CN113054889B - System for generating hydrogen by utilizing abandoned wind and abandoned light - Google Patents
System for generating hydrogen by utilizing abandoned wind and abandoned light Download PDFInfo
- Publication number
- CN113054889B CN113054889B CN202110445264.8A CN202110445264A CN113054889B CN 113054889 B CN113054889 B CN 113054889B CN 202110445264 A CN202110445264 A CN 202110445264A CN 113054889 B CN113054889 B CN 113054889B
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- Prior art keywords
- aluminum
- liquid
- power generation
- anode
- generation system
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 89
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 253
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 201
- 239000007788 liquid Substances 0.000 claims abstract description 124
- 238000010248 power generation Methods 0.000 claims abstract description 91
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 58
- 239000002699 waste material Substances 0.000 claims abstract description 52
- 238000004146 energy storage Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000006227 byproduct Substances 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000446 fuel Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 229910020830 Sn-Bi Inorganic materials 0.000 claims description 3
- 229910018728 Sn—Bi Inorganic materials 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 230000009970 fire resistant effect Effects 0.000 claims description 2
- 230000029087 digestion Effects 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 101
- 239000000243 solution Substances 0.000 description 34
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 23
- 239000010410 layer Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 239000012535 impurity Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 230000005611 electricity Effects 0.000 description 11
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 229910000838 Al alloy Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000000889 atomisation Methods 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- -1 hydroxide ions Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 2
- 229940039790 sodium oxalate Drugs 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000009461 vacuum packaging Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020814 NaAl(OH)4 Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- XAGFODPZIPBFFR-OUBTZVSYSA-N aluminium-28 atom Chemical compound [28Al] XAGFODPZIPBFFR-OUBTZVSYSA-N 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S10/00—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power
- H02S10/10—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power including a supplementary source of electric power, e.g. hybrid diesel-PV energy systems
- H02S10/12—Hybrid wind-PV energy systems
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
- F03D—WIND MOTORS
- F03D9/00—Adaptations of wind motors for special use; Combinations of wind motors with apparatus driven thereby; Wind motors specially adapted for installation in particular locations
- F03D9/10—Combinations of wind motors with apparatus storing energy
- F03D9/19—Combinations of wind motors with apparatus storing energy storing chemical energy, e.g. using electrolysis
-
- 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
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/14—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries for charging batteries from dynamo-electric generators driven at varying speed, e.g. on vehicle
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/34—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering
- H02J7/35—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering with light sensitive cells
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/56—Power conversion systems, e.g. maximum power point trackers
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/76—Power conversion electric or electronic aspects
-
- 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
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Abstract
The invention discloses a system for generating hydrogen by utilizing waste wind and waste light. The new energy power generation system in the system comprises a wind power generation system, a photovoltaic power generation system and a three-layer liquid energy storage system; electrolyzing the aluminum electrolysis cell to obtain liquid aluminum and releasing oxygen; the liquid aluminum is used for preparing an aluminum anode plate or aluminum powder; the aluminum air battery power generation system takes an aluminum anode plate as an anode to generate power, releases hydrogen and generates by-product aluminum oxide to be used as a raw material of an aluminum electrolysis cell; aluminum powder is hydrolyzed to release hydrogen, and byproduct alumina is generated to be used as a raw material of the aluminum electrolysis cell; the fuel cell power generation system takes oxygen released by the aluminum electrolysis cell, the aluminum air cell power generation system and hydrogen released by aluminum powder hydrolysis as raw materials to generate power, and generates byproduct water to be used as raw materials for aluminum powder hydrolysis; the new energy power generation system is electrically connected with an aluminum electrolysis cell and equipment for preparing an aluminum anode plate or aluminum powder by liquid aluminum respectively. The invention utilizes the wind and light discarding to generate hydrogen, and improves the digestion capability of wind power and photovoltaic power.
Description
Technical Field
The invention relates to the field of renewable energy source application, in particular to a system for generating hydrogen by utilizing waste wind and waste light.
Background
At present, in western areas such as Xinjiang and inner Mongolia in China, wind energy and solar energy resources are rich, and the development speed of wind power generation and photovoltaic power generation is extremely high. Wind power is different from thermal power, hydroelectric power and nuclear power, has the characteristics of strong intermittence, large fluctuation and the like, and has obvious negative effects on stable power angle, stable frequency, stable voltage, standby system, electric energy quality and the like of a power grid, and the effects become main obstacles for development of wind power and photovoltaic power and become difficult problems for wind power and photovoltaic power consumption. The wind and light discarding phenomenon is serious, and the investment waste is caused.
After wind power and photovoltaic power are connected to the network, the safety of a national power grid is guaranteed, particularly in midnight, the wind energy generates larger electric energy which cannot be connected to the network, the wind is required to be abandoned, and sometimes the light is required to be abandoned in daytime, so that how to consume the wind power and the photovoltaic power becomes the technical problem to be solved urgently.
Disclosure of Invention
Based on the above, it is necessary to provide a system for generating hydrogen by utilizing waste wind and waste light so as to improve the capability of absorbing wind power and photovoltaic power.
In order to achieve the above object, the present invention provides the following solutions:
a system for producing hydrogen by wind and light curtailment, comprising: a new energy power generation system, an aluminum electrolysis cell, an aluminum air battery power generation system and a fuel cell power generation system;
the new energy power generation system comprises a wind power generation system, a photovoltaic power generation system and a three-layer liquid energy storage system;
The aluminum electrolysis cell is used for electrolyzing aluminum oxide serving as a raw material to obtain liquid aluminum and releasing oxygen; the liquid aluminum is used for preparing an aluminum anode plate or aluminum powder;
the aluminum-air battery power generation system is used for generating power by taking the aluminum anode plate as an anode, releasing hydrogen and generating byproduct aluminum oxide to be used as a raw material of the aluminum electrolysis cell;
the aluminum powder is used for hydrolyzing and releasing hydrogen, and generates a byproduct alumina to be used as a raw material of the aluminum electrolysis cell;
the fuel cell power generation system is used for generating power by taking oxygen released by the aluminum electrolysis cell, hydrogen released by the aluminum air cell power generation system and hydrogen released by the aluminum powder hydrolysis as raw materials, and generating byproduct water to be used as the raw materials for the aluminum powder hydrolysis;
The new energy power generation system is electrically connected with the aluminum electrolysis cell, the equipment for preparing the aluminum anode plate by the liquid aluminum and the equipment for preparing the aluminum powder by the liquid aluminum respectively.
Optionally, the system for generating hydrogen by utilizing waste wind and waste light further comprises: an AC/DC converter, a first DC/DC converter, a second DC/DC converter, a DC bus, a third DC/DC converter, and a first DC/AC converter;
The wind power generation system is electrically connected with the DC bus through the AC/DC converter; the photovoltaic power generation system is electrically connected with the DC bus through the first DC/DC converter; the three-layer liquid energy storage system is electrically connected with the DC bus through the second DC/DC converter; the DC bus is electrically connected with the aluminum electrolysis cell through the third DC/DC converter; the DC bus is electrically connected with the equipment for preparing the aluminum anode plate by the liquid aluminum and the equipment for preparing the aluminum powder by the liquid aluminum through the first DC/AC converter respectively.
