US20220250904A1 - Dehydrogenation reaction device and system having the same - Google Patents
Dehydrogenation reaction device and system having the same Download PDFInfo
- Publication number
- US20220250904A1 US20220250904A1 US17/348,552 US202117348552A US2022250904A1 US 20220250904 A1 US20220250904 A1 US 20220250904A1 US 202117348552 A US202117348552 A US 202117348552A US 2022250904 A1 US2022250904 A1 US 2022250904A1
- Authority
- US
- United States
- Prior art keywords
- dehydrogenation
- acid
- aqueous solution
- dehydrogenation reaction
- hydrogen
- 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.)
- Abandoned
Links
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 187
- 150000004678 hydrides Chemical class 0.000 claims abstract description 77
- 239000007864 aqueous solution Substances 0.000 claims abstract description 75
- 239000000126 substance Substances 0.000 claims abstract description 47
- 239000006262 metallic foam Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 104
- 239000001257 hydrogen Substances 0.000 claims description 92
- 229910052739 hydrogen Inorganic materials 0.000 claims description 92
- 239000002253 acid Substances 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000000446 fuel Substances 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 25
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 25
- 235000019253 formic acid Nutrition 0.000 claims description 19
- 239000012279 sodium borohydride Substances 0.000 claims description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- -1 KAlH4 Substances 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000005484 gravity Effects 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012448 Lithium borohydride Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 4
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910003203 NH3BH3 Inorganic materials 0.000 claims description 3
- 229910020828 NaAlH4 Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 229910010084 LiAlH4 Inorganic materials 0.000 claims 1
- 229910010277 boron hydride Inorganic materials 0.000 claims 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 43
- 210000004027 cell Anatomy 0.000 description 32
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000009834 vaporization Methods 0.000 description 7
- 230000008016 vaporization Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229910000103 lithium hydride Inorganic materials 0.000 description 3
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Images
Classifications
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- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- 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
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
-
- 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
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
- H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
-
- 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04753—Pressure; Flow of fuel cell 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
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
-
- 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
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
-
- 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
-
- 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
- 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 disclosure relates to a dehydrogenation reaction device and a dehydrogenation reaction system including the same for supplying hydrogen to a fuel cell stack.
- a fuel cell and a hydrogen combustion device use hydrogen as a reaction gas, and in order to apply the fuel cell and the hydrogen combustion device to vehicles and various electronic products for example, a stable and continuous supply technology of hydrogen is required.
- a method of receiving hydrogen from a separately installed hydrogen supply source may be used. In this way, compressed hydrogen or liquid hydrogen may be used.
- a method of generating hydrogen through a reaction of a corresponding material after mounting a material in which hydrogen is stored on a device using hydrogen and supplying it to the device using hydrogen may be used.
- a method using a liquid hydride, a method using adsorption or absorbents/carbon, and a method using chemical hydrogen storage have been proposed.
- One embodiment provides a dehydrogenation reaction device capable of maximizing a hydrogen storage amount compared to a material by preventing vaporization of water and reducing a use amount of water through a device configuration capable of high temperature/high pressure operation.
- Another embodiment provides a dehydrogenation reaction system capable of reducing a water storage capacity by recycling water generated from a fuel cell, increasing a hydrogen storage capacity for the system, and reducing a system cost and weight by removing a gas-liquid separator and a recovery tank from the system.
- a dehydrogenation reaction device including a dehydrogenation reactor including: a solid chemical hydride; and an acid aqueous solution tank supplying an acid aqueous solution to the dehydrogenation reactor
- the dehydrogenation reactor includes a heating device, a cooling apparatus, a porous metal foam, or a combination thereof.
- the porous metal foam may be positioned in the center of the width direction of the dehydrogenation reactor and extend in the length direction of the dehydrogenation reactor, and the side of the length direction of at least the porous metal foam may be surrounded by the chemical hydride.
- the porous metal foam may be a porous nickel foam or a porous cobalt-nickel foam.
- the dehydrogenation reactor may include 0 parts by volume to 100 parts by volume of the porous metal foam with respect to 100 parts by volume of the chemical hydride,
- the acid aqueous solution may be supplied to the dehydrogenation reactor by gravity or a pump.
- the chemical hydride may include sodium borohydride (NaBH 4 ), lithium borohydride (LiBH 4 ), potassium borohydride (KBH 4 ), ammonium borohydride (NH 4 BH 4 ), ammonia borohydride (NH 3 BH 3 ), tetramethyl ammonium borohydride ((CH 3 ) 4 NH 4 BH 4 ), sodium aluminum hydride (NaAlH 4 ), lithium aluminum hydride (LiAlH 4 ), potassium aluminum hydride (KAlH 4 ), calcium diborohydride (Ca(BH 4 ) 2 ), magnesium diborohydride (Mg(BH 4 ) 2 ), sodium gallium hydride (NaGaH 4 ), lithium gallium hydride (LiGaH 4 ), potassium gallium hydride (KGaH 4 ), lithium hydride (LiH), calcium hydride (CaH 2 ), magnesium hydride (MgH 2 ), or mixture thereof.
- NaBH 4
- the acid may be sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, boric acid, a heteropoly acid, acetic acid, formic acid, malic acid, citric acid, tartaric acid, ascorbic acid, lactic acid, an oxalic acid, succinic acid, tauric acid, or a mixture thereof.
- the dehydrogenation reaction may be performed by reacting 1 mol of hydrogen atoms of the chemical hydride with an acid and water at a molar ratio of 0.5 to 2.
- the temperature of the dehydrogenation reaction may be 10° C. to 400° C.
- the pressure may be 1 bar to 100 bar.
- the gas product produced in the dehydrogenation reactor may include 99 volume % or greater of hydrogen and 1 volume % or less of water.
- a dehydrogenation reaction system including an acid aqueous solution tank including an acid aqueous solution; a dehydrogenation reactor including a chemical hydride of a solid state and receiving an acid aqueous solution from the acid aqueous solution tank to react the chemical hydride with the acid aqueous solution to generate hydrogen; and a fuel cell stack receiving hydrogen generated from the dehydrogenation reactor to be reacted with oxygen to generate water and simultaneously to generate electrical energy may be provided, wherein the water generated from the fuel cell stack is recycled to the acid aqueous solution tank, the dehydrogenation reactor, a separate water tank, or all of the above.
- the acid aqueous solution may be supplied to the dehydrogenation reactor by gravity or a pump.
- the dehydrogenation reaction system may further include a gas cooler that can be cooling the hydrogen generated from the dehydrogenation reactor, and a buffer tank that receives and stores hydrogen from the gas cooler.
- the dehydrogenation reaction system may further include a pressure regulator between the gas cooler and the buffer tank, between the buffer tank and the fuel cell stack, or both.
- the dehydrogenation reaction system may further include a sensor inside or outside the dehydrogenation reactor, a temperature sensor and a pressure sensor, or a mass flow meter between the buffer tank and the fuel cell stack.
- the acid aqueous solution tank may be pressurized by receiving hydrogen from the dehydrogenation reactor, the gas cooler, the buffer tank, or a combination thereof.
- the dehydrogenation reaction system may not include a gas-liquid separator to separate hydrogen and water from the reaction products produced in the dehydrogenation reactor.
- the dehydrogenation reaction system may further include a pump, a filter, or both.
- the dehydrogenation reaction device may maximize the amount of hydrogen storage compared to the material by preventing the vaporization of the water and reducing the amount of the water used through the device configuration capable of operating at high temperature/high pressure.
- the dehydrogenation reaction system may increase the conversion rate of the hydrolysis reaction by recycling the water generated from the fuel cell, and increasing the hydrogen storage capacity by removing the gas-liquid separator and the recovery tank from the system, and the system cost and weight may be reduced.
- FIG. 1 is a view schematically showing a dehydrogenation reaction device according to an embodiment.
- FIG. 2 is an enlarged cross-sectional view of a dehydrogenation reactor in FIG. 1 .
- FIG. 3 is a view schematically showing a dehydrogenation reaction device according to another embodiment.
