CN106256425B - A kind of quaternary composite material and its preparation method and application - Google Patents
A kind of quaternary composite material and its preparation method and application Download PDFInfo
- Publication number
- CN106256425B CN106256425B CN201610598767.8A CN201610598767A CN106256425B CN 106256425 B CN106256425 B CN 106256425B CN 201610598767 A CN201610598767 A CN 201610598767A CN 106256425 B CN106256425 B CN 106256425B
- Authority
- CN
- China
- Prior art keywords
- composite material
- iii
- quaternary composite
- nitric acid
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011219 quaternary composite Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 33
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- -1 metals ion Chemical class 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 238000005272 metallurgy Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 150000003983 crown ethers Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017504 Nd(NO3)3 Inorganic materials 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a kind of quaternary composite materials and its preparation method and application, wherein quaternary composite material, using low pole macroreticular resin as carrier, load simultaneously such as structural formula I compound represented I, such as II compound represented II of structural formula and such as III compound represented III of structural formula on carrier.The mass loadings such as chemical compounds I, compound ii and compound III are on carrier.The mass ratio of chemical compounds I and carrier is 1:8‑10.The carrier is ion exchange resin XAD 7.Quaternary composite material adsorption capacity provided by the invention is strong, and selectivity is good, and preparation method is simple and practicable, is recycled after being detached cobalt and nickel with elemental iron metallurgy industry separation industry.
Description
Technical field
The present invention relates to element sepatation technical fields, and in particular to a kind of quaternary composite material and preparation method thereof and should
With.
Background technology
Cobalt, nickel are valuable non-ferrous metals, are had extensively in high-tech areas such as national defence, space flight, atomic energy, chemical industry, electronics
General purposes.Cobalt nickel raw material further includes largely discarded teleoseal, the machine such as scrapped, waste and old electricity in addition to host mineral
Pond, spent catalyst, useless function alloy, melting waste slag etc..Contain a large amount of valuable metal nickel and cobalt in discarded teleoseal,
Processing recycling is carried out to it to be conducive to resource and recycle, and is of great significance to social sustainable development.
The main source of discarded teleoseal is useless kovar alloy electronic component, useless high magnetic permeability alloy steel and waste nickel catalyst
Deng common process flow mainly includes the following steps that：1) acidic leaching of valuable metal, 2) precipitation of infusion solution is removed
Iron, 3) purified cobalt nickel solution extraction and separation, 4) back extraction, precipitation respectively obtain cobalt nickel compound, 5) further calcining, hydrogen
Reduction obtains cobalt powder, nickel powder, and the committed step of the process flow is except iron and cobalt nickel detach.
In metallurgy industry separation industry, other metallic elements by cobalt nickel and iron etc. is needed to detach, in the prior art,
Still lack the technological means of simple possible.
Invention content
The present invention provides a kind of quaternary composite material and its preparation method and application, quaternary composite material adsorption capacities
By force, selectivity is good, and preparation method is simple and practicable, is divided cobalt and nickel with elemental iron suitable for metallurgy industry separation industry
From rear recycling.
A kind of quaternary composite material, using low pole macroreticular resin as carrier, load simultaneously is as shown in structural formula I on carrier
Chemical compounds I, such as II compound represented II of structural formula and such as III compound represented III of structural formula；
The compound for having the function of specific adsorption by three kinds in the present invention and low pole macroreticular resin are mutually compound, obtain
Quaternary composite material has specific adsorption effect for cobalt and nickel, for from containing alkali metal, alkaline-earth metal, rare earth element with
And in the multielement acidic aqueous solution of Typical transition metal, cobalt and nickel are separated.The further separation of cobalt and nickel can adopt
Use the prior art.
Preferably, the mass loadings such as chemical compounds I, compound ii and compound III are on carrier.
Chemical compounds I (the double pyridine derivates of double triazines), compound ii (the supermolecule knowledge of phase homogenous quantities are loaded on carrier simultaneously
Other reagent cup [4] leaf-comb ether, n-propyl-cup [4] leaf-comb -6, abbreviation BnPCalix [4] MC6) and compound III (2- tertiary butyls -2
Cyclohexyl -18- crown-s 6), it mutually cooperates between three kinds of loaded articles, generates the effect to cobalt and nickel specific adsorption.
The carrier is ion exchange resin XAD-7.Ion exchange resin XAD-7 is as a kind of market-oriented weak pole
Property macroreticular resin material, raw material are easy to get.
Preferably, the mass ratio of chemical compounds I and carrier is 1:8-10.The load capacity and change of compound ii and compound III
It is identical to close object I.