Optionally, the system for generating hydrogen by utilizing waste wind and waste light further comprises: a power supply converter; the aluminum air battery power generation system and the fuel battery power generation system supply power to electric equipment through the power supply converter; the power supply device is at least one of a direct current load, an alternating current load and a national power grid.
Optionally, the power supply converter comprises a fourth DC/DC converter and/or a second DC/AC converter.
Optionally, the three-layer liquid energy storage system is in a vacuum environment, and the three-layer liquid energy storage system comprises: the device comprises an energy storage tank, an anode structure, a cathode structure, a refractory structure, an anode liquid metal alloy, a cathode liquid metal and a first electrolyte;
The fire-resistant structure divides the energy storage tank into a charging area and an energy storage area; the bottom discharge port of the charging area is communicated with the energy storage area; the energy storage area is provided with the anode liquid metal alloy, the first electrolyte and the cathode liquid metal in sequence from bottom to top; the anode structure is in contact with the anode liquid metal alloy; the cathode structure is in contact with the cathode liquid metal.
Optionally, the anode structure comprises an anode wire and an anode graphite block; the cathode structure comprises a cathode lead and a cathode graphite block; the bottom of the anode liquid metal alloy is in contact with the anode graphite block; an anode lead is arranged at the bottom of the anode graphite block; the surface of the cathode liquid metal is contacted with the cathode graphite block; the cathode lead is connected with the cathode graphite block.
Optionally, the anode liquid metal alloy is liquid Sn-Bi, the cathode liquid metal is liquid Li, and the first electrolyte is Li-KI electrolyte.
Optionally, the aluminum electrolysis cell comprises a reaction cell, an anode, a cathode and a second electrolyte; the bottom of the reaction tank is inserted into the cathode; the anode is inserted into the side wall of the reaction tank; the second electrolyte is placed in the reaction tank; after the alumina enters the reaction tank, liquid aluminum is precipitated in a first set area where the cathode is located, and oxygen is released in a second set area where the anode is located.
Optionally, the anode is Ni-Fe-Al 2O3 metal ceramic, the cathode is made by spraying TiB 2 on the surface of steel, and the second electrolyte is NaF-AlF 3-BaF2-CaF2 melt.
Optionally, the aluminum air cell power generation system includes a cell stack body structure;
The cell stack main body structure comprises a single cell container, a filter screen, a waste liquid tank, a liquid storage tank and a pumping device; a single cell is placed in the single cell container; the bottom of the single cell container is provided with a liquid discharge hole; the filter screen is arranged at the bottom of the single cell container; the filter screen is of a drawer structure, the upper part of the filter screen is attached to the lower surface of the single cell container, and the lower part of the filter screen is of a metal reticular structure; the waste liquid tank is arranged below the filter screen; the liquid storage tank is communicated with the single cell container through the pumping device.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides a system for generating hydrogen by utilizing waste wind and waste light, wherein a new energy power generation system comprises a wind power generation system, a photovoltaic power generation system and a three-layer liquid energy storage system, and electricity generated by waste wind and waste light is stored by an energy storage battery and then is used for being electrolyzed into liquid aluminum and releasing oxygen by an aluminum cell. The liquid aluminum is used for preparing an aluminum anode plate or aluminum powder, the aluminum anode plate is used for an aluminum air battery power generation system to obtain direct current and hydrogen, aluminum oxide is produced as a byproduct, the aluminum powder is hydrolyzed to release hydrogen, and aluminum oxide is also produced as a byproduct. Hydrogen can be used in fuel cell power generation systems, and in hydrogen automobiles or hydrogen customers. And (5) returning the byproduct alumina to the aluminum electrolysis cell to further obtain liquid aluminum and release oxygen. The electricity generated by the aluminum air battery power generation system and the oxyhydrogen fuel battery power generation system can be directly used for direct current load and alternating current load, and can be directly connected into a national power grid after inversion. The invention utilizes the abandoned wind and abandoned light to generate the hydrogen, improves the digestion capability of wind power and photovoltaic power, and is energy-saving and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block diagram of a system for generating hydrogen by utilizing waste wind and waste light according to an embodiment of the present invention;
FIG. 2 is a block diagram of a three-layer liquid energy storage system provided by an embodiment of the present invention;
FIG. 3 is a block diagram of a low temperature aluminum electrolysis cell provided by an embodiment of the invention;
FIG. 4 is a schematic diagram of equal channel angular extrusion according to an embodiment of the present invention;
fig. 5 is a three-dimensional schematic diagram of a cell stack main body structure according to an embodiment of the present invention;
fig. 6 is a rear view of a stack body structure provided in an embodiment of the present invention;
FIG. 7 is a diagram of connection relationship of an auxiliary system according to an embodiment of the present invention;
FIG. 8 is a reaction flow chart of an alumina recovery system according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
Fig. 1 is a block diagram of a system for generating hydrogen by utilizing waste wind and waste light according to an embodiment of the present invention. Referring to fig. 1, the system for generating hydrogen by using waste wind and waste light in this embodiment includes: a new energy power generation system, an aluminum electrolysis cell 4, an aluminum air battery power generation system 5 and a fuel battery power generation system 6.
The new energy power generation system comprises a wind power generation system 1, a photovoltaic power generation system 2 and a three-layer liquid energy storage system 3. The aluminum electrolysis cell 4 is used for electrolyzing aluminum oxide serving as a raw material to obtain liquid aluminum and releasing oxygen; the liquid aluminum is used for preparing an aluminum anode plate or aluminum powder. The aluminum-air battery power generation system 5 is used for generating electricity by taking the aluminum anode plate as an anode, releasing hydrogen, and generating by-product alumina as a raw material of the aluminum electrolysis cell 4. The aluminum powder is used for hydrolyzing and releasing hydrogen, and generates by-product alumina as a raw material of the aluminum electrolysis cell 4. The fuel cell power generation system 6 is used for generating power by taking oxygen released by the aluminum electrolysis cell 4, hydrogen released by the aluminum air cell power generation system 5 and hydrogen released by the aluminum powder hydrolysis as raw materials, and generating byproduct water as raw materials for the aluminum powder hydrolysis. The new energy power generation system is electrically connected with the aluminum electrolysis cell 4, the equipment for preparing the aluminum anode plate by the liquid aluminum and the equipment for preparing the aluminum powder by the liquid aluminum respectively. The aluminum electrolysis cell 4 is a low-temperature aluminum electrolysis cell.
The system for generating hydrogen by utilizing the abandoned wind and the abandoned light further comprises: an AC/DC converter 7, a first DC/DC converter 8, a second DC/DC converter 9, a DC bus 10, a third DC/DC converter 11, a first DC/AC converter 12 and a power supply converter 13. The wind power generation system 1 is electrically connected to the DC bus 10 via the AC/DC converter 7; the photovoltaic power generation system 2 is electrically connected to the DC bus 10 through the first DC/DC converter 8; the three-layer liquid energy storage system 3 is electrically connected with the DC bus 10 through the second DC/DC converter 9; the DC bus 10 is electrically connected to the aluminium electrolysis cell 4 by means of the third DC/DC converter 11; the DC bus 10 is electrically connected to the apparatus for manufacturing an aluminum anode plate of liquid aluminum and the apparatus for manufacturing aluminum powder of liquid aluminum, respectively, through the first DC/AC converter 12.
