CN108358792A - The method that solid complex is extracted from the aqueous solution of the oxygen-containing acid group containing vanadium, obtained solid complex and application thereof - Google Patents
The method that solid complex is extracted from the aqueous solution of the oxygen-containing acid group containing vanadium, obtained solid complex and application thereof Download PDFInfo
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- CN108358792A CN108358792A CN201710487735.5A CN201710487735A CN108358792A CN 108358792 A CN108358792 A CN 108358792A CN 201710487735 A CN201710487735 A CN 201710487735A CN 108358792 A CN108358792 A CN 108358792A
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- Prior art keywords
- oxygen
- acid group
- solid
- solid complex
- vanadium
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- 239000007787 solid Substances 0.000 title claims abstract description 92
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 87
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 61
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 55
- 239000002253 acid Substances 0.000 title claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000001301 oxygen Substances 0.000 title claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003141 primary amines Chemical class 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000012074 organic phase Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 8
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims abstract description 7
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims abstract description 7
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005416 organic matter Substances 0.000 claims abstract description 5
- 238000005191 phase separation Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 23
- 239000006183 anode active material Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 125000002015 acyclic group Chemical group 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 11
- 238000007146 photocatalysis Methods 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 230000000536 complexating effect Effects 0.000 claims description 9
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910019501 NaVO3 Inorganic materials 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021144 KVO3 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910001784 vanadium mineral Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of to extract the method for solid complex, obtained solid complex and application thereof from the aqueous solution of the oxygen-containing acid group containing vanadium.The method includes：1) make pH value 2~4 the oxygen-containing acid group containing vanadium aqueous solution, with fatty race's straight chain primary amine (in isopropylamine, n-octyl amine, lauryl amine, cetylamine or octadecylamine any one or at least two mixture) organic solvent react；2) and then by water phase and organic phase separation；3) organic phase is separated by solid-liquid separation, obtains solid complex.The method of the present invention is suitable for the aqueous solution containing vanadium of preparation, industrial wastewater or containing vanadium leachate, it can be achieved that the reasonable application of secondary resource.Obtained solid complex can be used as novel environmental engineering functional material, it is used to prepare the presoma of battery, or the cost of material preparation containing vanadium is reduced, there is preferable application prospect for photocatalytic degradation organic matter directly as catalyst or with the compound composite catalyst that obtains of carrier.
Description
Technical field
The invention belongs to metallurgy environment engineering fields, are related to a kind of extraction solid network from the aqueous solution of the oxygen-containing acid group containing vanadium
The method for closing object, obtained solid complex and application thereof, and in particular to a kind of to be extracted from the aqueous solution of the oxygen-containing acid group containing vanadium
The solid complex and degrade as battery material presoma or catalysis material organic that the method for solid complex, extraction obtain
The purposes of object.
Background technology
Vanadium is a kind of important metal material, and the reserves in China occupy the 4th, the world, national You10Duo Ge provinces and cities (area)
There are vanadium mineral resource, vanadium to be widely used in multiple fields, vanadium has good application prospect in battery material, recently,
Many document report vanadic acid and its compound can individually or with the compound positive electrode as lithium ion battery of other materials
(G.Xu,H.He,H.Wan,R.Liu,X.Zeng,D.Sun, X.Huang and H.Wang,Journal of Applied
Electrochemistry,2016,46,879-885；S. Sarkar,A.Bhowmik,J.Pan,M.D.Bharadwaj and
S.Mitra,Journal of Power Sources,2016,329,179-189；A.Ottmann,G.S.Zakharova,
B.Ehrstein and R. Klingeler,Electrochimica Acta,2015,174,682-687；S.-S.Cao,J.-
F.Huang,H.-B. Ouyang,L.-Y.Cao,J.-Y.Li and J.-P.Wu,Materials Letters,2014,126,
20-23.) however, high cost of material constrains its further development as battery active material.Identical situation is also sent out
It is raw in the other application field of vanadium, for example, vanadium photocatalysis field also have well application prospect (R.Li, F. Zhang,
D.Wang,J.Yang,M.Li,J.Zhu,X.Zhou,H.Han and C.Li,Nature Communications,2013,4,
1432；G.Xi and J.Ye, Chemical Communications, 2010,46,1893-1895.), but cost of material
Problem is still the main reason for limiting its development.