- FIG. 4 is a graph showing a result of measuring a hydrogen storage capacity of a dehydrogenation reaction system using formic acid in several molar ratios in an Embodiment 1.
- FIG. 5 is a graph showing a result of measuring a hydrogen storage capacity of a dehydrogenation reaction system in an Embodiment 2.
- FIG. 6 is a graph showing a result of measuring a hydrogen storage capacity of a dehydrogenation reaction system in an Embodiment 3.
- FIG. 7 is a graph showing a result of measuring a hydrogen storage capacity of a dehydrogenation reaction system in an Embodiment 4.
- FIG. 8 and FIG. 9 are graphs showing results of measuring a hydrogen generation speed and a conversion rate of a dehydrogenation reaction system in an Embodiment 5.
- FIG. 10 is a graph showing a result of carrying out a hydrogen generating reaction capable of driving a 1 kW class fuel cell in an Embodiment 6.
- FIG. 1 is a view schematically showing a dehydrogenation reaction device according to an embodiment
- FIG. 2 is an enlarged cross-sectional view of a dehydrogenation reactor in FIG. 1 .
- a dehydrogenation reaction device is described in detail with reference to FIG. 1 and FIG. 2 ,
- a dehydrogenation reaction device 100 includes a dehydrogenation reactor 110 and an acid aqueous solution tank 120 .
- the dehydrogenation reactor 110 may be composed of a high temperature and high pressure vessel so that a dehydrogenation reaction may be carried out in high temperature and high pressure conditions.
- the dehydrogenation reactor 110 may have a shape such as a cylinder, a sphere, a cuboid, or a polygonal column, and particularly may have a cylinder shape.
- the dehydrogenation reactor 110 may have a high aspect ratio in which a ratio LID of a length L to a width D is high.
- the width D of the dehydrogenation reactor 110 is shorter than the length L.
- the aspect ratio LID of the length L to the width D may be 1 to 10, and for example, may be 5 to 8.
- the dehydrogenation reactor 110 has the high aspect ratio, it is possible to maximize release of reaction heat during the dehydrogenation reaction and minimize the use of a pump by utilizing a water level difference.
- the aspect ratio of the dehydrogenation reactor 110 may be omitted.
- the dehydrogenation reactor 110 includes a chemical hydride 111 of a solid state.
- the chemical hydride 111 as a solid state may be in a form of any one of a powder form, a granular form, a bead form, a microcapsule form, and a pellet form.
- an aqueous solution a concentration, in one example, of about 20% of the chemical hydride
- a large amount of the chemical hydride 111 may not be stored, but when the chemical hydride 111 is stored in a solid state, large capacity storage is possible.
- the chemical hydride may be any compound that may be hydrolyzed to generate hydrogen and a hydrolysate, for example, NaBH 4 , LiBH 4 , KBH 4 , NH 4 BH 4 , NH 3 BH 3 , (CH 3 ) 4 NH 4 BH 4 , NaAlH 4 , LiAlH 4 , KAlH 4 , Ca(BH 4 ) 2 , Mg(BH 4 ) 2 , NaGaH 4 , LiGaH 4 , KGaH 4 , LiH, CaH 2 , MgH 2 , or mixture thereof may be included.
- a hydrolysate for example, NaBH 4 , LiBH 4 , KBH 4 , NH 4 BH 4 , NH 3 BH 3 , (CH 3 ) 4 NH 4 BH 4 , NaAlH 4 , LiAlH 4 , KAlH 4 , Ca(BH 4 ) 2 , Mg(BH 4 ) 2 , Na
- the dehydrogenation reactor 110 is constructed in the form of cartridge to allow the dehydrogenation reactor 110 to be replaced, or the upper part is designed to be opened and closed so that the chemical hydride 111 may be injected or replaced, or a product is exhausted through the lower part and the chemical hydride 111 may be injected, thereby allowing the dehydrogenation reactor 110 to ensure system continuity. Additionally, the dehydrogenation reactor 110 may further include a part for exhausting a slurried hydrolysis reaction product and a part for injecting the chemical hydride 111 .
- the dehydrogenation reactor 110 may include a heating device that provides heat/temperature useful for the hydrolysis of the chemical hydride 111 or for separate purposes, a cooling apparatus 230 to exhaust reaction heat H when the hydrogen-generating reaction is an exothermic reaction, or a porous metal foam 112 to improve the reaction speed through a catalysis reaction.
- the heating device may use electricity or other heat sources
- the cooling apparatus 230 may be implemented as a refrigerant circulation device to exhaust heat generated by the hydrolysis of the chemical hydride 111 .
- the porous metal foam 112 has a cellular structure composed of a solid metal with gas-filled pores having a predetermined volume.
- the pores may be sealed (closed cell foam) or interconnected (opened-cell foam), and the porous metal foam 112 may be opened-cell foams.
- the porous metal foam 112 may have high porosity, and for example, only 5 volume % to 25 volume % of the entire volume may be metal. Accordingly, the porous metal foam 112 may be ultra-lightweight while having a high-surface area.
- the porous metal foam 112 may have various characteristics, for example, porosity, pore volume, thickness, alloy composition, or density.
- the porous metal foam 112 may be integrally formed, or may be disposed by stacking at least one or more thereof.
- the porous metal foam 112 may use various materials in consideration of increasing a reaction speed through the catalytic action as well as heat conduction.
- the porous metal foam 112 may be a porous nickel foam or a porous cobalt-nickel foam.
- the heat transfer may be accelerated and the reaction may be accelerated through the metal as the catalytic active sites. It may also help to release the heat of the reaction inside the dehydrogenation reactor 110 .
- it may act as a distributor so that the add aqueous solution may be evenly supplied inside the dehydrogenation reactor 110 .
- the porous metal foam 112 is positioned in the center of the width direction of the dehydrogenation reactor 110 and extends in the length direction of the dehydrogenation reactor 110 .
- the chemical hydride 111 may be positioned on the outer side in the width direction of the dehydrogenation reactor 110 , and the side in the length direction of the porous metal foam 112 may be surrounded by the chemical hydride 111 .
- porous metal foam 112 may be connected to the inlet side through which the acid aqueous solution supplied from the acid aqueous solution tank 120 inflows. At this time, the opposite surface of the surface where the porous metal foam 112 is connected to the dehydrogenation reactor 110 may be surrounded by the chemical hydride 111 .
- the porous metal foam 112 may uniformly distribute the acid aqueous solution to the chemical hydride 111 , maximize heat transfer, and act as a non-uniform catalyst for the dehydrogenation reaction. Accordingly, a barrier may be suppressed from being formed by by-products such as a borate, which may be generated from the chemical hydride 111 after the dehydrogenation reaction and the reaction delay are minimized, thereby maximizing the generation amount of hydrogen.
- the dehydrogenation reactor 110 may include the porous metal foam 112 in an amount of 0 to 100 parts by volume with respect to 100 parts by volume of the chemical hydride 111 , and for example, it may include 0 to 50 parts by volume thereof. If the porous metal foam 112 includes greater than 50 parts by volume per 100 parts by volume of the chemical hydride 111 , the amount of the hydrogen storage may decrease due to space constraints.
- the add aqueous solution tank 120 supplies the acid aqueous solution to the dehydrogenation reactor 110 .
- the dehydrogenation reaction device 100 is a system that generates hydrogen by injecting the aqueous acid solution into a dehydrogenation reactor 110 including the chemical hydride 111 of the solid state.
- the acid aqueous solution tank 120 may have a corrosion-resistant protective film such as Teflon coating to prevent corrosion by the acid aqueous solution.
- the acid aqueous solution shortens the reaction time by adjusting the pH of the chemical hydride 111 to promote the dehydrogenation reaction.
- the acid may be an inorganic acid such as sulfuric acid, nitric acid, phosphoric acid, boric acid, or hydrochloric acid, an organic acid such as heteropoly acid, acetic acid, formic acid, malic acid, citric acid, tartaric acid, ascorbic acid, lactic acid, oxalic acid, succinic acid, and tauric acid, or mixtures thereof, because the molecular weight is small compared to the hydrogen ion, and the system weight may be reduced and formic acid (HCOOH) may be used as it is safer than hydrochloric add in a high concentration state.
