CN117904434A - Palladium ion extractant material and preparation method thereof - Google Patents
Palladium ion extractant material and preparation method thereof Download PDFInfo
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- CN117904434A CN117904434A CN202311633496.1A CN202311633496A CN117904434A CN 117904434 A CN117904434 A CN 117904434A CN 202311633496 A CN202311633496 A CN 202311633496A CN 117904434 A CN117904434 A CN 117904434A
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- 239000000463 material Substances 0.000 title claims abstract description 19
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000605 extraction Methods 0.000 claims abstract description 45
- 239000012074 organic phase Substances 0.000 claims abstract description 40
- PIECBEFKHBWXIQ-UHFFFAOYSA-N oxadiazole;pyridine Chemical compound C1=CON=N1.C1=CC=NC=C1 PIECBEFKHBWXIQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003446 ligand Substances 0.000 claims abstract description 36
- 239000012071 phase Substances 0.000 claims abstract description 35
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 21
- 239000008346 aqueous phase Substances 0.000 claims abstract description 20
- HZTPKMIMXLTOSK-UHFFFAOYSA-N 2-bromohexanoic acid Chemical compound CCCCC(Br)C(O)=O HZTPKMIMXLTOSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- WHNAMGUAXHGCHH-UHFFFAOYSA-N 1-nitro-3-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC(C(F)(F)F)=C1 WHNAMGUAXHGCHH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 239000000284 extract Substances 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 14
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000003818 flash chromatography Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
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- 230000000536 complexating effect Effects 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002927 high level radioactive waste Substances 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000013110 organic ligand Substances 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000010983 kinetics study Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
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- 229930003231 vitamin Natural products 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Pyridine Compounds (AREA)
Abstract
The invention provides a palladium ion extractant material and a preparation method thereof, wherein pyridine-oxa-diazole ligand is used as an extractant, most Pd 2+ in a water phase can be extracted into an organic phase in a short time, and the extraction rate is extremely high; the selective extraction and separation of Pd 2+ under the acidic condition can be realized, the acidity application range is wide, and the extraction capacity is excellent in the range of 0.2-4M of nitric acid concentration; the extractant has excellent selectivity to Pd 2+ for an aqueous phase containing various metal ions; the pyridine-oxa-diazole extractant has good application prospect in separating and recovering Pd 2+ in high-level radioactive waste liquid; the m-nitrobenzotrifluoride is used as the diluent of the extraction system, has good dissolving capacity for organic ligands and extracts, and the 2-bromohexanoic acid can increase the lipophilicity of the extracts.
Description
Technical Field
The invention relates to the technical field of extractants, in particular to a palladium ion extractant material and a preparation method thereof.
Background
As a noble metal, the metal palladium has the characteristics of corrosion resistance, high temperature resistance, strong ductility and the like, and therefore, the metal palladium has wide application in the fields of medical appliances, pharmaceutical engineering, fuel cells, jewelry, automobile catalytic converters and the like.
On the other hand, pd 2+ has a tendency to coordinate with certain proteins, vitamins and DNA, thereby destroying some cellular structures. Besides being influenced by medicines and medical products polluted by trace Pd 2+, the waste containing Pd 2+ is extremely easy to pollute organisms and environment, causes potential harm and forms serious threat to human health. The high-level waste liquid generated in the spent fuel post-treatment process contains a large amount of palladium, and the recovery of palladium from the high-level waste liquid can not only greatly relieve the problem of palladium resource shortage in China, but also avoid the formation of independent phases in the nuclear waste liquid vitrification process, thereby reducing the risk of radioactive pollution.
Various techniques have been used for the recovery of fission-generated palladium from radioactive solutions in the past decades, among which liquid-liquid extraction is currently the most widely used separation method for treating high-level waste solutions due to its advantages of high efficiency, low cost, easy operation, etc. The high level waste liquid system is extremely complex and has strong radiation and strong acidity, which brings serious challenges to the structural stability and selectivity of the extractant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a palladium ion extractant material and a preparation method thereof.
The technical scheme of the invention is as follows: the palladium ion extractant material is pyridine-oxa-diazole ligand, and the pyridine-oxa-diazole ligand is used as the extractant for high-selectivity complexation Pd 2+, and has the structural formula:
wherein R is a C4-C8 hydrocarbon group.