In this case, if the higher vfanadium compound of purity can be recycled out with cheap cost from waste
It is directly used in the application of vanadium material, the application range of vanadium material will be expanded significantly, be of great significance.
Invention content
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of from the oxygen-containing acid group containing vanadium
The method of solid complex is extracted in aqueous solution, the solid complex and application thereof that extraction obtains.The method of the present invention not only can be with
It is prepared for laboratory, it is possibility to have imitate recycling vanadium metal in easy slave vanadium-containing water or leachate and be used as battery material
Presoma or catalyst greatly reduce the cost containing vanadium battery material and catalyst, while having carried out high level to secondary resource
Chemical combination reason utilizes.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of method for extracting solid complex from the aqueous solution of the oxygen-containing acid group containing vanadium,
It is characterized in that, the described method comprises the following steps：
(1) optionally adjust the oxygen-containing acid group containing vanadium pH value of water solution between 2~4, then with fatty race's linear primary
The organic solvent of amine mixes, reaction, generates complexing product；
(2) by step (1) react after the completion of mixed solution in water phase and organic phase separation；
(3) organic phase is separated by solid-liquid separation, obtains solid complex；
The acyclic straight primary amine is：Any one in isopropylamine, n-octyl amine, lauryl amine, cetylamine or octadecylamine
Or at least two mixture, the mixture is typical but non-limiting examples have：The mixture of isopropylamine and n-octyl amine, isopropyl
The mixture of the mixture of amine and lauryl amine, lauryl amine and cetylamine, isopropylamine, lauryl amine and octadecylamine mixture etc..
In the present invention, the acyclic straight primary amine can be pure material, can also be at least two acyclic straights primary
The mixture of amine.
" straight chain " in " the acyclic straight primary amine " refers to：Primary amine is in the endpoint of molecule carbon chain skeleton, rather than
On branch.
In the present invention, the complexing product that step (1) reaction generates, i.e. the complexing product of vanadic acid and organic matter.
Heretofore described " aqueous solution of the oxygen-containing acid group containing vanadium " refers to：Aqueous solution containing the oxygen-containing acid group of vanadium, such as containing
H2VO4 -, HV4O11 -, V6O16 2-And V10O26 2-.
In the present invention, " optional " described in step (1) refers to：If the pH values of the aqueous solution of the oxygen-containing acid group containing vanadium 2~4 it
Between, then without adjust pH value the step of；If the acidity of the aqueous solution of the oxygen-containing acid group containing vanadium is inadequate, i.e., pH value is more than 4, then carries out
The step of adjusting pH value；If the acidity of the aqueous solution of the oxygen-containing acid group containing vanadium is too strong, i.e., pH value is less than 2, then is also adjusted pH value
The step of.
By the present invention in that the oxygen-containing acid group containing vanadium with particular kind of acyclic straight primary amine and pH between 2~4
Aqueous solution mixes, and hydrogen bond complex reaction occurs, and generates the complexing product of vanadic acid and organic matter.
The particular kind of acyclic straight primary amine that the present invention uses can not only occur with the aqueous solution of the oxygen-containing acid group containing vanadium
Hydrogen bond complex reaction, obtains complex compound；Moreover, these solubility of particular kind of acyclic straight primary amine in organic solvent
It is relatively low, according to the similar principle that mixes, solid matter can be directly generated using it as extractant and the contact of vanadium oxyacid, so as to
To extract vanadic acid from the aqueous solution of the oxygen-containing acid group containing vanadium and directly generate solid complex.
In the present invention, the source of the aqueous solution of the oxygen-containing acid group containing vanadium is not construed as limiting, can be that laboratory preparation simulation is molten
Liquid can also be industrial actual waste water (such as vanadium-containing water) or leachate.
In the present invention, the anion in the aqueous solution of the oxygen-containing acid group containing vanadium can be the oxygen-containing acid group of vanadium, also may be used
Not only to contain the oxygen-containing acid group of vanadium but also contain other anion, other described anion can be chromate and/or other transition metal
Oxygen-containing acid group.For example, can be actual metal leachate, wherein 20g/L containing vanadic acid, chromic acid 5g/L, can also contain on a small quantity its
His impurity.
It can also contain impurity in the aqueous solution of the oxygen-containing acid group containing vanadium of the present invention.