- an inorganic acid such as sulfuric acid, nitric acid, phosphoric acid, boric acid, or hydrochloric acid
- an organic acid such as heteropoly acid, acetic acid, formic acid, malic acid, citric acid, tartaric acid, ascorbic acid, lactic acid, oxalic acid, succinic acid, and tauric acid, or mixtures thereof, because the
- the pH is maintained, in one example, at about 2 under the conditions described in the present disclosure, so it may be used relatively safely.
- captured carbon dioxide may be obtained through hydrogenation, so it is an important material in terms of a recycling of carbon dioxide.
- formate is converted to bicarbonate through a dehydrogenation reaction, whereby additional hydrogen may be obtained.
- the acid aqueous solution tank 120 is positioned above the dehydrogenation reactor 110 with respect to the direction of gravity, and the acid aqueous solution tank 120 may supply the acid aqueous solution to the dehydrogenation reactor 110 by gravity. That is, the acid aqueous solution tank 120 may supply the acid aqueous solution to the dehydrogenation reactor 110 due to the water level difference. Through this, it is possible to reduce the system cost and weight by minimizing the use of the pump.
- the present disclosure is not limited thereto, and the acid aqueous solution tank 120 may be positioned below the dehydrogenation reactor 110 in the gravity direction and the acid aqueous solution may be supplied to the dehydrogenation reactor 110 by a high pressure pump, In other words, when the acid aqueous solution is injected into the dehydrogenation reactor 110 through a high pressure pump, the pressure of the acid aqueous solution tank may be omitted, and in this case, the position limitation also disappears.
- the dehydrogenation reaction may be performed by reacting 1 mol of hydrogen atoms of the chemical hydride with an acid and water at a molar ratio of 0.5 to 2. If the molar ratio of acid and water is less than 0.5, the chemical hydride 111 may not react sufficiently, and if it is greater than 2, the system weight and reactor volume may increase.
- the dehydrogenation reaction may take place under high temperature and high pressure conditions. This prevents vaporization of water and reduces the amount of the used water, thereby maximizing the amount of generated hydrogen (the water vaporization temperature: 175° C. at 10 bar, 260° C. at 50 bar). In addition, the generation of CO 2 may also be suppressed through the pressurization operation of the dehydrogenation reactor 100 .
- the pressure of the dehydrogenation reaction may be 1 bar to 100 bar, or 5 bar to 50 bar. If the pressure of the dehydrogenation reaction is less than 1 bar, a decompression pump is used, which may increase the system weight. If the pressure is greater than 100 bar, the dehydrogenation reaction may be inhibited and the weight and volume of a high temperature/high pressure container may increase.
- the gas product generated in the dehydrogenation reactor may contain 99 volume % or greater of hydrogen, 1 volume % or less of water, and 0.1 volume % or less of other impurities.
- the generation speed of hydrogen in the dehydrogenation reactor 100 may be controlled by changing the injection speed of the acid aqueous solution or by changing the injection time (a valve open time) while fixing the injection speed.
- the injection time a valve open time
- one of the high pressure pump and the injection method of the acid aqueous solution by gravity may be selected.
- FIG. 3 is a view schematically showing a dehydrogenation reaction device according to another embodiment. Now, the dehydrogenation reaction system is described in detail with reference to FIG. 3 .
- the dehydrogenation reaction system 10 includes the dehydrogenation reactor 110 , the acid aqueous solution tank 120 , and the fuel cell stack 500 , and may selectively further include a gas cooler 300 and a buffer tank 400 .
- the dehydrogenation reactor 110 may increase the amount of hydrogen storage by disposing several reactors in parallel as needed.
- FIG. 3 shows that the gas cooler 300 is configured of a plurality of chambers sequentially connected to each other, but the present disclosure is not limited thereto, and the gas cooler 300 may be configured of a single chamber.
- the hydrogen cooled in the gas cooler 300 is transferred to the buffer tank 400 .
- the buffer tank 400 receives and stores a certain amount of the hydrogen gas.
- pressure regulators 610 , 620 may be further included between the dehydrogenation reactor 100 and the gas cooler 300 , between the gas cooler 300 and the buffer tank 400 , between the buffer tank 400 and the fuel cell stack 500 , or a combination thereof.
- a sensor, a temperature sensor, or a pressure sensor may be further included inside or outside the dehydrogenation reactor 100 .
- a mass flow meter 630 may be further included between the buffer tank 400 and the fuel cell stack 500 . Accordingly, the hydrogen gas may be stored in the buffer tank 400 at a constant pressure, and the hydrogen gas may be supplied to the fuel cell stack 500 at a desired pressure and mass.
- the acid aqueous solution tank 120 may be pressurized by using hydrogen generated in the dehydrogenation reactor 110 .
- the acid aqueous solution tank 120 may receive hydrogen directly from the dehydrogenation reactor 110 or may receive the hydrogen from the gas cooler 300 or the buffer tank 400 , or a combination thereof.
- the amount of hydrogen gas supplied to the acid aqueous solution tank 120 may be controlled by the valve 720 .
- the fuel cell stack 500 is positioned on a downstream side of the buffer tank 400 to receive the hydrogen gas from the buffer tank 400 .
- the hydrogen gas may be received from the buffer tank 400 through an intake port such as a valve.
- the fuel cell stack 500 generates water by reacting the supplied hydrogen with oxygen and simultaneously generates electrical energy.
- the water produced in the fuel cell stack 500 is exhausted through exhaust means such as valves, for example.
- the water exhausted from the fuel cell stack 500 is recycled to the acid aqueous solution tank 120 , the dehydrogenation reactor 110 , a separate water tank, or all of them, thereby increasing the hydrogen generation efficiency.
- the amount of the water supplied to the acid aqueous solution tank 120 or the dehydrogenation reactor 110 may be controlled by valves 730 and 740 .
- the fuel cell stack 500 may be any device that converts the hydrogen gas into usable electrical energy, and for example, it may be a proton exchange membrane fuel cell (PEMFC), an alkaline fuel cell (AFC), a phosphoric acid fuel cell (PAFC), a molten carbonate salt fuel cell (MCFC), or a solid oxide fuel cell (SOFC), etc., but the present disclosure is not limited thereto.
- PEMFC proton exchange membrane fuel cell
- AFC alkaline fuel cell
- PAFC phosphoric acid fuel cell
- MCFC molten carbonate salt fuel cell
- SOFC solid oxide fuel cell
- the fuel cell stack 500 may pass the generated electrical energy through a power converter such as a DC converter, an inverter, or a charge controller.
- the power converter may output a part of the electrical energy to an electrical load through a load interconnect, and the other part of the electrical energy may be sent back to the energy storage through a recharging interconnect. Another part of the electrical energy may be used to supply power to a control unit.
- the dehydrogenation reaction system 10 prevents the vaporization of the water through the high temperature and high pressure operation of the dehydrogenation reactor 100 and reduces the amount of the used water, so there is no need for a separate gas-liquid separator because the excess water is not included in the hydrogen gas after the reaction.
- the use of the pump may be minimized by allowing the acid aqueous solution tank 120 to supply the acid aqueous solution to the bottom of the dehydrogenation reactor 110 by gravity, however, if desired, a pump, a filter, or both may be further included.
- the pump may be used to supply the acid aqueous solution of the acid aqueous solution tank 120 to the dehydrogenation reactor 110 , to supply the hydrogen gas generated from the dehydrogenation reactor 110 to the gas cooler 300 , to supply the hydrogen gas cooled in the gas cooler 300 to the buffer tank 400 , to supply the hydrogen gas stored in the buffer tank 400 to the fuel cell stack 500 , to supply the hydrogen gas to the acid aqueous solution tank 120 , or to supply the water generated from the fuel cell stack 500 to the dehydrogenation reactor 110 or the acid aqueous solution tank 120 .
