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WO2024172664A1 - Procédé et installation de production d'ammoniac bleu - Google Patents

Procédé et installation de production d'ammoniac bleu Download PDF

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Publication number
WO2024172664A1
WO2024172664A1 PCT/NO2024/050040 NO2024050040W WO2024172664A1 WO 2024172664 A1 WO2024172664 A1 WO 2024172664A1 NO 2024050040 W NO2024050040 W NO 2024050040W WO 2024172664 A1 WO2024172664 A1 WO 2024172664A1
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Prior art keywords
reactor
gas
stream
ammonia
sorbent
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Inventor
Arnstein NORHEIM
Elisabeth HELGESTAD
Mogahid OSMAN
Mustafa SÆTERDAL KØMURCU
Per Håvard NYLØKKEN LIEN
Vidar GRAFF
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ZEG POWER AS
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ZEG POWER AS
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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
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • 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
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/0425—In-situ adsorption process during hydrogen production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/068—Ammonia synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C01B2203/0894—Generation of steam

Definitions

  • the present invention relates to a method and plant for production of ammonia from methane, natural gas, biogas or biomethane as feedstock materials.
  • the method and the plant for production of ammonia from methane uses an integrated technique of obtaining the desired product from the feedstock material, however without emission of carbon dioxide.
  • the human society has applied carbonaceous fossil fuels (coal, oil, and natural gas) extracted from the lithosphere as its primary source of energy.
  • fossil fuels coal, oil, and natural gas
  • the current intended use of these fossil fuels converts practically all of their carbon content to carbon dioxide being vented to the atmosphere.
  • the use of fossil fuels constitutes a man-made flux of carbon dioxide entering the atmosphere, where it subsequently will relatively rapidly be distributed among the three surface carbon reservoirs of the natural carbon cycle; the biosphere, atmosphere, and the hydrosphere.
  • the natural carbon cycle has no effective mechanism (on a timescale relevant for human societies) able to bring the lithospheric carbon extracted by humans back to the lithosphere. Practically all lithospheric carbon taken up by humans historically up to date is therefore accumulated in said surface carbon reservoirs.
  • Hydrogen gas is a promising candidate for carbon-free fuel replacing petroleumbased fuels because it only forms water vapour when combusted/oxidised, and further because it has a veiy high combustion heat (per mass).
  • Another advantage is that hydrogen is a relatively strong reduction agent which enables using it as a reduction agent in several chemical/metallurgical processes instead of the presently used carbon/coal.
  • hydrogen gas has a low volumetric energy density at atmospheric conditions. The gas needs to be strongly compressed to achieve a useful volumetric energy density making it necessary to store and handle the gas at pressures up to several hundred bar when applying it as a fuel/chemical energy carrier in vehicles, energy plants, etc.
  • hydrogen gas is, due to its small molecular size, an evasive gas which is relatively difficult to contain/store and handle leakproof. This is unfortunate because the gas is also highly explosive in air/oxygen. The combination of highly pressurised and relatively difficult to contain constitutes a non-negligible safety hazard when applying the gas as a chemical energy carrier/fuel.
  • Ammonia is receiving much attention in this regard due to having useful gravimetric and volumetric energy densities, it may be applied as a fuel by itself or mixed with other fuels in internal combustion engines, it may be applied as fuel in fuel cells, and it may be applied as a hydrogen storage. Ammonia contains 17 wt.% hydrogen which may be released by e.g. thermal catalytic cracking or electrooxidation. Furthermore, ammonia also has the advantage of being possible to transport and stored by current commercially available infrastructure.
  • ammonia is around 150 million metric tonnes and is used mainly in the fertiliser industry to make fertilisers and the weapons industry to make explosives.
  • ammonia is based on the Haber-Bosch process where hydrogen is catalytically reacted with nitrogen at elevated temperature s and pressures (typical 400 to 500 °C and above 10 MPa) to form ammonia:
  • the main objective of the invention is the provision of an integrated method for production of a hydrogen containing species having useful volumetric energy densities but associated with the benefit of an easy and safe handling and being produced from a carbonaceous feedstock material, in particular natural gas and/or other methane rich gas streams, which method is not associated with the emission of carbon dioxide.