The aluminum air battery power generation system 5 and the fuel battery power generation system 6 supply power to electric equipment through the power supply converter 13; the power supply device is at least one of a direct current load, an alternating current load and a national power grid. The power supply converter 13 comprises a fourth DC/DC converter and/or a second DC/AC converter.
The implementation process of the system for generating hydrogen by utilizing the waste wind and the waste light comprises the following steps:
The electricity generated by the wind power generation system 1 is alternating current and is converted into direct current suitable for the DC bus 10 through the AC/DC converter 7; the three-layer liquid energy storage system 3 is characterized by being capable of charging and discharging, and the current and the voltage of the DC bus 10 are kept stable by continuously charging or discharging through the second DC/DC converter 9 according to the balance of the power generation system and the power utilization system. The power supply is from a DC (direct current) bus, the low-temperature aluminum electrolysis cell is connected with the DC bus through a third DC/DC converter 11, and the low-temperature aluminum electrolysis cell has the main functions of electrolyzing aluminum oxide from an aluminum air battery power generation system 5 and byproduct aluminum oxide from the hydrolysis hydrogen production of aluminum powder to release oxygen to obtain liquid aluminum, wherein the liquid aluminum ingot is an aluminum ingot, and the liquid aluminum ingot is further processed into an aluminum anode plate serving as the anode plate of the aluminum air battery power generation system 5; or atomizing liquid aluminum into aluminum powder, and further hydrolyzing to prepare hydrogen. Wherein the aluminum anode plate preparation equipment and the atomization aluminum powder preparation equipment are also powered by a DC bus, and the current on the DC bus is converted into alternating current suitable for the DC bus by a first DC/AC converter 12. The aluminum air battery power generation system 5 is characterized in that an anode plate is manufactured by adopting equal-channel extrusion equipment, crystal grains are nano-sized, a corrosion inhibitor is not added in the aluminum air battery power generation system 5, hydrogen can be smoothly discharged and released, a byproduct is aluminum hydroxide, and the aluminum hydroxide is further calcined into aluminum oxide; aluminum powder and alkaline water react in hydrolysis equipment to generate hydrogen and aluminum hydroxide, the hydrogen and the aluminum hydroxide are further calcined into aluminum oxide, and the aluminum oxide is supplied to a low-temperature aluminum electrolysis cell as a raw material. The hydrogen in the fuel cell power generation system 6 comes from the aluminum air cell power generation system 5 and an aluminum powder hydrolysis reactor, the oxygen comes from a low-temperature aluminum electrolysis cell, the oxyhydrogen fuel cell generates power, and byproduct water is used for aluminum powder hydrolysis. The electricity generated by the aluminum air battery power generation system 5 and the fuel battery power generation system 6 is direct current and can be used by a direct current load through a fourth DC/DC converter; the second DC/AC converter can also be used for alternating current load; the second DC/AC converter can also be used for generating power to surf the internet, so that wind-solar power generation can be stably surf the internet.
As an optional implementation manner, the system for generating hydrogen by utilizing the waste wind and the waste light further comprises an intelligent control system; the intelligent control system is electrically connected with the wind power generation system 1, the photovoltaic power generation system 2, the three-layer liquid energy storage system 3, the aluminum electrolysis cell 4, the aluminum anode plate and the aluminum powder preparation equipment to detect electricity consumption and electricity generation of the wind power generation system 1, the photovoltaic power generation system 2, the three-layer liquid energy storage system 3, the aluminum electrolysis cell 4, the aluminum anode plate and the aluminum powder preparation equipment, and balance between electricity generation and electricity consumption is maintained.
As an alternative embodiment, the wind power generator in the wind power generation system 1 may be a doubly fed or directly driven wind power generator set, the wind power generator has an unloading device, the wind power generator can be unloaded when wind power cannot be consumed, and an alternating current-direct current (AC/DC) converter for wind power generation is connected with a transmission system (DC bus 10); the photovoltaic power generation system 2 is connected with a transmission system by a direct current (DC/DC) converter; the three-layer liquid energy storage battery in the three-layer liquid energy storage system 3 takes lithium as a negative electrode, bismuth-tin alloy as a positive electrode, the molar ratio of positive electrode to negative electrode Li: bi: sn=80:3:4 as an electrode pair, and binary molten salt with the molar ratio of LiI-KI of 58:42 as a eutectic electrolyte, wherein the working temperature is 290 ℃. The balance voltage of the battery is between 0.74 and 0.79, is relatively stable, and can be charged and discharged with large current density. The layer liquid energy storage system is connected into the DC bus 10 through the direct current converter, and has the functions of stabilizing the fluctuation and intermittence of wind power, absorbing power when wind power is larger than a load, and emitting power when wind power is smaller than the load, so that the voltage and the power in the exclusive system are kept stable, and the load requirement is met. In addition, the transmission system adopts a direct current bus, one end of wind power and photovoltaic power is rectified to convert alternating current into direct current, the direct current is sent to the direct current bus, and a filter is arranged on the rectifying side to filter characteristic harmonic waves.
As an alternative embodiment, the three-layer liquid energy storage system 3 is in a vacuum environment, for example, the three-layer liquid energy storage system 3 may be placed in a vacuum box. As shown in fig. 2, the three-layer liquid energy storage system 3 includes: the energy storage cell, anode structure, cathode structure, refractory structure 22, anode liquid metal alloy 17, cathode liquid metal 15, and first electrolyte 16. The refractory structure 22 divides the energy storage tank into a charging zone and an energy storage zone; the bottom discharge port of the charging area is communicated with the energy storage area; the energy storage area is provided with the anode liquid metal alloy 17, the first electrolyte 16 and the cathode liquid metal 15 from bottom to top in sequence; the anode structure is in contact with the anode liquid metal alloy 17; the cathode structure is in contact with the cathode liquid metal 15.
The anode structure comprises an anode wire 18 and an anode graphite block 19; the cathode structure includes a cathode lead 14 and a cathode graphite block 24; the bottom of the anode liquid metal alloy 17 is arranged in contact with the anode graphite block 19; the bottom of the anode graphite block 19 is provided with an anode lead 18; the surface of the cathode liquid metal 15 is contacted with the cathode graphite block 24; the cathode lead 14 is connected to the cathode graphite block 24. The anode graphite block 19 is a high purity graphite block.
The anode liquid metal alloy 17 is liquid Sn-Bi, the cathode liquid metal 15 is liquid metal Li, and the first electrolyte 16 is an Li-KI electrolyte. The material of the refractory structure 22 is a magnesia refractory material.
The energy storage groove is provided with a steel shell 20 and an insulating structure 21 from outside to inside in sequence; the material of the insulating structure 21 is a refractory or insulating material. During operation, the anode liquid metal alloy 17 is continuously fed from the feed port 23 of the feed zone and the cathode liquid metal 15 and the first electrolyte 16 are continuously fed from the feed port of the energy storage zone.
As an alternative implementation mode, the electrolysis temperature of the low-temperature aluminum liquid electrolysis tank is 700-800 ℃, the electrolyte in the low-temperature aluminum liquid electrolysis tank can be light electrolyte or heavy electrolyte, the density of the light electrolyte is lower than that of liquid aluminum, and the aluminum liquid is below the electrolyte during electrolysis; the density of heavy electrolyte is higher than that of liquid aluminum, and the aluminum liquid is above the electrolyte during electrolysis. Different forms of electrolytic cells are designed depending on the density of the electrolyte used. And adopting an inert anode and a cathode, and obtaining aluminum and oxygen during electrolysis. Depending on the purity of the alumina used, different purity grades of aluminum are obtained. The alumina is obtained by roasting a byproduct aluminum hydroxide after the aluminum-air battery is generated.
