WO2022189484A1 - Method for the preparation of a gaseous fuel - Google Patents
Method for the preparation of a gaseous fuel Download PDFInfo
- Publication number
- WO2022189484A1 WO2022189484A1 PCT/EP2022/055989 EP2022055989W WO2022189484A1 WO 2022189484 A1 WO2022189484 A1 WO 2022189484A1 EP 2022055989 W EP2022055989 W EP 2022055989W WO 2022189484 A1 WO2022189484 A1 WO 2022189484A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ammonia
- fuel cell
- solid oxide
- gaseous
- gas
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 55
- 239000007789 gas Substances 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000005336 cracking Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 3
- 229960000510 ammonia Drugs 0.000 claims description 51
- 238000007664 blowing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000003071 parasitic effect Effects 0.000 description 3
- 241001072332 Monia Species 0.000 description 2
- 239000004148 curcumin Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- 229910003218 Ni3N Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 235000013531 gin Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- QHGVXILFMXYDRS-UHFFFAOYSA-N pyraclofos Chemical compound C1=C(OP(=O)(OCC)SCCC)C=NN1C1=CC=C(Cl)C=C1 QHGVXILFMXYDRS-UHFFFAOYSA-N 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
-
- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
- H01M8/222—Fuel cells in which the fuel is based on compounds containing nitrogen, e.g. hydrazine, ammonia
-
- 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
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/40—Combination of fuel cells with other energy production systems
- H01M2250/407—Combination of fuel cells with mechanical energy generators
-
- 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
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a method for the prepara tion of a gaseous fuel based on ammonia and hydrogen.
- the gaseous fuel is by the invention prepared by cracking a part of an ammonia feed in a solid oxide fuel cell to hydrogen and nitrogen when operating the fuel cell at a reduced fuel utilization and mixing the hy- drogen and nitrogen containing off-gas from the fuel cell with the rest of the ammonia feed to the gases fuel. In that way a useful fuel for gas engines is prepared.
- Combustion engines cannot operate on pure ammonia due to its poor combustion characteristics but require a cofeed of another fuel with better properties.
- the hydrogen can conveniently be produced by cracking part of the ammonia in a dedicated cracking unit upstream the combustion engine.
- Such cracking units are, however, expensive and use up to 13 % of the lower heating value in the processed ammonia.
- Solid Oxide Fuel Cell can also be used to convert ammonia into heat and power in a stand-alone plant with very high efficiency.
- SOFC plants are unfortunately much more capital expensive compared to gas engines.
- SOFC stacks do, however, operate as very efficient ammonia crackers utilizing waste heat from the fuel cell operation to drive the ammonia cracking while at the same time producing power.
- combustion engines can not operate on pure ammonia. This can be solved by cracking part of the ammonia to hydrogen and nitrogen in a dedicated ammonia cracking unit. This requires, however a substantial investment and entails a loss in efficiency.
- a different fuel like f.inst. DME can be used as a combus tion property enhancer, but this will require a dual fuel system including storage facilities and the alternative fuel will also most likely be more expensive than ammonia if produced from renewable sources
- the present invention is based on to use the capability of SOFCs to crack ammonia into hydrogen and nitrogen in con junction with a gas engine so that enough of the ammonia is converted in the SOFC, when keeping the fuel utilization of the SOFC at a low range. Thereby a minimum amount of hydro gen in the fuel mix to the gas engine is provided by non- converted off gas from the SOFC plant.
- the invention provides a method for the preparation of a gaseous fuel comprising the steps of:
- step (c) introducing the first substream into a solid oxide fuel cell; (d) cracking the gaseous ammonia in the first substream to hydrogen and nitrogen by means of heat created by electro chemical reactions performed in the solid oxide fuel cell; (e) withdrawing an off-gas from the solid oxide fuel cell containing the hydrogen and nitrogen formed in step (d); (f) mixing the off-gas with the second substream of the gaseous ammonia to provide the gaseous fuel, wherein the solid oxide fuel cell is operated at a fuel utilization of between 35 and 70%.
- the fuel utilization i.e. the amount of ammonia and hydro gen converted in the SOFC is defined as:
- minimum fuel utilizations are obtained at operating volts of 0.7, 0.8 and 0.9 V to be 33.5 %, 40.4 % and 50.9 % respectively
- This invention provides the following advantages: • The investment in a dedicated cracking unit is avoided
- the SOFC unit can operate at low fuel utilization (ammo nia and hydrogen conversion) which makes it cheaper in in vestment in SOFC stacks
- the gaseous stream of ammonia is provided from a pressurized and liquid ammonia source, which is heated and expanded in an expander to form the gaseous stream of ammonia.
- a part of the off-gas from the solid oxide fuel cell is recycled to the anode of the fuel cell.
- elec trical energy When expanding pressurized ammonia in the expander, elec trical energy can be generated in the expander.
- the elec trical energy can be utilized for driving a number of de vices in the method according to the invention.
- electrical energy is generated in the expander.
- the electrical energy is utilized for op- erating a blower for blowing air into the cathode chamber of the solid oxide fuel cell. In an embodiment the electrical energy is utilized for op erating a compressor for recycling a part of the off-gas from the solid oxide fuel cell to the anode chamber of the fuel cell.
- the present invention can advantageously be used for the preparation of gas fuel for engines installed on maritime vessels and for revamping gas fuel systems for existing en gines. Additionally, the invention is useful for operating combined heat and power plants.
- Fig.l is a flow sheet showing a method ac cording to a specific embodiment of the invention.