The present invention also provides a kind of preparation methods of the quaternary composite material, include the following steps：
Chemical compounds I, compound ii and compound III are dissolved in dichloromethane, it is equal that carrier mixing is added in acquired solution
It is even, after revolving is dry, obtain quaternary composite material.
The mass ratio of chemical compounds I, compound ii and compound III is 1:1:1, it is dissolved in 450-550mL bis- per g chemical compounds Is
In chloromethanes, during revolving, most of dichloromethane is made to evaporate into closely dry state, under capillarity and physisorption,
Compound molecule enters in the gap of carrier, and then the material of nearly dry state is dried in vacuo at least 24 hours at 50-60 DEG C,
Obtain quaternary composite material.
The present invention also provides a kind of method using the quaternary composite material separation cobalt and nickel, by quaternary composite wood
Material is mixed with the aqueous solution of nitric acid containing various metals ion, and the cobalt ions and nickel ion in aqueous solution of nitric acid are by quaternary composite wood
Expect adsorbing separation, Co (II), Ni (II) and other metal ions are contained in the aqueous solution of nitric acid, other metal ions are Li
(I)、Na(I)、K(I)、Rb(I)、Ca(Ⅱ)、Mg(Ⅱ)、Ba(Ⅱ)、Nd(Ⅲ)、La(Ⅲ)、Ru(Ⅲ)、Yb(Ⅲ)、Y(Ⅲ)、
At least one of Fe (III), Zr (IV).
Preferably, it is mixed per g quaternarys composite material with 20-30mL aqueous solution of nitric acid.Quaternary provided by the invention is compound
Material selectivity is good, and separative efficiency is high, a small amount of to use, and can reach ideal separating effect.
In order to ensure separating effect, it is preferable that quaternary composite material exists with the aqueous solution of nitric acid containing various metals ion
(25 ± 5 DEG C) mixing and absorption at room temperature, adsorption time 120-180min.Mixing and absorption carries out under oscillating condition, oscillation speed
Rate is 120-150rpm.
When carrying out element sepatation, in aqueous solution of nitric acid in the concentration of nitric acid and aqueous solution of nitric acid metal ion concentration
Separating effect can be influenced, it is preferable that in aqueous solution of nitric acid, a concentration of 2-6mol/L of nitric acid.In aqueous solution of nitric acid, each gold
Belong to a concentration of the 5.0 × 10 of ion-4-1.0×10-3M。
Quaternary composite material adsorption capacity provided by the invention is strong, and selectivity is good, and preparation method is simple and practicable, is suitable for
It is recycled after being detached cobalt and nickel with elemental iron in metallurgy industry separation industry.
Description of the drawings
Fig. 1 is the MS-ESI positive spectrums for the target product C8-BTBP that embodiment 1 synthesizes；
Fig. 2 is the target product C8-BTBP's that embodiment 1 synthesizes1H NMR spectras；
Fig. 3 be embodiment 2 prepare quaternary composite material from aqueous solution of nitric acid the distribution coefficient of separating element cobalt and nickel
The relational graph changed with concentration of nitric acid.
Specific embodiment
The synthesis of 1 C8-BTBP of embodiment
The chemical equation of C8-BTBP synthesis is as follows：
It is as follows：
450.0mL anhydrous tetrahydro furans, 5.1g compound 18-diketone of 9,10- are sequentially added in 500mL single-necked flasks
With 10.0mL triethylamines, 2.2g compounds [2,2`]-bipyridyl -6,6`- diformamide hydrazone is added under agitation, in nitrogen
Under protection, 69-72 DEG C be refluxed reaction to solution become clarification (compound [2,2`]-bipyridyl -6,6`- diformamide hydrazone and
18-diketone of compound 9,10- is with molar ratio 1:2.2 are reacted, and diketone is excessive).
After stopping reaction, solid residue is filtered to remove, filtrate obtains crude product, then through anhydrous tetrahydro furan is distilled off
It is ground with anhydrous ether, filters and remove solvent and obtain solid, by the use of petrol ether/ethyl acetate as mobile phase (volume ratio 4:1) into
Row Column chromatography techniques detach and purifying, obtain target compound, 5h is dried in vacuo at 60 DEG C, finally obtain 2.5g golden yellow and consolidate
Body, yield 40.3%.
C8-BTBP characterization of compound
The elemental analysis of a.C8-BTBP, the results are shown in Table 1.
