CN106045976B - A kind of nitrogenous soft ligand derivatives and its synthesis and application - Google Patents

A kind of nitrogenous soft ligand derivatives and its synthesis and application Download PDF

Info

Publication number
CN106045976B
CN106045976B CN201610344005.5A CN201610344005A CN106045976B CN 106045976 B CN106045976 B CN 106045976B CN 201610344005 A CN201610344005 A CN 201610344005A CN 106045976 B CN106045976 B CN 106045976B
Authority
CN
China
Prior art keywords
nitric acid
adsorbent
aqueous solution
zirconium
compound
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
Application number
CN201610344005.5A
Other languages
Chinese (zh)
Other versions
CN106045976A (en
Inventor
张安运
徐雷
曹明乐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201610344005.5A priority Critical patent/CN106045976B/en
Publication of CN106045976A publication Critical patent/CN106045976A/en
Application granted granted Critical
Publication of CN106045976B publication Critical patent/CN106045976B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • 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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • 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
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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

Abstract

The invention discloses a kind of nitrogenous soft ligand derivatives and its synthesis and application, include the following steps：The nitrogenous soft ligand derivatives that the present invention synthesizes and carrier are compound as adsorbent, and adsorbent is mixed with the aqueous solution of nitric acid containing various metals ion, and the zirconium ion in aqueous solution of nitric acid is adsorbed by adsorbent separation.Every gram of adsorbent is mixed with 15~25 milliliters of aqueous solution of nitric acid.The carrier is coated the macro-pore SiO of polymer for surface2.In aqueous solution of nitric acid, a concentration of 0.4~6.0 mol/L of nitric acid.The present invention is without the use of the diluent with property in adsorption process and is diluted or dissolves, and does not need to add other organic compounds, selectivity is good, and separative efficiency is high, easy to operate, suitable for industrially separating and recovering noble metal zirconium.