As a pre-selection, the structural formula of R in the structural formula of the pyridine-oxadiazole ligand is classified into one of the following:
preferably, the invention also provides a preparation method of the palladium ion extractant material, which comprises the following steps:
S1) Synthesis of 2-amino-oxime-6-cyano-4-alkoxypyridine
S11), adding 4-alkoxypyridine-2, 6-dicarboxylic acid methyl ester into a methanol solution, then dropwise adding NH 4 OH, and vigorously stirring the obtained mixture at room temperature for 24 hours; the white precipitate formed was filtered and washed with ice-cooled water and dried under vacuum to give 4-alkoxypyridine-2, 6-dicarboxamide as a white solid;
S12), adding 4-alkoxypyridine-2, 6-dicarboxamide into anhydrous dichloromethane under nitrogen atmosphere, then adding pyridine into the suspension, and slowly adding trifluoroacetic anhydride; stirring at room temperature for 18 hours, then adding water to the resulting mixture; the organic phase was collected and the aqueous phase was extracted with dichloromethane; the combined organic phases were dried over anhydrous Na 2SO4 and concentrated under reduced pressure;
The residue was purified by flash chromatography on silica gel to give 2, 6-dicyano-4-alkoxypyridine as a white oil;
S13), adding a 50% by weight aqueous hydroxylamine solution to an ethanol solution of 2, 6-dicyano-4-alkoxypyridine; the solution was then stirred at room temperature for 24 hours; evaporating the solvent under vacuum, and purifying the product on silica gel to obtain 2-amino oxime-6-cyano-4-alkoxypyridine;
s2), synthesizing 4-alkoxypyridine-2, 6-diformyl chloride intermediate
Oxalyl chloride is added to a solution of 4-alkoxypyridine-2, 6-dicarboxylic acid in anhydrous dichloromethane and stirred for 1 hour, and the solvent is evaporated under vacuum to give a 4-alkoxypyridine-2, 6-dicarboxylic acid chloride intermediate;
s3) reacting the 2-amino oxime-6-cyano-4-alkoxypyridine prepared in step S1) with the 4-alkoxypyridine-2, 6-dicarboxylic acid dichloride intermediate prepared in step S2) to obtain intermediate compound T1:
Wherein R is a C4-C8 hydrocarbon group;
S4), reacting the intermediate compound T1 with tetrabutylammonium fluoride to obtain a pyridine-oxadiazole ligand T2:
wherein R is a C4-C8 hydrocarbon group.
Preferably, in step S3), the synthesis of the intermediate compound T1 is specifically:
Adding a 4-alkoxypyridine-2, 6-dicarboxylic acid dichloride intermediate solution containing methylene chloride to an anhydrous methylene chloride solution containing 2-amino oxime-6-cyano-4-alkoxypyridine and diisopropylethylamine;
After stirring the resulting solution for 5 hours, the solvent was removed under vacuum; the residue was dissolved in dichloromethane and after addition of a large amount of methanol with vigorous stirring, a large amount of white solid was produced; the white solid was collected by filtration to give intermediate compound T1.
Preferably, in step S4), the synthesis of the pyridine-oxadiazole ligand T2 is specifically:
adding a tetrahydrofuran solution of tetrabutylammonium fluoride to a solution of an intermediate compound T1 containing methylene chloride, stirring the resulting solution for 24 hours, and removing the solvent under vacuum; the residue was dissolved in dichloromethane and a large amount of methanol was added under vigorous stirring to form a large amount of white solid, which was collected by filtration to give pyridine-oxadiazole ligand T2.
Preferably, in the step S11), the molar ratio of the methyl 4-alkoxypyridine-2, 6-dicarboxylic acid to NH 4 OH is 1 (20-30).
Preferably, in the step S12), the molar ratio of the 4-alkoxypyridine-2, 6-dicarboxamide, pyridine and trifluoroacetic anhydride is 1 (4.5-6.0): 2.4-3.2.
Preferably, in the step S13), the molar ratio of the 2, 6-dicyano-4-alkoxypyridine to the hydroxylamine is 1 (1.0 to 1.1).
Preferably, in the step S2), the molar ratio of the raw material 4-alkoxypyridine-2, 6-dicarboxylic acid to oxalyl chloride is 1 (2-3).