In the present invention, if acidity is inadequate, i.e., pH value is more than 4, adjusts the reagent that the aqueous solution pH of the oxygen-containing acid group containing vanadium is used
It can be all acid, such as can be hydrochloric acid, acetic acid and sulfuric acid etc..
In the present invention, if acidity is too strong, i.e., pH value is less than 2, adjusts the reagent that the aqueous solution pH of the oxygen-containing acid group containing vanadium is used
It can be all highly basic, such as can be sodium hydroxide and potassium hydroxide etc..
Preferably, in the organic solvent of step (1) fatty race's straight chain primary amine, solvent is can dissolved fat race straight chain
The weakly polar organic solvent of primary amine preferably includes any one or a few the mixture in toluene, n-hexane or kerosene, but simultaneously
It is not limited to the above-mentioned substance enumerated, other are commonly used in the art can to dissolve acyclic straight primary amine (i.e. isopropyl of the present invention
In amine, n-octyl amine, lauryl amine, cetylamine or octadecylamine any one or at least two mixture) low pole it is organic molten
Agent can also be used for the present invention.
In the present invention, the solvent can be pure material, can also be the mixture of at least two solvents.
Preferably, in the organic solvent of step (1) fatty race's straight chain primary amine, acyclic straight primary amine it is mole dense
Degree be the oxygen-containing acid group containing vanadium aqueous solution in 0.5~2.0 times of molar concentration of V, for example, 0.5 times, 0.8 times, 1.0 times,
1.2 times, 1.4 times, 1.5 times, 1.7 times, 1.8 times or 2.0 times.If it should be pointed out that being related to mixture, molar concentration is calculated
When calculated according to total mol concentration.
Preferably, the volume of the organic solvent of step (1) fatty race's straight chain primary amine is the water of the oxygen-containing acid group containing vanadium
0.5~2.0 times of the volume of solution, for example, 0.5 times, 0.7 times, 0.8 times, 1.0 times, 1.3 times, 1.5 times, 1.6 times, 1.8 times
Or 2.0 times etc..In the present invention, the volume ratio of the organic solvent of fatty race's straight chain primary amine and the aqueous solution of the oxygen-containing acid group containing vanadium is again
Referred to as " compare ".
In the present invention, in step (1) reaction generally carry out at normal temperatures, i.e., 10 DEG C~35 DEG C, for example, 10 DEG C, 15 DEG C,
17 DEG C, 20 DEG C, 25 DEG C, 27 DEG C, 30 DEG C, 32 DEG C or 35 DEG C etc..Under normal conditions, without specially adding and subtracting temperature, if extreme
Under the conditions of, then it should maintain the temperature in 10 DEG C~35 DEG C.
As the optimal technical scheme of the method for the invention, step (1) is：Step (1) is：Optional adjust contains containing vanadium
The pH value of water solution of oxygen acid group between 2~4, then the solution of the oxygen-containing acid group containing vanadium by pH value between 2~4 with it is fatty
The organic solvent of race's straight chain primary amine is put into the same container, is reacted under conditions of earthquake or stirring.
Preferably, the device used that shakes is oscillator.
Preferably, any one in the stirring including but not limited to magneton stirring or stirring paddle stirring or two kinds of group
It closes.
Preferably, it is described concussion or stirring time be 5min~5h, for example, 5min, 10min, 15min, 30min,
45min, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 5h etc., preferably 30min~2h.
In the present invention, according to liquor capacity, mixing speed, mixing time also can be adjusted accordingly.
In the present invention, according to liquor capacity, agitating mode, mixing speed, mixing time also can adjust accordingly.
In the present invention, the separation described to step (2) is not construed as limiting by the way of, as long as can reach water phase and organic phase point
From purpose, typical but non-limiting mode has：Separatory funnel detaches, and supernatant liquor separation etc. is poured out with beaker.
As the optimal technical scheme of the method for the invention, step (2) is：Mixing after the completion of step (1) is reacted
Solution left standstill detaches water phase and organic phase in mixed solution.
Preferably, the time of the standing be 5min~5h, for example, 5min, 10min, 15min, 30min, 45min,
1h, 1.5h, 1.7h, 2h, 2.2h, 2.5h, 3h, 3.5h, 3.7h, 4h or 5h etc., preferably 30min~2h.According to liquor capacity,
Split-phase speed etc., time of repose can be slightly different, as long as can achieve the purpose that split-phase, those skilled in the art can be according to need
It is adjusted.
