CN115832379A - Preparation method and application of key material of electrolyte - Google Patents
Preparation method and application of key material of electrolyte Download PDFInfo
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- CN115832379A CN115832379A CN202310143627.1A CN202310143627A CN115832379A CN 115832379 A CN115832379 A CN 115832379A CN 202310143627 A CN202310143627 A CN 202310143627A CN 115832379 A CN115832379 A CN 115832379A
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 239000003792 electrolyte Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 82
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011651 chromium Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 239000003929 acidic solution Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 70
- 229910052804 chromium Inorganic materials 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 41
- 229910052742 iron Inorganic materials 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 21
- 238000002386 leaching Methods 0.000 claims description 19
- 229960002089 ferrous chloride Drugs 0.000 claims description 18
- -1 iron ions Chemical class 0.000 claims description 17
- 229910001430 chromium ion Inorganic materials 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910001018 Cast iron Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 239000002001 electrolyte material Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 229910021426 porous silicon Inorganic materials 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a preparation method and application of an electrolyte key material. The preparation method comprises the following steps: adding materials containing iron metal and chromium metal into an acidic solution, mixing, performing first solid-liquid separation to obtain a leachate, and performing evaporation concentration on the leachate to obtain the electrolyte key material. The method directly takes materials containing iron metal and chromium metal as raw materials to be mixed with the acidic solution, prepares the key material of the iron-chromium flow battery electrolyte in a short process, does not experience Cr (VI) in the process, and has clean process and short process.
Description
Technical Field
The invention belongs to the field of iron-chromium flow batteries, and relates to a preparation method and application of a key electrolyte material.
Background
The development of society needs to increase the need of clean new energy, and the iron-chromium flow battery is a promising clean energy at present due to the advantages of system energy and power independence, long cycle life, high energy, high safety performance and low cost.
At present, the key material of the electrolyte of the iron-chromium flow battery is a mixed solution of chromium chloride and ferrous chloride.
CN112510237A discloses a preparation process of an iron-chromium flow battery electrolyte, which comprises adding chromium trichloride hexahydrate, ferrous chloride tetrahydrate and hydrochloric acid in sequence into pure water, and reacting to obtain the iron-chromium flow battery electrolyte. However, the preparation processes of chromium chloride hexahydrate and ferrous chloride tetrahydrate undergo multiple processes of oxidation, reduction and the like, and have the disadvantages of long flow, high cost and pollution hidden danger.
CN112993358A discloses a method and a system for preparing an electrolyte of a ferrochromium redox cell, in which chromium chloride and hydrochloric acid are dissolved, and then ferrous oxide is added and mixed, and the electrolyte is obtained after dissolution, but the sources of chromium chloride and ferrous oxide are purchased in the spot, and the production cost is high.
Therefore, how to produce a key material of the iron-chromium flow battery electrolyte with high safety performance and high chemical performance at low cost is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a preparation method and application of a key material of an electrolyte.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of a key material of an electrolyte, which comprises the following steps:
adding materials containing iron metal and chromium metal into an acidic solution, mixing, performing first solid-liquid separation to obtain a leachate, and performing evaporation concentration on the leachate to obtain the electrolyte key material.
The method directly takes materials containing iron metal and chromium metal as raw materials to be mixed with the acidic solution, prepares the key material of the iron-chromium flow battery electrolyte in a short process, does not experience Cr (VI) in the process, and has clean process and short process.
As a preferred technical scheme of the invention, the key material of the electrolyte is a mixed thick slurry of chromium chloride and ferrous chloride, and the concentrations of chromium ions and iron ions in the mixed thick slurry are as follows:
1 to 5mol/L of trivalent chromium ion
1 to 5mol/L of divalent iron ions.
The concentration of the three chromium ions is 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L, and the concentration of the divalent iron ions may be 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L, but the divalent iron ions are not limited to the values listed above, and other values not listed above within the above numerical ranges are also applicable.