As shown in fig. 3, the low temperature aluminum electrolysis cell comprises a reaction cell 31, an anode 25, a cathode 26 and a second electrolyte 27; the bottom of the reaction tank 31 is inserted into the cathode 26; the anode 25 is inserted into the side wall of the reaction tank 31; the second electrolyte is placed in the reaction tank 31; after alumina enters the reaction tank 31, liquid aluminum 28 is precipitated in a first set area where the cathode 26 is located, and oxygen is released in a second set area where the anode 25 is located. The liquid aluminum is collected in an aluminum collecting chamber 29, which is an aluminum collecting chamber with aluminum oxide sprayed on the cast iron surface.
The anode 25 is an annular inert anode 25, and the anode 25 is specifically made of Ni-Fe-Al 2O3 metal ceramic; the cathode 26 is made of steel surface sprayed TiB 2; the second electrolyte 27 is a heavy electrolyte, and the second electrolyte 27 is specifically a NaF-AlF 3-BaF2-CaF2 melt. The reaction tank 31 is a thermal insulator, and the material of the reaction tank 31 is sic—bn.
The low-temperature aluminum electrolysis cell also comprises a steel reticular baffle plate 30 with the surface coated with TiB 2; one end of the steel mesh separator 30 is fixed to one end of the anode 25, the fixed end is located inside the side wall of the reaction tank 31, the other end of the anode 25 extends to the outside of the reaction tank 31, and the other end of the steel mesh separator 30 extends into the second electrolyte 27.
The heavy electrolyte used in the low temperature aluminum electrolysis cell described above may also be an electrolyte composed of 30% AlF 3、20％CaF2、15％MgF2、25％BaF2 and 10% KF, the melting point of which is 630 ℃.
The working process is as follows: the raw material high-purity aluminum oxide comes from a product of an aluminum-air battery power generation system 5 discharge product aluminum hydroxide calcined at 1000-1100 ℃, enters the low-temperature aluminum electrolysis cell, is dissolved in liquid electrolyte, the solubility is 2-3%, the electrolyte density is 3-3.5 g/cm 3, the electrolyte is heavy electrolyte, the high-purity liquid aluminum is a cathode 26, the high-purity graphite is connected with the liquid aluminum, the Ni-Fe alloy is an anode 25, and the working temperature is 700-800 ℃; the metal aluminum is continuously precipitated in the cathode 26 area, is taken out periodically, has the purity of 99.99 percent, and continuously releases oxygen in the anode area.
The liquid aluminum produced in the low-temperature aluminum electrolysis cell is used for preparing an aluminum anode plate or aluminum powder.
The process for preparing the aluminum anode plate by adopting the equal-channel extrusion equipment and the rolling equipment comprises the following steps:
(1) Processing the nanocrystalline aluminum anode by adopting equal-channel extrusion equipment:
Casting liquid aluminum (4-6N) obtained by low-temperature aluminum electrolysis into a cylinder with the diameter of 10-20 cm and the length of 20cm, and performing equal channel angular Extrusion (ECAP) to obtain a nanocrystalline aluminum cylinder; the angle phi of equal channel angular extrusion is 30-70 degrees, phi is 90 degrees, the extrusion passes are 5-10 times, the extrusion pressure is 50-90T, phi is the outer arc angle of the equal channel extrusion device through which the sample passes, phi is the angle at which the sample passes in and out of the two channels when passing through the equal channel extrusion device, a is a plunger, b is the sample, and c is a die, as shown in figure 4. By adopting the equal channel angular extrusion technology, the microstructure of the high-purity aluminum sample is changed into a nanocrystalline structure, the grain size is reduced, the tiny and uniform grain structure improves the uniformity of the microstructure on the whole, and the galvanic corrosion among grains is reduced, so that the hydrogen evolution rate is reduced, the discharge efficiency is improved, and the mass energy density of the nanocrystalline aluminum material serving as a negative electrode material is greatly improved. Test data show that the grain size of the nanocrystalline aluminum material prepared by equal channel extrusion is 90-220 nm, the hydrogen evolution rate is 0.087 mL-min -1·cm-2, which is far lower than the hydrogen evolution rate (0.6-2 mL-min -1·cm-2) of aluminum alloy in the prior art, the open circuit voltage of an aluminum air dye cell formed by the prepared nanocrystalline pure aluminum material in 4M NaOH solution is 1.882V, the open circuit voltage of an aluminum air fuel cell formed by an as-cast pure aluminum cathode is only 1.591V, the specific capacity of the nanocrystalline pure aluminum material reaches 2408mAhg -1, the specific energy reaches 3725 Wh-kg -1 under the current density of 10 mA-cm -2, the specific capacity of the as-cast pure aluminum cathode is only 1631 mA-h-g -1, the specific energy is only 2267 Wh-kg -1, and the energy density is improved by 64.3%; the specific energy of the nanocrystalline pure high-purity aluminum material cathode reaches 4200 Wh-kg -1, which is improved by 60% compared with the cast pure aluminum alloy cathode.
Table 1 summarizes the average voltage, capacity density, electrode efficiency, and energy density of the aluminum air fuel cell at different current densities. The open circuit voltage of the aluminum air battery composed of the nanocrystalline aluminum negative electrode is 1.882V when the pressure is 70 tons and the extrusion is 7 times, and the open circuit voltage of the aluminum air battery composed of the cast aluminum negative electrode is only 1.591V when the psi is 30 degrees; the specific capacity of the nanocrystalline high-purity aluminum cathode reaches 2408mA.h.g -1 under the current density of 10 mA.cm -2, the specific energy reaches 3725 Wh.kg -1, the specific capacity of the high-purity aluminum cathode is only 1631 mA.hg -1, the specific energy is only 2267 Wh.kg -1, the energy density of the nanocrystalline aluminum cathode is improved by 64.3%, and the hydrogen evolution corrosion rate is reduced to about one fifth of that of the as-cast coarse crystal. With the increase of the current density, the capacity density is continuously increased, and the capacity density reaches 2900mA.h.g -1 under the current density of 50 mA.cm -2, and the electrode efficiency of the two reaches more than 95%. This is because at high current densities, discharge is the primary reaction, the potential of the negative electrode has dropped more, and hydrogen evolution corrosion of the nanocrystalline aluminum material is suppressed and reduced to a small extent. The energy density increases and then decreases with increasing current density. At low current density, corrosion of the negative electrode plays a decisive role in the performance of the battery, and the more corrosion-resistant negative electrode has higher energy density; at high current densities, the polarization of the cell controls the performance of the cell, and the decrease in energy density due to the voltage drop appears very quickly. In comparison, the benefits of refined grains gradually weaken with the increase of current density, the voltages of two aluminum cathodes are equivalent at 30mA cm -2, and the capacity densities are equivalent at 50mA cm -2. The uniform and fine grains have larger electrochemical activity and can reduce the hydrogen evolution corrosion rate, so that the self-discharge rate of the battery is low, and the battery can provide higher energy density under lower current density.