In the present invention, the separation of solid and liquid described to step (3) is not construed as limiting by the way of, as long as can reach separation of solid and liquid
Purpose, typical but non-limiting mode have：Filtering or centrifugation etc..
As the optimal technical scheme of the method for the invention, the method further includes after separation of solid and liquid, to separation
Obtained solid is washed and is dried.
In the present invention, the solvent used in washing process is not construed as limiting, as long as can reach claimed below：Solid network
It closes object not dissolving in the solvent, and impurity dissolves in the solvent, typical but non-limiting solvent has：Ethyl alcohol or water etc..
Preferably, described wash is：It is first washed with water, then is washed with ethyl alcohol.
Preferably, the number of washing includes but not limited to that 2 times, 3 times or 4 are inferior.
In the present invention, dry mode is not construed as limiting, including but not limited to air drying, vacuum drying or high temperature are dry
It is dry.
Preferably, if the mode of the drying is vacuum drying or high temperature drying, drying temperature is 20~80 DEG C, such as 20
DEG C, 30 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C etc..
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) pH value of water solution of the oxygen-containing acid group containing vanadium is optionally adjusted between 2~4, then by pH value between 2~4
The solution of the oxygen-containing acid group containing vanadium and the organic solvent of fatty race's straight chain primary amine be put into the same container, earthquake or stirring
Under conditions of react 30min~2h；
(2) by step (1) react after the completion of mixed solution stand 30min~2h, detach mixed solution in water phase and
Organic phase；
(3) organic phase is separated by solid-liquid separation, isolated solid is washed and dried, obtain solid complexing
Object.
Second aspect, the present invention provide the solid complex that method is prepared as described in relation to the first aspect.
The third aspect, the present invention provide the solid complex or second aspect that method as described in relation to the first aspect is prepared
The solid complex prepares the purposes of battery active material as presoma.
In the present invention, the battery active material can be the battery active material of doping, can also be undoped electricity
Pond active material.
It is excellent to not making typical case as the method that presoma prepares battery active material using solid complex in the present invention
The method of choosing has method one and method two, specifically,
Method one is：By the precursor mixed solution containing solid complex, directly as in water heating kettle；Then, constant temperature
100 DEG C~200 DEG C heating 10h~5 day, obtain battery anode active material.
In method one, the solid described in second aspect may be used in the precursor mixed solution containing solid complex
Complex compound is obtained with solvent mixed preparing, directly can also contain solid using what first aspect the method step (2) obtained
The organic phase of complex compound.
Method two is：Solid complex keeps in nitrogen atmosphere to 600 DEG C of calcining 1h~2h, 5 DEG C of heating rate/
Min obtains battery anode active material.
Preferably, the method further includes being doped to live with the anode for preparing doping to battery anode active material
The step of property material, specially：Then battery anode active material and doped source mixing, ball milling 1h~2h are heated in air
To 600 DEG C~900 DEG C, 5h~10h, the battery anode active material adulterated are kept；
Preferably, the doped source include the combination containing any one in Ni, Co or Mn or at least two salt and/
Or oxide, preferably any one in nickel oxide, manganese oxide or cobalt oxide or at least two combination.
The present invention also provides the methods for preparing anode using battery anode active material, specially：Anode is lived
Property substance, carbon black and polyvinylidene fluoride (polyvinylidene difluoride, PVDF) mixing, prepare anode sizing agent, and
Anode is prepared using traditional handicraft.
Preferably, it is the electricity in terms of 100% by the gross mass of battery positive electrode active material, carbon black and polyvinylidene fluoride
The mass percentage of pond positive active material is 70%~80%, and the mass percentage of carbon black is 10%~20%, is gathered inclined
The mass percentage of difluoroethylene is 10%.
Fourth aspect, the present invention provide a kind of catalyst, and the catalyst is prepared comprising first aspect the method
Solid complex or second aspect described in solid complex；
Preferably, the solid complex is used for the organic matter in photocatalytic degradation aqueous solution as catalyst.
Preferably, the solid complex and catalyst carrier, which combine, forms composite catalyst for photocatalysis.