Description

A kind of nitrogenous soft ligand derivatives and its synthesis and application
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of nitrogenous soft ligand derivatives and its synthesis and should With.
Background technology
With the utilization of nuclear energy.Correspondingly nuclear fuel is post-processed, the processing of generated high activity liquid waste and Disposition, is to be related to one of key factor of nuclear power development.
At present, to high activity liquid waste, there are mainly two types of methods of disposal in the world：Glass solidification method and separation transmuting method.From warp The composite factors such as Ji, environment consider that separation transmuting method is a kind of more promising processing method.For a long time, countries in the world Actinides and long-life fission product are all isolated from high activity liquid waste in positive research, so that uranium, plutonium return to nuclear fuel and follow Ring uses.Minor actinides and long-life fission product can be allowed to transmuting into short life sliver member in the reactor of special designing Element, so as to during high activity liquid waste is transformed into, low radioactive waste liquid, so that shallow ground disposal or earth's surface are disposed.In this way, to biology and ring Radiological hazard caused by border is possible is preferably minimized.
By studying for many years, have proposed several separation process in the world, as the U.S. TRUEX (with amide methyl oxidation phosphorus- Tributyl phosphate is extractant) flow；DIDPA (using diiso decyl phosphoric acid as extractant) flow of Japan；The DIAMEX of France (using bisamide as extractant) flow；TRPO (using trialkylphosphine oxide as extractant) flow of China etc..However, the height of power reactor In radioactive waste liquid 1g/L is may be up to containing a large amount of zirconium, concentration.
In with tributyl phosphate being the PUREX flows of extractant, zirconium is easy to and the catabolite of tributyl phosphate is sent out Raw coordination forms precipitation, seriously affects the mass transport process of post processing flow, so as to carry out normal post-processing operation. In application TRPO extraction procedures processing power reactor high activity liquid waste, TRPO extractions Zr's is very capable, easily forms third phase, makes TRPO flows can not be carried out continuously operation.
The main method for removing Zr from high activity liquid waste at present is adsorption separation method, and removal high activity liquid waste is detached using silica gel In zirconium.Silica gel absorption has many advantages：It is easy to operate, practical, there is very strong selectivity to the zirconium in acid system.Its Shortcoming is that the operating time is long, and exchange capacity has certain limitations, and waste liquid amount is big.
Zhao can be bright et al. (《Tsinghua University's dissertation for the bachelor's degree》, silica gel adsorbs Zr (IV) from acid simulated high-level radioactive waste The research of behavior, 1998) it discloses and a kind of silica gel is used to be detached from simulated high-level radioactive waste as adsorbent in acid condition The method of Zr (IV), in this method, Zr (IV) is slower by the rate of silica gel absorption, needs can be only achieved balance within about 50 hours, And it is relatively low to the adsorption capacity of Zr (IV), and the variation of acidity has a significant impact to absorption behavior, acidity is only more than 1.2mol/ L HNO3When, it can just efficiently separate Zr (IV) and Pu (IV).
Lin Can lifes et al. (《Nuclear and radiochemistry》, high adsorption activity silica gel is to zirconium separation row in simulated high-level radioactive waste For research, 22 (3), 156-160) disclose it is a kind of using making high adsorption activity silica gel separating zirconium from simulated high-level radioactive waste by oneself Method, which has good absorption property and selectivity to zirconium, but the static capacity of zirconium and Sorption ratio are still So relatively low, equilibration time still needs to 48 hours.
Silica gel absorption is lacked from high activity liquid waste except Zr has a preferable application prospect, but there is also adsorption capacity is low Point.Therefore, silica gel how is improved to the adsorption capacity of Zr or efficient adsorbent is selected to remove the Zr in high activity liquid waste, in this respect Work wait further to study.
Invention content
The present invention provides a kind of nitrogenous soft ligand derivatives and its synthesis and application, the nitrogenous soft ligand derivatives of synthesis It is compound as adsorbent with carrier, can from acid water phase adsorbing separation zirconium, high selectivity is easy to operate, and separative efficiency is high, Suitable for industrially separating and recovering noble metal zirconium.
A kind of nitrogenous soft ligand derivatives, as shown in structural formula I：
The present invention also provides a kind of synthetic methods of the nitrogenous soft ligand derivatives, include the following steps：
Step 1, compound ii is dissolved in tetrahydrofuran, obtains mixed solution；
Step 2, after mixed solution, compound III, catalyst being mixed, reaction is stirred at reflux, up to raw material, the reaction was complete, It is post-treated, obtain compound I.
Compound I's is entitled：6,6'- bis- (5,6- dinonyl -1,2,4- triazine -3- bases) -2,2'- bipyridyls, referred to as： C9-BTBP。