  • the integrated method should overcome the above outlined problems.
  • the objective is the provision of an integrated method with an improved heat management. Further, any intermediate product occurring in the method and being further processed in the integrated method to obtain the desired hydrogen containing species should be fully consumed in the integrated method. Even further, the feedstock material should preferably be a biobased feedstock material.
  • a further objective is the provision of an integrated method providing opportunities for profiting from interferences between the parts of the processes to be integrated.
  • An even further objective of the invention is the provision of a plant suitable for executing the method for production of a hydrogen containing species having useful volumetric energy densities, which method does not leave a carbon footprint.
  • the invention is based on the realisation that a compact and efficient integrated process for producing blue ammonia is obtained by combining sorption enhanced steam reforming to convert a methane rich gas, such as e.g. natural gas, methane, biogas or biomethane, to hydrogen gas with a Ca-loop to capture CO2 and using air separation to obtain oxygen gas utilised in an oxyfuel combustion to provide the thermal energy needed to run the regeneration of the Ca-based CO2 absorbent and to provide the nitrogen gas required for the synthesis of ammonia.
  • a methane rich gas such as e.g. natural gas, methane, biogas or biomethane
  • This combination has the advantage of needing relatively few process units/process steps and that the ammonia synthesis may be made in an atmosphere free from undesired gas compounds that normally are present in gas streams produced from SMR, ATR and other process schemes (CO, CH4, CO2). Furthermore, the process has the advantage of producing more or less the correct stoichiometric ratio of hydrogen to nitrogen to synthesise ammonia.
  • the integrated process is adapted in a way that the feedstock material for the Haber-Bosch synthesis can be directly used.
  • - forming a stream of hydrogen gas by: feeding a feed stream of a methane rich gas, preferably natural gas, and a feed stream of steam into a first reactor 10 containing a lean CO2-sorbent and performing a sorption-enhanced reforming of the methane rich gas forming a stream of hydrogen gas and carbon dioxide which is absorbed/adsorbed by and converting the lean CO2-sorbent to a stream of rich CCh-sorbent,
  • the overall goal is achieved by the claimed invention, which overall goal refers to the production of a hydrogen containing species with a high energy density in an integrated method, which production uses a carbonaceous feed stock material, without release of carbon dioxide.
  • ammonia one possible species having useful volumetric energy densities is ammonia.
  • One possible route of obtaining ammonia is the conversion of methane or a methane containing gas, preferably biogas or biomethane, via steam reforming and the Haber-Bosch process.
  • a process of obtaining hydrogen via steam reforming and the process of obtaining ammonia from hydrogen via Haber-Bosch synthesis is depicted in more detail.
  • typical operation conditions in the SMR reactor are temperatures of 800 to 900 °C and 2 to 3 MPa pressure
  • typical operation conditions in the WGS reactor are temperatures of 200 to 450 °C and from 0.1 to 8 MPa pressure.
  • the reactions involved are:
  • FIG. 1 A process diagram illustrating an example of a typical ammonia Haber-Bosch production process using natural gas as hydrogen feedstock is shown in figure 1.
  • the natural gas (marked with letters “NG” on the figure) enters a first process step 1 which is a desulphurisation stage removing eventual sulphur in the natural gas feedstock.
  • the next step shown as a stapled box marked with reference number 2, is an optional pre-reforming step to break down higher hydrocarbons such as e.g. propane, butane etc. to methane.
  • the feedstock enters the steam methane reforming step 3. Since, as seen from eqn. (2), the SMR- reaction is highly endothermic, it is necessary to supply a considerable amount of heat to enable the reaction to continue.
  • step 3 This is usually obtained by supplying combustion air and combusting a part of the natural gas feedstock in the SMR- reactor(s) in step 3.
  • the supply of combustion air also has the function of providing nitrogen gas.
  • step 4 is the water-gas shift step completing the hydrogen production process steps.
  • the gas mixture is subject to a separation step (shown as box 5) to remove the CO2 from the process stream.
  • the gas separation may be obtained by e.g. pressure swing absorption.
  • Process step 6 is a methanation process to remove eventual remains of CO and/or CO2 in the gas stream.