Preferably, the preparation method of the composite catalyst is：Solid complex and catalyst carrier are mixed, then existed
300 DEG C~600 DEG C calcining 0.5h~3h are kept in air or nitrogen atmosphere, obtain composite catalyst.
Preferably, the catalyst carrier includes the combination of any one or two kinds in graphene or carbon nanotube.
The present invention also provides the processes for using the catalyst of the present invention to be used for photochemical catalyst：Catalyst is put into band degradation
In the aqueous solution of substance, illumination, light wave is a length of ultraviolet to visible light region, and the optional ozone that is added assists, then the pH of solution
6~8 are adjusted to, 30min~3h is reacted, specific catalyst amount and reaction time determine according to catalyst content and pollutant concentration
It is fixed.
Compared with the prior art, the present invention has the advantages that：
(1) this patent is conceived to directly recycles high vanadium concentrations material from waste water using shorter flow, can directly from
Recycling vanadium metal and secondary use is carried out in the aqueous solution of the oxygen-containing acid group containing vanadium, vanadium-containing water or leachate, is applied in work(
In energy material, the manufacturing cost of functional material is reduced, there is application prospect well.
(2) this method is by adjusting the pH values of the aqueous solution of the oxygen-containing acid group containing vanadium, the waste water of water containing vanadium or leachate 2~4
Between, and it is (arbitrary in isopropylamine, n-octyl amine, lauryl amine, cetylamine or octadecylamine with particular kind of acyclic straight primary amine
It is a kind of or at least two mixture) occur hydrogen bond complex reaction, solid can be directly generated, only need filtration washing drying
Required solid material, i.e. solid complex are obtained, flow is short, and method is easy, is swift in response and safe.
(3) solid complex of the invention can be used as presoma and be used to prepare battery active material, and can further be made
Containing vanadium cell；Moreover, the solid complex of the present invention can also be directly as catalyst, or it is compounded to form with catalyst carrier compound
Catalyst is used for photochemical catalyst field, greatly reduces the cost containing vanadium battery material and catalyst, at the same to secondary resource into
It has gone high-valued reasonable application, has had a extensive future.
Description of the drawings
Fig. 1 is the photo of 1 obtained solid sample of embodiment；
Fig. 2 is the stereoscan photograph of 1 obtained solid sample of embodiment；
Fig. 3 is the infrared spectrogram of 1 obtained solid sample of embodiment；
Fig. 4 is the Raman spectrogram of 1 obtained solid sample of embodiment；
Fig. 5 is the thermal gravimetric analysis results of 1 obtained solid sample of embodiment；
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
A method of from battery material presoma is prepared in aqueous solution containing vanadium, include the following steps：
(1) 0.02mol/L NaVO are prepared3Sulfuric acid tune pH to 2.0 is added in aqueous solution 50mL；Match 0.02mol/L 18 again
Amine aqueous solution 50mL (solvent is toluene).
(2) above-mentioned two solution is poured into 200mL beakers, 30min is stirred with magneton under room temperature；
(3) the solution left standstill 30min after the completion of reacting step (2), is then demultiplex out organic phase.
(4) organic phase is filtered, is washed 3 times with ethyl alcohol, be washed with water and wash 3 times, then washed 1 time with ethyl alcohol, then by sample
Product obtain solid sample, i.e. solid complex as being dried in 60 DEG C of a conventional ovens.
Battery anode active material is prepared as presoma using the solid complex, detailed process is：
By organic phase that step (3) is isolated directly as a small amount of hydrogenperoxide steam generator in water heating kettle, is added, constant temperature is kept
100 DEG C are heated 3 days, are then taken out, are obtained battery anode active material.
Anode is prepared using the battery anode active material, and is further assembled into containing vanadium cell, detailed process is：
By 70% battery anode active material of mass fraction, 20% carbon black and 10% polyvinylidene fluoride (PVDF) are together
Mixing prepares anode；It is further assembled into containing vanadium cell using the anode.
The solid complex and catalyst carrier obtained using step (4) prepares composite catalyst for photocatalysis, specifically
Process is：Composite catalyst is put into the aqueous solution with degradation material, illumination, light wave is a length of ultraviolet to visible light region, adds
Enter ozone auxiliary, then the pH of solution is adjusted to 6~8, reacts 30min~3h, specific catalyst amount and reaction time according to urging
Agent content and pollutant concentration determine.