Preferably, in the step S3), the molar ratio of the 4-alkoxypyridine-2, 6-diformyl chloride, the 2-amino oxime-6-cyano-4-alkoxypyridine and the diisopropylethylamine is 1:2 (3-4).
Preferably, in the step S4), the molar ratio of the intermediate compound T1 to tetrabutylammonium fluoride is 1 (0.2 to 0.25).
Preferably, the invention also provides a palladium ion extraction system, which comprises an organic phase and an aqueous phase, wherein the volume ratio of the organic phase to the aqueous phase is 1:1: the organic phase comprises:
Extractant material: pyridine-oxadiazole ligands;
a diluent: m-nitrobenzotrifluoride;
Phase modifier: 2-bromohexanoic acid;
Wherein the concentration of the 2-bromohexanoic acid is 1M; the concentration of the pyridine-oxadiazole ligand is 0.1-10 mM;
The water phase is nitric acid solution containing metal ions with the concentration of 0-100 ppm, wherein the metal ions are one or more of Pd and Ni, la, gd, eu, yb, sm, pr, ba, sr, fe, nd, rb, cs, re, mo, na; the concentration of nitric acid is 0.2-4M.
The extraction system can extract most Pd 2+ in the water phase into the organic phase in a short time.
The beneficial effects of the invention are as follows:
1. According to the invention, the pyridine-oxa-diazole ligand is used as an extractant, most Pd 2+ in the water phase can be extracted into the organic phase in a short time, and the extraction rate is extremely high; the selective extraction and separation of Pd 2+ under the acidic condition can be realized, the acidity application range is wide, and the extraction capacity is excellent in the range of 0.2-4M of nitric acid concentration;
2. the extractant has excellent selectivity to Pd 2+ for an aqueous phase containing various metal ions; the pyridine-oxa-diazole extractant has good application prospect in separating and recovering Pd 2+ in high-level radioactive waste liquid;
3. The m-nitrobenzotrifluoride is used as the diluent of the extraction system, has good dissolving capacity for organic ligands and extracts, and the 2-bromohexanoic acid can increase the lipophilicity of the extracts.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a pyridine-oxadiazole ligand T2-1 prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a pyridine-oxadiazole ligand T2-1 prepared in example 1 of the present invention;
FIG. 3 is a mass spectrum of a pyridine-oxadiazole ligand T2-1 prepared in example 1 of the present invention;
FIG. 4 is a graph showing the extraction rate versus time for Pd 2+ in example 2 of the present invention;
FIG. 5 is a graph showing the extraction yield versus the concentration of the extractant of Pd 2+ in example 3 of the present invention; ;
FIG. 6 is a graph showing the concentration of nitric acid and Pd 2+ extraction yield in example 4 of the present invention;
FIG. 7 is a bar chart showing the extraction yield of each metal ion in example 5 of the present invention.
Detailed Description
The following is a further description of embodiments of the invention, taken in conjunction with the accompanying drawings:
example 1
The embodiment provides a preparation method of a pyridine-oxa-diazole ligand with an isobutyl alkyl chain, which comprises the following steps:
S1), to a solution of Compound 1 (1.6 g,6.00 mmol) in methanol (50 mL) was added dropwise NH 4 OH (28% in water, 12.0mL,0.12mol,20.0 eq.) and the resulting mixture was stirred vigorously at room temperature for 24 hours; the white precipitate formed was filtered and washed with ice-cooled water and dried under vacuum to give compound 2 (1.18 g, 83%) as a white solid; the synthesis flow is as follows:
S2), pyridine (1.02 g,12.9mmol,4.5 eq.) was added to a suspension of compound 2 (680 mg,2.9 mmol) in dry dichloromethane (100 mL) under nitrogen atmosphere, and trifluoroacetic anhydride (1.45 g,6.89mmol,2.4 eq.) was slowly added; after stirring the resulting mixture at room temperature for 18 hours, water (75 mL) was added; the organic phase was collected and the aqueous phase was extracted with dichloromethane (50 mL); the combined organic phases were dried over anhydrous Na 2SO4 and concentrated under reduced pressure; the residue was purified by flash chromatography on silica gel (dichloromethane as eluent) to give compound 3 (480 mg, 84%) as a white oil; the synthesis flow is as follows:
S3), to an ethanol solution of Compound 3 (201 mg,1.0mmol,1 eq.) was added a 50% by weight aqueous hydroxylamine solution (66 mg,1.0mol,1.0 eq.) and the solution was stirred at room temperature for 24 hours; the solvent was evaporated in vacuo and the product was purified on silica gel (95/5, dichloromethane/methanol) to give compound 4 (159 mg, 68%) as a colourless solid; the synthesis flow is as follows:
S4), oxalyl chloride (274 mg,2.16 mmol) was added to a solution of compound 5 (172 mg,0.72 mmol) in anhydrous dichloromethane and stirred for 1 hour, the solvent was evaporated under vacuum to give compound 6 (196 mg, 99%) as follows:
S5), adding a solution of compound 6 containing dichloromethane to an anhydrous dichloromethane solution containing compound 4 (337 mg,1.44 mmol) and diisopropylethylamine (280 mg,2.16 mmol); after stirring the resulting solution for 5 hours, the solvent was removed under vacuum; the residue was dissolved in dichloromethane and after addition of a large amount of methanol with vigorous stirring, a large amount of white solid was produced; the white solid was collected by filtration and characterized as target compound T1-1 (444 mg, 92%); the synthesis flow is as follows:
s6), to a solution of T1-1 (350 mg,0.52 mmol) in dichloromethane (30 mL) was added a solution of tetrabutylammonium fluoride (30.5 mg,0.12 mmol) in tetrahydrofuran; after stirring the resulting solution for 24 hours, the solvent was removed under vacuum; the residue was dissolved in dichloromethane and a large amount of methanol was added with vigorous stirring to form a large amount of white solid; the white solid was collected by filtration and characterized as target compound T2-1 (320 mg, 97%), synthetic procedure as follows:
Example 2
The embodiment provides a Pd 2+ extraction separation system, which consists of an organic phase and a water phase, wherein each of the organic phase and the water phase is 3mL; the organic phase takes m-nitrobenzotrifluoride as a diluent, 2-bromohexanoic acid as a phase modifier and pyridine-oxadiazole ligand as an extractant; the concentration of 2-bromohexanoic acid was 1M and the concentration of pyridine-oxadiazole ligand was 3mM;
The water phase is nitric acid solution containing Pd 2+; wherein, the initial concentration of Pd 2+ is 100ppm; the nitric acid concentration was 3M.
The extraction flow is as follows: dissolving 2-bromohexanoic acid and pyridine-oxa-diazole ligand in m-nitrobenzotrifluoride as organic phase, dissolving palladium nitrate and nitric acid in water as aqueous phase, then taking 3mL of each of the organic phase and the aqueous phase, loading into a centrifuge tube, vigorously shaking for a certain time at 25 ℃, taking 200 mu L of aqueous phase after centrifugal phase separation for detecting the residual concentration of Pd 2+, simultaneously taking 200 mu L of organic phase, ensuring that the phase ratio is always 1/1 in the process, and taking the point until the extraction is balanced.
Example 3
The embodiment provides a Pd 2+ extraction separation system, which consists of an organic phase and a water phase, wherein each of the organic phase and the water phase is 0.5mL;
The organic phase takes m-nitrobenzotrifluoride as a diluent, 2-bromohexanoic acid as a phase modifier and pyridine-oxadiazole ligand as an extractant;
Wherein the concentration of the 2-bromohexanoic acid is 1M, and the concentration of the pyridine-oxadiazole ligand is 0.1-10 mM;
the aqueous phase is a nitric acid solution containing Pd 2+, wherein the initial concentration of Pd 2+ is 100ppm; the nitric acid concentration was 3M.
The extraction process comprises the following steps: 2-bromohexanoic acid and pyridine-oxa-diazole ligand are dissolved in m-nitrobenzotrifluoride to be used as organic phase, palladium nitrate and nitric acid are dissolved in water to be used as water phase, then 0.5mL of each of the organic phase and the water phase is taken and put into a centrifuge tube, violent shaking is carried out for more than 8 hours at 25 ℃, and 200 mu L of water phase is taken for detecting the residual concentration of Pd 2+ after centrifugal phase separation.
