CN105771904A - Magnetic adsorbent as well as preparation method thereof, and recycling of palladium in nitric acid medium - Google Patents
Magnetic adsorbent as well as preparation method thereof, and recycling of palladium in nitric acid medium Download PDFInfo
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Abstract
The invention relates to a magnetic adsorbent as well as a preparation method thereof, and recycling of palladium in a nitric acid medium. Through amidation catalyzed by EDC.HCL and NHS, a polyaza polycarboxylic acid derivative is modified on the outer surface of an amino-functionalized magnetic microsphere, and a core-shell structure adsorbent, provided with a Fe3O4 magnetic nanoparticle as a core, SiO2 as a protective shell, and the polyaza polycarboxylic acid derivative modified on the outer edge of the shell, is prepared. The preparation technology has the advantages of low energy consumption, low cost and simple operation. The magnetic adsorbent has large palladium adsorption capacity and high adsorption rate in a relatively wide nitric acid concentration range; even under interference from various high-level liquid waste fission product nuclides, the magnetic adsorbent exerts excellent selective separation ability; however, palladium absorbed on the surface of the adsorbent can be eluted by a nitric acid solution containing 5% thiourea, thereby facilitating recycling.
Description
Technical field
The invention belongs to the utilization of resources and environmental protection technical field, particularly to a kind of magnetic adsorbent and preparation method thereof with to the recovery of palladium in nitric acid medium.
Background technology
The present age at the energy and environment two principal themes, increasingly serious with the problem such as greenhouse effect, haze pollution, actively development energy density is high, the nuclear energy of cleaning low-carbon (LC), can not only be effectively improved energy resource structure, alleviate ambient pressure, be more beneficial for ensureing the energy and the economic security of country.According to the planning of China nuclear power Long-and Medium-term Development (National Development and Reform Commission. nuclear power Long-and Medium-term Development planning 2005-2020,2007.), by the year two thousand twenty, China runs nuclear power installation and is up to 58,000,000 kilowatts, is building 30,000,000 kilowatts.But, nuclear fuel all can produce substantial amounts of radioactive liquid waste in the process of circulation and post processing, and wherein human lives and ecological environment are constituted potentially hazardous by the sliver nucleic of strong heat release and actinium series nucleic.Therefore, the new separation technology of research and development environmental protection realizes the Selective Separation of sliver, actinium series nucleic, and sustainable use and environmental conservation to resource all have important strategic importance.
Palladium is as a member of platinum group metal, and the content in the earth's crust is only about 10-6, but the physicochemical property of its brilliance, it is widely used in the field such as shape selective catalysis and automotive components manufacture.But, the limited resource provision of nature is difficult to meet the demand of people's sustainable growth.In recent years, the sliver palladium in high-level waste causes everybody concern gradually.According to the literature, the sliver palladium total amount that the spentnuclear fuel of power reactor was accumulated in the year two thousand thirty is up to 1000t, will alleviate the present situation of current palladium resource supply and demand imbalance to a great extent.Secondly, in 6 kinds of isotopes of sliver palladium, only have the Pd107 that content is 17% and there is radioactive and maximum ray energy only have 35Kev, be a kind of more weak β ray, can apply in a lot of industrial materials.It addition, sliver palladium is easily formed single-phase in the process of the final glass solidification of high-level waste, this can be substantially reduced the stability of glass solidified body, easily causes the leakage of radwaste.Therefore, the Selective Separation studying sliver palladium all has important directive significance in the field such as hydrometallurgy and nuclear fuel reprocessing.
At present, in nitric acid medium, the separation method of sliver palladium mainly has: ion exchange, solvent extraction and absorption method.In comparison, absorption method because of the operation few, easy of the secondary liquid waste of its generation, cost of material is low and separation efficiency is high advantage, the enrichment being applied in high-level waste low concentration sliver palladium gradually with separate.Tsing-Hua University successively reports amidized dicyclohexyl 18 hat six ether (GangYe, etal.SeparationandPurificationTechnology.2013,106,38-46) with amidized calixarenes crown ether (GangYe, etal.ChemicalEngineeringJournal.2013,232,319-326) mesoporous silicon oxide modified is to the separation of sliver palladium in nitric acid medium, and achieves comparatively ideal result.But, mesoporous material is put by force at nuclear fuel reprocessing, peracid when separation then become a difficult problem.Additionally, the sorbent material of conventional solid abstraction technique, if mesoporous silicon, CNT, organometallic skeletal structure are in the process of chromatographic column filler separation nucleic, also facing the problem that the resistance to mass tranfer caused because post pressure raises is excessive, these all limit its application in actual industrial.