In order to ensure combined coefficient, it is preferable that the ratio of the amount of the substance of compound III and compound ii is 1：2~3.
Catalyst described in step 2 is triethylamine, can promote the progress of reaction, in step 2, under stirring, will change It closes object III and catalyst of triethylamine (TEA) is added in mixed solution, be stirred at reflux reaction, using TLC tracking reactions until raw material Stop reaction after the reaction was complete.
To improve the utilization rate of raw material, the complexity of post processing is reduced, it is preferable that the use of compound II and tetrahydrofuran Amount is than being 1g：60~70mL.
The amount ratio of compound III and catalyst is 1g：4~5mL.
Reaction temperature is 60~78 DEG C in step 2, and preferably 69~72 DEG C, reaction temperature is too low, and reflux is insufficient, reaction Rate is slower；Reaction temperature is excessively high, then reacts excessively acutely, and side reaction increases, and is unfavorable for the progress of control reaction.
The reaction time is 10~20h, preferably 10~12h in step 2, using TLC tracking reactions after raw material exhausts Stop reaction.
The higher product of purity in order to obtain, it is preferable that the post processing in step 2 includes：
Revolving is filtered to reaction product successively, with being filtered after triturated under ether, with ethyl acetate, petroleum ether and triethylamine Mixed solution as solvent, isolated and purified using silica gel column chromatography isolation technics, purified product is vacuum dried To compound I.
Preferably, in the mixed solution of ethyl acetate, petroleum ether and triethylamine, ethyl acetate, petroleum ether and triethylamine Volume ratio be 3：1：0.01.
Preferably, vacuum drying temperature is 50~70 DEG C.
Compound I provided by the invention has good suction-operated to zr element, based on this suction-operated, the present invention A kind of method of adsorbing separation zirconium is additionally provided, is included the following steps：By adsorbent and the nitric acid aqueous solution containing various metals ion Solution mixes, and the zirconium ion in aqueous solution of nitric acid is adsorbed by adsorbent separation, and the adsorbent is supported on by compound I on carrier It is made.
The preparation method of the adsorbent is as follows：
Compound I is dissolved in organic solvent, carrier is added in and is uniformly mixed, after revolving is dry, obtain adsorbent.
The carrier is coated the macro-pore SiO of polymer for surface2.Specially silicon substrate-styrene-divinylbenzene polymerization Object.
The separating effect that the content of compound I will influence zirconium in adsorbent, when content is too low, adsorbent to the absorption of zirconium compared with It is weak, it is impossible to realize being kept completely separate for zirconium；During too high levels, the manufacturing cost of adsorbent will be increased.Preferably, compound I with The mass ratio of carrier is 1：3~10.Further preferably, the mass ratio of compound I and carrier is 1：8~1:10.
Containing Zr (II) and other metal ions in the aqueous solution of nitric acid, other metal ions are Li (I), Na (I), K (I)、Rb(I)、Cs(I)、Ca(Ⅱ)、Mg(Ⅱ)、Sr(Ⅱ)、Ba(Ⅱ)、Nd(Ⅲ)、La(Ⅲ)、Ru(Ⅲ)、Yb(Ⅲ)、Y (III), at least one of Fe (III) and Mo (VI).
In aqueous solution of nitric acid, a concentration of 5.0 × 10 per metal ion species-4~5.0 × 10-2Mol/L.Nitric acid is water-soluble In liquid, the concentration of metal ion can influence separating effect, the excessive concentration of metal ion, it is possible to more than the absorption point of adsorbent From ability；The concentration of metal ion is too low, then can reduce separative efficiency.Further preferably, a concentration of 2.0 per metal ion species ×10-3~5.0 × 10-3Mol/L.
In the aqueous solution of nitric acid, a concentration of 0.4~6.0 mol/L of nitric acid.
In order to ensure separating effect, it is preferable that every gram of adsorbent is mixed with 15~25 milliliters of aqueous solution of nitric acid.It is further excellent Choosing, every gram of adsorbent are mixed with 20 milliliters of aqueous solution of nitric acid.
Adsorbent and aqueous solution of nitric acid mixing and absorption, adsorption temp are 298~318K, and adsorption time is 5~210min.It inhales The time of contact of attached dose and aqueous solution will influence separating effect, and time of contact is too short, and absorption is not yet complete, and time of contact is long, Reduce separative efficiency.Further preferably, adsorption temp 298K, adsorption time are 60~120min.
Adsorbent and aqueous solution of nitric acid mixing and absorption, mixing and absorption carry out under oscillating condition, oscillation rate for 120~ 150rpm。
The nitrogenous soft ligand derivatives that the present invention synthesizes are compound as adsorbent with carrier, can be adsorbed from acid water phase Separating zirconium, high selectivity is easy to operate, and separative efficiency is high, suitable for industrially separating and recovering noble metal zirconium.
Description of the drawings
Fig. 1 is compound C9-BTBP in embodiment 11H NMR characterize collection of illustrative plates；
The MSI-MS cations that Fig. 2 is compound C9-BTBP in embodiment 1 characterize collection of illustrative plates；
The MSI-MS anion that Fig. 3 is compound C9-BTBP in embodiment 1 characterize collection of illustrative plates；
Fig. 4 is the distribution coefficient using adsorbent separating element zirconium from aqueous solution of nitric acid of embodiment 4 with concentration of nitric acid The relational graph of variation；
