying Of Gases (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102020200905.8A DE102020200905A1 (de) | 2020-01-27 | 2020-01-27 | Verfahren zur Ammoniaksynthese und Anlage zur Herstellung von Ammoniak |
PCT/EP2021/050597 WO2021151672A1 (fr) | 2020-01-27 | 2021-01-13 | Procédé de synthèse d'ammoniac et installation pour préparation d'ammoniac |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4097051A1 true EP4097051A1 (fr) | 2022-12-07 |
Family
ID=74236149
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21701683.1A Pending EP4097051A1 (fr) | 2020-01-27 | 2021-01-13 | Procédé de synthèse d'ammoniac et installation pour préparation d'ammoniac |
Country Status (4)
Country | Link |
---|---|
US (1) | US20230034962A1 (fr) |
EP (1) | EP4097051A1 (fr) |
DE (1) | DE102020200905A1 (fr) |
WO (1) | WO2021151672A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102021122602B4 (de) * | 2021-09-01 | 2024-03-28 | Uniper Technologies GmbH | Anlage und Verfahren zur kontinuierlichen Herstellung von Ammoniak unter Verwendung von erneuerbaren Energien |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4107277A (en) | 1976-07-13 | 1978-08-15 | Da Rosa Aldo Vieira | Process for production of ammonia |
JP4117417B2 (ja) * | 2002-03-15 | 2008-07-16 | 日立造船株式会社 | アンモニアの製造方法、及びその装置 |
TWI427035B (zh) * | 2011-08-02 | 2014-02-21 | Univ Nat Pingtung Sci & Tech | 氨製備裝置 |
EP2589426B1 (fr) | 2011-11-02 | 2016-06-08 | Casale Sa | Procédé pour éliminer des oxydes d'azote de fumées de combustion avec génération sur site d'ammoniac |
DE102017204208A1 (de) | 2017-03-14 | 2018-09-20 | Thyssenkrupp Ag | Verfahren und Anlage zur Erzeugung und Aufbereitung eines Synthesegasgemisches |
DE102017011601A1 (de) | 2017-12-14 | 2019-06-19 | Linde Aktiengesellschaft | Ammoniaksynthese mit internem Kühlkreislauf |
DE102017222948A1 (de) * | 2017-12-15 | 2019-01-24 | Thyssenkrupp Ag | Produktion von Ammoniak und Wasserstoff mit direkter Stromeinspeisung aus Offshore Energiegewinnungsanlagen |
-
2020
- 2020-01-27 DE DE102020200905.8A patent/DE102020200905A1/de active Pending
-
2021
- 2021-01-13 WO PCT/EP2021/050597 patent/WO2021151672A1/fr unknown
- 2021-01-13 EP EP21701683.1A patent/EP4097051A1/fr active Pending
- 2021-01-13 US US17/793,351 patent/US20230034962A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
DE102020200905A1 (de) | 2021-07-29 |
WO2021151672A1 (fr) | 2021-08-05 |
US20230034962A1 (en) | 2023-02-02 |
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