Nitrogen heterocyclic ring carboxylic acid derivates is the saturated macrocycle molecule that a class contains multiple C, N, O atom, atom N is the distribution in high degree of symmetry in ring, the carboxyl arm being close to is outside ring, multiple O, atom N can be provided simultaneously to participate in the coordination model construction of transition metal, part heavy metal and rare metal, be widely used in nuclear-magnetism development and put in the medical domains such as medicine labelling.But up to now, about the nitrogen heterocyclic ring carboxylic acid derivates coordination situation to noble metal, particularly relate to the sharp separation of sliver palladium in high-level waste and then not yet report.It addition, nitrogen heterocyclic ring carboxylic acid derivates is because of the existence of carboxyl and atom N, soluble loss in nitric acid environment, it is necessary to modified in solid phase material surface, to realize metal biosorption is separated.
Summary of the invention
Not enough for prior art, the invention provides a kind of magnetic adsorbent and preparation method thereof with to the recovery of palladium in nitric acid medium.
A kind of magnetic adsorbent, it is with Fe3O4Magnetic nanoparticle is nuclear core, SiO2For protection shell, nitrogen heterocyclic ring carboxylic acid derivates modifies the core-shell structure magnetic adsorbent in shell outer rim；Containing atom N on the ring skeleton of described nitrogen heterocyclic ring carboxylic acid derivates, the atom N on ring skeleton is connected with carboxyl arm, and described carboxyl arm is positioned at outside ring.
Further, described nitrogen heterocyclic ring carboxylic acid derivates is Isosorbide-5-Nitrae, 7-7-triazacyclononane-Isosorbide-5-Nitrae, 7-triacetic acid, 1,4,7,10-tetraazacyclododecanands-Isosorbide-5-Nitrae, 7,10-tetraacethyls, 1,4,8,11-tetraazacyclododecane tetradecanes-Isosorbide-5-Nitrae, 8,11-tetraacethyls, 1,4,7,10,13-five-nitrogen heterocyclic pentadecanes-Isosorbide-5-Nitrae, 7,10,13-pentaacetic acids or Isosorbide-5-Nitrae, 7,10,13,16-hexanitrogen heterocycle octadecane-Isosorbide-5-Nitrae, 7,10,13,16-six acetic acid.
The preparation method of above-mentioned a kind of magnetic adsorbent, comprises the following steps:
(1) nitrogen heterocyclic ring carboxylic acid derivates is dissolved in the biological buffer solutions that pH is 5.2～5.6, under nitrogen protection, adds catalyst EDC HCl and NHS, stirring reaction 1h under room temperature, prepare the activated intermediate of nitrogen heterocyclic ring carboxylic acid derivates；
(2) in above-mentioned reactant liquor, add the magnetic microsphere of amino functional, after ultrasonic disperse, temperature and the response time of control system terminate to amidation process, after Magnet separation product, with the alternately washing of 0.1mol/LHCl solution, second alcohol and water for several times, 45 DEG C of vacuum drying 12h, prepare core-shell structure magnetic adsorbent；The magnetic microsphere of described amino functional is with Fe3O4Magnetic nanoparticle is nuclear core, SiO2For protecting shell, containing terminal amino group structure on shell.
In the reaction system of step (1), often activation 1mmol nitrogen heterocyclic ring carboxylic acid derivates, the mol ratio that amount is 9.95～40.05mmol, EDC HCl and NHS addition that need to add catalyst EDC HCl is (2～2.5): 1.
In the reaction system of step (1), described biological buffer solutions is the morpholino b acid aqueous solution of 1.0mol/L, and the amount of addition is the every 1.0mmol nitrogen heterocyclic ring carboxylic acid derivates of 45～55mL biological buffer solutions.
In the reaction system of step (2), the magnetic microsphere addition of described amino functional is the every 1mmol nitrogen heterocyclic ring carboxylic acid derivates of 0.45～0.55g.
The reaction system of step (2), controls reaction first stirring reaction 8h at 25 ± 0.2 DEG C, after be adjusted at 4 ± 0.2 DEG C standing 12～16h.