Fig. 5 is that the distribution coefficient of separating element zirconium varies with temperature from aqueous solution of nitric acid using the adsorbent of embodiment 4 Relational graph.
Specific embodiment
Embodiment 1
The synthetic route of the present embodiment is as follows：
The synthesis step of the present embodiment includes：
(1) 6.6g 10 is put, 20-diketone of 11- (i.e. compound ii) is dissolved to obtain in 450mL tetrahydrofurans Bright solution；
(2) 2.6g [2,2`]-bipyridyl -6,6`- diformamide hydrazones are added in into step 1 acquired solution under agitation (i.e. compound III) and 12.5mL catalyst of triethylamine (TEA) form mixed solution, and reaction 12h, profit are stirred at reflux at 70 DEG C It is reacted after the reaction was complete up to raw material and stopped with TLC (thin-layer chromatographic analysis) tracking.
(3) after reaction stops, cooling is stood, filters and removes solid impurity, filtrate removes solvent through revolving and obtains crude product, Then it with triturated under ether, filters and obtains solid, use petrol ether/ethyl acetate/triethylamine (volume ratio 3：1：0.01) conduct Solvent is isolated and purified by silica gel column chromatography isolation technics, and purified components obtain orange solid after 60 DEG C of vacuum drying Body 2.6g, i.e. compound I (C9-BTBP), yield 38.9%.
The structure of compound C9-BTBP is characterized as below：
(a)1H NMR(400MHz,CDCl3,298K)
Compound is dissolved in deuterochloroform under the conditions of 25 DEG C, tests target compound C9-BTBP's1H NMR Collection of illustrative plates, as shown in Figure 1, wherein each peak is attributed to：
δ(ppm):8.99 (d, J=7.8Hz, 2H), 8.59 (d, J=7.6Hz, 2H), 8.08 (t, J=7.8Hz, 2H), 3.08 (t, J=7.8Hz, 4H), 2.95 (t, J=7.8Hz, 4H), 1.9 (m, 8H), 1.41 (m, 48H), 0.88 (m, 12H).
It is the proton peak of deuterochloroform at δ=7.2ppm in Fig. 1, unimodal at δ=5.3ppm is in methylene chloride The peak that proton is formed, chemical shift and numbers of hydrogen atoms etc. point out result and are consistent with the structural information of C9-BTBP.
(b)MSI-MS
The MS-ESI positive spectrums of C9-BTBP are tested in methanol solution, as a result see Fig. 2, analysis result shows [M+ Na+]=841.7, [M+K+]=857.5, calculated value m/z are 818.7.The theoretical molecular weight of C9-BTBP be 818.7, this result with The theoretical value of C9-BTBP molecular weight is consistent, and MS-ESI interpretations of result explanation successfully synthesizes target compound.
The MS-ESI negative spectrums of C9-BTBP are tested in methanol solution, as a result see Fig. 3, analysis result shows [M- H]=817.7, calculated value m/z is 818.7.The theoretical molecular weight of C9-BTBP is 818.7, this result and C9-BTBP molecular weight Theoretical value is consistent, and MS-ESI interpretations of result explanation successfully synthesizes target compound.
Embodiment 2
The synthesis step of the present embodiment includes：
(1) 6.6g 10 is put, 20-diketone of 11- (i.e. compound ii) is dissolved to obtain in 400mL tetrahydrofurans Bright solution；
(2) 2.2g [2,2`]-bipyridyl -6,6`- diformamide hydrazones are added in into step 1 acquired solution under agitation (i.e. compound III) and 8.8mL catalyst of triethylamine (TEA) form mixed solution, and reaction 10h is stirred at reflux at 70 DEG C, is utilized TLC (thin-layer chromatographic analysis) tracking reaction stops after up to raw material, the reaction was complete.
(3) after reaction stops, cooling is stood, filters and removes solid impurity, filtrate obtains crude product through rotating away solvent, Then it with triturated under ether, filters and obtains solid, use petrol ether/ethyl acetate/triethylamine (volume ratio 3：1：0.01) conduct Solvent is isolated and purified by silica gel column chromatography isolation technics, and purified components obtain orange solid after 60 DEG C of vacuum drying Body, i.e. compound I (C9-BTBP), yield 36.4%.
Embodiment 3
The synthesis step of the present embodiment includes：
(1) 6.6g 10 is put, 20-diketone of 11- (i.e. compound ii) is dissolved to obtain in 460mL tetrahydrofurans Bright solution；
(2) 3.3g [2,2`]-bipyridyl -6,6`- diformamide hydrazones are added in into step 1 acquired solution under agitation (i.e. compound III) and 16.5mL catalyst of triethylamine (TEA) form mixed solution, and reaction 17h, profit are stirred at reflux at 78 DEG C It is reacted after the reaction was complete up to raw material and stopped with TLC (thin-layer chromatographic analysis) tracking.
(3) after reaction stops, cooling is stood, filters and removes solid impurity, filtrate obtains crude product through rotating away solvent, Then it with triturated under ether, filters and obtains solid, use petrol ether/ethyl acetate/triethylamine (volume ratio 3：1：0.01) conduct Solvent is isolated and purified by silica gel column chromatography isolation technics, and purified components obtain orange solid after 60 DEG C of vacuum drying Body, i.e. compound I (C9-BTBP), yield 33.8%.
Embodiment 4
The synthesis step of the present embodiment includes：
(1) 6.6g 10 is put, 20-diketone of 11- (i.e. compound ii) is dissolved to obtain in 450mL tetrahydrofurans Bright solution；
(2) 2.8g [2,2`]-bipyridyl -6,6`- diformamide hydrazones are added in into step 1 acquired solution under agitation (i.e. compound III) and 11.8mL catalyst of triethylamine (TEA) form mixed solution, and reaction 20h, profit are stirred at reflux at 60 DEG C It is reacted after the reaction was complete up to raw material and stopped with TLC (thin-layer chromatographic analysis) tracking.