Table 1
| C, % | H, % | N, % | |
| Theoretical value | 75.73 | 9.86 | 14.42 |
| Experiment value | 75.48 | 9.82 | 14.64 |
The molecular formula of C8-BTBP is C48H74N8, measure C, H, N experiment value and match with theoretical value, illustrate the 6,6'- of synthesis
Bis- (5,6- bis--octyl group -1,2,4- triazine -3- bases) -2,2'- bipyridyls
(C8-BTBP) it is the target compound to be synthesized.
B.MS-ESI is analyzed, the result is shown in Figure 1.
The MS-ESI positive spectrums of C8-BTBP are tested, analysis result shows：[M+H+]=763.6, [M-2H++Na+]
=783.0, [M+Na+]=785.5, calculated value m/z are 762.6.The theoretical molecular weight of C8-BTBP be 762.6, this result with
The theoretical value of C8-BTBP molecular weight is consistent.MS-ESI analytic explanations have synthesized target compound.
c.1H NMR are analyzed, and as a result see Fig. 2.
The 1H NMR spectras of the C8-BTBP compounds of synthesis are tested, analysis result shows：(1HNMR(CDCl3,
400MHz):δ=0.8-0.9ppm, m, 4 × CH3,12H；δ=1.2-1.6ppm, m, 20 × CH2,40H；δ=1.8-1.9ppm,
m,4×CH2, 8H；δ=2.9-3.0ppm, t, 4 × CH2,8H；δ=8.1ppm, t, Ar-H, 2H；δ=8.7ppm, d, Ar-H, 2H；
δ=9.0ppm, d, Ar-H, 2H.
δ=7.2ppm is the peak of deuterochloroform in Fig. 2, and unimodal at δ=5.3ppm is proton shape in methylene chloride
Into peak, chemical shift and numbers of hydrogen atoms etc. point out result and are consistent with the structural information of C8-BTBP.
Embodiment 2
The C8-BTBP (structural formula I compound represented) that respectively prepared by 0.2g embodiments 1,0.2g crown ethers (the tertiary fourths of 2-
Base -2- cyclohexyl -18- crown-s 6, i.e. II compound represented of structural formula) and 0.2g glasss of fragrant leaf-comb (n-propyls-cup [4]-mono-
Crown- 6, i.e. III compound represented of structural formula) solid is dissolved in 100.0mL dichloromethane, and fully dissolving obtains faint yellow clear
Clear solution；1.8g ion exchange resin XAD-7 is added in into this faint yellow clear solution to stir evenly, and use rotary evaporation
Instrument, at reduced pressure conditions rotary evaporation dichloromethane is made to evaporate into material to nearly dry state, the then material of nearly dry state again
It is dried in vacuo at 55 DEG C for 24 hours, three kinds of organic functions ligands is supported on ion exchange resin XAD-7, it is compound to obtain quaternary
Material.
Embodiment 3
The C8-BTBP (structural formula I compound represented) that respectively prepared by 0.2g embodiments 1,0.2g crown ethers (the tertiary fourths of 2-
Base -2- cyclohexyl -18- crown-s 6, i.e. II compound represented of structural formula) and 0.2g glasss of fragrant leaf-comb (n-propyls-cup [4]-mono-
Crown- 6, i.e. III compound represented of structural formula) solid is dissolved in 90.0mL dichloromethane, and fully dissolving obtains faint yellow clarification
Solution；1.6g ion exchange resin XAD-7 is added in into this faint yellow clear solution to stir evenly, and use Rotary Evaporators,
Rotary evaporation makes dichloromethane evaporate into material to nearly dry state at reduced pressure conditions, then again the material of nearly dry state 50
It is dried in vacuo at DEG C for 24 hours, three kinds of organic functions ligands is supported on ion exchange resin XAD-7, obtain quaternary composite material.
Embodiment 4
The C8-BTBP (structural formula I compound represented) that respectively prepared by 0.2g embodiments 1,0.2g crown ethers (the tertiary fourths of 2-
Base -2- cyclohexyl -18- crown-s 6, i.e. II compound represented of structural formula) and 0.2g glasss of fragrant leaf-comb (n-propyls-cup [4]-mono-
Crown- 6, i.e. III compound represented of structural formula) solid is dissolved in 110.0mL dichloromethane, and fully dissolving obtains faint yellow clear
Clear solution；2.0g ion exchange resin XAD-7 is added in into this faint yellow clear solution to stir evenly, and use rotary evaporation
Instrument, at reduced pressure conditions rotary evaporation dichloromethane is made to evaporate into material to nearly dry state, the then material of nearly dry state again
It is dried in vacuo at 60 DEG C for 24 hours, three kinds of organic functions ligands is supported on ion exchange resin XAD-7, it is compound to obtain quaternary
Material.