  • a compression stage 7 before the gas stream is ready for entering the Haber-Bosch step (shown as box 8) converting the nitrogen and hydrogen content of the gas to ammonia.
  • the final step (shown as box 9) is cooling and condensing the ammonia to the liquid state.
  • methane is an effective hydrogen source by one molecule of methane forming four molecules of hydrogen gas. However, it is also formed one molecule of carbon dioxide.
  • a modem methane- fed Haber-Bosch process produces 1.5 to 1.6 tons of CO2 for each ton of produced NH3 making the ammonia industry accounting for 1.2 % of the anthropogenic CO2 emissions (Smith et al. (2020) [Ref 1]).
  • Calcium oxide, CaO is known to be an effective CO2 absorbent at relatively high temperatures making it suitable for post combustion carbon capturing from hot flue gases by simply contacting the flue gas with solid CaO at a temperature of 500 to 700 °C in a first reactor, often labelled as a carbonator. At these conditions, the CO2 in the flue gas reacts with the CaO absorbent to form calcium carbonate, CaCOs:
  • the calcium carbonate formed in the carbonator may be transferred to a second reactor, often labelled as a calciner, and heated until the calcium carbonate dissociates to form solid calcium oxide and a concentrated gas phase of CO 2:
  • the steam methane reforming process may be enhanced to a higher hydrogen yield by applying a CO 2 absorbent such as e.g. CaO in the steam reformer which removes formed CO 2 in the steam reformer and thus drives the equilibrium in reaction (3) towards forming more hydrogen.
  • a CO 2 absorbent such as e.g. CaO
  • the steam reforming process is known as a sorption enhanced reforming (SER) process.
  • Yin et al. (2011) [Ref 3] discloses a process for producing a syngas suitable for producing ammonia from a coal mine drainage gas, typically containing water vapour, air, methane and minor amounts of CO2.
  • SE-ATR sorption enhanced autothermal reforming
  • a sorption enhanced autothermal reforming process is fed with methane, water vapour/steam, air, CaO, and optionally oxygen, and performs both the steam methane reforming reaction, eqn. (2), the water-gas shift reaction, eqn. (3), the carbonising reaction, eqn. (5), and an autothermal reaction simultaneously in the same reactor.
  • the autothermal reaction (ATR) is:
  • Figure 2 which is a facsimile of figure 2 of Yin et al. (2019), show the integration of CaO-loop to capture and collect the CO2 formed in the SE-ATR step by combining a calciner with the SE-ATR reactor.
  • the energy required to run the calciner is obtained by oxyfuel combustion of a fuel in the calciner, and the oxygen is obtained by an air separation unit.
  • sorption-enhanced reforming (SER) of the methane rich gas refers to a process where hydrocarbons present in the methane rich gas are reacted with gaseous water (steam) in a combined/single-step steam reforming and water gas shift reaction to form hydrogen gas and carbon dioxide, which the latter is absorbed onto a Ca-based CCh-sorbent present in the first reactor.
  • An example of the overall reaction is given by eqn. (4) for the combined steam reforming and water-gas shift of methane.
  • other hydrocarbons such as e.g. butane, propane, etc. which may be present in the methane rich gas will also be converted to hydrogen and carbon dioxide.
  • the SER renders the hydrogen produced in an initial step to be so called blue hydrogen since the carbon dioxide is captured by the CO2- sorbent.
  • the state-of-the-art known distinguishing methods of producing hydrogen from methane.
  • the SER is one of it.
  • the invention may apply any catalyst and/or temperature and pressure regime which causes the hydrocarbons of the methane rich gas and steam to react in a combined/single-step steam reforming and water gas shift reaction producing hydrogen and carbon dioxide.
  • typical operation conditions in the SMR reactor when operated individually for the production of hydrogen, are temperatures of 800 to 900 °C and 2 to 3 MPa pressure
  • typical operation conditions in the WGS reactor are temperatures of 200 to 450 °C and from 0.1 to 8 MPa pressure.
  • suited catalysts include nickel and/or platinum based heterogeneous catalysts.