(3) after reaction stops, cooling is stood, filters and removes solid impurity, filtrate obtains crude product through rotating away solvent, Then it with triturated under ether, filters and obtains solid, use petrol ether/ethyl acetate/triethylamine (volume ratio 3：1：0.01) conduct Solvent is isolated and purified by silica gel column chromatography isolation technics, and purified components obtain orange solid after 60 DEG C of vacuum drying Body, i.e. compound I (C9-BTBP), yield 37.4%.
Embodiment 5
The compound C9-BTBP that 0.5 gram of embodiment 1 is prepared is dissolved in 50.0mL dichloromethane, is fully dissolved Obtain golden solution；4.5 grams of carrier S iO are added in into this golden solution2- P is stirred evenly, and carrier is made to be mixed with compound Uniformly, make dichloromethane volatilization most of to material to nearly dry state through depressurizing rotary evaporation, inhaled in capillarity and physics Organic molecule is made to enter SiO under attached effect2In-P apertures, then the material of nearly dry state is dried in vacuo for 24 hours at 55 DEG C again, Obtain composite material C9-BTBP/SiO2- P, i.e. adsorbent.
Carrier S iO2- P is a kind of organic high polymer complex carrier of particle containing porous silicon dioxide carrier, specially silicon Base-styrene-divinylbenzene polymer, preparation method are as follows：
(1) by the SiO of macropore2It is washed, filtered with concentrated nitric acid, deionized water is washed till neutrality, repetition more than 10 times, drying.
(2) vacuum and have under argon gas protective condition, with 1,2,3- trichloropropane and m- dimethylbenzene for solvent, to macro-pore SiO2 The middle m/p- formyl styrene for adding in 48.7g, the m/p- divinylbenzenes of 8.9g, 72.2g dioctyls face phthalic acid ester, 54.0g benzoin methyl acid sodium, 0.56g α, α-idol bis-isobutyronitrile and 0.57g1,1 '-idol dicyclohexyl amine -1- nitriles, by room temperature gradually 90 DEG C are heated to, and is kept for 13 hours, later, is gradually cooled to room temperature.
(3) it washed respectively with acetone and methanol, filter above-mentioned product, repeat more than 10 times, it is dry.
Embodiment 6~12
(1) by alkali metal salt LiNO3、NaNO3、KNO3、RbNO3、CsNO3；Alkali salt Mg (NO3)2、Ca(NO3)2、Sr (NO3)2、Ba(NO3)2；Transition metal salt Fe (NO3)3、(NH4)6Mo7O24·4H2O、ZrO(NO3)2；The nitrate of noble metal Ru is molten Liquid；Rare-earth oxide Y2O3, rare-earth metal nitrate La (NO3)3、Yb(NO3)3And Nd (NO3)3It is molten Deng 17 kinds of metal salts Deionized water is added in salpeter solution and is configured to the aqueous solution of nitric acid mother liquor containing various metals ion simultaneously, and aqueous solution of nitric acid is female Concentration of nitric acid in liquid is 4.0 mol/Ls, a concentration of 2.0~5.0 × the 10 of each metal ion-3Mol/L.
(2) concentrated nitric acid and deionized water are added in aqueous solution of nitric acid mother liquor, adjusts the concentration of nitric acid in aqueous solution of nitric acid Respectively 0.4,1.0,2.0,3.0,4.0,5.0,6.0 mol/Ls, be about 5.0 × 10 per the concentration of metal ion species-4Mole/ It rises, occurrence is measured by ICP-OES or AA240.
(3) aqueous solution of 7 different concentration of nitric acid containing 17 kinds of metallic elements for obtaining step (2) respectively with implementation Adsorbent contact mixing prepared by example 5, amount ratio during mixing are：0.15g adsorbents are corresponded to per 3.0mL aqueous solution of nitric acid；
(4) mixed liquor obtained by step (3) is subjected to adsorption experiment, oscillator oscillation on TAITEC MM-10 type oscillators Rate is 120rpm, is operated under room temperature 298K, adsorption time 120min, and after absorption reaches balance, solid-liquid two-phase is divided From, phase of fetching water after separation, the content of each metallic element in water phase is then measured respectively.
As shown in figure 4, abscissa is concentration of nitric acid in Fig. 4, ordinate is the absorption result of embodiment 6~12 for distribution Number.As seen from Figure 4, when concentration of nitric acid is 0.4 mol/L, the best results of separating element zirconium, the distribution coefficient of zirconium reaches It is less than 3 mls/g to 105 mls/g, and for the distribution coefficient of other 16 metal ion species, illustrates suction provided by the invention It is attached dose selectively strong to zirconium, it is suitable for from containing multiple metallic element water phase that zirconium is carried out to efficiently separate recycling, application range It is extremely wide.
Embodiment 13~17
Experiment condition and step are same as Example 9, and the difference lies in by aqueous solution of nitric acid, concentration of nitric acid is solid It is set to 3.0 mol/Ls, adsorption time 120min changes adsorption temp as 298K, 303K, 308K, 313K and 318K successively, For gained separating resulting as shown in figure 5, abscissa is adsorption temp in Fig. 5, ordinate is distribution coefficient.
As seen from Figure 5, as the temperature increases, which gradually increases the adsorption capacity of zirconium, temperature 318K When, the distribution coefficient highest of zirconium reaches 91.0 mls/g, and is less than 3 mls/g to the distribution coefficient of other 16 metal ions, Illustrate that adsorbent provided by the invention is selectively strong to zirconium, be suitable for from containing multiple metallic element water phase carrying out zirconium efficient Separation and recovery, application range are extremely wide.