Characterization：
As shown in Figure 1, as seen from the figure, which is insoluble in appointing for the photo of the present embodiment obtained solid sample
The yellow solid of what solvent.
The stereoscan photograph of the present embodiment obtained solid sample is as shown in Fig. 2, as seen from the figure, microscopic appearance is
Solid layer structure.
The infrared spectrum of the present embodiment obtained solid sample is as shown in figure 3, as seen from the figure, which contains
The functional groups such as V=O, V-O, C-C.
The Raman spectrum of the present embodiment obtained solid sample is as shown in figure 4, as seen from the figure, which contains
The functional groups such as V=O, V-O, C-C.
The thermal gravimetric analysis results of the present embodiment obtained solid sample are as shown in figure 5, as seen from the figure, in air range
The solid masses loss for having 76% has 78.46% solid masses loss within the scope of nitrogen, and vanadium is reduced within the scope of nitrogen
For lower valency, therefore remaining quality is relatively low.
Embodiment 2
A method of from battery material presoma is prepared in aqueous solution containing vanadium, include the following steps：
(1) the practical vanadic acid leachate of use, pH=4, containing vanadium 15g/L, chromium 3g/L and other a small amount of impurity；Again
With 0.2mol/L octadecylamines solution (solvent is kerosene).
(2) 100mL water phases (i.e. practical vanadic acid leachate), 200mL organic phases (i.e. octadecylamine solution) is taken to pour into 500mL
In separatory funnel, puts and keep 25 DEG C of concussion 30min in an oscillator；
(3) the solution left standstill 30min after the completion of reacting step (2), is then demultiplex out organic phase.
(4) organic phase is filtered, is washed 3 times with ethyl alcohol, be washed with water and wash 3 times, then washed 1 time with ethyl alcohol, then by sample
Product are dried as in 60 DEG C of a conventional ovens to get to final solid product, i.e. solid complex.
The solid complex obtained using step (4) prepares battery anode active material as presoma, and detailed process is：
By the solid complex that step (4) obtains kept in nitrogen atmosphere 600 DEG C calcining 1~2h, 5 DEG C of heating rate/
Min obtains battery active material；Then, which is mixed, ball milling 2h with nickel oxide, then heated in air
To 800 DEG C, 6h, the battery anode active material adulterated are kept.
Anode is prepared using the battery anode active material, and is further assembled into containing vanadium cell, detailed process is：
By 80% battery anode active material of mass fraction, 10% carbon black and 10% polyvinylidene fluoride (PVDF) are together
Mixing prepares anode；It is further assembled into containing vanadium cell using the anode.
Photocatalysis is used for as catalyst using the solid complex that step (4) obtains, detailed process is：By step (4)
Obtained solid complex is put into the aqueous solution with degradation material, illumination directly as catalyst, and light wave is a length of ultraviolet extremely may be used
Ozone auxiliary is added in light-exposed region, and then the pH of solution is adjusted to 6~8, reacts 30min~3h, specific catalyst amount and reaction
Time determines according to catalyst content and pollutant concentration.
Embodiment 3
Except by 0.02mol/L NaVO3Aqueous solution replaces with 0.04mol/L KVO3Aqueous solution, and octadecylamine replaces with 12
Outside amine, other preparation methods and condition are same as Example 1.
The solid complex containing vanadium can equally be prepared through this embodiment, can be prepared containing vanadium electricity using the complex compound
Composite catalyst can also be prepared for photocatalysis directly as catalyst or using it in pond.
Embodiment 4
Except by 0.02mol/L NaVO3Aqueous solution replaces with 0.01mol/L NaVO3Outside aqueous solution, other preparation methods and
Condition is same as Example 1.
The solid complex containing vanadium can equally be prepared through this embodiment, can be prepared containing vanadium electricity using the complex compound
Composite catalyst can also be prepared for photocatalysis directly as catalyst or using it in pond.
Embodiment 5
Except sulfuric acid tune pH to 2.0 is replaced with hydrochloric acid tune pH to 3.0, and octadecylamine replaces with outside isopropylamine, other preparations
Method and condition is same as Example 1.
The solid complex containing vanadium can equally be prepared through this embodiment, can be prepared containing vanadium electricity using the complex compound
Composite catalyst can also be prepared for photocatalysis directly as catalyst or using it in pond.