- the filter may substantially remove unwanted particles included in the hydrogen gas by filtering the generated hydrogen gas.
- the filter may be positioned between the dehydrogenation reactor 110 , the gas cooler 300 , the buffer tank 400 , or the fuel cell stack 500 , particularly between the buffer tank 400 and the fuel cell stack 500 .
- the dehydrogenation reaction system 10 may include an outlet for exhausting the mixture of the chemical hydride, the acid, and the water after the reaction has been completed, and may include a device for removing reaction by-products other than hydrogen and the water or converting it to other materials.
- the chemical hydride 111 is charged into the high temperature and high pressure dehydrogenation reactor 110 .
- the acid aqueous solution mixed in a specific molar ratio is injected using a syringe or a high-pressure pump.
- the injection speed may be adjusted from 0.01 mL/min to 20 mL/min, and may vary depending on the size of the dehydrogenation reactor 110 and the amount of the chemical hydride 111 .
- the pressure and the temperature are measured, and a predetermined pressure and temperature are maintained through valve control and cooling.
- H 2 O may be injected first and then the acid may be injected.
- the hydrogen conversion rate may be calculated by Equation 1 below, and the flow rate and the purity are measured using a mass flow meter and gas chromatography (GC).
- Embodiment 1 in Embodiment 1, the reaction like Reaction Formula 2 below is performed, in the room temperature/room pressure condition, a reaction molar sum of HCOOH and H 2 O is maintained as 4 (for example, to minimize water usage), and as the reacted result, it was confirmed that hydrogen was generated under the condition of 0.25 mol to 1 mol of HCOOH, and hydrogen, which was close to the theoretical storage amount, was generated particularly at 0.5 mol.
- the reaction temperature and pressure were increased, and as the result confirming the optimum reaction conditions, the hydrogen storage capacity of 6 wt % or greater (theoretical value: 6.5 wt %) was confirmed in the temperature of 100° C. to 250° C. and the pressure of 5 bar to 50 bar, particularly the conversion rate of 97% was achieved at the range of 100° C. to 250° C. and 30 bar to 50 bar.
- H 2 O may be reduced to 2 mol, and the hydrogen storage capacity may theoretically reach 8.3 wt % and experimentally 7.0 wt % (the room temperature/room pressure condition: 5.5 wt %).
- the dehydrogenation reactor capable of including NaBH 4 at 110 g was manufactured and the hydrogen generation reaction (the hydrogen generation speed of 15 L/min) capable of driving a 1 kW class fuel cell was produced, and the result thereof is shown in FIG. 10 .
Abstract
Description
- This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0017384 filed in the Korean Intellectual Property Office on Feb. 8, 2021, the entire contents of which are incorporated herein by reference.
- The present disclosure relates to a dehydrogenation reaction device and a dehydrogenation reaction system including the same for supplying hydrogen to a fuel cell stack.
- Due to depletion of fossil energy and environmental pollution problems, there is a great demand for renewable and alternative energy, and hydrogen is attracting attention as one of such alternative energies.
- A fuel cell and a hydrogen combustion device use hydrogen as a reaction gas, and in order to apply the fuel cell and the hydrogen combustion device to vehicles and various electronic products for example, a stable and continuous supply technology of hydrogen is required.
- In order to supply hydrogen to a device that uses hydrogen, a method of receiving hydrogen from a separately installed hydrogen supply source may be used. In this way, compressed hydrogen or liquid hydrogen may be used.
- Alternatively, a method of generating hydrogen through a reaction of a corresponding material after mounting a material in which hydrogen is stored on a device using hydrogen and supplying it to the device using hydrogen may be used. For this method, for example, a method using a liquid hydride, a method using adsorption or absorbents/carbon, and a method using chemical hydrogen storage have been proposed.
- However, in the case of the method using a liquid hydride, since the hydride is diluted and used with a low concentration to maintain the liquid state even after a hydrolysis reaction of the hydride is completed, a volume of the storage tank is large and a separate recovery tank is also required. In addition, a gas-liquid separator may be required because excess moisture is contained in the hydrogen gas after the reaction. This increases the volume and weight of the system as a whole and decreases the hydrogen storage capacity.
- The above information disclosed in this Background section is only for enhancement of understanding of the background of the disclosure, and therefore it may contain information that does not form the prior art that is already known in this country to a person of ordinary skill in the art.
- One embodiment provides a dehydrogenation reaction device capable of maximizing a hydrogen storage amount compared to a material by preventing vaporization of water and reducing a use amount of water through a device configuration capable of high temperature/high pressure operation.
- Another embodiment provides a dehydrogenation reaction system capable of reducing a water storage capacity by recycling water generated from a fuel cell, increasing a hydrogen storage capacity for the system, and reducing a system cost and weight by removing a gas-liquid separator and a recovery tank from the system.
- According to an embodiment, a dehydrogenation reaction device including a dehydrogenation reactor including: a solid chemical hydride; and an acid aqueous solution tank supplying an acid aqueous solution to the dehydrogenation reactor is provided, wherein the dehydrogenation reactor includes a heating device, a cooling apparatus, a porous metal foam, or a combination thereof.
- The porous metal foam may be positioned in the center of the width direction of the dehydrogenation reactor and extend in the length direction of the dehydrogenation reactor, and the side of the length direction of at least the porous metal foam may be surrounded by the chemical hydride.
- The porous metal foam may be a porous nickel foam or a porous cobalt-nickel foam.
- The dehydrogenation reactor may include 0 parts by volume to 100 parts by volume of the porous metal foam with respect to 100 parts by volume of the chemical hydride,
- The acid aqueous solution may be supplied to the dehydrogenation reactor by gravity or a pump.
- The chemical hydride may include sodium borohydride (NaBH4), lithium borohydride (LiBH4), potassium borohydride (KBH4), ammonium borohydride (NH4BH4), ammonia borohydride (NH3BH3), tetramethyl ammonium borohydride ((CH3)4NH4BH4), sodium aluminum hydride (NaAlH4), lithium aluminum hydride (LiAlH4), potassium aluminum hydride (KAlH4), calcium diborohydride (Ca(BH4)2), magnesium diborohydride (Mg(BH4)2), sodium gallium hydride (NaGaH4), lithium gallium hydride (LiGaH4), potassium gallium hydride (KGaH4), lithium hydride (LiH), calcium hydride (CaH2), magnesium hydride (MgH2), or mixture thereof.
- The acid may be sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, boric acid, a heteropoly acid, acetic acid, formic acid, malic acid, citric acid, tartaric acid, ascorbic acid, lactic acid, an oxalic acid, succinic acid, tauric acid, or a mixture thereof.
- In the dehydrogenation reactor, the dehydrogenation reaction may be performed by reacting 1 mol of hydrogen atoms of the chemical hydride with an acid and water at a molar ratio of 0.5 to 2.
- In the dehydrogenation reactor, the temperature of the dehydrogenation reaction may be 10° C. to 400° C., and the pressure may be 1 bar to 100 bar.
- The gas product produced in the dehydrogenation reactor may include 99 volume % or greater of hydrogen and 1 volume % or less of water.
- According to another embodiment, a dehydrogenation reaction system including an acid aqueous solution tank including an acid aqueous solution; a dehydrogenation reactor including a chemical hydride of a solid state and receiving an acid aqueous solution from the acid aqueous solution tank to react the chemical hydride with the acid aqueous solution to generate hydrogen; and a fuel cell stack receiving hydrogen generated from the dehydrogenation reactor to be reacted with oxygen to generate water and simultaneously to generate electrical energy may be provided, wherein the water generated from the fuel cell stack is recycled to the acid aqueous solution tank, the dehydrogenation reactor, a separate water tank, or all of the above.
- The acid aqueous solution may be supplied to the dehydrogenation reactor by gravity or a pump.
- The dehydrogenation reaction system may further include a gas cooler that can be cooling the hydrogen generated from the dehydrogenation reactor, and a buffer tank that receives and stores hydrogen from the gas cooler.
