CN115927882B - Method for separating vanadium and nickel - Google Patents
Method for separating vanadium and nickel Download PDFInfo
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- CN115927882B CN115927882B CN202211666763.0A CN202211666763A CN115927882B CN 115927882 B CN115927882 B CN 115927882B CN 202211666763 A CN202211666763 A CN 202211666763A CN 115927882 B CN115927882 B CN 115927882B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 123
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 60
- 150000007524 organic acids Chemical class 0.000 claims abstract description 61
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 239000011343 solid material Substances 0.000 claims abstract description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 13
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 32
- 238000004064 recycling Methods 0.000 abstract description 16
- 230000002829 reductive effect Effects 0.000 abstract description 13
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002893 slag Substances 0.000 abstract description 10
- 238000001556 precipitation Methods 0.000 abstract description 7
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 44
- 238000002386 leaching Methods 0.000 description 22
- 239000011259 mixed solution Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for separating vanadium and nickel, which comprises the following steps: (1) Mixing and filtering the solid material containing vanadium and nickel with a reducing organic acid to obtain a nickel complex precipitate and a vanadium complex solution; (2) Mixing the inorganic acid with the vanadium-containing complex solution obtained in the step (1), cooling for crystallization, centrifuging and filtering to obtain a vanadium-containing solution and a reducing organic acid; the reducing organic acid in the step (1) comprises any one or a combination of at least two of formic acid, citric acid, glyoxylic acid and oxalic acid. The invention can avoid the mutual entrainment phenomenon generated by the combination of vanadate and nickel ions during separation, so that vanadium enters the solution in the form of vanadium complex, nickel enters the slag phase in the form of nickel complex precipitation, the deep separation of vanadium and nickel is promoted, the recycling of the reducing organic acid is realized, and the separation cost is reduced; the method has the advantages of simple flow, mild condition, wide operation range and easy application in industrial production.
Description
Technical Field
The invention belongs to the technical field of separation, and relates to a method for separating vanadium and nickel.
Background
Vanadium and nickel are used as important strategic metal resources, have excellent physical and chemical properties, are widely applied to industries such as steel, nonferrous metals, chemistry and chemical industry, and have important recycling significance, and have wide sources such as waste catalysts and nonferrous metal smelting waste residues. However, due to the unique chemical properties of vanadium and nickel in acidic solutions, nickel vanadate is extremely easily formed, increasing the difficulty of separation.
At present, the separation process of vanadium and nickel comprises wet leaching, wherein the process mainly utilizes sulfuric acid solution to leach vanadium-nickel-containing materials to obtain vanadium-nickel-containing acidic solution, and then utilizes an extraction separation or ion exchange method to realize vanadium-nickel separation.
CN111235384B discloses a method for separating and extracting vanadium and nickel from waste catalyst, mixing the waste catalyst containing vanadium and nickel with carbonaceous reducing agent, calcium chloride, vanadium-nickel collector and water, pelletizing to obtain pellets, then performing primary roasting and secondary roasting, and performing magnetic separation after roasting to obtain nickel-rich vanadium sponge iron alloy; then, carrying out two-stage roasting and water leaching treatment on the nickel-rich vanadium sponge iron alloy, and separating to obtain vanadium leaching liquid and nickel slag; mixing nickel slag and sulfuric acid, and performing two-stage sintering and water leaching to obtain nickel leaching liquid and leaching slag; and (5) recycling leaching slag. The technical scheme has the advantages of simple process, low cost, high nickel-vanadium extraction rate, recycling of iron element, suitability for industrial application and the like, but the method has higher energy loss.
CN113549764B discloses a process for recovering rare earth elements, nickel and vanadium from FCC spent catalyst. The method comprises the following steps: acid leaching treatment is carried out on the calcined FCC spent catalyst to obtain leaching liquid; carrying out a first contact reaction on the leaching solution and potassium sulfate to obtain a first mixed solution, and regulating the pH value of the first mixed solution to 3-4 to obtain a second mixed solution; extracting and separating the second mixed solution in the presence of an extracting agent to obtain a water phase and an oil phase; wherein the aqueous phase contains VO 4 3-, and the oil phase contains Ni 2+. According to the technical scheme, rare earth elements, nickel and vanadium can be comprehensively recovered, and the recovery rate of the rare earth elements, nickel elements and vanadium elements can be higher, but the pollution problem of organic matters can be caused by extraction and separation, so that the recycling of acid solutions is not facilitated.