As a preferred technical solution of the present invention, the material containing iron metal and chromium metal comprises any one of or a combination of at least two of chromium metal and iron metal mixture, ferrochrome, chromium-based alloy, chromium-containing cast iron or chromium-containing slag, wherein the combination is exemplified by the following typical but non-limiting examples: a combination of chromium and iron metal and a mixture of chromium and iron metal, a combination of chromium and chromium-based alloy, a combination of chromium-based alloy and chromium-containing cast iron, or a combination of chromium-containing cast iron and chromium-containing slag, and the like, preferably a mixture of chromium and iron metal and/or ferrochrome, more preferably ferrochrome.
The granularity of the material containing the iron metal and the chromium metal is-800 to-100 meshes, wherein the granularity can be-800 meshes, -700 meshes, -600 meshes, -500 meshes, -400 meshes, -300 meshes, -200 meshes or-100 meshes, and the like, but the material is not limited to the enumerated numerical values, and other numerical values in the numerical value range are also applicable.
The invention adopts finer granularity, which can improve the reaction rate and ensure the utilization rate of chromium and iron.
As a preferred embodiment of the present invention, the acidic solution includes a hydrochloric acid solution.
The molar fraction of the hydrochloric acid solution is 6 to 12mol/L, wherein the molar fraction can be 6mol/L, 7mol/L, 8mol/L, 9 mol/L, 10 mol/L, 11mol/L or 12mol/L, and the like, but the hydrochloric acid solution is not limited to the enumerated numerical values, and other numerical values not enumerated in the numerical value range are also applicable.
The ratio of the molar amount of the chromium metal and the iron metal in the material containing the iron metal and the chromium metal to the molar amount of HCl in the hydrochloric acid solution is 1 (3 to 3.5), wherein the ratio can be 1.
The use amount of the hydrochloric acid solution is selected, so that the utilization rate of chromium and iron in material flow is improved as much as possible, and the acidity of the leachate is reduced as much as possible, so that the obtained leachate is convenient to further evaporate and concentrate to obtain the chromium chloride-ferrous chloride mixed thick slurry with high mass fractions of chromium and iron.
The material containing iron metal and chromium metal is added into the hydrochloric acid solution in a divided manner, the divided adding times are 2-5 times, each feeding time interval is 10-30min, the times can be 2 times, 3 times, 4 times or 5 times, and the like, the time interval can be 10min, 12 min, 14 min, 16 min, 18 min, 20 min, 22 min, 24 min, 26 min, 28 min or 30min, and the like, but the method is not limited to the enumerated values, and other unrecited values in the numerical value range are also applicable.
According to the invention, the reaction rate can be controlled by gradually adding the material containing chromium and iron into the hydrochloric acid solution in batches, and the problem of material escape caused by violent reaction to generate gas is effectively avoided.
In a preferred embodiment of the present invention, the mixing temperature is 20 to 100 ℃, and the temperature may be 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and preferably 40 to 80 ℃.
The mixing time is 1 to 10h, wherein the mixing time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, and the like, but the mixing time is not limited to the enumerated values, other non-enumerated values in the numerical value range are also applicable, and the mixing time is preferably 2 to 8h, and more preferably 3 to 6h.
The mixed atmosphere is a shielding gas, which is a non-oxidizing gas including any one of nitrogen, argon or helium or a combination of at least two thereof, wherein the combination is typically but not limited to: a combination of nitrogen and argon, a combination of argon and helium, a combination of nitrogen and helium, or the like, and nitrogen is preferable.
The mixing is carried out in a multi-stage countercurrent mode, and an acidic solution is added during the last stage of leaching.
The number of stages of the multistage countercurrent can be set according to needs, and for example, the multistage countercurrent can be two stages, three stages, five stages and the like. The counter-current reaction mode is favorable for improving the utilization rate of chromium and iron in material flow as much as possible and reducing the acidity of the leachate as much as possible, so that the obtained leachate is convenient for further evaporation and concentration to obtain chromium chloride-ferrous chloride mixed thick slurry with high mass fractions of chromium and iron.
As a preferable technical solution of the present invention, the first solid-liquid separation obtains a leachate and a leaching residue.
And the leached slag is washed and then recycled as a material containing iron metal and chromium metal.