A kind of magnetic adsorbent is to the recovery of palladium in nitric acid medium, and described magnetic adsorbent, after vacuum drying, joins in the salpeter solution of palladium, after ultrasonic 5min, with 200r/min vibration to adsorption equilibrium under the constant temperature of 25 ± 0.2 DEG C.
The salpeter solution of described palladium, nitric acid acidity is 0.01～5.0mol/L, and the concentration of palladium is 48～52mg/L.
Often processing the salpeter solution of palladium described in 10mL, the magnetic absorption dosage of addition is 0.09～0.11g.
A kind of magnetic adsorbent is to the recovery of palladium in nitric acid medium, and described magnetic adsorbent, after vacuum drying, joins in high activity liquid waste analog material liquid, after ultrasonic 5min, with 200r/min vibration to adsorption equilibrium under the constant temperature of 25 ± 0.2 DEG C；In described high activity liquid waste analog material liquid, nitric acid acidity is 0.9～1.1mol/L, and sliver nucleic includes K, Cs, Sr, Ba, Cd, Ni, Nd, Cr, Ru, Fe, Pd, and corresponding mass concentration is 48～52mg/L.
Often processing high activity liquid waste analog material liquid described in 10mL, the magnetic absorption dosage of addition is 0.1～0.15g.
The palladium of described magnetic adsorbent surface adsorption, adopts the salpeter solution desorption of 5% thiourea under the constant temperature of 25 ± 0.2 DEG C, it is achieved recycle.
Absorption principle: multiple atom N on nitrogen heterocyclic ring carboxylic acid derivates ring and the O atom of carboxyl arm, stable complex can be built in nitric acid medium with palladium, the sequestering power of other sliver nucleic is affected by the restriction of ring cavity size, atom N and carboxyl arm O atom Protonation effect, and the degree of freedom restriction on solid phase material surface, the corresponding complex structure of more difficult formation in nitric acid medium, therefore has Selective recognition and separating property to the palladium in nitric acid medium.
The invention have the benefit that
1) present invention is by the amidation process of EDC HCl and NHS catalysis, and nitrogen heterocyclic ring carboxylic acid derivates is modified the SiO of magnetic composite microsphere2Shell outer rim, it is prepared for the novel magnetic adsorbent with nucleocapsid structure, and preparation technology energy consumption is low, easy and simple to handle, adopt the biological buffer that low toxicity, environmental pollution are little as reaction dissolvent, avoid the consumption of organic solvent in conventional adsorbent preparation process, reduce operating cost, economic and environment-friendly, it is easy to accomplish to amplify and produce.
2) the nitrogen heterocyclic ring carboxylic acid derivates of the magnetic adsorbent finishing that prepared by the present invention, within the scope of wider concentration of nitric acid, palladium adsorption capacity is big, the rate of adsorption is fast, and under the interference of multiple high activity liquid waste sliver nucleic, palladium is shown splendid Selective Separation ability, and the palladium of adsorbent surface absorption with the salpeter solution eluting of 5% thiourea, can be beneficial to recycling.
3) magnetic adsorbent of our bright preparation has good superparamagnetic performance, is easily isolated, shortens the cycle of solid-liquid separation in Solid-Phase Extraction under outside the action of a magnetic field, is suitable to put by force, operation under low acid extreme condition, and cost is low, separation efficiency is high.
Accompanying drawing explanation
Fig. 1 (a) is the magnetic microsphere transmission electron microscope photo of amino functional in embodiment 1；
Fig. 1 (b) is the transmission electron microscope photo of magnetic adsorbent in embodiment 1；
Fig. 2 (a) is Fe3O4The X ray of magnetic nanoparticle derives spectrogram；Fig. 2 (b) is the derivative spectrogram of the X ray of the magnetic microsphere of amino functional in embodiment 1；Fig. 2 (c) is the derivative spectrogram of the X ray of magnetic adsorbent in embodiment 1；
Fig. 3 is the curve chart of the magnetic adsorbent adsorption rate to palladium and concentration of nitric acid.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.It is emphasized that the description below is merely exemplary, rather than in order to limit the scope of the present invention and application thereof.