CN101838735B discloses a method for separating and extracting valuable metals from acid leaching solution of nickel-molybdenum multi-metal metallurgical materials, which is used for extracting nickel, molybdenum and vanadium in acid leaching solution, and is characterized in that the pH value of the pre-adjusted solution is 0.1-2.0, molybdenum and vanadium in the pre-adjusted solution are adsorbed by anion exchange resin, the negative molybdenum-vanadium resin is desorbed by ammonia water or sodium hydroxide solution to obtain a mixed solution of molybdenum vanadate, the mixed solution of molybdenum vanadate is produced by combining an ammonium salt precipitation method and a strong base anion exchange method, pure molybdate and vanadate are produced by the mixed solution, the pH value of the mixed solution is adjusted by adding alkali after the exchange to remove impurities, the mixed solution is filtered, and the filtrate is recovered by a cation exchange resin adsorption method or a solvent extraction method or a precipitation method.
In summary, the invention provides a method for separating vanadium and nickel, which reduces the separation cost, improves the separation efficiency, and can realize the deep separation of vanadium and nickel and the recycling of acid solution.
Disclosure of Invention
The invention aims to provide a method for separating vanadium and nickel, which has the advantages of improving the separation efficiency, simplifying the separation step, reducing the separation cost and realizing the deep separation of vanadium and nickel. In order to achieve the aim of the invention, the invention adopts the following technical scheme:
The invention provides a method for separating vanadium and nickel, which comprises the following steps:
(1) Mixing and filtering the solid material containing vanadium and nickel with a reducing organic acid to obtain a nickel complex precipitate and a vanadium complex solution;
(2) Mixing the inorganic acid with the vanadium-containing complex solution obtained in the step (1), cooling for crystallization, centrifuging and filtering to obtain a vanadium-containing solution and a reducing organic acid;
The reducing organic acid in the step (1) comprises any one or a combination of at least two of formic acid, citric acid, glyoxylic acid and oxalic acid.
The pentavalent vanadium of vanadate in the solid material is reduced into low valent vanadium under the action of the reducing organic acid, so that the phenomenon of mutual entrainment generated by combining vanadate and nickel ions during separation is avoided, vanadium enters the solution in the form of vanadium complex, nickel enters the slag phase in the form of nickel complex precipitation, the deep separation of vanadium and nickel is promoted, and the separation efficiency is improved; under the decomplexing action of inorganic acid, the vanadium-containing complex solution dissociates low-valence vanadium from the reducing organic acid, so that the recycling of the reducing organic acid is realized, and the separation cost is reduced; the method has the advantages of simple flow, mild condition, wide operation range and easy application in industrial production.
The source of the reducing organic acid in the step (1) comprises fresh reducing organic acid and/or the reducing organic acid obtained in the step (2).
Preferably, the concentration of the reducing organic acid in the step (1) is 1 to 3mol/L, for example, 1mol/L, 1.3mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.3mol/L, 2.5mol/L, 2.8mol/L or 3mol/L, but not limited to the recited values, and other non-recited values within the numerical range are equally applicable, preferably 2 to 3mol/L.
Preferably, the temperature of the mixing in step (1) is 80-100deg.C, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100deg.C, but not limited to the values recited, other non-recited values within the range of values are equally applicable, preferably 95-100deg.C.
The mixing temperature of the solid material containing vanadium and nickel and the reducing organic acid is controlled within the range of 80-100 ℃, so that vanadium enters the solution in the form of vanadium complex, and nickel enters the slag phase in the form of nickel complex, thereby being beneficial to realizing the high-efficiency separation of vanadium and nickel and avoiding the mutual entrainment of vanadium and nickel; when the temperature is lower than 80 ℃, the leaching rate of vanadium is low, and the mutual entrainment phenomenon of vanadium and nickel is serious; when the temperature is higher than 100 ℃, the reducing organic acid is easy to decompose and volatilize, and the recycling rate of the reducing organic acid is reduced.
Preferably, the mixing time in step (1) is 30-300min, for example, 30min, 50min, 100min, 150min, 200min, 250min or 300min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 180-300min.
Preferably, the solid-to-liquid ratio of the solid material to the reducing organic acid in step (1) is 1 (5-10), for example, but not limited to, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, and other non-enumerated values in the numerical range are equally applicable, and the unit of the solid-to-liquid ratio is kg/L.