- The dehydrogenation reaction system may further include a pressure regulator between the gas cooler and the buffer tank, between the buffer tank and the fuel cell stack, or both.
- The dehydrogenation reaction system may further include a sensor inside or outside the dehydrogenation reactor, a temperature sensor and a pressure sensor, or a mass flow meter between the buffer tank and the fuel cell stack.
- The acid aqueous solution tank may be pressurized by receiving hydrogen from the dehydrogenation reactor, the gas cooler, the buffer tank, or a combination thereof.
- The dehydrogenation reaction system may not include a gas-liquid separator to separate hydrogen and water from the reaction products produced in the dehydrogenation reactor.
- The dehydrogenation reaction system may further include a pump, a filter, or both.
- The dehydrogenation reaction device according to an embodiment may maximize the amount of hydrogen storage compared to the material by preventing the vaporization of the water and reducing the amount of the water used through the device configuration capable of operating at high temperature/high pressure.
- The dehydrogenation reaction system according to another embodiment may increase the conversion rate of the hydrolysis reaction by recycling the water generated from the fuel cell, and increasing the hydrogen storage capacity by removing the gas-liquid separator and the recovery tank from the system, and the system cost and weight may be reduced.
-
FIG. 1 is a view schematically showing a dehydrogenation reaction device according to an embodiment. -
FIG. 2 is an enlarged cross-sectional view of a dehydrogenation reactor inFIG. 1 . -
FIG. 3 is a view schematically showing a dehydrogenation reaction device according to another embodiment. -
FIG. 4 is a graph showing a result of measuring a hydrogen storage capacity of a dehydrogenation reaction system using formic acid in several molar ratios in an Embodiment 1. -
FIG. 5 is a graph showing a result of measuring a hydrogen storage capacity of a dehydrogenation reaction system in anEmbodiment 2. -
FIG. 6 is a graph showing a result of measuring a hydrogen storage capacity of a dehydrogenation reaction system in anEmbodiment 3. -
FIG. 7 is a graph showing a result of measuring a hydrogen storage capacity of a dehydrogenation reaction system in an Embodiment 4. -
FIG. 8 andFIG. 9 are graphs showing results of measuring a hydrogen generation speed and a conversion rate of a dehydrogenation reaction system in anEmbodiment 5. -
FIG. 10 is a graph showing a result of carrying out a hydrogen generating reaction capable of driving a 1 kW class fuel cell in an Embodiment 6. - The advantages, features, and aspects that are described hereinafter should become apparent from the following description of the embodiments with reference to the accompanying drawings, which is set forth hereinafter. However, the present disclosure may be not limited to embodiments that are described herein. Although not specifically defined, all of the terms including the technical and scientific terms used herein have meanings understood by persons having ordinary skill in the art. The terms have specific meanings coinciding with related technical references and the present specification as well as lexical meanings. In other words, the terms are not to be construed as having idealized or formal meanings. Throughout the specification and claims which follow, unless explicitly described to the contrary, the word “comprise/include” or variations such as “comprises/includes” or “comprising/including” should be understood to imply the inclusion of stated elements but not the exclusion or any other elements.
- The terms of a singular form may include plural forms unless referred to the contrary.
- In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like reference numerals designate like elements throughout the specification.
- It should be understood that when an element such as a layer, film, region, or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
-
FIG. 1 is a view schematically showing a dehydrogenation reaction device according to an embodiment, andFIG. 2 is an enlarged cross-sectional view of a dehydrogenation reactor inFIG. 1 . Now, a dehydrogenation reaction device is described in detail with reference toFIG. 1 andFIG. 2 , - Referring to
FIG. 1 , adehydrogenation reaction device 100 includes adehydrogenation reactor 110 and an acidaqueous solution tank 120. - The
dehydrogenation reactor 110 may be composed of a high temperature and high pressure vessel so that a dehydrogenation reaction may be carried out in high temperature and high pressure conditions. For example, thedehydrogenation reactor 110 may have a shape such as a cylinder, a sphere, a cuboid, or a polygonal column, and particularly may have a cylinder shape. - Referring to
FIG. 2 , thedehydrogenation reactor 110 may have a high aspect ratio in which a ratio LID of a length L to a width D is high. Here, the width D of thedehydrogenation reactor 110 is shorter than the length L. - In the
dehydrogenation reactor 110, the aspect ratio LID of the length L to the width D may be 1 to 10, and for example, may be 5 to 8. When thedehydrogenation reactor 110 has the high aspect ratio, it is possible to maximize release of reaction heat during the dehydrogenation reaction and minimize the use of a pump by utilizing a water level difference. However, when the reaction heat generated in thedehydrogenation reactor 110 is removed through thecooling apparatus 230, the aspect ratio of thedehydrogenation reactor 110 may be omitted. - The
dehydrogenation reactor 110 includes achemical hydride 111 of a solid state. - The
chemical hydride 111 as a solid state, for example, may be in a form of any one of a powder form, a granular form, a bead form, a microcapsule form, and a pellet form. When thechemical hydride 111 is stored in an aqueous solution (a concentration, in one example, of about 20% of the chemical hydride), a large amount of thechemical hydride 111 may not be stored, but when thechemical hydride 111 is stored in a solid state, large capacity storage is possible. - The chemical hydride may be any compound that may be hydrolyzed to generate hydrogen and a hydrolysate, for example, NaBH4, LiBH4, KBH4, NH4BH4, NH3BH3, (CH3)4NH4BH4, NaAlH4, LiAlH4, KAlH4, Ca(BH4)2, Mg(BH4)2, NaGaH4, LiGaH4, KGaH4, LiH, CaH2, MgH2, or mixture thereof may be included.
- The
dehydrogenation reactor 110 is constructed in the form of cartridge to allow thedehydrogenation reactor 110 to be replaced, or the upper part is designed to be opened and closed so that thechemical hydride 111 may be injected or replaced, or a product is exhausted through the lower part and thechemical hydride 111 may be injected, thereby allowing thedehydrogenation reactor 110 to ensure system continuity. Additionally, thedehydrogenation reactor 110 may further include a part for exhausting a slurried hydrolysis reaction product and a part for injecting thechemical hydride 111. - The
dehydrogenation reactor 110 may include a heating device that provides heat/temperature useful for the hydrolysis of thechemical hydride 111 or for separate purposes, acooling apparatus 230 to exhaust reaction heat H when the hydrogen-generating reaction is an exothermic reaction, or aporous metal foam 112 to improve the reaction speed through a catalysis reaction. - For example, the heating device may use electricity or other heat sources, and the
cooling apparatus 230 may be implemented as a refrigerant circulation device to exhaust heat generated by the hydrolysis of thechemical hydride 111. - The
porous metal foam 112 has a cellular structure composed of a solid metal with gas-filled pores having a predetermined volume. The pores may be sealed (closed cell foam) or interconnected (opened-cell foam), and theporous metal foam 112 may be opened-cell foams, Theporous metal foam 112 may have high porosity, and for example, only 5 volume % to 25 volume % of the entire volume may be metal. Accordingly, theporous metal foam 112 may be ultra-lightweight while having a high-surface area. In addition, theporous metal foam 112 may have various characteristics, for example, porosity, pore volume, thickness, alloy composition, or density. Theporous metal foam 112 may be integrally formed, or may be disposed by stacking at least one or more thereof. - The
porous metal foam 112 may use various materials in consideration of increasing a reaction speed through the catalytic action as well as heat conduction. For example, theporous metal foam 112 may be a porous nickel foam or a porous cobalt-nickel foam. In the case of using the porous nickel foam or the porous cobalt-nickel foam, the heat transfer may be accelerated and the reaction may be accelerated through the metal as the catalytic active sites. It may also help to release the heat of the reaction inside thedehydrogenation reactor 110. In addition, it may act as a distributor so that the add aqueous solution may be evenly supplied inside thedehydrogenation reactor 110. - The
porous metal foam 112 is positioned in the center of the width direction of thedehydrogenation reactor 110 and extends in the length direction of thedehydrogenation reactor 110. At this time, thechemical hydride 111 may be positioned on the outer side in the width direction of thedehydrogenation reactor 110, and the side in the length direction of theporous metal foam 112 may be surrounded by thechemical hydride 111. - In addition, the
porous metal foam 112 may be connected to the inlet side through which the acid aqueous solution supplied from the acidaqueous solution tank 120 inflows. At this time, the opposite surface of the surface where theporous metal foam 112 is connected to thedehydrogenation reactor 110 may be surrounded by thechemical hydride 111. - The
porous metal foam 112 may uniformly distribute the acid aqueous solution to thechemical hydride 111, maximize heat transfer, and act as a non-uniform catalyst for the dehydrogenation reaction. Accordingly, a barrier may be suppressed from being formed by by-products such as a borate, which may be generated from thechemical hydride 111 after the dehydrogenation reaction and the reaction delay are minimized, thereby maximizing the generation amount of hydrogen. - The
dehydrogenation reactor 110 may include theporous metal foam 112 in an amount of 0 to 100 parts by volume with respect to 100 parts by volume of thechemical hydride 111, and for example, it may include 0 to 50 parts by volume thereof. If theporous metal foam 112 includes greater than 50 parts by volume per 100 parts by volume of thechemical hydride 111, the amount of the hydrogen storage may decrease due to space constraints. - The add
aqueous solution tank 120 supplies the acid aqueous solution to thedehydrogenation reactor 110. In other words, thedehydrogenation reaction device 100 is a system that generates hydrogen by injecting the aqueous acid solution into adehydrogenation reactor 110 including thechemical hydride 111 of the solid state. - In addition, since a separate recovery tank in some cases may not used, the cost and weight of the system may be reduced. In particular, there is a merit that it may be easily exhausted under pressure conditions above 100° C. and above atmospheric pressure when the product is present in the form of a slurry with high fluidity in the container.