TABLE 1
(2) Rolling high-purity aluminum anode plate by adopting rolling equipment
After the equal channel is subjected to large plastic deformation, rolling on a metal cold rolling mill, wherein the rolled anode has the following dimensions: 17 cm. Times.17.5 cm. Times.0.5 cm, the aluminum electrode area was 296.4cm 2.
The manufacturing process of the anode electric sheet comprises the following steps:
① High-purity Al ingots (99.99%) are subjected to cold deformation treatment, and as-cast samples are subjected to large plastic deformation on equal channel equipment for 7 times and then are deformed to be 0.5cm thick by adopting multiple passes on a double-roller mill.
② The as-cast sample is subjected to water quenching after being subjected to heat preservation for 4 hours at 480 ℃ in a box-type resistance furnace of SX-12-17 type.
The nanocrystalline aluminum sheet is used as a negative electrode, an air electrode is used as a positive electrode, 6mol/LNaOH is used as electrolyte, and a single battery is formed and subjected to discharge test. The discharge characteristic of the aluminum-air power supply monomer is that the open circuit voltage is higher (1.81V), the output cutoff voltage of the monomer is 0.2V, the working current density of the monomer is about 84.35mA/cm 2, the time for the stable output of the monomer is at least 5h, namely the monomer is discharged at 25A, the output duration of the voltage is 1.6V is more than or equal to 5h, and the embodiment performs a discharge test for 5 h. From the discharge characteristics of the aluminum-air power supply unit, it is known that: the area size of the single aluminum alloy determines the current size, the thickness of the single aluminum alloy determines the capacity size, and the single working current density is about 84.35mA/cm 2. In order to design a monomer with discharge current more than or equal to 25A, the reaction area of the monomer aluminum alloy is at least more than or equal to 298cm 2. Considering the production process of the monomer air-permeable membrane, the effective reaction area of the monomer aluminum alloy can be designed to be 298cm 2 (170 mm multiplied by 175 mm), the thickness of the monomer aluminum alloy is designed to be 0.05cm, thus the power of each monomer is 40W, and the capacitance is 100Ah. The 25 monomers were combined in series to 1kW.
The preparation process of the aluminum powder comprises the following steps:
The high-temperature aluminum liquid is sent to a nitrogen atomization device through a liquid guide groove, is continuously heated in the nitrogen atomization device, is atomized into small liquid drops under the action of venturi effect, and is rapidly solidified into aluminum powder under the protection and cooling of ambient nitrogen; specifically, the high Wen Lvye is continuously heated in an atomizing furnace and kept at a certain atomizing temperature, high-temperature aluminum liquid is sprayed into an atomizing chamber by an atomizing nozzle at the front end of the atomizing furnace to be atomized into small liquid drops under the action of the liquid level pressure and the venturi effect of atomizing nitrogen of an annular atomizer, and is rapidly solidified into aluminum powder under the protection and cooling of ambient nitrogen, and the aluminum powder is sucked into an aluminum powder classifying unit for classification by a high-pressure fan, so that aluminum powder with different medium particle diameters is separated and sent into a charging bucket. Respectively conveying the powder to an aluminum powder vacuum packaging machine by a dense-phase pneumatic conveying system for vacuum packaging; the production processes of atomizing, grading, packaging and the like of the high-temperature aluminum liquid are all required to be performed under the protection of nitrogen; the temperature of the atomizing furnace is controlled between 850 and 900 ℃, and slag is strictly fished out to prevent the nozzle of the atomizer from being blocked; the atomization temperature is controlled at 720-780 ℃, the pressure of atomized nitrogen is controlled at 2.2-2.5 MPa, the flow rate of atomized nitrogen is controlled at 350-400 m/s, and the nozzle gap is controlled at 0.40-0.55 mm.
As an alternative embodiment, the overall structure of the aluminum air cell power generation system 5 includes two parts of a cell stack main body structure and an auxiliary system. The main structure of the cell stack comprises a cell container, a filter screen, a liquid storage tank, a waste liquid tank and the like. The auxiliary system comprises an electrolyte circulation system, a heat exchange system, a gas purification system, an alumina recovery system, an electric control system and the like.
With the increase of the serial number of the single batteries, the inner ring current of the batteries is greatly increased, namely the heat loss is greatly increased. The magnitude of the inner loop current was tested when the number of series monomers was varied. When 5 single cells are connected in series, the output current of the single cells is almost equal to the output current of the whole battery module, which means that the inner loop current is small, i.e., the loss is low. When 30 single batteries are connected in series, the inner loop current accounts for about 13.6% of the total output current, and the electric quantity loss caused by heat generation of the inner loop current is also acceptable.
In the overall design of the battery, the problem that the inner ring currents of different single batteries are different due to the differences of solution concentration, polar plate components, part sizes, ambient temperature and the like is also required to be considered. This results in the possibility that the aluminum electrode in the unit cell having a large inner ring current is consumed first, so that the reliability of the cell stack system is also lowered when the number of unit cells connected in series in the unit cell package is small. Therefore, in order to meet the power output requirement, 28 single bodies are taken as a group, and the battery pack is designed into a two-group structure, the rated output voltage of the battery pack is 48V, the output current is 110A, and the rated power is 5kW.
The stack body structure is shown in fig. 5 and 6. Referring to fig. 5 and 6, the stack body structure includes a cell container 32, a filter screen 33, a waste liquid tank 38, a liquid storage tank 35, and a pumping device 36. The top of the cell container 32 is a sliding type cover plate, and a cell is placed in the cell container 32; the bottom of the single cell container 32 is provided with a drain hole corresponding to an electromagnetic switch valve at the bottom of the single cell. The strainer 33 is provided at the bottom of the cell container 32; the filter screen 33 is of a drawer structure, the upper part of the filter screen 33 is attached to the lower surface of the single cell container 32, and the lower part of the filter screen 33 is of a metal mesh structure for filtering and collecting aluminum hydroxide precipitate; the waste liquid tank 38 is arranged below the filter screen 33, and the waste liquid tank 38 is used for collecting the electrolyte after the reaction; the reservoir 35 communicates with the cell container 32 through the pumping means. The pumping device 36 allows electrolyte to enter the cell container 32 through the dispenser when in operation, and allows electrolyte to enter the reservoir 35 through the inlet 34 of the reservoir 35 when not in operation. The bottom of the waste liquid tank 38 is provided with a waste liquid outlet 37.
An auxiliary system is arranged on one side of the main structure of the cell stack. As shown in fig. 7, the electronic control system 47 is connected to the stack body structure 40, and the electronic control system 47 is connected to a display on which various data of the battery pack including voltage, current, etc. are displayed. The electronic control system 47 commands the operation or stopping of the stack body structure 40. The stack body structure 40 is connected to a liquid pump 43. The electrolyte circulation system is composed of a liquid pump 43, a small-sized lead-acid battery, a waste liquid tank 38, a liquid storage filtering structure (liquid storage tank and filter) 45, connecting pipelines and the like. After the battery pack switch is turned on, the lead-acid storage battery supplies power to the direct-current liquid pump 43, and the electrolyte in the liquid storage tank 35 is equally divided by the liquid separator and injected into each single battery. Note that the electrolyte should be slightly excessive or the drain ports of the individual cells should be opened for a period of time so that a certain amount of liquid is present in the waste liquid tank 38 for subsequent electrolyte circulation operation. After a few minutes, the reaction rate reached a maximum, after which the reaction rate was maintained at a steady higher level. At this time, the drain port below each cell is opened in a small width, and at the same time, the liquid pump 43 is operated to feed the electrolyte in the waste liquid tank 38 to each cell through the liquid separator, and at this time, the liquid feed rate is the same as the liquid drain rate. The liquid pump 43 can be operated at a lower power during this process. In the operation process, when the load of the aluminum-air battery system is small and power redundancy exists, the lead-acid storage battery can be charged. The impurities generated by the reaction can be effectively removed in the electrolyte circulation process due to the filtering of the filter screen 33, and the scouring effect is also achieved on the internal space of the battery cell. In addition, a hydroxide ion concentration sensor should be provided at the drain port of the single cell, and when the electrolyte concentration does not support the rapid progress of the battery reaction, a new electrolyte should be pumped from the reservoir 35 for replacement.