Preferably, the mass fraction of vanadium element in the solid material in step (1) is 30-45wt%, for example, 30wt%, 33wt%, 35wt%, 38wt%, 40wt%, 43wt%, or 45wt%, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the mass fraction of nickel element in the solid material in step (1) is 10-15wt%, for example, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt%, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the volume ratio of the inorganic acid in step (2) to the vanadium-containing complex solution obtained in step (1) is 1 (1-3), and may be, for example, 1:1, 1:1.5, 1:2, 1:2.5 or 1:3, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the mineral acid in step (2) is sulfuric acid and/or hydrochloric acid.
The concentration of the sulfuric acid is preferably 9.2 to 18.4mol/L, and may be, for example, 9.2mol/L, 11mol/L, 13mol/L, 15mol/L, 17mol/L or 18.4mol/L, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the concentration of the hydrochloric acid is 6-12mol/L, for example, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L or 12mol/L, but the concentration is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Illustratively, when the inorganic acid is sulfuric acid, the vanadium-containing solution obtained in step (2) is vanadyl sulfate solution; when the inorganic acid is hydrochloric acid, the vanadium-containing solution obtained in the step (2) is a vanadium oxychloride solution.
Preferably, the temperature of the mixing in step (2) is 20-60 ℃, for example, 20 ℃, 25 ℃, 30 ℃,35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 40-60 ℃.
The mixing temperature of the vanadium-containing complex solution and the inorganic acid is controlled within the range of 20-60 ℃, so that the dissociation of low-valence vanadium and the reductive organic acid is facilitated, the cyclic utilization of the reductive organic acid is realized, when the temperature is 40-60 ℃, the reaction rate is easy to control, the dissociation efficiency is high, and the cyclic utilization rate of the reductive organic acid is high; but when the temperature is lower than 20 ℃, the reaction rate is slow and the reaction time is long; when the temperature is higher than 60 ℃, the reaction temperature is not easy to control, and the degradation loss of the reducing organic acid can be caused.
Preferably, the mixing time in step (2) is 30-60min, for example, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the temperature of the cooling crystallization in the step (2) is 2 to 25 ℃, for example, 2 ℃,5 ℃, 10 ℃, 15 ℃,20 ℃ or 25 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 10 to 25 ℃.
Preferably, the cooling crystallization time in the step (2) is 60-300min, for example, 60min, 100min, 150min, 200min, 250min or 300min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the rotational speed of the centrifugation in the step (2) is 1400-2300r/min, for example, 1400r/min, 1600r/min, 1800r/min, 2000r/min, 2100r/min or 2300r/min, but the present invention is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the centrifugation time in step (2) is 30-60min, for example, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
As a preferred technical solution of the method according to the invention, the method comprises the steps of:
(1) Mixing solid materials containing vanadium and nickel with 1-3mol/L reducing organic acid according to a solid-liquid ratio of 1 (5-10) kg/L at 80-100 ℃ for 30-300min, and filtering to obtain nickel complex precipitate and vanadium complex solution;
The reducing organic acid comprises any one or a combination of at least two of formic acid, citric acid, glyoxylic acid or oxalic acid;
(2) Mixing inorganic acid and the vanadium-containing complex solution obtained in the step (1) according to the volume ratio of 1 (1-3) at 20-60 ℃ for 30-60min, cooling and crystallizing at 2-25 ℃ for 60-300min, centrifuging and filtering to obtain the vanadium-containing solution and the reducing organic acid.
Compared with the prior art, the invention has the following beneficial effects:
The pentavalent vanadium of vanadate in the solid material is reduced into low valent vanadium under the action of the reducing organic acid, so that the phenomenon of mutual entrainment generated by combining vanadate and nickel ions during separation is avoided, vanadium enters the solution in the form of vanadium complex, nickel enters the slag phase in the form of nickel complex precipitation, the deep separation of vanadium and nickel is promoted, and the separation efficiency is improved; under the decomplexing action of inorganic acid, the vanadium-containing complex solution dissociates low-valence vanadium from the reducing organic acid, so that the recycling of the reducing organic acid is realized, and the separation cost is reduced; the method has the advantages of simple flow, mild condition, wide operation range and easy application in industrial production.
Drawings
FIG. 1 is a flow chart of the vanadium and nickel separation performed in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for separating vanadium and nickel, the flow chart of which is shown in fig. 1, and the method comprises the following steps:
(1) Mixing a solid material containing vanadium and nickel with a reducing organic acid with the concentration of 2.5mol/L at the solid-to-liquid ratio of 1:8kg/L for 240min at the temperature of 90 ℃, and filtering to obtain a nickel complex precipitate and a vanadium complex solution; the reducing organic acid is glyoxylic acid;
(2) Mixing sulfuric acid with the concentration of 10mol/L with the vanadium-containing complex solution obtained in the step (1) according to the volume ratio of 1:2 at 50 ℃ for 45min, cooling and crystallizing at 15 ℃ for 180min, and centrifuging and filtering to obtain the vanadium-containing solution and the reducing organic acid.