Embodiment 5-11
(1) by alkali nitrates LiNO3、NaNO3、KNO3、RbNO3；Alkaline earth nitrate Mg (NO3)2、Ca(NO3)2、
Ba(NO3)2；The nitrate solution of Ru；Transition metal salt Fe (NO3)3、ZrO(NO3)2、Co(NO3)2、Ni(NO3)2And rare earth gold
Belong to oxide Y2O3, rare-earth metal nitrate La (NO3)3、Yb(NO3)3、Nd(NO3)3It is dissolved in deionized water and is configured to nitric acid
A concentration of 4.0M and the aqueous solution of nitric acid simultaneously containing 16 kinds of metallic elements, 16 contained metal ion species in the aqueous solution of nitric acid
Concentration respectively may be about 2.0 × 10-3-5.0×10-3M。
(2) it adds in concentrated nitric acid in aqueous solution of nitric acid and deionized water is diluted, adjust the nitric acid in aqueous solution of nitric acid
Concentration is respectively 0.4,1.0,2.0,3.0,4.0,5.0,6.0M, a concentration of 5.0 × 10 per metal ion species-4M。
(3) nitric acid aqueous solution of different concentration of nitric acid for obtaining the quaternary composite material that embodiment 2 is prepared from step (2)
Solution is mixed respectively, and amount ratio during mixing is：0.15g quaternary composite materials are corresponded to per 3.0mL aqueous solution of nitric acid.
(4) mixed liquor obtained by step (3) is carried out concussion on TAITECMM-10 type oscillators makes solid liquid phase fully connect
It touches, oscillator oscillation rate is 120rpm, temperature 298K, and for absorption is made to reach balance, duration of oscillation is set as 120min, so
Spectrum (ICP-OES) and atomic absorption spectrum (AA240) occurs to water phase before and after absorption with plasma inductive coupling atom afterwards
The content of middle each element is detected.
For the absorption result of embodiment 5-11 as shown in figure 3, when concentration of nitric acid is 2.0mol/L, the quaternary composite material is same
When adsorbing separation element cobalt and nickel ability it is most strong, distribution coefficient be more than 10000cm3Contained cobalt and nickel are inhaled in/g, i.e. water phase
Attached rate is 100%.At the same time, which is respectively less than the adsorption isothermequation of other 14 kinds of coexisting ions
20cm3/ g, this result shows that the quaternary composite material concentration of nitric acid be more than 2.0M under the conditions of, can efficiently with high selectivity
By cobalt and nickel and other metals, such as iron, alkali metal, alkaline-earth metal, transition metal and rare earth element phase separation, application prospect
It is wide.
Claims (9)
1. a kind of quaternary composite material, which is characterized in that using low pole macroreticular resin as carrier, load such as structure simultaneously on carrier
I compound represented I of formula, such as II compound represented II of structural formula and such as III compound represented III of structural formula；
The mass loadings such as chemical compounds I, compound ii and compound III are on carrier.
2. quaternary composite material as described in claim 1, which is characterized in that the mass ratio of chemical compounds I and carrier is 1:8-10.
3. quaternary composite material as claimed in claim 1 or 2, which is characterized in that the carrier is ion exchange resin XAD-
7。
It is 4. a kind of such as the preparation method of claim 1-3 any one of them quaternary composite materials, which is characterized in that including following
Step：
Chemical compounds I, compound ii and compound III are dissolved in dichloromethane, carrier is added in acquired solution and is uniformly mixed,
After revolving is dry, quaternary composite material is obtained.
5. a kind of method using such as claim 1-3 any one of them quaternarys composite material separation cobalt and nickel, feature exists
In quaternary composite material being mixed with the aqueous solution of nitric acid containing various metals ion, cobalt ions and nickel in aqueous solution of nitric acid
Ion is by quaternary composite material adsorbing separation, containing Co (II), Ni (II) and other metal ions in the aqueous solution of nitric acid,
His metal ion is Li (I), Na (I), K (I), Rb (I), Ca (II), Mg (II), Ba (II), Nd (III), La (III), Ru (III),
At least one of Yb (III), Y (III), Fe (III), Zr (IV).
6. the method for quaternary composite material separation cobalt and nickel is utilized as claimed in claim 5, which is characterized in that answered per g quaternarys
Condensation material is mixed with 20-30mL aqueous solution of nitric acid.
7. the method for quaternary composite material separation cobalt and nickel is utilized as claimed in claim 5, which is characterized in that quaternary composite wood
Material and the mixing and absorption at room temperature of the aqueous solution of nitric acid containing various metals ion, adsorption time 120-180min.