The heat exchange system is specifically a coolant circulation system 44. The coolant circulation system 44 is connected to a cooling device provided in the stack body structure 40. The cooling device is a rectangular aluminum alloy cooling plate with the size of 700mm x 500mm x 14mm and is arranged in the middle of the single battery. The aluminum alloy heat dissipation plate contains a liquid cooling pipe with an inner diameter of 10mm. Distilled water is selected as a coolant in the cooling water tank, and is pumped into the cooling pipe through the direct-current water pump, and the liquid outlet of the cooling pipe is connected to the cooling water tank. Because the water tank and the outside convection heat exchange area is larger, the cooling water does not need an additional cooling device in the circulation process. The cooling water tank is also connected with the liquid inlet of each single battery, when the battery reaction needs to be suspended, after the electrolyte completely flows into the waste liquid tank 38, the cooling water is made to flush the polar plate, so that the influence of residual hydroxide ions can be reduced, and the corrosion rate of the anode of the battery is reduced as much as possible.
The gas cleaning system is embodied as a carbon dioxide water scrubber 39. The air enters the carbon dioxide water scrubber 39, the carbon dioxide is absorbed by the water, the clean air enters the cell stack main body structure 40, the cell stack main body structure 40 emits hydrogen and water vapor when working, the hydrogen enters the membrane separation device 41, and the hydrogen enters the hydrogen collecting device 42 for collection.
The alumina recovery system 46 is connected to the tank 35 filtration system. The alumina recovery system 46 is described in detail below.
The purpose of the alumina recovery system 46 is to ultimately recover the resulting high purity alumina product by recovering the reacted precipitate and the remaining electrolyte from the reaction.
XRD diffraction analysis was performed on the precipitate on the filter screen 33, and the aluminum hydroxide was used as the main component of the precipitate by comparing with the standard PDF card of the crystal. While aluminum hydroxide is soluble in strong acids at certain temperatures. This makes its recovery process easier.
Dissolving a certain amount of precipitate with concentrated sulfuric acid, crystallizing to obtain aluminum sulfate, and preparing the prepared aluminum sulfate into 0.2mol/L solution. Preparing 2.0mol/L ammonium carbonate solution, adding a certain amount of dispersing agent, slowly adding the prepared aluminum sulfate solution, stirring for 1h after the addition is finished, aging and suction filtering. In the suction filtration process, the precipitate is washed with distilled water several times and then with absolute ethanol several times. And (3) putting the filter cake obtained by suction filtration into a baking oven for drying to obtain the ammonium aluminum carbonate precursor.
And finally, calcining step by step, namely, calcining at low temperature at about 300 ℃, and then calcining at high temperature by heating to 1200 ℃ to obtain the monodisperse alpha-Al 2O3.
For a liquid in which the aluminum air cell power generation system 5 is operated for one cycle (about 30 days), it is readily known that the main component thereof is sodium metaaluminate, which is between 160g and 320 g/L. The impurity elements contained in the corrosion inhibitor or the catalyst mainly comprise silicon, zinc, magnesium, calcium and the like, and the impurity ions are required to be precipitated step by step in the impurity removing process and filtered and removed. Thus, the flow of liquid recycled alumina from the aluminum air cell power generation system 5 is as follows:
Firstly, adding excessive calcium oxide into a sodium metaaluminate solution, reacting the calcium oxide with the sodium metaaluminate solution to generate calcium hydroxide, reacting the calcium hydroxide with the sodium metaaluminate to generate calcium aluminate hydrate (3CaO.Al 2O3·6H2 O), reacting SiO 2(OH)2 2- ions in the solution on the surface layer of the calcium aluminate hydrate to generate hydrated garnet precipitate, and removing silicon impurities in the solution; after silicon impurities are removed, adding a proper amount of sodium sulfide into the solution, and reacting sulfur ions with zinc ions in the solution to generate zinc sulfide precipitate, so that the zinc ions are removed; adding sodium oxalate into the solution, stirring, and filtering to remove magnesium oxalate and calcium salt precipitate.
Then, in the magnetic stirring reaction kettle 50, the potassium aluminate solution after impurity removal is raised to a specified temperature, seed crystals are added for mixing and stirring, and mixed gas of CO 2、N2 is introduced at a certain flow rate to increase the supersaturation degree of the solution and promote the solution to be decomposed into two products of aluminum hydroxide and sodium carbonate. Stopping ventilation after decomposing to the end point, and carrying out solid-liquid separation by adopting a vacuum filtration mode. And washing the aluminum hydroxide filter cake with deionized water and drying.
Concentrated hydrochloric acid can be used to dissolve different types of aluminum hydroxide. This step may also be similar to the previous step of recovering the solid waste produced by the aluminium air cell, i.e. dissolving with sulfuric acid to obtain an aluminium sulfate salt. And (3) dripping the Al 3+ salt solution into the NH 4HCO3 solution to react to generate the ammonium aluminum carbonate. After the aluminum ammonium carbonate is precipitated, vacuum drying or drying is carried out, and the dried aluminum ammonium carbonate is pyrolyzed at high temperature, so that aluminum oxide particles which do not agglomerate, are uniformly distributed and have grain refinement and the grain size of about 50nm can be finally generated.
And (3) sanding the generated alumina, refining the granularity, and drying the sanded alumina to obtain a nano alumina finished product.
The two recovery processes are very similar in operation for preparing alumina after obtaining aluminum salt, and the overall reaction processes comprise acid dissolution, vacuum filtration, drying and multi-step calcination, and the recovery processes are overlapped.
For industrial production and cost savings, multiple aluminum air batteries may be combined with a single recovery unit. The method comprises the following steps: the common reaction tank and the filtering equipment are used for performing primary treatment; an acid dissolution reaction tank and a filtering device for dissolving the aluminum hydroxide on the filter screen 33 after the reaction and precipitating the aluminum hydroxide generated after the reaction of the waste liquid; the magnetic stirring reaction kettle 50 is used for a reaction process requiring gas to be introduced under a closed condition and fully stirred; the vacuum suction filtration device is used for suction filtration to obtain an ammonium aluminum carbonate filter cake; an oven for drying the generated ammonium aluminum carbonate cake; the industrial calciner is used for calcining to generate nano alumina finished products with better dispersity. These devices are all common reaction devices in industrial production and are easy to obtain.
As shown in fig. 8, the solid line is the line of waste liquid after the reaction of the aluminum air cell, and the dotted line is the line of solid product on the screen 33 after the reaction of the aluminum air cell.