Example 2
The embodiment provides a method for separating vanadium and nickel, which comprises the following steps:
(1) Mixing a solid material containing vanadium and nickel with a 1mol/L reducing organic acid according to a solid-to-liquid ratio of 1:10kg/L at 80 ℃ for 180min, and filtering to obtain a nickel complex precipitate and a vanadium complex solution; the reducing organic acid is citric acid;
(2) Mixing sulfuric acid with the concentration of 9.2mol/L with the vanadium-containing complex solution obtained in the step (1) according to the volume ratio of 1:1 at 40 ℃ for 60min, cooling and crystallizing at 5 ℃ for 60min, centrifuging and filtering to obtain the vanadium-containing solution and the reducing organic acid.
Example 3
The embodiment provides a method for separating vanadium and nickel, which comprises the following steps:
(1) Mixing a solid material containing vanadium and nickel with a reducing organic acid with the concentration of 3mol/L at the solid-to-liquid ratio of 1:5kg/L at 100 ℃ for 300min, and filtering to obtain a nickel complex precipitate and a vanadium complex solution; the reducing organic acid is oxalic acid;
(2) Mixing sulfuric acid with the concentration of 18.4mol/L with the vanadium-containing complex solution obtained in the step (1) according to the volume ratio of 1:3 at 60 ℃ for 30min, cooling and crystallizing at 25 ℃ for 300min, and centrifuging and filtering to obtain the vanadium-containing solution and the reducing organic acid.
Example 4
This example provides a method for separating vanadium and nickel, which is the same as example 1 except that the reducing organic acid in step (1) is formic acid.
Example 5
This example provides a method for separating vanadium and nickel, which is the same as example 1 except that the sulfuric acid in step (2) is replaced by hydrochloric acid in equal volume.
Example 6
This example provides a method for separating vanadium and nickel, which is the same as example 1 except that the mixing temperature of the solid material and the reducing organic acid in step (1) is 70 ℃.
Example 7
This example provides a method for separating vanadium and nickel, which is the same as example 1 except that the mixing temperature of the solid material and the reducing organic acid in step (1) is 110 ℃.
Example 8
This example provides a method for separating vanadium and nickel, which is the same as example 1 except that the mixing temperature of the inorganic acid in step (2) and the vanadium-containing complex solution obtained in step (1) is 20 ℃.
Example 9
This example provides a method for separating vanadium and nickel, which is the same as example 1 except that the mixing temperature of the inorganic acid in step (2) and the vanadium-containing complex solution obtained in step (1) is 10 ℃.
Example 10
This example provides a method for separating vanadium and nickel, which is the same as example 1 except that the mixing temperature of the inorganic acid in step (2) and the vanadium-containing complex solution obtained in step (1) is 70 ℃.
Performance testing
For the methods provided in examples 1-10, nickel leaching rate, vanadium leaching rate and reducing organic acid recycling rate were tested, wherein the nickel leaching rate and vanadium leaching rate (LE) were calculated from the following formulas:
where m a is the total mass of the leaching residue, m b is the total mass of the roasting residue, C i is the concentration of the diluted metal element measured by ICP-OES, n is the dilution factor, V is the volume before dilution, m 1 is the mass of the solid sample dissolved in HNO 3, and X i is the content of the metal element in the roasting residue.
The reducing recycling efficiency is calculated according to the molar quantity of the organic acid radical in the crystallization substance, and the content of the organic acid radical is obtained by a chromatograph test.
The results are shown in Table 1.
TABLE 1
As shown in Table 1, in the method provided by the invention, the leaching rate of nickel is about 6%, the leaching rate of vanadium can be up to more than 95%, and the recycling rate of the reducing organic acid can be up to more than 80%.