Embodiment 1: the preparation method of a kind of magnetic adsorbent, comprises the following steps:
(1) by 1.0mmol nitrogen heterocyclic ring carboxylic acid derivates 1; 4,7,10-tetraazacyclododecanands-1; 4; 7,10-tetraacethyls (DOTA) are dissolved in 50mL morpholino b acid biological buffer solutions, and regulating pH buffering interval is 5.4～5.5; under nitrogen protection; add catalyst 25.0mmolEDC HCl and 10mmolNHS, stirring reaction 1h under room temperature, prepare the activated intermediate of nitrogen heterocyclic ring carboxylic acid derivates DOTA.
(2) in above-mentioned reactant liquor add 0.5g amino functional magnetic microsphere (preparation of the magnetic microsphere of amino functional is with reference to relevant document WangXiangke, etal.ChemicalEngineeringJournal.2014,235,275-283), after ultrasonic disperse, first at 25 ± 0.2 DEG C of temperature, under churned mechanically effect, react 8h, be cooled to 4 ± 0.2 DEG C and stand 12h.After Magnet separation product, with the alternately washing of 0.1mol/LHCl, second alcohol and water for several times, vacuum drying 12h at 45 DEG C, prepare required core-shell structure magnetic adsorbent.
The transmission electron microscope photo of the magnetic microsphere that Fig. 1 (a) is amino functional, it is possible to substantially observe nuclear core Fe3O4(the black part that color is deeper) particle diameter is about 300nm, SiO2Shell (grey parts that color is shallower) thickness is about 20nm.The transmission electron microscope photo that Fig. 1 (b) is magnetic adsorbent, its original shell pattern and thickness do not have significant change, illustrate that nitrogen heterocyclic ring carboxylic acid derivates is mainly modified at SiO2The edge of shell.
Fig. 2 (a) is Fe3O4The X ray of magnetic nanoparticle derives spectrogram, corresponding crystal face respectively (111), (220), (311), (400), (422), (511), (440), belongs to standard Fe3O4The centroid cubic crystal system of card；The X ray of the magnetic microsphere that Fig. 2 (b) is amino functional derives spectrogram, the X ray that Fig. 2 (c) is magnetic adsorbent derives spectrogram, can be seen that the functionalization of amino and the modification of organic molecule nitrogen heterocyclic ring carboxylic acid derivates, all without changing original Fe3O4Crystalline structure.
Embodiment 2: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette 50mg/L palladium solution 10mL that nitric acid acidity is 0.01mol/L in conical flask, add the magnetic adsorbent 0.1g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out the supernatant, by the mass concentration of Atomic Absorption Spectrometry wherein palladium, calculate this adsorbent now adsorption rate E=99.8% to palladium according to adsorption equilibrium formula.
Embodiment 3: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette 50mg/L palladium solution 10mL that nitric acid acidity is 0.1mol/L in conical flask, add the magnetic adsorbent 0.1g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out the supernatant, by the mass concentration of Atomic Absorption Spectrometry wherein palladium, calculate this adsorbent now adsorption rate E=98.2% to palladium according to adsorption equilibrium formula.
Embodiment 4: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette 50mg/L palladium solution 10mL that nitric acid acidity is 0.5mol/L in conical flask, add the magnetic adsorbent 0.1g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out the supernatant, by the mass concentration of Atomic Absorption Spectrometry wherein palladium, calculate this adsorbent now adsorption rate E=90.3% to palladium according to adsorption equilibrium formula.Embodiment 5: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette 50mg/L palladium solution 10mL that nitric acid acidity is 1.0mol/L in conical flask, add the magnetic adsorbent 0.1g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out the supernatant, by the mass concentration of Atomic Absorption Spectrometry wherein palladium, calculate this adsorbent now adsorption rate E=76.7% to palladium according to adsorption equilibrium formula.Embodiment 6: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette 50mg/L palladium solution 10mL that nitric acid acidity is 2.0mol/L in conical flask, add the magnetic adsorbent 0.1g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out the supernatant, by the mass concentration of Atomic Absorption Spectrometry wherein palladium, calculate this adsorbent now adsorption rate E=66.1% to palladium according to adsorption equilibrium formula.Embodiment 7: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette 50mg/L palladium solution 10mL that nitric acid acidity is 3.0mol/L in conical flask, add the magnetic adsorbent 0.1g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out the supernatant, by the mass concentration of Atomic Absorption Spectrometry wherein palladium, calculate this adsorbent now adsorption rate E=60.7% to palladium according to adsorption equilibrium formula.Embodiment 8: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette 50mg/L palladium solution 10mL that nitric acid acidity is 4.0mol/L in conical flask, add the magnetic adsorbent 0.1g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out the supernatant, by the mass concentration of Atomic Absorption Spectrometry wherein palladium, calculate this adsorbent now adsorption rate E=53.1% to palladium according to adsorption equilibrium formula.Embodiment 9: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette 50mg/L palladium solution 10mL that nitric acid acidity is 5.0mol/L in conical flask, add the magnetic adsorbent 0.1g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out the supernatant, by the mass concentration of Atomic Absorption Spectrometry wherein palladium, calculate this adsorbent now adsorption rate E=50.3% to palladium according to adsorption equilibrium formula.