- The acid
aqueous solution tank 120 may have a corrosion-resistant protective film such as Teflon coating to prevent corrosion by the acid aqueous solution. - The acid aqueous solution shortens the reaction time by adjusting the pH of the
chemical hydride 111 to promote the dehydrogenation reaction. - The acid may be an inorganic acid such as sulfuric acid, nitric acid, phosphoric acid, boric acid, or hydrochloric acid, an organic acid such as heteropoly acid, acetic acid, formic acid, malic acid, citric acid, tartaric acid, ascorbic acid, lactic acid, oxalic acid, succinic acid, and tauric acid, or mixtures thereof, because the molecular weight is small compared to the hydrogen ion, and the system weight may be reduced and formic acid (HCOOH) may be used as it is safer than hydrochloric add in a high concentration state. In the case of formic add, as a weak add, the pH is maintained, in one example, at about 2 under the conditions described in the present disclosure, so it may be used relatively safely. In addition, captured carbon dioxide may be obtained through hydrogenation, so it is an important material in terms of a recycling of carbon dioxide. In addition, formate is converted to bicarbonate through a dehydrogenation reaction, whereby additional hydrogen may be obtained.
- The acid
aqueous solution tank 120 is positioned above thedehydrogenation reactor 110 with respect to the direction of gravity, and the acidaqueous solution tank 120 may supply the acid aqueous solution to thedehydrogenation reactor 110 by gravity. That is, the acidaqueous solution tank 120 may supply the acid aqueous solution to thedehydrogenation reactor 110 due to the water level difference. Through this, it is possible to reduce the system cost and weight by minimizing the use of the pump. However, the present disclosure is not limited thereto, and the acidaqueous solution tank 120 may be positioned below thedehydrogenation reactor 110 in the gravity direction and the acid aqueous solution may be supplied to thedehydrogenation reactor 110 by a high pressure pump, In other words, when the acid aqueous solution is injected into thedehydrogenation reactor 110 through a high pressure pump, the pressure of the acid aqueous solution tank may be omitted, and in this case, the position limitation also disappears. - For this purpose, the acid
aqueous solution tank 120 may have the same pressure as thedehydrogenation reactor 110 or higher than the pressure of thedehydrogenation reactor 110, and avalve 710 such as a solenoid valve may be mounted between the addaqueous solution tank 120 and thedehydrogenation reactor 110. In this case, the addaqueous solution tank 120 does not need to be positioned on thedehydrogenation reactor 110, and may be disposed in a position equivalent to or lower than that of thedehydrogenation reactor 110. For example, the pressurization of the acidaqueous solution tank 120 may be performed by using hydrogen generated in thedehydrogenation reactor 110. Instead of using the above methods, the acidic aqueous solution at atmospheric pressure may be injected into thedehydrogenation reactor 110 using a high pressure pump. - In the
dehydrogenation reaction device 100, a dehydrogenation reaction in which hydrogen is produced by the hydrolysis reaction of thechemical hydride 111 with an acid aqueous solution proceeds. - For example, when the
chemical hydride 111 is NaBH4 and the acid is HCOOH, the dehydrogenation reaction as shown in Reaction Formula 1 below occurs. -
NaBH4+HCOOH+4H2O→HCOONa+H3BO3+H2O+4H2→HCO3Na+H3BO3+5H2 [Reaction Formula 1] - In the
dehydrogenation reactor 110, the dehydrogenation reaction may be performed by reacting 1 mol of hydrogen atoms of the chemical hydride with an acid and water at a molar ratio of 0.5 to 2. If the molar ratio of acid and water is less than 0.5, thechemical hydride 111 may not react sufficiently, and if it is greater than 2, the system weight and reactor volume may increase. - On the other hand, when the acid aqueous solution is used to generate hydrogen from hydrolysis with the
chemical hydride 111, water is easily vaporized and loss due to elevated temperature by an exothermic reaction (a water vaporization temperature: 100° C. at 1 bar), so that the amount of hydrogen generated (i.e., a hydrogen storage capacity) may be declined. - Therefore, the dehydrogenation reaction may take place under high temperature and high pressure conditions. This prevents vaporization of water and reduces the amount of the used water, thereby maximizing the amount of generated hydrogen (the water vaporization temperature: 175° C. at 10 bar, 260° C. at 50 bar). In addition, the generation of CO2 may also be suppressed through the pressurization operation of the
dehydrogenation reactor 100. - Also, if excess water is included in a hydrogen gas after the reaction, an additional gas-liquid separator may be required, and accordingly the volume and weight of the entire system may be increased and then the hydrogen storage capacity may be decreased. However, high temperature and high pressure operation of the
dehydrogenation reactor 100 may increase the hydrogen storage capacity and reduce the system cost and weight. - For example, in the case of the system using NaBH4 and formic acid (HCOOH), the temperature of the dehydrogenation reaction may be 10° C. to 400° C., or 100° C. to 250 ° C. When the temperature of the dehydrogenation reaction is less than 10° C., the acid or acid aqueous solution may be coagulated or separated, and when the temperature is greater than 400° C., a side reaction such as an occurrence of carbon monoxide may increase.
- The pressure of the dehydrogenation reaction may be 1 bar to 100 bar, or 5 bar to 50 bar. If the pressure of the dehydrogenation reaction is less than 1 bar, a decompression pump is used, which may increase the system weight. If the pressure is greater than 100 bar, the dehydrogenation reaction may be inhibited and the weight and volume of a high temperature/high pressure container may increase.
- Accordingly, the gas product generated in the dehydrogenation reactor may contain 99 volume % or greater of hydrogen, 1 volume % or less of water, and 0.1 volume % or less of other impurities.