Claims (5)

  1. A kind of 1. method of adsorbing separation zirconium, which is characterized in that include the following steps：By adsorbent with containing various metals ion Aqueous solution of nitric acid mixing, the zirconium ion in aqueous solution of nitric acid is adsorbed by adsorbent separation, and the adsorbent is loaded by compound I It is made on carrier,
  2. 2. the method for adsorbing separation zirconium as described in claim 1, which is characterized in that in the aqueous solution of nitric acid, nitric acid it is dense It spends for 0.4~6.0 mol/L.
  3. 3. the method for adsorbing separation zirconium as described in claim 1, which is characterized in that the preparation method of the adsorbent is as follows：
    Compound I is dissolved in organic solvent, carrier is added in and is uniformly mixed, after revolving is dry, obtain adsorbent.
  4. 4. the method for adsorbing separation zirconium as described in claim 1, which is characterized in that the carrier is coated polymer for surface Macro-pore SiO2。
  5. 5. the method for adsorbing separation zirconium as described in claim 1, which is characterized in that the mass ratio of compound I and carrier is 1：3 ~10.
CN201610344005.5A 2016-05-20 2016-05-20 A kind of nitrogenous soft ligand derivatives and its synthesis and application Expired - Fee Related CN106045976B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610344005.5A CN106045976B (en) 2016-05-20 2016-05-20 A kind of nitrogenous soft ligand derivatives and its synthesis and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610344005.5A CN106045976B (en) 2016-05-20 2016-05-20 A kind of nitrogenous soft ligand derivatives and its synthesis and application