Fig. 3 is in nitric acid medium, magnetic adsorbent adsorption rate E and concentration of nitric acid C (HNO to palladium3) curve chart, palladium is had stronger absorption property by magnetic adsorbent within the scope of the concentration of nitric acid of 0.01～5.0mol/L, and adsorption rate is more than 50%, and adsorption rate is relatively low with the rising of concentration of nitric acid, concentration of nitric acid is lower than 1.0mol/L, and the adsorption rate of palladium is more than 76% by magnetic adsorbent；Concentration of nitric acid is lower than 0.5mol/L, and the adsorption rate of palladium is more than 90% by magnetic adsorbent；Concentration of nitric acid is lower than 0.1mol/L, and the adsorption rate of palladium is more than 98% by magnetic adsorbent；Concentration of nitric acid is 0.01mol/L, and the adsorption rate of palladium is reached 99.8% by magnetic adsorbent；This is primarily due under high concentration of nitric acid, and atom N and the O atom of carboxyl arm in ring understand protonation, thus causing H+Adsorption site with palladium competitive adsorbate surface.
Embodiment 10: recycling of magnetic adsorbent
Selecting the salpeter solution parsing agent as palladium of 5% thiourea, wherein concentration of nitric acid is 0.5mol/L.Embodiment 4 will reach the magnetic adsorbent after adsorption equilibrium, after Magnet separates, with deionized water wash 4-5 time, to remove the salpeter solution of the palladium of residual non-adsorbed, after 60 DEG C of dry 12h of vacuum, it is transferred in conical flask, and add the salpeter solution of 5% thiourea, vibrate 2h with 200r/min in the constant temperature air bath of 25 ± 0.2 DEG C, after centrifugation solid, take out supernatant sample, by the mass concentration of Atomic Absorption Spectrometry palladium.Calculating, according to adsorption equilibrium formula, the eluting rate that now palladium is accumulative is 92%.As shown in table 1, after magnetic adsorbent round-robin 4 times, to the absorption property of palladium without obvious reduction.
Table 1
Embodiment 11: the magnetic adsorbent of embodiment 1 gained is to the recovery of palladium in nitric acid medium
Pipette high activity liquid waste sliver radionuclide solution 10mL that nitric acid acidity is 1.0mol/L in conical flask, add the magnetic adsorbent 0.15g of embodiment 1 gained, after ultrasonic 5min, with 200r/min vibration 24h the constant temperature air bath of 25 ± 0.2 DEG C in.After Magnet separating adsorbent, take out residue clear liquid, measure each sliver nucleic K with inductively-coupled plasma spectrometer (ICP-OES), Cs, Sr, Ba, Cd, Ni, Nd, Cr, Ru, Fe, the mass concentration of Pd, calculating this adsorbent according to adsorption equilibrium formula is now 93.1% to the adsorption rate of palladium, and the adsorption rate of other sliver nucleic is all below 5%, and concrete outcome is shown in Table 2.
Table 2
Claims (13)
1. a magnetic adsorbent, it is characterised in that it is with Fe3O4Magnetic nanoparticle is nuclear core, SiO2For protection shell, nitrogen heterocyclic ring carboxylic acid derivates modifies the core-shell structure magnetic adsorbent in shell outer rim；Containing atom N on the ring skeleton of described nitrogen heterocyclic ring carboxylic acid derivates, the atom N on ring skeleton is connected with carboxyl arm, and described carboxyl arm is positioned at outside ring.