As a preferable technical scheme of the invention, the leached residues are washed and then subjected to second solid-liquid separation to obtain tailings.
As a preferable technical scheme of the invention, steam condensate water generated by the evaporation concentration is used for washing tailings in the first solid-liquid separation.
As a preferable technical scheme of the invention, an impurity removing agent is added into the leachate for purification treatment.
The material containing chromium metal and iron metal in the present invention contains other components that react with the hydrochloric acid solution, including but not limited to manganese, titanium, copper, zinc, nickel, etc. In the invention, by adding the impurity removing agent, the impurity components can be removed in a mode of generating insoluble solid and/or being absorbed, thereby achieving the purpose of purification. When the purifying solution is used as a key material to prepare the electrolyte, the electrochemical performance of the electrolyte is better than that before purification.
The impurity removing agent includes any one of ammonium chloride, ammonium sulfate, ammonium citrate, ammonium oxalate, triethanolamine, sulfamic acid, acidic cation exchange resin, modified bentonite, diatomaceous earth, porous silica or porous boron nitride or a combination of at least two thereof, wherein the combination is typically but not limited to: a combination of ammonium chloride and ammonium sulfate, a combination of ammonium sulfate and ammonium citrate, a combination of ammonium oxalate and triethanolamine, a combination of sulfamic acid and an acidic cation exchange resin, a combination of modified bentonite and diatomaceous earth, a combination of diatomaceous earth and porous silica, or a combination of porous silica and porous boron nitride, and the like.
The impurity removing agent accounts for 0.01 to 2 percent of the mass fraction of the leachate, wherein the mass fraction can be 0.01 percent, 0.05 percent, 0.1 percent, 0.2 percent, 0.3 percent, 0.4 percent, 0.5 percent, 0.6 percent, 0.7 percent, 0.8 percent, 0.9 percent, 1 percent, 1.1 percent, 1.2 percent, 1.3 percent, 1.4 percent, 1.5 percent, 1.6 percent, 1.7 percent, 1.8 percent, 1.9 percent or 2 percent, and the like, but the impurity removing agent is not limited to the enumerated numerical values, and other non-enumerated numerical values in the numerical value range are also applicable.
The purification treatment is carried out under the condition of stirring or oscillation, and the purification treatment time is 1 to 8h, wherein the time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h and the like, but the purification treatment time is not limited to the numerical values listed, other numerical values not listed in the numerical value range are also applicable, and the purification treatment time is preferably 2 to 5h.
The temperature of the purification treatment is 20 to 90 ℃, wherein the temperature can be 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, but is not limited to the enumerated values, and other values in the numerical range are also applicable, and are preferably 30 to 85 ℃.
And filtering after the purification treatment to obtain a purified mixed solution containing iron chloride and chromium chloride, wherein the filter residue is purified residue.
And the purified slag and the leaching slag are washed together and then are recycled as materials containing iron metal and chromium metal.
The second purpose of the invention is to provide the application of the preparation method of the key electrolyte material, which is applied to the field of iron-chromium flow batteries.
Compared with the prior art, the invention has the following beneficial effects:
the method directly takes materials containing iron metal and chromium metal as raw materials to be mixed with the acidic solution, prepares the key material of the iron-chromium flow battery electrolyte in a short process, does not experience Cr (VI) in the process, and has clean process and short process. The preparation method comprises the following steps: (1) Protective gas is used for protection in the reaction process, so that the potential explosion safety hazard of hydrogen generated by the reaction is eliminated, and the oxidation of ferrous iron is avoided; (2) By controlling the proportion of the materials to the hydrochloric acid and adopting a countercurrent leaching mode, on one hand, the utilization rate of chromium and iron in the material flow is improved, and on the other hand, the acidity of the leaching solution is reduced, so that the chromium chloride-ferrous chloride mixed thick slurry with high mass fractions of chromium and iron can be obtained by further evaporation and concentration.