Example 4
The embodiment provides a Pd 2+ extraction separation system, which consists of an organic phase and a water phase, wherein each of the organic phase and the water phase is 0.5mL;
The organic phase takes m-nitrobenzotrifluoride as a diluent, 2-bromohexanoic acid as a phase modifier and pyridine-oxadiazole ligand as an extractant; wherein the concentration of 2-bromohexanoic acid is 1M and the concentration of pyridine-oxadiazole ligand is 3mM;
The water phase is nitric acid solution containing Pd 2+; wherein, the initial concentration of Pd 2+ is 100ppm; the concentration of nitric acid is 0.2-4M;
The extraction process comprises the following steps: 2-bromohexanoic acid and pyridine-oxa-diazole ligand are dissolved in m-nitrobenzotrifluoride to be used as organic phase, palladium nitrate and nitric acid are dissolved in water to be used as water phase, then 0.5mL of each of the organic phase and the water phase is taken and put into a centrifuge tube, violent shaking is carried out for more than 8 hours at 25 ℃, and 200 mu L of water phase is taken for detecting the residual concentration of Pd 2+ after centrifugal phase separation.
Example 5
The embodiment provides a Pd 2+ extraction separation system, which consists of an organic phase and a water phase, wherein each of the organic phase and the water phase is 1mL;
The organic phase takes m-nitrobenzotrifluoride as a diluent, 2-bromohexanoic acid as a phase modifier and pyridine-oxadiazole ligand as an extractant; the concentration of 2-bromohexanoic acid was 1M and the concentration of pyridine-oxadiazole ligand was 3mM;
The aqueous phase is a nitric acid solution containing 17 metal ions. The metal ions contained include Pd, ni, la, gd, eu, yb, sm, pr, ba, sr, fe, nd, rb, cs, re, mo, na ions, each having an initial concentration of 100ppm; the nitric acid concentration was 3M.
The extraction process comprises the following steps: dissolving 2-bromohexanoic acid and pyridine-oxa-diazole ligand in m-nitrobenzotrifluoride to serve as an organic phase, dissolving palladium nitrate and nitric acid in water to serve as a water phase, then taking 1mL of each of the organic phase and the water phase, loading into a centrifuge tube, vigorously shaking at 25 ℃ for more than 8 hours, centrifuging and separating phases, and taking 500 mu L of the water phase after centrifugal phase separation for detecting the residual concentration of each metal ion.
Performance analysis:
1. the pyridine-oxadiazole ligand T2-1 prepared in example 1, in which the isobutyl group is an alkyl chain, was characterized and tested for performance.
The test method is as follows:
compound structure detection: using a AVANCE III MHz nuclear magnetic resonance apparatus from Bruker, switzerland, the solvent is deuterated chloroform;
Mass spectrometry detection: the T2-1 prepared in example 1 was dissolved in methylene chloride to prepare a solution with a concentration of 1mg/mL, and mass spectrometry was performed by using a TSQ Endura ultra-high performance liquid chromatography tandem triple quadrupole mass spectrometer (ThermoFisher Co., USA).
Extraction kinetics study: the Pd 2+ concentration in the aqueous phase after various extraction times for example 2 was determined using an inductively coupled plasma emission spectrometer iCAP 5110.
Extraction stoichiometry calculation: the Pd 2+ concentration in the aqueous phase after extraction of example 3 was determined using an inductively coupled plasma emission spectrometer iCAP 5110.
Aqueous phase acidity vs. extraction performance test: the Pd 2+ concentration of example 4 in the aqueous phase after extraction was determined using an inductively coupled plasma emission spectrometer iCAP 5110.
Extraction selectivity test: the concentration of each metal ion in the aqueous phase after extraction of example 5 was determined using an inductively coupled plasma emission spectrometer iCAP 5110.
The test results were as follows:
the nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the pyridine-oxadiazole ligand T2-1 prepared in example 1 are shown in FIGS. 1 and 2. The peak energy of ：1H NMR(400MHz,Chloroform-d)δ8.13(s,2H),8.03-7.96(m,2H),7.41-7.33(m,2H),4.05(d,J＝6.4Hz,2H),3.96(d,J＝6.4Hz,4H),2.21(m,3H),1.12(d,J＝6.9Hz,6H),1.09(d,J＝6.6Hz,12H).13C NMR(100MHz,Chloroform-d)δ174.60,167.99,167.46,166.68,148.90,145.37,135.53,117.90,116.51,114.22,112.57,75.69,28.05,19.02. nuclear magnetic resonance hydrogen spectrum and carbon spectrum can be seen to correspond to the target product one by one, and the quantity is reasonable; from the mass spectrum (FIG. 3), it can be seen that the relative molecular mass in the figure is 653.2944, which is consistent with the relative molecular mass after the synthesized T2-1 is complexed with NH 4+. As can be seen from the results of the combination of the above nuclear magnetism and mass spectrometry, the product obtained in example 1 was T2-1.