As can be seen from comparison of examples 6, 7 and 1, the mixing temperature of the solid material containing vanadium and nickel and the reducing organic acid is controlled within 80-100deg.C, which is favorable for reducing pentavalent vanadium of vanadate in the solid material into low valent vanadium under the action of the reducing organic acid, avoiding the mutual entrainment phenomenon generated by combining vanadate and nickel ion during separation, and further leading vanadium to enter solution in the form of vanadium complex, and nickel to enter slag phase in the form of nickel complex precipitation, so as to promote deep separation of vanadium and nickel; when the temperature is lower than 80 ℃, the leaching rate of vanadium is reduced, when the temperature is 70 ℃, the leaching rate of vanadium is only 77.0%, and the mutual entrainment phenomenon of vanadium and nickel is serious; when the temperature is higher than 100 ℃, the reducing organic acid is easy to decompose and volatilize, the recycling rate of the reducing organic acid is reduced, and when the mixing temperature is 110 ℃, the recycling rate of the reducing organic acid is only 75.31 percent.
As is clear from the comparison of examples 8 and 9 with example 1, the cyclic utilization rate of the reducing organic acid does not change much with the decrease of the mixing temperature of the inorganic acid and the vanadium-containing complex solution, but the reaction rate is slow and the reaction time is too long; as is clear from a comparison of example 10 and example 1, when the mixing temperature of the inorganic acid and the vanadium-containing complex solution is too high, the recycling rate of the reducing organic acid is lowered.
In summary, the invention provides a method for separating vanadium and nickel, wherein pentavalent vanadium of vanadate in solid materials is reduced to low valent vanadium under the action of reducing organic acid, so that the phenomenon of mutual entrainment generated by combining vanadate and nickel ions during separation is avoided, vanadium enters solution in the form of vanadium complex, nickel enters slag phase in the form of nickel complex precipitation, the deep separation of vanadium and nickel is promoted, and the separation efficiency is improved; under the decomplexing action of inorganic acid, the vanadium-containing complex solution dissociates low-valence vanadium from the reducing organic acid, so that the recycling of the reducing organic acid is realized, and the separation cost is reduced; the method has the advantages of simple flow, mild condition, wide operation range and easy application in industrial production.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (19)
1. A method for separating vanadium and nickel, the method comprising the steps of:
(1) Mixing and filtering the solid material containing vanadium and nickel with a reducing organic acid to obtain a nickel complex precipitate and a vanadium complex solution;
(2) Mixing the inorganic acid with the vanadium-containing complex solution obtained in the step (1), cooling for crystallization, centrifuging and filtering to obtain a vanadium-containing solution and a reducing organic acid;
In step (1), the reducing organic acid comprises any one or a combination of at least two of formic acid, citric acid, glyoxylic acid or oxalic acid; the temperature of the mixing is 80-100 ℃; the solid-to-liquid ratio of the solid material to the reducing organic acid is 1 (5-10) kg/L;
In step (2), the temperature of the mixing is 20-60 ℃; the temperature of the cooling crystallization is 2-25 ℃.
2. The method of claim 1, wherein the concentration of the reducing organic acid in step (1) is 1-3mol/L.
3. The process of claim 2, wherein the concentration of the reducing organic acid in step (1) is 2-3mol/L.
4. The method of claim 1, wherein the temperature of the mixing of step (1) is 95-100 ℃.
5. The method of claim 1, wherein the mixing of step (1) is for a period of 30-300 minutes.
6. The method of claim 5, wherein the mixing of step (1) is for a period of 180-300 minutes.
7. The method according to claim 1, wherein the mass fraction of vanadium element in the solid material of step (1) is 30-45wt%.
8. The method according to claim 1, wherein the mass fraction of nickel element in the solid material in step (1) is 10-15wt%.
9. The method of claim 1, wherein the volume ratio of the inorganic acid in step (2) to the vanadium-containing complex solution obtained in step (1) is 1 (1-3).