- The generation speed of hydrogen in the
dehydrogenation reactor 100 may be controlled by changing the injection speed of the acid aqueous solution or by changing the injection time (a valve open time) while fixing the injection speed. Considering system cost and convenience, one of the high pressure pump and the injection method of the acid aqueous solution by gravity may be selected. -
FIG. 3 is a view schematically showing a dehydrogenation reaction device according to another embodiment. Now, the dehydrogenation reaction system is described in detail with reference toFIG. 3 . - Referring to
FIG. 3 , thedehydrogenation reaction system 10 includes thedehydrogenation reactor 110, the acidaqueous solution tank 120, and thefuel cell stack 500, and may selectively further include agas cooler 300 and abuffer tank 400. - Since the description of the
dehydrogenation reactor 110 and the acidaqueous solution tank 120 is the same as described above, a repeated description is omitted. - The
dehydrogenation reactor 110 may increase the amount of hydrogen storage by disposing several reactors in parallel as needed. - Hydrogen generated from the
dehydrogenation reactor 110 is transferred to thegas cooler 300. Thegas cooler 300 cools the supplied hydrogen. The cooling temperature of hydrogen is not particularly limited in the present disclosure, and as an example, it may be a temperature of 10° C. to 60° C. -
FIG. 3 shows that thegas cooler 300 is configured of a plurality of chambers sequentially connected to each other, but the present disclosure is not limited thereto, and thegas cooler 300 may be configured of a single chamber. - The hydrogen cooled in the
gas cooler 300 is transferred to thebuffer tank 400. Thebuffer tank 400 receives and stores a certain amount of the hydrogen gas. - If desired,
pressure regulators dehydrogenation reactor 100 and thegas cooler 300, between thegas cooler 300 and thebuffer tank 400, between thebuffer tank 400 and thefuel cell stack 500, or a combination thereof. A sensor, a temperature sensor, or a pressure sensor may be further included inside or outside thedehydrogenation reactor 100. Amass flow meter 630 may be further included between thebuffer tank 400 and thefuel cell stack 500. Accordingly, the hydrogen gas may be stored in thebuffer tank 400 at a constant pressure, and the hydrogen gas may be supplied to thefuel cell stack 500 at a desired pressure and mass. - Meanwhile, as described above, the acid
aqueous solution tank 120 may be pressurized by using hydrogen generated in thedehydrogenation reactor 110. The acidaqueous solution tank 120 may receive hydrogen directly from thedehydrogenation reactor 110 or may receive the hydrogen from thegas cooler 300 or thebuffer tank 400, or a combination thereof. At this time, the amount of hydrogen gas supplied to the acidaqueous solution tank 120 may be controlled by thevalve 720. - The
fuel cell stack 500 is positioned on a downstream side of thebuffer tank 400 to receive the hydrogen gas from thebuffer tank 400. For example, the hydrogen gas may be received from thebuffer tank 400 through an intake port such as a valve. - The
fuel cell stack 500 generates water by reacting the supplied hydrogen with oxygen and simultaneously generates electrical energy. The water produced in thefuel cell stack 500 is exhausted through exhaust means such as valves, for example. At this time, the water exhausted from thefuel cell stack 500 is recycled to the acidaqueous solution tank 120, thedehydrogenation reactor 110, a separate water tank, or all of them, thereby increasing the hydrogen generation efficiency. At this time, the amount of the water supplied to the acidaqueous solution tank 120 or thedehydrogenation reactor 110 may be controlled byvalves 730 and 740. - The
fuel cell stack 500 may be any device that converts the hydrogen gas into usable electrical energy, and for example, it may be a proton exchange membrane fuel cell (PEMFC), an alkaline fuel cell (AFC), a phosphoric acid fuel cell (PAFC), a molten carbonate salt fuel cell (MCFC), or a solid oxide fuel cell (SOFC), etc., but the present disclosure is not limited thereto. - For example, the
fuel cell stack 500 may pass the generated electrical energy through a power converter such as a DC converter, an inverter, or a charge controller. The power converter may output a part of the electrical energy to an electrical load through a load interconnect, and the other part of the electrical energy may be sent back to the energy storage through a recharging interconnect. Another part of the electrical energy may be used to supply power to a control unit. - The
dehydrogenation reaction system 10 prevents the vaporization of the water through the high temperature and high pressure operation of thedehydrogenation reactor 100 and reduces the amount of the used water, so there is no need for a separate gas-liquid separator because the excess water is not included in the hydrogen gas after the reaction. - In the
dehydrogenation reaction system 10, the use of the pump may be minimized by allowing the acidaqueous solution tank 120 to supply the acid aqueous solution to the bottom of thedehydrogenation reactor 110 by gravity, however, if desired, a pump, a filter, or both may be further included. - For example, the pump may be used to supply the acid aqueous solution of the acid
aqueous solution tank 120 to thedehydrogenation reactor 110, to supply the hydrogen gas generated from thedehydrogenation reactor 110 to thegas cooler 300, to supply the hydrogen gas cooled in thegas cooler 300 to thebuffer tank 400, to supply the hydrogen gas stored in thebuffer tank 400 to thefuel cell stack 500, to supply the hydrogen gas to the acidaqueous solution tank 120, or to supply the water generated from thefuel cell stack 500 to thedehydrogenation reactor 110 or the acidaqueous solution tank 120. - The filter may substantially remove unwanted particles included in the hydrogen gas by filtering the generated hydrogen gas. The filter may be positioned between the
dehydrogenation reactor 110, thegas cooler 300, thebuffer tank 400, or thefuel cell stack 500, particularly between thebuffer tank 400 and thefuel cell stack 500. - In addition, optionally, the
dehydrogenation reaction system 10 may include an outlet for exhausting the mixture of the chemical hydride, the acid, and the water after the reaction has been completed, and may include a device for removing reaction by-products other than hydrogen and the water or converting it to other materials. - Hereinafter, specific embodiments of the disclosure are presented. However, the embodiments described below are only intended to specifically illustrate or describe the disclosure and are not to limit the scope of the disclosure.
- (Evaluation Method of Dehydrogenation Reaction)
- The
chemical hydride 111 is charged into the high temperature and highpressure dehydrogenation reactor 110. The acid aqueous solution mixed in a specific molar ratio is injected using a syringe or a high-pressure pump. At this time, the injection speed may be adjusted from 0.01 mL/min to 20 mL/min, and may vary depending on the size of thedehydrogenation reactor 110 and the amount of thechemical hydride 111. - The pressure and the temperature are measured, and a predetermined pressure and temperature are maintained through valve control and cooling. In some cases, H2O may be injected first and then the acid may be injected.
- The hydrogen conversion rate may be calculated by Equation 1 below, and the flow rate and the purity are measured using a mass flow meter and gas chromatography (GC).
-
The hydrogen conversion rate=((the amount of hydrogen exhausted to the outside of the reactor through the mass flow meter)+(the pressure at the room temperature after the reaction)×(the reactor volume))/(the theoretical hydrogen production amount) [Equation 1] - By using the
dehydrogenation reaction system 10 according to an embodiment, in the room temperature and the room pressure condition, the dehydrogenation reaction was performed by using NaBH4 as thechemical hydride 111 and HCOOH as the acid, and at this time, the hydrogen storage capacity (the H2 storage capacity, wt %) was measured by performing the dehydrogenation reaction while changing the reaction molar ratio of NaBH4:αHCOOH:βH2O to 0≤α≤1, 3≤β≤4, and α+β=4, and the result is shown inFIG. 4 . - Referring to
FIG. 4 , in Embodiment 1, the reaction likeReaction Formula 2 below is performed, in the room temperature/room pressure condition, a reaction molar sum of HCOOH and H2O is maintained as 4 (for example, to minimize water usage), and as the reacted result, it was confirmed that hydrogen was generated under the condition of 0.25 mol to 1 mol of HCOOH, and hydrogen, which was close to the theoretical storage amount, was generated particularly at 0.5 mol. -
- The reaction molar ratio of NaBH4:αHCOOH:βH2O is fixed as α=0.5 and β=3.5, while changing the temperature to 25° C. to 300° C. and the pressure to 1 bar to 50 bar, and the hydrogen storage capacity was measured and the result thereof is shown
FIG. 5 . - Referring to
FIG. 5 , In order to obtain the same hydrogen generation amount as the theoretical value by preventing the water vaporization, the reaction temperature and pressure were increased, and as the result confirming the optimum reaction conditions, the hydrogen storage capacity of 6 wt % or greater (theoretical value: 6.5 wt %) was confirmed in the temperature of 100° C. to 250° C. and the pressure of 5 bar to 50 bar, particularly the conversion rate of 97% was achieved at the range of 100° C. to 250° C. and 30 bar to 50 bar. - In the condition of 180° C. and 30 bar, while changing the reaction molar ratio of NaBH4:αHCOOH:βH2O to α=0.5 and 2≤β≤4, the hydrogen storage capacity was measured and the result thereof is shown in
FIG. 6 . - Referring to
FIG. 6 , as a result of checking the condition for the minimization of the usage amount of the water under a high temperature/high pressure condition, in the case of HCOOH of 0.5 mol, H2O may be reduced to 2 mol, and the hydrogen storage capacity may theoretically reach 8.3 wt % and experimentally 7.0 wt % (the room temperature/room pressure condition: 5.5 wt %). - In the condition of 180° C. and 30 bar, while changing the reaction molar ratio of NaBH4:αHCOOH:βH2O to 0≤α≤0.7, 1.8≤β≤2.5, and α+β=2.5, the hydrogen storage capacity was measured and the result thereof is shown in FIG. 7.