Drawings
Fig. 1 is a block diagram of a method for preparing a key material of an electrolyte of a ferrochrome flow battery in embodiment 3 of the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a preparation method of an electrolyte key material, which comprises the following steps:
adding materials containing iron metal and chromium metal into a hydrochloric acid solution, mixing, performing first solid-liquid separation to obtain a leachate, and performing evaporation concentration on the leachate to obtain the key material of the electrolyte.
The method comprises the following steps:
(1) Mixing metal chromium powder (60 g) with a granularity of-200 meshes and metal iron powder (40 g) to obtain a mixture, and dividing the mixture into three parts of 10g, 30g and 60 g; under the protection of nitrogen atmosphere, controlling the dosage of the hydrochloric acid solution to ensure that the molar weight of HCl is 3 times of the total molar weight of chromium and iron in the mixture, adding 6M hydrochloric acid solution into a reactor, and starting stirring; sequentially adding the three parts of mixture into a reactor, wherein the interval of each time of feeding is 30min; after the addition is finished, continuously stirring and reacting for 10 hours;
(2) After the reaction in the step (1), obtaining leachate and leaching residues after the slurry is subjected to first solid-liquid separation;
(3) And (3) evaporating and concentrating the leachate obtained in the step (2), wherein the amount of evaporated water is 300mL, so as to obtain a chromium chloride-ferrous chloride mixed concentrated slurry, wherein the molar concentrations of trivalent chromium ions and divalent iron ions are 1.82mol/L and 1.23mol/L in sequence, and the chromium chloride-ferrous chloride mixed concentrated slurry can be used as a key material for preparing the electrolyte of the ferrochrome flow battery.
Example 2
The embodiment provides a preparation method of an electrolyte key material, which comprises the following steps:
adding materials containing iron metal and chromium metal into a hydrochloric acid solution, mixing, performing first solid-liquid separation to obtain a leachate, and performing evaporation concentration on the leachate to obtain the key material of the electrolyte.
The method comprises the following steps:
(1) The mass fractions of chromium, iron, silicon, manganese and nickel in the ferrochrome powder are 69.28%, 23.61%, 0.79%, 0.60% and 0.23% in sequence. Dividing ferrochrome powder (100 g) of-100 meshes into three parts of 20g, 30g and 50 g; under the protection of nitrogen atmosphere, controlling the dosage of the hydrochloric acid solution to ensure that the molar weight of HCl is 3.2 times of the total molar weight of chromium and iron in the ferrochrome powder, adding 10M hydrochloric acid solution into a reactor, starting stirring and heating to 60 ℃; sequentially adding the three parts of mixture into a reactor, wherein the feeding interval is 10min each time; after the addition is finished, stirring and reacting for 3 hours at 60 ℃;
(2) After the reaction in the step (1), performing solid-liquid separation (first solid-liquid separation) on the slurry to obtain a leaching solution and leaching residues; adding 2 percent of reduced iron powder, 0.5 percent of ammonium chloride, 0.2 percent of triethanolamine and 0.01 percent of sulfamic acid by mass of the solution into the leachate at 30 ℃, stirring and reacting for 8 hours, and then carrying out solid-liquid separation to obtain a purified mixed solution containing iron and chromium chlorides, wherein the filter residue is purified residue. Carrying out subsequent washing steps on the purified slag and the leaching slag;
(3) And (3) evaporating and concentrating the purified solution obtained in the step (2), wherein the amount of evaporated water is 100mL, so as to obtain chromium chloride-ferrous chloride mixed concentrated slurry, wherein the molar concentrations of trivalent chromium ions and divalent iron ions are 4.11mol/L and 1.28mol/L in sequence, and the concentrations of silicon, manganese and nickel are less than 50mg/L, so that the chromium chloride-ferrous chloride mixed concentrated slurry can be used as a key material for preparing the electrolyte of the iron-chromium flow battery. And (3) steam condensate water generated by evaporation thickening is used for washing the slag in the step (2).
Example 3
The embodiment provides a preparation method of an electrolyte key material as shown in a block diagram of fig. 1, and the preparation method comprises the following steps:
adding materials containing iron metal and chromium metal into a hydrochloric acid solution, mixing, performing first solid-liquid separation to obtain a leachate, and performing evaporation concentration on the leachate to obtain the key material of the electrolyte.