10. The method of claim 1, wherein the mineral acid of step (2) is sulfuric acid and/or hydrochloric acid.
11. The method of claim 10, wherein the sulfuric acid has a concentration of 9.2 to 18.4mol/L.
12. The method of claim 10, wherein the hydrochloric acid has a concentration of 6-12mol/L.
13. The method of claim 1, wherein the temperature of the mixing of step (2) is 40-60 ℃.
14. The method of claim 1, wherein the mixing of step (2) is for a period of 30-60 minutes.
15. The method of claim 1, wherein the cooling crystallization in step (2) is at a temperature of 10-25 ℃.
16. The method of claim 1, wherein the cooling crystallization of step (2) takes about 60 to 300 minutes.
17. The method of claim 1, wherein the centrifugation in step (2) is performed at a rotational speed of 1400-2300r/min.
18. The method of claim 1, wherein the centrifugation of step (2) is for a period of 30-60 minutes.
19. The method according to claim 1, characterized in that it comprises the steps of:
(1) Mixing solid materials containing vanadium and nickel with 1-3mol/L reducing organic acid according to a solid-liquid ratio of 1 (5-10) kg/L at 80-100 ℃ for 30-300min, and filtering to obtain nickel complex precipitate and vanadium complex solution;
The reducing organic acid comprises any one or a combination of at least two of formic acid, citric acid, glyoxylic acid or oxalic acid;
(2) Mixing inorganic acid and the vanadium-containing complex solution obtained in the step (1) according to the volume ratio of 1 (1-3) at 20-60 ℃ for 30-60min, cooling and crystallizing at 2-25 ℃ for 60-300min, centrifuging and filtering to obtain the vanadium-containing solution and the reducing organic acid.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298581A (en) * | 1980-04-15 | 1981-11-03 | Cabot Corporation | Process for recovering chromium, vanadium, molybdenum and tungsten values from a feed material |
| WO2004099079A1 (en) * | 2003-05-12 | 2004-11-18 | Clean Teq Pty Ltd | A method for producing an electrolytic solution containing vanadium |
| CN105692698A (en) * | 2016-02-24 | 2016-06-22 | 中南大学 | Method for deeply separating molybdenum and vanadium in solution containing molybdenum and vanadium |
| CN105986123A (en) * | 2015-02-11 | 2016-10-05 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing waste catalyst reductive organic acid |
| CN108535455A (en) * | 2018-04-04 | 2018-09-14 | 武汉新能源研究院有限公司 | Heavy metal vanadium in a kind of petroleum coke, nickel occurrence patterns extract identification method step by step |
| CN111778404A (en) * | 2020-08-14 | 2020-10-16 | 眉山顺应动力电池材料有限公司 | Leaching separation method of nickel-cobalt-molybdenum-phosphorus-vanadium alloy material |
| CN112226629A (en) * | 2020-09-14 | 2021-01-15 | 广东芳源环保股份有限公司 | Method for removing impurities from nickel solution by using reusable polymetallic salt as complexing agent |
| JP2021130863A (en) * | 2020-02-21 | 2021-09-09 | 日本管機工業株式会社 | Method for separating vanadium, method for producing electrolyte for redox flow battery, apparatus for separating vanadium, and apparatus for producing electrolyte for redox flow battery |
| CN113789446A (en) * | 2021-08-23 | 2021-12-14 | 常州大学 | Method for recovering molybdenum, vanadium and nickel metals from waste catalyst |
| CN114275815A (en) * | 2021-12-16 | 2022-04-05 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium solution |
-
2022
- 2022-12-23 CN CN202211666763.0A patent/CN115927882B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298581A (en) * | 1980-04-15 | 1981-11-03 | Cabot Corporation | Process for recovering chromium, vanadium, molybdenum and tungsten values from a feed material |
| WO2004099079A1 (en) * | 2003-05-12 | 2004-11-18 | Clean Teq Pty Ltd | A method for producing an electrolytic solution containing vanadium |
| CN105986123A (en) * | 2015-02-11 | 2016-10-05 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing waste catalyst reductive organic acid |
| CN105692698A (en) * | 2016-02-24 | 2016-06-22 | 中南大学 | Method for deeply separating molybdenum and vanadium in solution containing molybdenum and vanadium |
| CN108535455A (en) * | 2018-04-04 | 2018-09-14 | 武汉新能源研究院有限公司 | Heavy metal vanadium in a kind of petroleum coke, nickel occurrence patterns extract identification method step by step |
| JP2021130863A (en) * | 2020-02-21 | 2021-09-09 | 日本管機工業株式会社 | Method for separating vanadium, method for producing electrolyte for redox flow battery, apparatus for separating vanadium, and apparatus for producing electrolyte for redox flow battery |
| CN111778404A (en) * | 2020-08-14 | 2020-10-16 | 眉山顺应动力电池材料有限公司 | Leaching separation method of nickel-cobalt-molybdenum-phosphorus-vanadium alloy material |
| CN112226629A (en) * | 2020-09-14 | 2021-01-15 | 广东芳源环保股份有限公司 | Method for removing impurities from nickel solution by using reusable polymetallic salt as complexing agent |
| CN113789446A (en) * | 2021-08-23 | 2021-12-14 | 常州大学 | Method for recovering molybdenum, vanadium and nickel metals from waste catalyst |
| CN114275815A (en) * | 2021-12-16 | 2022-04-05 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium solution |
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