  • the temperature in the first reactor will be in the range from 500 to 750 °C, preferably from 550 to 725 °C, more preferably from 600 to 700 °C, and most preferably from 625 to 675 °C, and the pressure is in the range from 0.1 to 8 MPa, preferably from 0.15 to 5 MPa, more preferably from 0.2 to 3 MPa, more preferably from 0.25 to 2.5 MPa or less, and most preferably from 0.3 to 2 MPa.
  • the temperature range is significantly lower as under typical operation conditions; further, the pressure range is slightly lower as under typical operation conditions.
  • a preferable combined temperature/pressure regime is 500 to 700°C and 0.1 to less than 2.5 MPa, more preferred 0.3 to 2 MPa.
  • the temperature in the first reactor will be in the range from 500 to 700 °C, and most preferably from 600 to 650 °C, and the pressure is in the range from 0.1 to 2.5 MPa or less, and most preferably from 0.3 to 2 MPa.
  • an air separation unit encompasses any known process and device able to separate the nitrogen and oxygen content of air into two separate gas phases. Examples of suitable processes includes pressure swing absorption, vacuum pressure swing absorption, membrane separation, cryogenic separation etc.
  • temperature induced desorption of the enriched CCh-sorbent encompasses any thermal treatment causing a desorption of the sorbent enriched with CO2 and thus regenerates the sorbent for use in the sorption-enhanced reforming of the methane rich gas and produces a gaseous CCh-phase which may be passed on to a downstream CO2 storage facility (not shown on the figures).
  • the steam to carbon is understood as known by a skilled person, i.e. it means the molar quotient of H2O versus C atoms.
  • the S/C ratio is from 2 to 5, preferably from 2.5 to 4, more preferred 3 to 3.5.
  • the method of claim 1 represents an integrated method.
  • several process steps are implemented which process steps’ operation parameters might have an impact on other - in particular subsequent - process steps.
  • the below verification of the invention shows that the implementation of the process steps succeeds. There is thus a way of implementing a hydrogen production step by means of an SER process together with an ammonia production step by means of a Haber-Bosch process.
  • the optimal relationship between temperature, pressure and steam to carbon ratio can be found by simulation.
  • the optimal relationship in between temperature and pressure lays in the above mentioned ranges.
  • a further issue in the development of an integrated method refers to the impurities in the hydrogen stream. While in non-integrated production processes of hydrogen, purification steps are applied independently from subsequent steps, integrated methods tend to minimize intermediate measures and to use the intermediate products as received. It turned out that the molar fraction of methane increases with lowering temperature and a steep increase of the molar fraction of methane is found around 650°C towards lower temperatures (under conditions of 15 bar pressure and a S/C ratio of 4). On the other hand, with an onset of about 700°C, the mol fraction of carbon monoxide and carbon dioxide increases with increasing temperature.
  • the method for manufacturing ammonia according to the invention represents an integrated method by combining the SER process for hydrogen production, with the ammonia production.
  • the heat management of the second reactor i.e. the SER reactor is considered. It turned out that the heat management in view of the SER reactor gives raise to improvements.
  • the method of manufacturing ammonia comprises the essential steps of providing heat energy to run said desorption of said enriched CCh-sorbent by: feeding a fuel and said stream of oxygen to the second reactor (20) and performing an oxyfuel combustion of said fuel, and sequestrating said stream of carbon dioxide by: passing said stream of carbon dioxide to a downstream carbon dioxide storage facility, see the respective feature of claim 1.
  • the ammonia stems from the purge of the third reactor.
  • the invention may apply any temperature and pressure regime in the second reactor which makes enriched sorbent (from the first reactor) to desorb and release its CO2- content and regenerates the sorbent (which is sent back to the first reactor).
  • the temperature in the second reactor will typically be in the range from 700 to 1000 °C, preferably from 750 to 950 °C, more preferably from 800 to 900 °C, and most preferably from 825 to 875 °C
  • the pressure in the second reactor will typically be in the range from 100 to 400 kPa, preferably from 105 to 350 kPa, and most preferably from 110 to 300 kPa.
  • the invention is not tied to any specific CCh-absorbent but may utilize any sorbent capable of cycled sorption and desorption of carbon dioxide at the above defined temperatures and pressure regimes for the sorption-enhanced reforming of the methane rich gas and the temperature induced desorption of the enriched CO2- sorbent.