FIG. 4 is a plot of Pd 2+ extraction time versus extraction time for example 2. It can be seen that: at the initial stage, pd 2+ is rapidly extracted into an organic phase, 68% can be extracted in 120 minutes, the equilibrium is reached in about 360 minutes, the extraction rate reaches 98%, and quantitative extraction is basically realized.
FIG. 5 is a plot of Pd 2+ extraction versus extractant concentration for example 3. It can be seen that: the fitted curve is a straight line with a slope close to 1.5, which indicates that there may be two cases where the complexation ratio of T2-2 to Pd 2+ is 1:1 and 1:2 in the extracted organic phase, i.e. the extraction stoichiometric ratio of the two is 1:1 or 1:2.
FIG. 6 is a plot of Pd 2+ extraction versus nitric acid concentration for example 4. It can be seen that: in the whole acidity range, the system has excellent extraction capacity to Pd 2+, and almost all quantitative extraction is realized.
FIG. 7 is a bar graph of the extraction yield of each metal ion of example 5. It can be seen that: the adsorption rate of the system to Pd 2+ ions reaches 98.5%, the excellent adsorption capacity is shown, and other ions are only extracted in a small amount, rb (11.2%), gd (7.4%), eu (8.2%), yb (7.5%), sm (8.0%), nd (7.5%), re (8.4%). The results show that the adsorbent has excellent selectivity to Pd 2+, and further proves that the adsorbent has good practical application potential.
In summary, the pyridine-oxadiazole is used as an extractant, so that most Pd 2+ in a water phase can be extracted into an organic phase in a short time, and the extraction rate is extremely high; the acidity of the extractant has wide application range and excellent extraction capacity within the range of 0.2-4M nitric acid concentration; the extractant exhibits excellent selectivity for Pd 2+ even for aqueous phases containing a variety of metal ions. Therefore, the pyridine-oxa-diazole extractant has good application prospect in separating and recovering Pd 2 + in high-level radioactive waste liquid.
The foregoing embodiments and description have been provided merely to illustrate the principles and best modes of carrying out the invention, and various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A palladium ion extractant material characterized in that: the extractant is pyridine-oxa-diazole ligand, and the pyridine-oxa-diazole ligand is used for highly-selectively complexing Pd 2+, and has the structural formula:
wherein R is a C4-C8 hydrocarbon group.
2. A palladium ion extractant material according to claim 2, wherein: the structural formula of R in the structural formula of the pyridine-oxadiazole ligand is divided into one of the following structural formulas:
3. A process for preparing a palladium ion extractant material as claimed in claim 1 or 2, comprising the steps of:
S1) Synthesis of 2-amino-oxime-6-cyano-4-alkoxypyridine
S11), adding 4-alkoxypyridine-2, 6-dicarboxylic acid methyl ester into a methanol solution, then dropwise adding NH 4 OH, and vigorously stirring the obtained mixture at room temperature for 24 hours; the white precipitate formed was filtered and washed with ice-cooled water and dried under vacuum to give 4-alkoxypyridine-2, 6-dicarboxamide as a white solid;
S12), adding 4-alkoxypyridine-2, 6-dicarboxamide into anhydrous dichloromethane under nitrogen atmosphere, then adding pyridine into the suspension, and slowly adding trifluoroacetic anhydride; stirring at room temperature for 18 hours, then adding water to the resulting mixture; the organic phase was collected and the aqueous phase was extracted with dichloromethane; the combined organic phases were dried over anhydrous Na 2SO4 and concentrated under reduced pressure;
The residue was purified by flash chromatography on silica gel to give 2, 6-dicyano-4-alkoxypyridine as a white oil;
S13), adding a 50% by weight aqueous hydroxylamine solution to an ethanol solution of 2, 6-dicyano-4-alkoxypyridine; the solution was then stirred at room temperature for 24 hours; evaporating the solvent under vacuum, and purifying the product on silica gel to obtain 2-amino oxime-6-cyano-4-alkoxypyridine;
s2), synthesizing 4-alkoxypyridine-2, 6-diformyl chloride intermediate
Oxalyl chloride is added to a solution of 4-alkoxypyridine-2, 6-dicarboxylic acid in anhydrous dichloromethane and stirred for 1 hour, and the solvent is evaporated under vacuum to give a 4-alkoxypyridine-2, 6-dicarboxylic acid chloride intermediate;
s3) reacting the 2-amino oxime-6-cyano-4-alkoxypyridine prepared in step S1) with the 4-alkoxypyridine-2, 6-dicarboxylic acid dichloride intermediate prepared in step S2) to obtain intermediate compound T1:
Wherein R is a C4-C8 hydrocarbon group;
S4), reacting the intermediate compound T1 with tetrabutylammonium fluoride to obtain a pyridine-oxadiazole ligand T2:
wherein R is a C4-C8 hydrocarbon group.