- Referring to
FIG. 7 , for the minimization of the usage amount of the water, after fixing the molar ratio sum of HCOOH and H2O as 2.5, as a result of measuring the amount of hydrogen generated according to the HCOOH molar ratio, it was confirmed that the hydrogen storage capacity was 6 wt % or greater in the range of 0.3 mol to 0.5 mol of HCOOH. - The hydrogen generation speed and the conversion rate were measured while changing the injection speed of the acid aqueous solution, and the result thereof is shown in
FIG. 8 andFIG. 9 and is summarized in Table 1. - In
FIG. 9 , the reaction molar ratio of NaBH4:αHCOOH:βH2O was α=0.5 and β=3.5. -
TABLE 1 Acid aqueous solution 0.021 ml/min 0.043 ml/min 0.086 ml/min injection speed Feed (NaBH4) injection amount 0.4 g/0.867 ml 0.4 g/0.867 ml 0.4 g/0.867 ml Starting temperature 25° C. 25° C. 25° C. Reaction temperature 45° C. 65° C. 75° C. Hydrogen generation speed1) 15.4 ml/min 41 ml/min 80.8 ml/min conversion rate 85% 85% 84% - 1) Hydrogen Generation Speed Based on Initial 10 Minutes
- Referring to
FIG. 8 ,FIG. 9 , and Table 1, it is confirmed that the hydrogen generation speed increases as the injection speed of the acid aqueous solution increases. In addition, it was confirmed that the total amount of the generated hydrogen was the same at the conversion rate of 85% and there was no reaction decline due to the increase of speed. That is, it can be seen that the rate of hydrogen generation can be controlled by changing the injection rate of the aqueous add solution. - Based on the results of
FIG. 8 ,FIG. 9 , and Table 1, the dehydrogenation reactor capable of including NaBH4 at 110 g was manufactured and the hydrogen generation reaction (the hydrogen generation speed of 15 L/min) capable of driving a 1 kW class fuel cell was produced, and the result thereof is shown inFIG. 10 . - In addition, the dehydrogenation reaction proceeded while changing the system operation and control conditions as shown in Table 2 below, and the results are summarized in Table 2.
-
TABLE 2 NaBH4(SBH) 70 g 70 g 176 g 160 g 70 g 70 g 70 g injection amount HCOOH:H2O 0.5:3.5 0.5:3.5 0.5:3.5 0.5:3.5 0.5:3.5 0.5:3.5 0.5:2 molar ratio Injection 8 4 4 4 4 4 2.5 equivalent equivalents equivalents equivalents equivalents equivalents equivalents equivalents ([molFA+ molH2O]/molSBH) Valve on/off time 3 s/27 s 3 s/27 s 3 s/12 s 3 s/12 s 3 s/12 s 3 s/12 s 3 s/12 s (acid aqueous solution injection) Reactor 50 bar 50 bar 20 bar 50 bar 30 bar 30 bar 30 bar predetermined pressure Starting pressure 50 bar 50 bar 20 bar 50 bar 30 bar Room Room pressure pressure Reactor inside 203° C. 201° C. 172° C. 190° C. 222° C. — 216° C. maximum temperature Conversion rate 100% 100% 75.5% 84% 100% — 75.8% Product volume 180 L 180 L 342 L 363 L 180 L — 137 L Product form Liquid + solid Liquid + solid Solid Slurry Top solid, Viscous liquid Solid (Swelling) Bottom at100° C. (viscoelastic) slurry Uniqueness — — Internal — — — — clogging - While this disclosure has been described in connection with what is presently considered to be practical embodiments, it is to be understood that the disclosure is not limited to the disclosed embodiments. On the contrary, the present disclosure is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
-
- 10: dehydrogenation reaction system
- 100: dehydrogenation reaction device
- 110: dehydrogenation reactor
- 111. chemical hydride
- 112: porous metal foam
- 120: acid aqueous solution tank
- 230: cooling apparatus
- 300: gas cooler
- 400: buffer tank
- 500: fuel cell stack
- 610, 620: pressure regulator
- 630: mass flow meter
- 710, 720, 730, 740: valve
Claims (19)
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5372617A (en) * | 1993-05-28 | 1994-12-13 | The Charles Stark Draper Laboratory, Inc. | Hydrogen generation by hydrolysis of hydrides for undersea vehicle fuel cell energy systems |
US20020081235A1 (en) * | 2000-07-13 | 2002-06-27 | Baldwin Edward W. | Method and apparatus for controlled generation of hydrogen by dissociation of water |
US20050036941A1 (en) * | 2003-08-14 | 2005-02-17 | Bae In Tae | Hydrogen generator |
US20070020172A1 (en) * | 2005-02-08 | 2007-01-25 | Hyenergy Systems, Inc. | Solid chemical hydride dispenser for generating hydrogen gas |
US20070207085A1 (en) * | 2004-03-26 | 2007-09-06 | Tomasz Troczynski | Power Systems Utilizing Hydrolytically Generated Hydrogen |
WO2007136629A2 (en) * | 2006-05-17 | 2007-11-29 | Millennium Cell, Inc. | Methods and devices for hydrogen generation from solid hydrides |
US20150207160A1 (en) * | 2012-07-16 | 2015-07-23 | Prometheus Wirless Limited | Fuel Cell Apparatus, Composition and Hydrogen Generator |
-
2021
- 2021-02-08 KR KR1020210017384A patent/KR20220114180A/en active Search and Examination
- 2021-06-15 US US17/348,552 patent/US20220250904A1/en not_active Abandoned
- 2021-07-05 CN CN202110756121.9A patent/CN114914498A/en active Pending
-
2023
- 2023-11-07 US US18/387,793 patent/US20240076182A1/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5372617A (en) * | 1993-05-28 | 1994-12-13 | The Charles Stark Draper Laboratory, Inc. | Hydrogen generation by hydrolysis of hydrides for undersea vehicle fuel cell energy systems |
US20020081235A1 (en) * | 2000-07-13 | 2002-06-27 | Baldwin Edward W. | Method and apparatus for controlled generation of hydrogen by dissociation of water |
US20050036941A1 (en) * | 2003-08-14 | 2005-02-17 | Bae In Tae | Hydrogen generator |
US20070207085A1 (en) * | 2004-03-26 | 2007-09-06 | Tomasz Troczynski | Power Systems Utilizing Hydrolytically Generated Hydrogen |
US20070020172A1 (en) * | 2005-02-08 | 2007-01-25 | Hyenergy Systems, Inc. | Solid chemical hydride dispenser for generating hydrogen gas |
WO2007136629A2 (en) * | 2006-05-17 | 2007-11-29 | Millennium Cell, Inc. | Methods and devices for hydrogen generation from solid hydrides |
US20150207160A1 (en) * | 2012-07-16 | 2015-07-23 | Prometheus Wirless Limited | Fuel Cell Apparatus, Composition and Hydrogen Generator |
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CN114914498A (en) | 2022-08-16 |
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