For the solid product route on the screen 33 after the reaction. First, the reaction mixture enters an acid dissolution reaction tank and a filtration device 49, where the reaction occurs and the reaction product is filtered. In the acid dissolution reaction tank and the filtration device 49, a certain amount of precipitate was dissolved with concentrated sulfuric acid, and aluminum sulfate was obtained by crystallization, and then the prepared aluminum sulfate was prepared into a solution of 0.2 mol/L. Preparing 2.0mol/L ammonium carbonate solution, adding a certain amount of dispersing agent, slowly adding the prepared aluminum sulfate solution, stirring for 1h after the addition is finished, aging and suction filtering. In the suction filtration process, the precipitate is washed with distilled water several times and then with absolute ethanol several times. And (5) putting a filter cake obtained by the vacuum filtration device into an oven 52 for drying to obtain the ammonium aluminum carbonate precursor.
And finally, calcining step by step, namely, calcining at low temperature at about 300 ℃, and then calcining at high temperature by heating to 1200 ℃ to obtain the monodisperse alpha-Al 2O3. This step is carried out in an industrial calciner 53.
For the post-reaction waste liquid route of the aluminum air battery.
Firstly, adding excessive calcium oxide into a sodium metaaluminate solution in a common reaction tank and a filtering device 48, reacting the calcium oxide with the sodium metaaluminate solution to generate calcium hydroxide, reacting the calcium hydroxide with the sodium metaaluminate to generate hydrated calcium aluminate (3CaO.Al 2O3·6H2 O), reacting SiO 2(OH)2 2- ions in the solution on the surface layer of the hydrated calcium aluminate to generate hydrated garnet precipitate, and removing silicon impurities in the solution; after silicon impurities are removed, adding a proper amount of sodium sulfide into the solution, and reacting sulfur ions with zinc ions in the solution to generate zinc sulfide precipitate, so that the zinc ions are removed; adding sodium oxalate into the solution, stirring, and filtering to remove magnesium oxalate and calcium salt precipitate.
Then, in the magnetic stirring reaction kettle 50, the potassium aluminate solution after impurity removal is raised to a specified temperature, seed crystals are added for mixing and stirring, and mixed gas of CO 2、N2 is introduced at a certain flow rate to increase the supersaturation degree of the solution and promote the solution to be decomposed into two products of aluminum hydroxide and sodium carbonate. After the decomposition to the end point, the aeration is stopped, and the solid-liquid separation is performed by using the vacuum filtration device 51. And washing the aluminum hydroxide filter cake with deionized water and drying.
Concentrated hydrochloric acid can be used to dissolve different types of aluminum hydroxide. This step may also be similar to the previous step of recovering the solid waste produced by the aluminium air cell, i.e. dissolving with sulfuric acid to obtain an aluminium sulfate salt. And (3) dripping the Al 3+ salt solution into the NH 4HCO3 solution to react to generate the ammonium aluminum carbonate. After the aluminum ammonium carbonate is precipitated, vacuum drying or drying is carried out, and the dried aluminum ammonium carbonate is pyrolyzed at high temperature, so that aluminum oxide particles which do not agglomerate, are uniformly distributed and have grain refinement and the grain size of about 50nm can be finally generated.
The aluminum powder hydrogen production process comprises the following steps:
Aluminum powder reacts with aqueous solution added into an aluminum water reactor to prepare hydrogen; or the aluminum powder reacts with the alkaline aqueous solution added into the aluminum water reactor to prepare hydrogen, and the prepared hydrogen is output to a hydrogenation device. Specifically, aluminum powder reacts with an aqueous solution added into an aluminum water reactor to prepare hydrogen, and the reaction equation is as follows:
2Al+6H2O→Al(OH)3↓+3H2↑
The water solution is one or more of tap water, pure water and salt water; the brine is sodium chloride or potassium chloride aqueous solution with the mass ratio concentration of 5-40%.
The aluminum powder reacts with alkaline aqueous solution added into an aluminum water reactor to prepare hydrogen, and the reaction equation is as follows:
2Al+6H2O+2NaOH→2NaAl(OH)4+3H2↑
NaAl(OH)4→NaOH+Al(OH)3↓
The aqueous alkali solution is sodium hydroxide or potassium hydroxide aqueous solution with the mass ratio concentration of 5-60 percent.
Discharging aluminum hydroxide precipitate generated in the hydrogen preparation process to a rotary sintering furnace for sintering and decomposing to obtain aluminum oxide powder, packaging and transporting the aluminum oxide powder back to the aluminum electrolysis cell 4 for re-electrolysis to enter the next cycle, and forming a closed circulation loop. Specifically, the temperature of the sintering decomposition process of the rotary sintering furnace is controlled to be 450-500 ℃.
The hydrogen treatment process comprises the following steps:
In the discharging process of the aluminum-air battery power generation system 5, no corrosion inhibitor is added, and the generated hydrogen and the hydrogen containing alkali vapor generated by the hydrolysis of aluminum powder are converged and enter a hydrogen drying tower to be dried, so that pure hydrogen with the purity of 99.9% is obtained after purification. Purification utilizes a Pressure Swing Adsorption (PSA) method, which utilizes the difference of adsorption characteristics of gas components on an adsorbent and the principle that the adsorption quantity changes with pressure, and realizes gas separation through a periodical pressure change process. PSA technology features: the method has the advantages of low energy consumption, high product purity, simple process flow, low pretreatment requirement, convenient and reliable operation, high automation degree and the like, and the recovery rate can reach 96 percent. And then the hydrogen is pressed into a high-pressure hydrogen storage container for storage by a high-purity oil-free booster hydrogen compressor, and then enters a hydrogenation machine to hydrogenate the fuel cell automobile by a pressure reducing valve.
The power generation process of the fuel cell comprises the following steps:
the fuel cell power generation system 6 includes a hydrogen and oxygen storage tank to which the hydrogenation apparatus adds acceptable hydrogen. Oxygen as a byproduct of low-temperature aluminum electrolysis needs to enter a purifier for purification treatment due to impurities and moisture. The purifier is mainly composed of three parts: the dehydrator mainly has the function of eliminating moisture in oxygen; a dryer for further removing water produced by the reaction; the hydrocarbon remover is internally provided with a catalyst for removing impurities such as carbon monoxide, methane and the like. And after the qualified high-purity oxygen comes out of the purifier, pressurizing to 15MPa through a second section of the membrane press, and delivering the qualified high-purity oxygen to an oxygen storage tank of the qualified fuel cell. After the oxyhydrogen fuel cell works, direct current electric energy is generated, and water is produced as a byproduct. This water is used to supplement the aluminum powder hydrogen production process.
An intelligent control system:
The system comprises five monitoring points, namely wind power output, photovoltaic power output, three-layer liquid energy storage battery output and input, low-temperature aluminum electrolysis input, anode plate and aluminum powder production input. The intelligent control system always keeps balance of input power and output power of the balanced transmission system and stable output voltage. When the wind power and the photovoltaic power are larger than the sum of the input power of the load, the three-layer liquid battery is charged, and when the wind power and the photovoltaic power are smaller than the sum of the input power of the load, the output power of the three-layer liquid battery makes up the deficiency.