  • sorbents include particulate CaO, particulate CaO doped with one or more of; Na, K, La, Ce, and Zr.
  • the doped or undoped particulate CaO may in one alternative be supported by CaZrOs, CeO2, La2Oa, AI2O3.
  • the doped or undoped CaO may be a double-salt or mineral containing 20-50 wt% MgO and 50-80 wt% CaO.
  • the invention is not tied to any particular particle size of the sorbent, but may apply any particle size and particle size distribution being suited to cyclic sorption and desorption of carbon dioxide at the above defined temperatures and pressure regimes for the sorption-enhanced reforming of the methane rich gas and the temperature induced desorption of the enriched CO2-sorbent.
  • the dso particle size is typically in the range of 1 pm to 5 mm, preferably from 5 pm to 3 mm, more preferably from 10 pm to 2 mm, more preferably from 50 pm to 1 mm, more preferably from 100 pm to 0.5 mm, and most preferably from 150 pm to 0.4 mm.
  • the particle sizes as used herein are the diameter of the grain/particle as determined by standard ISO 9276-1:1998 for irregular particles based on the volume of the grain/particle. I.e. the diameter of the grain/particle is determined as being considered equal to the diameter of a sphere having the same volume as the irregular grain/particle, and where the dso particle size is determined by ISO 9276- 2:2001.
  • the temperature induced desorption of the enriched CO2-sorbent is in the method according to the first aspect of the invention described to take place in a second reactor. This does, however, not imply that there must be applied to physically separate reactors, but may alternatively also encompass a single two-chamber reactor where the sorption-enhanced steam reforming is taking place in a first chamber and where the temperature induced desorption is taking place in a second chamber.
  • the invention relates to a plant suitable for executing the method according to the first aspect of the invention, wherein the plant comprises:
  • a first reactor 10 containing a lean CCh-sorbent and a steam reforming catalyst and adapted to perform a sorption-enhanced steam reforming of a methane rich gas, preferably natural gas,
  • a third reactor 50 adapted to perform a Haber-Bosch synthesis of hydrogen and nitrogen to form ammonia, wherein the plant further comprises:
  • first gas pipeline 13 adapted to transferring hydrogen gas from the first reactor 10 to the mixing, and optionally a compression, unit 30,
  • a fourth gas pipeline 42 adapted to transfer nitrogen gas from the air separation unit 40 to the mixing, and optionally a compression, unit 30,
  • a fifth gas pipeline 31 adapted to transfer the mixed, and optionally compressed, hydrogen and nitrogen gas from the mixing, and optionally a compression, unit 30 to the third reactor 50, and
  • third transportation line 51 adapted to transport ammonia from the third reactor 50 to a downstream ammonia product handling facility.
  • the invention according to the first or second aspect of the invention may further comprise a first heat exchanger 15 located on the first inlet 11 and which preheats the stream of methane rich gas entering the first reactor 10 by heat exchanging it with the stream of hydrogen exiting the first reactor 10.
  • the invention according to the first or second aspect of the invention relates to a plant, which comprises a sixth gas pipeline 54 adapted to transfer a purge gas from the third reactor 50 to the second reactor 20.
  • This embodiment is associated with the beneficial effect that ammonia which is not recovered as product can be used as a fuel for the second reactor 20.
  • the purge gas from the third reactor 50 comprises non converted hydrogen.
  • the purge gas comprises hydrogen which can be used as fuel in the second reactor 20.
  • the invention according to the first or second aspect of the invention may further comprise a second heat exchanger 16 located on the first gas pipeline 13 and which regenerates waste heat from the stream of hydrogen gas flowing therein by producing steam.
  • the steam may be applied to supply the first reactor 10 and/or the second reactor 20.
  • the invention according to the first or second aspect of the invention may further comprise a third heat exchanger 24 located on the second gas pipeline 23 and which regenerates waste heat from the stream of carbon dioxide flowing therein to produce steam
  • the steam may be applied to supply the first reactor 10 and/or the second reactor 20.