2. a kind of magnetic adsorbent according to claim 1, it is characterised in that described nitrogen heterocyclic ring carboxylic acid derivates is Isosorbide-5-Nitrae, 7-7-triazacyclononane-Isosorbide-5-Nitrae, 7-triacetic acid, 1,4,7,10-tetraazacyclododecanands-Isosorbide-5-Nitrae, 7,10-tetraacethyls, 1,4,8,11-tetraazacyclododecane tetradecanes-Isosorbide-5-Nitrae, 8,11-tetraacethyls, 1,4,7,10,13-five-nitrogen heterocyclic pentadecanes-Isosorbide-5-Nitrae, 7,10,13-pentaacetic acids or Isosorbide-5-Nitrae, 7,10,13,16-hexanitrogen heterocycle octadecane-Isosorbide-5-Nitrae, 7,10,13,16-six acetic acid.
3. the preparation method of a kind of magnetic adsorbent described in claim 1 or 2, it is characterised in that comprise the following steps:
(1) nitrogen heterocyclic ring carboxylic acid derivates is dissolved in the biological buffer solutions that pH is 5.2～5.6, under nitrogen protection, adds catalyst EDC HCl and NHS, stirring reaction 1h under room temperature, prepare the activated intermediate of nitrogen heterocyclic ring carboxylic acid derivates；
(2) in above-mentioned reactant liquor, add the magnetic microsphere of amino functional, after ultrasonic disperse, temperature and the response time of control system terminate to amidation process, after Magnet separation product, with the alternately washing of 0.1mol/LHCl solution, second alcohol and water for several times, 45 DEG C of vacuum drying 12h, prepare core-shell structure magnetic adsorbent；The magnetic microsphere of described amino functional is with Fe3O4Magnetic nanoparticle is nuclear core, SiO2For protecting shell, containing terminal amino group structure on shell.
4. the preparation method of a kind of magnetic adsorbent according to claim 3, it is characterized in that, in the reaction system of step (1), often activation 1mmol nitrogen heterocyclic ring carboxylic acid derivates, the mol ratio that amount is 9.95～40.05mmol, EDC HCl and NHS addition that need to add catalyst EDC HCl is (2～2.5): 1.
5. the preparation method of a kind of magnetic adsorbent according to claim 3, it is characterized in that, in the reaction system of step (1), described biological buffer solutions is the morpholino b acid aqueous solution of 1.0mol/L, and the amount of addition is the every 1.0mmol nitrogen heterocyclic ring carboxylic acid derivates of 45～55mL biological buffer solutions.
6. the preparation method of a kind of magnetic adsorbent according to claim 3, it is characterised in that in the reaction system of step (2), the magnetic microsphere addition of described amino functional is the every 1mmol nitrogen heterocyclic ring carboxylic acid derivates of 0.45～0.55g.
7. the preparation method of a kind of magnetic adsorbent according to claim 3, it is characterised in that the reaction system of step (2), controls reaction first stirring reaction 8h at 25 ± 0.2 DEG C, after be adjusted at 4 ± 0.2 DEG C standing 12～16h.
8. a kind of magnetic adsorbent described in claim 1 is to the recovery of palladium in nitric acid medium, it is characterized in that, described magnetic adsorbent, after vacuum drying, joins in the salpeter solution of palladium, after ultrasonic 5min, with 200r/min vibration to adsorption equilibrium under the constant temperature of 25 ± 0.2 DEG C.
9. according to claim 8 a kind of magnetic adsorbent to the recovery of palladium in nitric acid medium, it is characterised in that the salpeter solution of described palladium, nitric acid acidity is 0.01～5.0mol/L, and the concentration of palladium is 48～52mg/L.
10. according to claim 9 a kind of magnetic adsorbent to the recovery of palladium in nitric acid medium, it is characterised in that often processing the salpeter solution of palladium described in 10mL, the magnetic absorption dosage of addition is 0.09～0.11g.
11. a kind of magnetic adsorbent described in claim 1 is to the recovery of palladium in nitric acid medium, it is characterized in that, described magnetic adsorbent, after vacuum drying, joins in high activity liquid waste analog material liquid, after ultrasonic 5min, with 200r/min vibration to adsorption equilibrium under the constant temperature of 25 ± 0.2 DEG C；In described high activity liquid waste analog material liquid, nitric acid acidity is 0.9～1.1mol/L, and sliver nucleic includes K, Cs, Sr, Ba, Cd, Ni, Nd, Cr, Ru, Fe, Pd, and corresponding mass concentration is 48～52mg/L.