- the feedstock is pressurized ammonia either taken from a pressurized tank or pumped in the form of liquid, refriger ated ammonia.
- the ammonia is vaporized in heat exchanger El by sensible heat in exhaust gas from a gas engine and is further heated by the same exhaust gas in heat exchanger E2 before it is expanded to near atmospheric pressure in a turboexpander .
- This expander is used to generate electric power and uses the exergy invested in condensing the ammonia in the ammo nia plant.
- Part of the ammonia is subsequently sent to the gas engine via an optional cooler, E9.
- the rest of the am monia is then mixed with gas recirculated from the anode in the SOFC and then heated to the operating temperature of the SOFC in the feed/effluent heat exchanger E3.
- the ammo nia and recirculated anode off gas is converted to elec- tricity and heat in the anode chamber of the SOFC.
- the am monia will be effectively cracked in the anode chamber driven by the waste heat from oxidation the resulting hy drogen.
- the conversion of the hydrogen in the SOFC is deliberately kept low as the main purpose is supply the hydrogen to the gas engine.
- the anode off gas is cooled down in the anode feed/effluent exchanger E3 and then split into two streams, 2081 and 1070.
- minor stream, 2081 is fur ther cooled in the anode recycle feed/effluent heat ex changer, E200, and then in the cooler, E100, before enter- ing the anode recycle gas blower.
- the anode recycle stream is provided to supply a hydrogen rich gas back to E3 and the SOFC in order to avoid material degradation due to nitriding by pure ammonia according to:
- Ni + NH 3 Ni 3 N + 1.5 3 ⁇ 4
- a relevant amount of air is added to the fuel stream and the mixture is combusted in a gas engine providing (elec tric) power and a hot exhaust gas.
- the exhaust gas is used to preheat the ammonia in heat exchanger E2 and is then further cooled in cooler E5 and finally used to evaporate the ammonia in El.
- air is provided by an air blower and sent to the cathode feed/effluent heat ex changer, E4, which brings the temperature up to the operat ing temperature of the SOFC.
- the depleted air leaving the SOFC cathode is used for preheat in E4 and finally cooled down in the cooler E6.
- the heat released in E, E6, E100 and E7 can be used as dis trict heating.
- the present invention focuses on minimizing the investment of the combined SOFC + Gas Engine system, as the present capital investment for SOFC are very high.
- the operating regime is thus changed to have a low fuel utilization in the SOFC - enough to provide a minimum of hydrogen to the gas engine and at the same time provide enough temperature increase across the SOFC to enable operation of the heat exchanger E3 and E4 without unduly large heat exchange sur faces.
- the low fuel utilization provides other benefits because a lower amount of waste heat that have to be removed by the air stream which reduces the size and in- vestment in the air blower and exchanger E4 compared with
- Stack area (Average Nernst potential - Operating Volt age)/Area specific Resistance Due to the average higher operating temperature of the ded icated SOFC this is somewhat overestimating the stack area for this option but on the other hand the lower operating temperature as per the invention will prolong the lifetime of the stacks.
- the SOFC + gas engine as per the invention obviously has a lower electrical efficiency but it should recalled that in- vestment for a gas engine is probably around 500 $/kW but at present it is probably 4 - 10 times higher for the SOFC system and the stack replacements are also expensive.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020237029585A KR20230154824A (en) | 2021-03-10 | 2022-03-09 | Method for producing gaseous fuel |
JP2023555175A JP2024513317A (en) | 2021-03-10 | 2022-03-09 | Method for producing gas fuel |
EP22712558.0A EP4305695A1 (en) | 2021-03-10 | 2022-03-09 | Method for the preparation of a gaseous fuel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DKPA202100250 | 2021-03-10 | ||
DKPA202100250 | 2021-03-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022189484A1 true WO2022189484A1 (en) | 2022-09-15 |
Family
ID=80937242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2022/055989 WO2022189484A1 (en) | 2021-03-10 | 2022-03-09 | Method for the preparation of a gaseous fuel |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP4305695A1 (en) |
JP (1) | JP2024513317A (en) |
KR (1) | KR20230154824A (en) |
WO (1) | WO2022189484A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023110199A1 (en) * | 2021-12-13 | 2023-06-22 | Robert Bosch Gmbh | Fuel cell device and system having a fuel cell device |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080248353A1 (en) * | 2007-04-05 | 2008-10-09 | Malcolm James Grieve | Energy conversion device including a solid oxide fuel cell fueled by ammonia |
WO2015107972A1 (en) * | 2014-01-16 | 2015-07-23 | 信哉 荒木 | Ammonia engine |
-
2022
- 2022-03-09 EP EP22712558.0A patent/EP4305695A1/en active Pending
- 2022-03-09 KR KR1020237029585A patent/KR20230154824A/en unknown
- 2022-03-09 WO PCT/EP2022/055989 patent/WO2022189484A1/en active Application Filing
- 2022-03-09 JP JP2023555175A patent/JP2024513317A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080248353A1 (en) * | 2007-04-05 | 2008-10-09 | Malcolm James Grieve | Energy conversion device including a solid oxide fuel cell fueled by ammonia |
WO2015107972A1 (en) * | 2014-01-16 | 2015-07-23 | 信哉 荒木 | Ammonia engine |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023110199A1 (en) * | 2021-12-13 | 2023-06-22 | Robert Bosch Gmbh | Fuel cell device and system having a fuel cell device |
Also Published As
Publication number | Publication date |
---|---|
KR20230154824A (en) | 2023-11-09 |
EP4305695A1 (en) | 2024-01-17 |
JP2024513317A (en) | 2024-03-25 |
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