  • the invention according to the first or second aspect of the invention may further comprise a fourth heat exchanger 32 located on the fifth gas pipeline 31 and which preheats the ammonia syngas exiting the mixing, and optionally compression, unit 30 by heat exchanging it with ammonia exiting the Haber-Bosch reactor 50.
  • a fourth heat exchanger 32 located on the fifth gas pipeline 31 and which preheats the ammonia syngas exiting the mixing, and optionally compression, unit 30 by heat exchanging it with ammonia exiting the Haber-Bosch reactor 50.
  • the invention according to the first or second aspect of the invention may further comprise a fifth heat exchanger 52 located on the third transportation line 51 and which regenerates waste heat from the stream of ammonia being transported therein to produce steam
  • the steam may be applied to supply the first reactor 10 and/or the second reactor 20.
  • the invention according to the first or second aspect of the invention may further comprise one or more of:
  • first separator 17 located on the first gas pipeline 13 and which is adapted to separate eventual unwanted gaseous constituents from the hydrogen gas to provide a purified hydrogen gas to the mixing, and optionally compressing, unit 30,
  • a second separator 53 located on the third transportation line 51 and which is adapted to separate eventual unwanted constituents from the ammonia being transported therein to provide a purified ammonia product
  • a third separator 25 located on the second gas pipeline 23 and which is adapted to separate eventual unwanted constituents from the carbon dioxide flowing therein to provide a purified carbon dioxide stream.
  • the invention relates to a use of a methane containing gas, preferably pure methane, natural gas, liquid petroleum gas, wet natural gas, biogas or biomethane, in an integrated method for producing ammonia which integrated method comprises a sorption enhanced reforming (SER) process and a Haber-Bosch process.
  • a methane containing gas preferably pure methane, natural gas, liquid petroleum gas, wet natural gas, biogas or biomethane
  • Figure 1 is a flow diagram over a prior art ammonia production process based on Haber-Borsch synthesis and steam reforming of methane as hydrogen source.
  • Figure 2 is a facsimile of fig. 2 of [ref. 3] showing a flow diagram of a prior art process for forming ammonia syngas from coal mine drainage gas.
  • Figure 3 is a flow diagram showing an example embodiment of a process for producing blue ammonia according to the present invention.
  • Figure 4 is a flow diagram showing another example embodiment of a process for producing blue ammonia according to the present invention.
  • Figure 5 shows the graphs exhibiting the temperature sensitivity on the hydrogen and ammonia product at 1.5 bar in the reformer.
  • Figure 6 shows the graphs exhibiting the pressure sensitivity on the hydrogen and the ammonia product.
  • the invention is verified by a thermodynamical simulation using the Aspen Plus® Process Simulation Software on the process shown schematically in figure 4.
  • the model was fed with an input stream of natural gas, which when passing the point marked with roman number I on the figure, had a temperature of 10 °C, a pressure of 180 kPa and flowed with a mass flow rate of 6225 kg/hr.
  • the chemical composition (in mole%) of the natural gas feed was set to be 92.58 % methane, 3.82 % ethane, 0.73 % propane, 0.34 % isobutane, 0.13 % n-butane, 0.06 % isopentane, 0.03 % n-pentane, 0.11 % cyclohexane, 0.58 % carbon dioxide, and 1.62 % nitrogen.
  • the natural gas After passing the point marked with roman number I, the natural gas is preheated by being heat exchanged with passes through a first heat exchanger 15 which preheats the natural gas by heat exchanging it in a heat exchanger 15 with the hydrogen flow exiting the first reactor 10.
  • the model assumed further an inlet stream 12 of steam, in an amount and at a temperature which, after mixing with the feed stream of preheated natural gas exiting the first heat exchanger 15, results in a combined feed flow of natural gas and steam when passing the point marked with roman number II on the figure and then enters the first reactor 10 was determined to have a mass flow rate of 27938 kg/hr, a temperature of 450 °C, and a pressure of 160 kPa.
  • the chemical composition (in mole%) of the mixed flow passing point II was calculated to be 23.83 % methane, 0.84 % ethane, 0.16 % propane, 0.07 % isobutane, 0.03 % n- butane, 0.01 % isopentane, 0.01 % n-pentane, 0.02 % cyclohexane, 0.20 % carbon monoxide, 0.27 % carbon dioxide, 0.06 % nitrogen, 69.31 % steam, 4.65 % hydrogen.