Embodiment 6
In addition to the mixture that octadecylamine is replaced with n-octyl amine and cetylamine, other preparation methods and condition and embodiment 2
It is identical.
The solid complex containing vanadium can equally be prepared through this embodiment, can be prepared containing vanadium electricity using the complex compound
Composite catalyst can also be prepared for photocatalysis directly as catalyst or using it in pond.
Embodiment 7
Except the volume of water phase (i.e. practical vanadic acid leachate) is adjusted to 200mL, and time of repose is adjusted to outside 2h,
His preparation method and condition are same as Example 2.
The solid complex containing vanadium can equally be prepared through this embodiment, can be prepared containing vanadium electricity using the complex compound
Composite catalyst can also be prepared for photocatalysis directly as catalyst or using it in pond.
Comparative example 1
In addition to pH is adjusted to 9, other preparation methods and condition are same as Example 1.
At a high ph, which can not carry out, and also be unable to get the complexing product.
Comparative example 2
In addition to pH is adjusted to 6, other preparation methods and condition are same as Example 1.
A small amount of complex product is generated after then filtering.
Comparative example 3
In addition to pH is adjusted to 1, other preparation methods and condition are same as Example 1.
This method can equally meet requirement of experiment, but the acid amount consumed during adjusting pH is excessive, wastes raw material.
Comparative example 4
In addition to octadecylamine is replaced with N1923, other preparation methods and condition are same as Example 1.
The complex compound then generated can preferably be dissolved in organic solvent, can not product only be complexed by solid is obtained by filtration.
Comparative example 5
In addition to octadecylamine is replaced with JMT, other preparation methods and condition are same as Example 1.
The complex compound then generated can preferably be dissolved in organic solvent, can not product only be complexed by solid is obtained by filtration.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of method for extracting solid complex from the aqueous solution of the oxygen-containing acid group containing vanadium, which is characterized in that the method packet
Include following steps：
(1) optionally adjust the oxygen-containing acid group containing vanadium pH value of water solution between 2~4, then with fatty race's straight chain primary amine
Organic solvent mixes, reaction, generates complexing product；
(2) by step (1) react after the completion of mixed solution in water phase and organic phase separation；
(3) organic phase is separated by solid-liquid separation, obtains solid complex；
The acyclic straight primary amine is：In isopropylamine, n-octyl amine, lauryl amine, cetylamine or octadecylamine any one or extremely
Few two kinds of mixture.
2. according to the method described in claim 1, it is characterized in that, the aqueous solution of the oxygen-containing acid group containing vanadium described in step (1) includes
Prepare simulated solution or industrial actual waste water or leachate in laboratory；
Preferably, the anion in the aqueous solution of the oxygen-containing acid group containing vanadium described in step (1) only has the oxygen-containing acid group of vanadium；
Preferably, the oxygen-containing acid group of the existing vanadium of anion in the aqueous solution of the oxygen-containing acid group containing vanadium described in step (1) contains it again
His anion, other described anion are preferably chromate and/or the oxygen-containing acid group of other transition metal；
Preferably, also contain impurity in the aqueous solution of the oxygen-containing acid group containing vanadium described in step (1)；
Preferably, the reagent that step (1) the aqueous solution pH for adjusting the oxygen-containing acid group containing vanadium is used is acid or alkali, the acid include
Any one or a few mixture in hydrochloric acid, acetic acid or sulfuric acid.
3. method according to claim 1 or 2, which is characterized in that step (1) fatty race's straight chain primary amine it is organic
In solvent, solvent is the weakly polar organic solvent of energy dissolved fat race straight chain primary amine, is preferably included in toluene, n-hexane or kerosene
Any one or a few mixture；
Preferably, the acyclic straight primary amine is the mixture of pure material or several acyclic straight primary amine；
Preferably, the solvent is the mixture of pure material or several solvents；
Preferably, in the organic solvent of step (1) fatty race's straight chain primary amine, the molar concentration of acyclic straight primary amine is
0.5~2.0 times of the molar concentration of V in the aqueous solution of the oxygen-containing acid group containing vanadium；
Preferably, the volume of the organic solvent of step (1) fatty race's straight chain primary amine is the aqueous solution of the oxygen-containing acid group containing vanadium
0.5~2.0 times of volume；
Preferably, the temperature of step (1) described reaction be room temperature, i.e., 10 DEG C~35 DEG C.