Publications (2)

Publication Number Publication Date
CN106045976A CN106045976A (en) 2016-10-26
CN106045976B true CN106045976B (en) 2018-07-06

Family

ID=57176638

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610344005.5A Expired - Fee Related CN106045976B (en) 2016-05-20 2016-05-20 A kind of nitrogenous soft ligand derivatives and its synthesis and application

Country Status (1)

Country Link
CN (1) CN106045976B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539775A (en) * 2012-07-12 2014-01-29 中国科学院大连化学物理研究所 Dipyridine bridged bis-triazine compounds and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539775A (en) * 2012-07-12 2014-01-29 中国科学院大连化学物理研究所 Dipyridine bridged bis-triazine compounds and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Separation and complexation of palladium(II) with a new soft N-donor ligand 6,60-bis(5,6-dinonyl-1,2,4-triazin-3-yl)-2,20-bipyridine (C9-BTBP) in nitric acid medium;New Journal of Chmeistry;《New Journal of Chmeistry》;20160510;第40卷(第7期);6374-6383 *
Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants;Michael G.B. Drew et al.;《polyhedron》;20051128;第25卷(第4期);第888-900页 *

Also Published As

Publication number Publication date
CN106045976A (en) 2016-10-26

Similar Documents

Publication Publication Date Title
GB2587072A (en) Large-scale preparation method for highly stable cesium removal adsorbent, product thereof and use thereof
CN106048266A (en) Method for separating and concentrating trace amounts of uranium from large amounts of thorium
CN102936237B (en) Calixarene and method for separating and purifying thorium by calizarene
Chu et al. CMPO-calix [4] arenes with spacer containing intramolecular hydrogen bonding: Effect of local rigidification on solvent extraction toward f-block elements
CN106892835A (en) Double two sweet amide ligands and preparation method thereof and the group of the lanthanides containing double two sweet amide ligands/actinium series separating and extracting system
CN105838880A (en) Method of adsorbing and separating palladium with high-molecular-based pillararene
CN106555062B (en) Uranium recovery method
CN105561927B (en) A kind of method using nitrogenous material adsorbing separation palladium
CN114572960B (en) Preparation method of graphite oxide alkyne membrane material for adsorption separation of uranium
CN105854842B (en) A kind of method from water phase adsorbing separation molybdenum
CN106045976B (en) A kind of nitrogenous soft ligand derivatives and its synthesis and application
Dai et al. Homogeneous liquid–liquid extraction of europium from aqueous solution with ionic liquids
CN105753861B (en) Phenanthroline derivative, and preparation method and application thereof
CN112462410A (en) Method for analyzing plutonium in waste ion exchange resin sample
Deepika et al. Studies on separation of minor actinides from lanthanides from high level waste by extraction chromatography using 2, 6-bistriazinyl pyridine
CN111485125A (en) Method for recovering technetium from spent fuel post-treatment waste liquid
Dai et al. Extraction behavior of cesium from nitric acid medium with calix [4]-bis [(4-tert-butyl-1, 2-phenylene)-crown-6]
JP2011047665A (en) Solid extractant for radioactive element
CN109749081A (en) A kind of covalent frame material of hydrazone class functionalization and its synthesis and application
CN101802930A (en) purification of metals
CN114635037B (en) Method for extracting and separating trivalent lanthanide and/or trivalent actinide
CN113470843A (en) Method for producing radioactive isotope
CN109317116A (en) A kind of compound resin and preparation method thereof and recovery method to palladium in nitric acid medium
CN110180512A (en) The carbon-based asymmetric supermolecule of double crown containing naphtho- hybrid material of one kind and its preparation method and application
CN114560889B (en) Asymmetric phospho-pyridine triazine derivative and synthetic method thereof

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180706