  • the feed stream is contacted with particulate CaO and a heterogenous nickel catalyst which induces an exothermic sorption enhanced steam reforming of the hydrocarbons producing hydrogen gas and enriched sorbent (calcium carbonate).
  • the calcium carbonate produced inside the first reactor 10 holds a temperature of 700 °C and is transported with a mass flow rate of 28826 kg/hr via the first transportation line 14 from the first reactor 10 to the second reactor 20.
  • the gaseous effluent exiting the first reactor 10 exits via the first gas pipeline 13 is determined to have a mass flow rate of 15263 kg/hr, a temperature of 7000 °C, and a pressure of 160 kPa.
  • the chemical composition (in mole%) of the gaseous flow passing point III was determined to be 7.26 % methane, 63,24 % hydrogen, 28.30 % steam, 0.51 % nitrogen, 0.40 % carbon monoxide, 0.29 % carbon dioxide, and trace amounts of ethane, propane, isobutane, n-butane, isopentane, n-pentane, and cyclohexane.
  • the gaseous effluent is cooled by passing through the first heat exchanger 15 and then a second heat exchanger 16 to extract more exergy of the effluent, and purified in a first separator 17, here a pressure swing separator, to form a pure hydrogen flow which when passing the point marked with roman number IV on the figure flowed in an amount of 2089 kg/hr and had a temperature of 20 °C and a pressure of 136 kPa.
  • the gas was 100 % hydrogen.
  • the hydrogen flow was then mixed with a flow of nitrogen gas provided by an air separation unit 40 and passed on to a mixer and compressor 30 forming a mixed and compressed ammonia syngas, which when passing the point marked with roman numeral V on the figure, had a mass flow of 12289 kg/hr and a temperature of 74 °C and a pressure of 25.75 MPa,
  • the chemical composition (in mole%) of the ammonia syngas was determined to be 74.19 % hydrogen, 25,18 % nitrogen and 0.63 % argon.
  • the ammonia syngas was then mixed with a purge gas and preheated by a fourth heat exchanger 32 and passed into the third reactor 50 which converts the ammonia syngas into ammonia by the Haber-Bosch process.
  • the ammonia produced in the third reactor 50 is cooled by passing through the fourth heat exchanger 32 and then a fifth heat exchanger 52 and then purified by a second separator 53.
  • the ammonia stream passing through the point marked with roman numeral VI on the figure had a mass flow of 11752 kg/hr, a temperature of 20 °C and a pressure of 2 MPa.
  • the chemical composition (in mole%) of the ammonia stream was 99.39 % ammonia, 0.03 % hydrogen, 0.05 % nitrogen, and 0.53 % argon.
  • the air separation unit 40 passes the oxygen rich gas produced when separating out nitrogen (for the ammonia synthesis) via the fourth gas pipeline into the third inlet 22 where the oxygen rich gas is mixed with a fuel, here natural gas, and some steam and then passed into the second reactor 20 to sustain an oxyfuel combustion providing the heat energy required to desorb the calcium carbonate transferred from the first reactor 10 and converting it to (regenerated) sorbent, CaO, which is transferred via the second transportation line to the first reactor 10.
  • a fuel here natural gas
  • the mixture of fuel and oxygen rich gas entering the second reactor 20 had, when passing the point marked with roman numeral VII on the figure, a mass flow rate of 14742 kg/hr, a temperature of 96 °C and a pressure of 200 kPa.
  • the chemical composition (in mole%) of the gaseous flow passing point VII was determined to be 11.58 % methane, 16.12 % hydrogen, 32.89 % oxygen, 32.29 % steam, 2.93 % nitrogen, 0.64 % carbon monoxide, 0.46 % carbon dioxide, 2.43 % argon, 0.67 % ammonia, and trace amounts of ethane, propane, isobutane, and n-butane, isopentane, n-pentane, and cyclohexane.
  • the hydrogen and ammonia in the stream are from purge gas applied in the third reactor and then sent to reactor 20 for energy optimization.