In the system for generating hydrogen by utilizing waste wind and waste light, the electricity generated by waste wind and waste light is stored by an energy storage battery and then is used for converting low-temperature aluminum electrolysis of an inert electrode into aluminum energy and releasing oxygen. The aluminum ingot is further extruded and rolled into a nanocrystalline anode aluminum plate or aluminum powder is prepared by an atomization method, the nanocrystalline aluminum anode plate is used for an aluminum air battery power generation system 5 to obtain direct current and hydrogen, aluminum hydroxide is produced as a byproduct, aluminum powder and alkaline water are hydrolyzed to release hydrogen, and aluminum hydroxide is also produced as a byproduct. The pure hydrogen is obtained by drying and impurity removal of the hydrogen, and can be used for a fuel cell power generation system 6, a hydrogen car or a hydrogen customer. The byproduct aluminum hydroxide is calcined at 1100-1200 ℃ to obtain aluminum oxide, and the aluminum oxide is returned to low-temperature aluminum electrolysis to further obtain pure aluminum and release oxygen. The electricity generated by the aluminum air battery power generation system 5 and the fuel battery power generation system 6 can be directly used for direct current load and alternating current load, or can be directly connected into a national power grid after inversion.
The system for generating hydrogen by utilizing the abandoned wind and abandoned light has the following advantages:
(1) The wind power and the photoelectricity of the abandoned wind can reach 100 percent to be utilized, and the abandoned wind is matched with the three-layer liquid energy storage battery, so that the output power is stable, the voltage is stable, the alternating current load and the direct current load demands are met, and the abandoned wind can be changed into stable alternating current to be connected with the internet through the aluminum air battery power generation system 5 and the fuel cell power generation system 6.
(2) The aluminum oxide is electrolyzed by low-temperature aluminum to obtain metal aluminum, wind energy and light energy are converted into aluminum energy, the aluminum can be transported, wind power and photoelectricity are generally installed in desert or western regions of China, water is deficient, and aluminum is more convenient and feasible than hydrogen.
(3) Aluminum powder hydrogen production and aluminum air battery hydrogen production to obtain byproduct alumina, returning the byproduct alumina to a low-temperature aluminum electrolysis system, recycling aluminum in the low-temperature aluminum electrolysis system, wherein the aluminum only plays a role of an energy-carrying carrier.
(4) The aluminum powder for hydrogen production is beneficial to low-cost preparation and use of hydrogen energy and the development of hydrogen energy technology.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present invention and the core ideas thereof; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (4)
1. A system for producing hydrogen by wind and light abandoning power, comprising: a new energy power generation system, an aluminum electrolysis cell, an aluminum air battery power generation system and a fuel cell power generation system;
the new energy power generation system comprises a wind power generation system, a photovoltaic power generation system and a three-layer liquid energy storage system;
The aluminum electrolysis cell is used for electrolyzing aluminum oxide serving as a raw material to obtain liquid aluminum and releasing oxygen; the liquid aluminum is used for preparing an aluminum anode plate or aluminum powder;
the aluminum-air battery power generation system is used for generating power by taking the aluminum anode plate as an anode, releasing hydrogen and generating byproduct aluminum oxide to be used as a raw material of the aluminum electrolysis cell;
the aluminum powder is used for hydrolyzing and releasing hydrogen, and generates a byproduct alumina to be used as a raw material of the aluminum electrolysis cell;
the fuel cell power generation system is used for generating power by taking oxygen released by the aluminum electrolysis cell, hydrogen released by the aluminum air cell power generation system and hydrogen released by the aluminum powder hydrolysis as raw materials, and generating byproduct water to be used as the raw materials for the aluminum powder hydrolysis;
The new energy power generation system is electrically connected with the aluminum electrolysis cell, the equipment for preparing the aluminum anode plate by the liquid aluminum and the equipment for preparing the aluminum powder by the liquid aluminum respectively;
The system further comprises: an AC/DC converter, a first DC/DC converter, a second DC/DC converter, a DC bus, a third DC/DC converter, and a first DC/AC converter;
The wind power generation system is electrically connected with the DC bus through the AC/DC converter; the photovoltaic power generation system is electrically connected with the DC bus through the first DC/DC converter; the three-layer liquid energy storage system is electrically connected with the DC bus through the second DC/DC converter; the DC bus is electrically connected with the aluminum electrolysis cell through the third DC/DC converter; the DC bus is electrically connected with the equipment for preparing the aluminum anode plate by the liquid aluminum and the equipment for preparing the aluminum powder by the liquid aluminum through the first DC/AC converter respectively;
the system further comprises: a power supply converter; the aluminum air battery power generation system and the fuel battery power generation system supply power to electric equipment through the power supply converter; the electric equipment is at least one of a direct current load, an alternating current load and a national power grid;
The power supply converter comprises a fourth DC/DC converter and/or a second DC/AC converter;
the three-layer liquid energy storage system is in a vacuum environment, and the three-layer liquid energy storage system comprises: the device comprises an energy storage tank, an anode structure, a cathode structure, a refractory structure, an anode liquid metal alloy, a cathode liquid metal and a first electrolyte;
The fire-resistant structure divides the energy storage tank into a charging area and an energy storage area; the bottom discharge port of the charging area is communicated with the energy storage area; the energy storage area is provided with the anode liquid metal alloy, the first electrolyte and the cathode liquid metal in sequence from bottom to top; the anode structure is in contact with the anode liquid metal alloy; the cathode structure is in contact with the cathode liquid metal;
the anode structure comprises an anode lead and an anode graphite block; the cathode structure comprises a cathode lead and a cathode graphite block; the bottom of the anode liquid metal alloy is in contact with the anode graphite block; an anode lead is arranged at the bottom of the anode graphite block; the surface of the cathode liquid metal is contacted with the cathode graphite block; the cathode lead is connected with the cathode graphite block;
The anode liquid metal alloy is liquid Sn-Bi, the cathode liquid metal is liquid metal Li, and the first electrolyte is LI-KI electrolyte.
2. The system for producing hydrogen by utilizing waste wind and waste light power according to claim 1, wherein the aluminum electrolysis cell comprises a reaction cell, an anode, a cathode and a second electrolyte; the bottom of the reaction tank is inserted into the cathode; the anode is inserted into the side wall of the reaction tank; the second electrolyte is placed in the reaction tank; after the alumina enters the reaction tank, liquid aluminum is precipitated in a first set area where the cathode is located, and oxygen is released in a second set area where the anode is located.
3. The system for producing hydrogen by utilizing waste wind and waste light power according to claim 2, wherein the anode is made of Ni-Fe-Al 2O3 metal ceramic, the cathode is made of steel surface sprayed TiB 2, and the second electrolyte is NaF-AlF 3-BaF2-CaF2 melt.
4. The system for producing hydrogen by utilizing waste wind and waste light as in claim 1 wherein said aluminum air cell power generation system comprises a cell stack body structure;
The cell stack main body structure comprises a single cell container, a filter screen, a waste liquid tank, a liquid storage tank and a pumping device; a single cell is placed in the single cell container; the bottom of the single cell container is provided with a liquid discharge hole; the filter screen is arranged at the bottom of the single cell container; the filter screen is of a drawer structure, the upper part of the filter screen is attached to the lower surface of the single cell container, and the lower part of the filter screen is of a metal reticular structure; the waste liquid tank is arranged below the filter screen; the liquid storage tank is communicated with the single cell container through the pumping device.
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