4. according to claim 1-3 any one of them methods, which is characterized in that step (1) is：Optional adjusting is oxygen-containing containing vanadium
The pH value of water solution of acid group is between 2~4, the then solution of the oxygen-containing acid group containing vanadium by pH value between 2~4 and fatty race
The organic solvent of straight chain primary amine is put into the same container, is reacted under conditions of earthquake or stirring；
Preferably, the device used that shakes is oscillator；
Preferably, the stirring includes that magneton stirs or stir any one in paddle stirring；
Preferably, the time of the concussion or stirring is 5min~5h, preferably 30min~2h.
5. according to claim 1-4 any one of them methods, which is characterized in that step (2) is：Step (1) is reacted and is completed
Mixed solution afterwards is stood, and detaches water phase and organic phase in mixed solution；
Preferably, the time of the standing is 5min~5h, preferably 5min~2h；
Preferably, step (2) separation includes separatory funnel separation by the way of, is poured out with beaker in supernatant liquor separation
Any one；
Preferably, step (3) separation of solid and liquid includes any one in filtering or centrifuging by the way of.
6. according to claim 1-5 any one of them methods, which is characterized in that the method further includes in separation of solid and liquid
Afterwards, isolated solid is washed and is dried；
Preferably, the solvent used in the washing process includes the mixture of any one or two kinds in ethyl alcohol or water；
Preferably, described wash is：It is first washed with water, then is washed with ethyl alcohol.
7. according to claim 1-6 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) pH value of water solution of the oxygen-containing acid group containing vanadium is optionally adjusted between 2~4, then the containing between 2~4 by pH value
The solution of the oxygen-containing acid group of vanadium and the organic solvent of fatty race's straight chain primary amine are put into the same container, the item of earthquake or stirring
30min~2h is reacted under part；
(2) mixed solution after the completion of reacting step (1) stands 30min~2h, detaches the water phase and organic in mixed solution
Phase；
(3) organic phase is separated by solid-liquid separation, isolated solid is washed and dried, solid complex is obtained.
8. the solid complex being prepared such as any one of claim 1-7 the methods, which is characterized in that the solid complexing
Object is made of vanadic acid and organic matter complexing.
9. such as the use of any one of claim 1-7 solid complexes or solid complex according to any one of claims 8 being prepared
On the way, which is characterized in that the solid complex prepares battery active material as presoma；
Preferably, battery active material is prepared via a method which to obtain：By the precursor mixed solution containing solid complex,
Directly as in water heating kettle；Then, 100~200 DEG C of heating 10h~5 day of constant temperature, obtain battery anode active material；
Preferably, battery active material is prepared via a method which to obtain：Solid complex is kept 600 DEG C in nitrogen atmosphere
1h~2h is calcined, 5 DEG C/min of heating rate obtains battery anode active material；
Preferably, the method further includes being doped battery anode active material to prepare the battery positive electrode active material of doping
The step of material, specially：Then battery anode active material and doped source mixing, ball milling 1h~2h are heated to 600 in air
~900 DEG C, keep 5h~10h, the battery anode active material adulterated；
Preferably, the doped source includes the salt and/or oxygen of the combination containing any one in Ni, Co or Mn or at least two
In compound, preferably nickel oxide, manganese oxide or cobalt oxide any one or at least two combination.
10. a kind of catalyst, which is characterized in that the catalyst includes that any one of claim 1-7 the methods are prepared
Solid complex or solid complex according to any one of claims 8；
Preferably, the solid complex is used for photocatalysis as catalyst；
Preferably, the solid complex and catalyst carrier, which combine, forms composite catalyst for photocatalysis；
Preferably, the preparation method of the composite catalyst is：
Solid complex and catalyst carrier are mixed, 300 DEG C~600 DEG C calcinings are then kept in air or nitrogen atmosphere
0.5h~3h obtains composite catalyst；
Preferably, the catalyst carrier includes the combination of any one or two kinds in graphene or carbon nanotube.
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| CN111668031A (en) * | 2019-03-05 | 2020-09-15 | 中国科学院过程工程研究所 | Vanadium nitride-pore carbon nano composite material and preparation method and application thereof |
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