8. the method for quaternary composite material separation cobalt and nickel is utilized as claimed in claim 5, which is characterized in that aqueous solution of nitric acid
In, a concentration of 2-6mol/L of nitric acid.
9. the method for quaternary composite material separation cobalt and nickel is utilized as claimed in claim 5, which is characterized in that aqueous solution of nitric acid
In, a concentration of 5.0 × 10 per metal ion species-4-1.0×10-3M。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610598767.8A CN106256425B (en) | 2016-07-25 | 2016-07-25 | A kind of quaternary composite material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610598767.8A CN106256425B (en) | 2016-07-25 | 2016-07-25 | A kind of quaternary composite material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106256425A CN106256425A (en) | 2016-12-28 |
| CN106256425B true CN106256425B (en) | 2018-06-19 |
Family
ID=57713708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610598767.8A Expired - Fee Related CN106256425B (en) | 2016-07-25 | 2016-07-25 | A kind of quaternary composite material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106256425B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101093735A (en) * | 2007-04-11 | 2007-12-26 | 浙江大学 | Adsorbent in use for separating heating element Cs, preparation and application |
| US9068247B2 (en) * | 2012-05-01 | 2015-06-30 | Dow Global Technologies Llc | Nickel and cobalt recovery using continuous ion exchange |
-
2016
- 2016-07-25 CN CN201610598767.8A patent/CN106256425B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101093735A (en) * | 2007-04-11 | 2007-12-26 | 浙江大学 | Adsorbent in use for separating heating element Cs, preparation and application |
| US9068247B2 (en) * | 2012-05-01 | 2015-06-30 | Dow Global Technologies Llc | Nickel and cobalt recovery using continuous ion exchange |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106256425A (en) | 2016-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105734288B (en) | The phosphine extractant of neutrality containing amino is used for the purposes and method of extraction separation of quadravalence cerium | |
| Ohto et al. | Specific extraction behavior of amide derivative of calix [4] arene for silver (I) and gold (III) ions from highly acidic chloride media | |
| Chang et al. | Study on separation of rare earth elements in complex system | |
| CN103451433B (en) | A kind of method extracting precious metal from spent noble metals bearing catalysts | |
| CN1827592B (en) | Process for producing cyclohexanone oxime | |
| CN105734289B (en) | The neutral phosphine extractant containing amino is used for the purposes and method of extract and separate thorium | |
| CN105017225B (en) | Triazinyldipyridyl derivative as well as synthetic method and application thereof | |
| CN106399686A (en) | Acidic ionic liquid and method for separating and purifying rare earth or rare and precious metals by solvent extraction coupling electrolytic process | |
| CN100363134C (en) | Method for preparing nano nickel powder by precipitation-hydrogen reduction process | |
| CN105695748B (en) | A kind of method using phenodiazine acid amides hydrazone pyridine derivate adsorbing separation palladium | |
| CN105734287B (en) | A kind of method of separation of quadravalence cerium, thorium and rare earth | |
| CN106140112B (en) | It is a kind of from acidic aqueous solution simultaneously separate palladium caesium strontium method | |
| CN103131859A (en) | Comprehensive recycling method for metals in superalloy scrap | |
| CN106256425B (en) | A kind of quaternary composite material and its preparation method and application | |
| CN102140089B (en) | Thiacalix [8] arene diethyl acetamide as well as synthesis method and application thereof | |
| CN110184463A (en) | Method that is a kind of while extracting golden simple substance and the second metal simple-substance | |
| CN101492433B (en) | Green synthesis of 2-methylte-trahydrofuran | |
| CN105753861B (en) | Phenanthroline derivative, and preparation method and application thereof | |
| Chen et al. | A green separation process of Ag via a Ti 4 (embonate) 6 cage | |
| CN111961849B (en) | Method for extracting and separating scandium | |
| CN113564389A (en) | Method for recovering rhenium from molybdenum smelting waste acid by using secondary amine impregnated resin | |
| CN109651240A (en) | The method of organic ligand H2dtp and metal-organic framework materials and their preparation method and application, Separation of Thorium and rare earth | |
| CN105566292A (en) | Multi-nitrogen heterocyclic picolinamide derivative and synthetic method and application thereof | |
| CN102502777A (en) | Method for preparing silver nitrate with various types of silver-ion-containing waste water as raw materials | |
| El Hussaini | Extraction of niobium from sulfate leach liquor of Egyptian ore sample by triazoloquinazolinone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180619 |