The preparation method comprises the following steps:
(1) The material is chromium-containing cast iron with a grain size of-300 meshes, wherein the mass fractions of chromium, iron and vanadium are 26%, 66% and 0.81% in sequence. A three-stage countercurrent reaction mode is adopted, each stage of solid sample is equally divided into two parts, materials are added at intervals of 30min, and the whole system is protected by nitrogen. During the first-order reaction, 100g of chromium-containing cast iron with the grain size of-300 meshes is added to react with the second-order filtrate; the three-stage reaction uses 8M hydrochloric acid solution, and the dosage of the hydrochloric acid solution is controlled to ensure that the molar quantity of HCl is 3.3 times of the total molar quantity of chromium and iron in the ferrochrome powder. The temperature of the countercurrent reaction is 80 ℃, and each stage of reaction lasts for 2 hours;
(2) After the reaction in the step (1), performing solid-liquid separation (first solid-liquid separation) on the slurry to obtain a leaching solution and leaching residues; adding 1.5 percent of reduced iron powder, 0.2 percent of ammonium oxalate, 0.2 percent of triethanolamine and 0.01 percent of porous boron nitride based on the mass of the solution into the leaching solution at the temperature of 80 ℃, stirring and reacting for 5 hours, and then carrying out solid-liquid separation (filtration) to obtain a purified liquid, wherein the filter residue is purified residue. The purified slag and the leaching slag are subjected to subsequent washing, and tailings are obtained through solid-liquid separation (second solid-liquid separation) after washing;
(3) And (3) evaporating and concentrating the purified solution obtained in the step (2), wherein the amount of evaporated water is 400mL, so as to obtain chromium chloride-ferrous chloride mixed concentrated slurry, wherein the molar concentrations of trivalent chromium ions and divalent iron ions are 1.62 mol/L and 4.52mol/L in sequence, and the concentrations of silicon, manganese and nickel are less than 50mg/L, so that the chromium chloride-ferrous chloride mixed concentrated slurry can be used as a key material for preparing the electrolyte of the iron-chromium flow battery. And (3) steam condensate water generated by evaporation and concentration is used for washing the slag in the step (2).
Example 4
This example was carried out under the same conditions as in example 1 except that the amount of the hydrochloric acid solution was controlled so that the molar amount of HCl was 3 times to 3.5 times the total molar amount of chromium and iron in the mixture. Obtaining the chromium chloride-ferrous chloride mixed concentrated slurry, wherein the molar concentrations of trivalent chromium ions and divalent iron ions are 1.46mol/L and 0.91mol/L in sequence.
Example 5
This example was carried out under the same conditions as in example 1 except that the amount of the hydrochloric acid solution was controlled so that the molar amount of HCl was 3 times to 2 times the total molar amount of chromium and iron in the mixture. Obtaining the chromium chloride-ferrous chloride mixed concentrated slurry, wherein the molar concentrations of trivalent chromium ions and divalent iron ions are 3.58mol/L and 2.21mol/L in sequence.
Example 6
This example was carried out under the same conditions as in example 1 except that the amount of the hydrochloric acid solution was controlled so that the molar amount of HCl was changed to 4 times as much as 3 times the total molar amount of chromium and iron in the mixture. Obtaining the chromium chloride-ferrous chloride mixed concentrated slurry, wherein the molar concentrations of trivalent chromium ions and divalent iron ions are 0.93mol/L and 0.57mol/L in sequence.
Example 7
This example was carried out under the same conditions as example 1 except that the mixed protective atmosphere was replaced with an air atmosphere. In the obtained chromium chloride-ferrous chloride mixed concentrated slurry, the molar concentrations of trivalent chromium ions and divalent iron ions are 1.82mol/L and 0.94mol/L in sequence. Because an air atmosphere is used, the ferrous iron in it is partially oxidized to ferric iron.