4. A method of preparing a palladium ion extractant material according to claim 3, wherein: in the step S3), the synthesis of the intermediate compound T1 specifically includes:
Adding a 4-alkoxypyridine-2, 6-dicarboxylic acid dichloride intermediate solution containing methylene chloride to an anhydrous methylene chloride solution containing 2-amino oxime-6-cyano-4-alkoxypyridine and diisopropylethylamine;
After stirring the resulting solution for 5 hours, the solvent was removed under vacuum; the residue was dissolved in dichloromethane and after addition of a large amount of methanol with vigorous stirring, a large amount of white solid was produced; the white solid was collected by filtration to give intermediate compound T1.
5. A method of preparing a palladium ion extractant material according to claim 3, wherein: in the step S4), the synthesis of the pyridine-oxadiazole ligand T2 is specifically as follows:
adding a tetrahydrofuran solution of tetrabutylammonium fluoride to a solution of an intermediate compound T1 containing methylene chloride, stirring the resulting solution for 24 hours, and removing the solvent under vacuum; the residue was dissolved in dichloromethane and a large amount of methanol was added under vigorous stirring to form a large amount of white solid, which was collected by filtration to give pyridine-oxadiazole ligand T2.
6. A method of preparing a palladium ion extractant material according to claim 3, wherein:
In the step S11), the molar ratio of the 4-alkoxypyridine-2, 6-dicarboxylic acid methyl ester to the NH 4 OH is 1 (20-30);
In the step S12), the molar ratio of the 4-alkoxypyridine-2, 6-dimethylformamide to the pyridine to the trifluoroacetic anhydride is 1 (4.5-6.0) (2.4-3.2);
in the step S13), the molar ratio of the 2, 6-dicyano-4-alkoxypyridine to the hydroxylamine is 1 (1.0-1.1).
7. A method of preparing a palladium ion extractant material according to claim 3, wherein: in the step S2), the molar ratio of the raw material 4-alkoxypyridine-2, 6-dicarboxylic acid to oxalyl chloride is 1 (2-3).
8. A method of preparing a palladium ion extractant material according to claim 3, wherein: in the step S3), the mol ratio of the 4-alkoxypyridine-2, 6-diformyl chloride, the 2-amino oxime-6-cyano-4-alkoxypyridine and the diisopropylethylamine is 1:2 (3-4).
9. A method of preparing a palladium ion extractant material according to claim 3, wherein: in the step S4), the molar ratio of the intermediate compound T1 to tetrabutylammonium fluoride is 1 (0.2-0.25).
10. A palladium ion extraction system using the extractant material of claim 1 or 2, comprising an organic phase and an aqueous phase, wherein the volume ratio of the organic phase to the aqueous phase is 1:1: wherein the organic phase comprises:
Extractant material: pyridine-oxadiazole ligands;
a diluent: m-nitrobenzotrifluoride;
Phase modifier: 2-bromohexanoic acid;
Wherein the concentration of the 2-bromohexanoic acid is 1M; the concentration of the pyridine-oxadiazole ligand is 0.1-10 mM;
The water phase is nitric acid solution containing metal ions with the concentration of 0-100 ppm, wherein the metal ions are one or more of Pd and Ni, la, gd, eu, yb, sm, pr, ba, sr, fe, nd, rb, cs, re, mo, na; the concentration of nitric acid is 0.2-4M;
The extraction system can extract most Pd 2+ in the water phase into the organic phase in a short time.
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