12. a kind of magnetic adsorbent is to the recovery of palladium in nitric acid medium according to claim 11, it is characterised in that often processing high activity liquid waste analog material liquid described in 10mL, the magnetic absorption dosage of addition is 0.1～0.15g.
13. a kind of magnetic adsorbent described in-12 any claim is to the recovery of palladium in nitric acid medium according to Claim 8, it is characterized in that, the palladium of described magnetic adsorbent surface adsorption, adopts the salpeter solution desorption of 5% thiourea under the constant temperature of 25 ± 0.2 DEG C, it is achieved recycle.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106237947A (en) * | 2016-08-31 | 2016-12-21 | 上海美吉生物医药科技有限公司 | Magnetic microsphere of high density carboxyl modified and preparation method thereof |
| CN108503602A (en) * | 2018-04-28 | 2018-09-07 | 浙江树人学院 | It is a kind of efficiently can Magneto separate remove palladium reagent preparation and application |
| CN110215899A (en) * | 2019-04-01 | 2019-09-10 | 重庆科技学院 | A kind of amino acid functionalised metal-organic framework materials and its preparation method and application |
| CN113117754A (en) * | 2021-04-14 | 2021-07-16 | 上海理工大学 | Flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst and preparation method and application thereof |
| CN113564368A (en) * | 2021-08-24 | 2021-10-29 | 华中科技大学 | Method for recovering nickel and cobalt from petroleum cracking catalyst dust |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012091125A1 (en) * | 2010-12-28 | 2012-07-05 | 東ソー株式会社 | Method for collecting precious metals from solution containing precious metal ions, extractant or adsorbent used therefor, and back extractant or desorbent |
| CN102574099A (en) * | 2009-08-21 | 2012-07-11 | 东曹株式会社 | Palladium ion adsorbent and method for separating and recovering palladium using same |
| CN102614683A (en) * | 2012-04-05 | 2012-08-01 | 浙江大学 | Method for separating element palladium and sub-actinide elements from high-level waste |
-
2016
- 2016-03-09 CN CN201610133543.XA patent/CN105771904B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574099A (en) * | 2009-08-21 | 2012-07-11 | 东曹株式会社 | Palladium ion adsorbent and method for separating and recovering palladium using same |
| WO2012091125A1 (en) * | 2010-12-28 | 2012-07-05 | 東ソー株式会社 | Method for collecting precious metals from solution containing precious metal ions, extractant or adsorbent used therefor, and back extractant or desorbent |
| CN102614683A (en) * | 2012-04-05 | 2012-08-01 | 浙江大学 | Method for separating element palladium and sub-actinide elements from high-level waste |
Non-Patent Citations (2)
| Title |
|---|
| CHIH-CHIA HUANG,ET AL: "Enhancing transversal relaxation for magnetite nanoparticles in MR imaging using Gd3+-chelated mesoporous silica shells", 《ACS NANO》 * |
| 吴奉承等: "氮杂大环配体修饰的介孔二氧化硅对硝酸介质中裂片靶的选择性分离", 《第三届全国核化学与放射化学青年学术研讨会论文摘要集》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106237947A (en) * | 2016-08-31 | 2016-12-21 | 上海美吉生物医药科技有限公司 | Magnetic microsphere of high density carboxyl modified and preparation method thereof |
| CN106237947B (en) * | 2016-08-31 | 2019-07-30 | 上海美吉生物医药科技有限公司 | The magnetic microsphere and preparation method thereof of high density carboxyl modified |
| CN108503602A (en) * | 2018-04-28 | 2018-09-07 | 浙江树人学院 | It is a kind of efficiently can Magneto separate remove palladium reagent preparation and application |
| CN108503602B (en) * | 2018-04-28 | 2023-05-23 | 浙江树人学院 | Preparation and application of efficient magnetic separation palladium removal reagent |
| CN110215899A (en) * | 2019-04-01 | 2019-09-10 | 重庆科技学院 | A kind of amino acid functionalised metal-organic framework materials and its preparation method and application |
| CN110215899B (en) * | 2019-04-01 | 2022-03-25 | 重庆科技学院 | Amino acid functionalized metal organic framework material and preparation method and application thereof |
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| CN113564368A (en) * | 2021-08-24 | 2021-10-29 | 华中科技大学 | Method for recovering nickel and cobalt from petroleum cracking catalyst dust |
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