The results of the discharge capacity and energy efficiency of the cells assembled using the key materials of examples 1-7 are shown in table 1, using the key materials of the electrolytes prepared in examples 1-7 applied to an iron-chromium flow battery.
The specific assembling method of the iron-chromium flow battery comprises the following steps: key materials obtained in the examples were taken and analytically pure CrCl was added 3 ·6H 2 O、FeCl 2 ·4H 2 And preparing electrolyte with trivalent chromium ions and divalent iron ions of which the molar concentrations are 2mol/L and 1.5mol/L in sequence by using O and pure water. Because the molar concentrations of trivalent chromium ions and divalent iron ions in the key materials are different, the use amount of the pure medicines is analyzed when the key materials are applied is directly influenced. And taking 50mL of electrolyte prepared from the mixed concentrated slurry as a positive electrode electrolyte and a negative electrode electrolyte respectively, and assembling the iron-chromium flow battery. Wherein the battery diaphragm is a perfluorosulfonic acid membrane (purchased from new energy Limited of liter of Wuhan), and the effective area of the diaphragm is 25cm 2 The electrode is graphite felt, the bipolar plate is graphite plate, and the current density is 80mA/cm 2 . The single cell is subjected to constant current charge and discharge under the condition of 35 ℃, and the cut-off voltage is 0.7V to 1.2V.
TABLE 1
As can be seen from the above table, in addition to the usage amount of the analysis pure chemical when the molar concentrations of the trivalent chromium ions and the divalent iron ions in the key material are different and directly affect the electrolyte configured to be 2mol/L and 1.5mol/L in sequence when the key material is applied, the usage amount of the hydrochloric acid solution, the impurity removing agent, the atmosphere, and the like involved in the preparation steps of the key material in each embodiment also affect the performance of the key material when the key material is applied to the battery.
Specifically, (1) from example 1 and examples 4 to 6, it was found that since the hydrochloric acid concentration in the key material varies depending on the amount of the hydrochloric acid solution, the discharge capacity decreases and the energy efficiency decreases when it is applied to the battery as the hydrochloric acid concentration increases. This is mainly due to the fact that the acidity is too large and the hydrogen evolution phenomenon is severe, thus reducing the capacity and efficiency of the battery; (2) The energy efficiency of the performance of the batteries obtained in the embodiments 2 and 3 is up to 83 percent, and the main reason is that the content of harmful metal ions in the electrolyte is greatly reduced under the action of the impurity removing agent, so that the occurrence of a hydrogen evolution phenomenon is greatly reduced, the discharge capacity is increased, and the energy efficiency is improved; (3) Example 7, because the process is carried out in an air atmosphere and a protective atmosphere is not adopted, part of ferrous iron is oxidized into ferric iron, and the valence state of the electrolyte is unbalanced, so that the performance of the battery is affected.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the key material of the electrolyte is characterized by comprising the following steps:
adding materials containing iron metal and chromium metal into an acidic solution, mixing, performing first solid-liquid separation to obtain a leachate, and performing evaporation concentration on the leachate to obtain the electrolyte key material.
2. The preparation method according to claim 1, wherein the key electrolyte material is a mixed concentrated slurry of chromium chloride and ferrous chloride, and the concentrations of chromium ions and iron ions in the mixed concentrated slurry are as follows:
1 to 5mol/L of trivalent chromium ion
1 to 5mol/L of divalent iron ions.
3. The method for preparing the alloy according to claim 1, wherein the material containing iron metal and chromium metal comprises any one of or a combination of at least two of chromium metal and iron metal mixture, ferrochrome, chromium-based alloy, chromium-containing cast iron or chromium-containing slag;
the granularity of the material containing the iron metal and the chromium metal is-800 to-100 meshes.
4. The method of claim 1, wherein the acidic solution comprises a hydrochloric acid solution;
the mole fraction of the hydrochloric acid solution is 6 to 12mol/L;
the ratio of the molar weight of the chromium metal and the iron metal in the material containing the iron metal and the chromium metal to the molar weight of HCl in the hydrochloric acid solution is 1 (3 to 3.5);
the material containing iron metal and chromium metal is added into the hydrochloric acid solution in a manner of adding for several times, wherein the number of times of adding for several times is 2-5, and the time interval of each time of adding is 10-30min.