  • the chemical composition (in mole%) of the gaseous flow passing point VIII was determined to be 1.03 % oxygen, 54.10 % steam, 2.21 % nitrogen, 40.32 % carbon dioxide, 1.84 % argon, 0.51 % ammonia, and trace amounts of carbon monoxide, hydrogen, methane, ethane, propane, isobutane, and n-butane, isopentane, n-pentane, and cyclohexane.
  • the gaseous effluent from the second reactor 20 is cooled by passing through a third heat exchanger 24, purified by being passed through a third separator 25 and compressed by a compressor 26 to form a CO2 rich gas flow suited for storage.
  • the CO2 rich gas flow had when passing the point marked with roman numeral VIII on the figure a mass flow rate of 18276 kg/hr, a temperature of 143 °C and a pressure of 1.5 MPa.
  • the chemical composition (in mole%) of the gaseous flow passing point VIII was determined to be 2.24 % oxygen, 0.43 % steam, 4.83 % nitrogen, 87.95 % carbon dioxide, 4.00 % argon, 0.55 % ammonia, and trace amounts of carbon monoxide and hydrogen.
  • Fig. 6 The effect of the pressure on the production of hydrogen and ammonia is shown in Fig. 6. It was found that an increased pressure reduces the volumetric throughput of the plant, which therefore reduces the plant footprint. If the feed stream enters at the higher operational pressure, the increased pressure reduces the compression duty and increases the system efficiency. The trade-off by increasing the pressure and keeping other operational parameters constant represents a reduced hydrogen production and ammonia production. Increased pressure requires a high steam to carbon ratio to obtain the same reaction yield. This increases the energy demand of the process and reduces the system efficiency. If the process is operated at higher pressures, it requires higher operating temperatures to avoid impurities in the reformate in the reformer.

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Abstract

L'invention concerne un procédé et une installation de fabrication d'ammoniac bleu, une synthèse de Haber-Bosch étant utilisée pour produire de l'ammoniac à partir d'azote et d'hydrogène, l'azote étant obtenu par séparation d'air et l'hydrogène étant obtenu par un reformage à la vapeur amélioré par sorption de gaz riche en méthane, et le CO2 formé étant capturé en étant absorbé/adsorbé dans le reformage à la vapeur amélioré par sorption, puis désorbé pour former une phase CCh concentrée appropriée pour le stockage à l'aide d'une boucle de sorbant. L'énergie thermique requise pour faire fonctionner la boucle de sorbant est obtenue par oxy-combustion à l'aide de l'oxygène gazeux provenant de la même unité de séparation d'air.
PCT/NO2024/050040 2023-02-16 2024-02-15 Procédé et installation de production d'ammoniac bleu Ceased WO2024172664A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210147787A1 (en) * 2019-11-20 2021-05-20 Oakbio, Inc. Bioreactors with Integrated Catalytic Nitrogen Fixation
WO2022229838A1 (fr) * 2021-04-27 2022-11-03 Energean Italy S.P.A. Procédé de production d'hydrogène à partir d'une charge d'hydrocarbures

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210147787A1 (en) * 2019-11-20 2021-05-20 Oakbio, Inc. Bioreactors with Integrated Catalytic Nitrogen Fixation
WO2022229838A1 (fr) * 2021-04-27 2022-11-03 Energean Italy S.P.A. Procédé de production d'hydrogène à partir d'une charge d'hydrocarbures

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MARTINEZ I ET AL.: "Hydrogen production through sorption enhanced steam reforming of natural gas: Thermodynamic plant assessment", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 38, no. 35, 11 October 2013 (2013-10-11), AMSTERDAM, NL, pages 15180 - 15199, XP028762396, DOI: 10.1016/j.ijhydene.2013.09.062 *
YAN YONGLIANG ET AL.: "Techno-economic analysis of low-carbon hydrogen production by sorption enhanced steam methane reforming ( SE -SMR) processes", ENERGY CONVERSION AND MANAGEMENT, vol. 226, 30 October 2020 (2020-10-30), OXFORD, GB, XP086387272, DOI: 10.1016/j.enconman.2020.113530 *

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