5. The method for preparing the resin composition according to claim 1, wherein the mixing temperature is 20 to 100 ℃;
the mixing time is 1 to 10 hours;
the mixed atmosphere is protective gas, the protective gas is non-oxidizing gas, and the non-oxidizing gas comprises any one or the combination of at least two of nitrogen, argon or helium;
the mixing is carried out in a multi-stage countercurrent mode, and an acidic solution is added during the last stage of leaching.
6. The method according to claim 1, wherein the first solid-liquid separation is performed to obtain a leaching solution and a leaching residue;
and the leached slag is washed and then is recycled as a material containing iron metal and chromium metal.
7. The method according to claim 6, wherein the leached residues are washed and then subjected to a second solid-liquid separation to obtain tailings.
8. The production method according to claim 7, wherein steam condensate water produced by the evaporative concentration is used for washing tailings in the first solid-liquid separation.
9. The preparation method according to claim 6, characterized in that an impurity removing agent is added into the leaching solution for purification treatment;
the impurity removing agent comprises any one or the combination of at least two of ammonium chloride, ammonium sulfate, ammonium citrate, ammonium oxalate, triethanolamine, sulfamic acid, acidic cation exchange resin, modified bentonite, diatomite, porous silicon dioxide or porous boron nitride;
the impurity removing agent accounts for 0.01 to 2 percent of the mass of the leaching solution;
the purification treatment is carried out under the condition of stirring or oscillation, and the purification treatment time is 1 to 8h;
the temperature of the purification treatment is 20 to 90 ℃;
filtering after the purification treatment to obtain a purified mixed solution containing iron chloride and chromium chloride, wherein the filter residue is purification residue;
and the purified slag and the leaching slag are washed together and then are recycled as materials containing iron metal and chromium metal.
10. The application of the preparation method of the electrolyte key material as described in any one of claims 1 to 9, wherein the preparation method is applied to the field of iron-chromium flow batteries.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117457955A (en) * | 2023-09-28 | 2024-01-26 | 斯瑞尔环境科技股份有限公司 | Method for preparing iron-chromium electrolyte by using carbon ferrochromium |
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|---|---|---|---|---|
| US4150975A (en) * | 1977-07-12 | 1979-04-24 | Toyo Soda Manufacturing Co., Ltd. | Process for producing metallic chromium |
| JPS60148068A (en) * | 1984-01-12 | 1985-08-05 | Agency Of Ind Science & Technol | Manufacture of electrolyte in redox cell |
| JPS6122575A (en) * | 1984-07-09 | 1986-01-31 | Sumitomo Electric Ind Ltd | Cell construction |
| JPH06325784A (en) * | 1993-05-10 | 1994-11-25 | Tsurumi Soda Co Ltd | Manufacture of electrolyte for redox battery |
| CN102460812A (en) * | 2009-05-28 | 2012-05-16 | 迪亚能源股份有限公司 | Preparation of flow cell battery electrolytes from raw materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150975A (en) * | 1977-07-12 | 1979-04-24 | Toyo Soda Manufacturing Co., Ltd. | Process for producing metallic chromium |
| JPS60148068A (en) * | 1984-01-12 | 1985-08-05 | Agency Of Ind Science & Technol | Manufacture of electrolyte in redox cell |
| JPS6122575A (en) * | 1984-07-09 | 1986-01-31 | Sumitomo Electric Ind Ltd | Cell construction |
| JPH06325784A (en) * | 1993-05-10 | 1994-11-25 | Tsurumi Soda Co Ltd | Manufacture of electrolyte for redox battery |
| CN102460812A (en) * | 2009-05-28 | 2012-05-16 | 迪亚能源股份有限公司 | Preparation of flow cell battery electrolytes from raw materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117457955A (en) * | 2023-09-28 | 2024-01-26 | 斯瑞尔环境科技股份有限公司 | Method for preparing iron-chromium electrolyte by using carbon ferrochromium |
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