CN105771904B - A kind of magnetic adsorbent and preparation method thereof and the recycling to palladium in nitric acid medium - Google Patents
A kind of magnetic adsorbent and preparation method thereof and the recycling to palladium in nitric acid medium Download PDFInfo
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Abstract
The present invention relates to a kind of magnetic adsorbents and preparation method thereof and the recycling to palladium in nitric acid medium.Nitrogen heterocyclic ring carboxylic acid derivates are modified to the magnetic microsphere outer surface of amino functional, are prepared for Fe by the amidation process being catalyzed by EDC HCl and NHS3O4Magnetic nanoparticle is core, SiO2To protect shell, nitrogen heterocyclic ring carboxylic acid derivates are modified in the core-shell structure adsorbent of shell outer rim, and low energy consumption by preparation process, at low cost, easy to operate.Magnetic adsorbent is within the scope of wider concentration of nitric acid, it is big to palladium adsorption capacity, the rate of adsorption is fast, and under the interference of a variety of high activity liquid waste sliver nucleic, splendid Selective Separation ability is shown to palladium, and the palladium of adsorbent surface absorption can be eluted with the nitric acid solution of 5% thiocarbamide, be conducive to be recycled.
Description
Technical field
The invention belongs to the utilization of resources and environmental protection technical field, in particular to a kind of magnetic adsorbent and its preparation side
Method and the recycling to palladium in nitric acid medium.
Background technique
It is increasingly serious the problems such as with greenhouse effects, haze pollution in the present age of the energy and environment two principal themes, actively
The nuclear energy for developing energy density height, cleaning low-carbon, not only can effectively improve energy resource structure, alleviates environmental pressure, is more advantageous to guarantor
Hinder the energy and economic security of country.According to the planning of China's nuclear power Long-and Medium-term Development (in National Development and Reform Commission's nuclear power
Long-range developmental program 2005-2020,2007.), by arriving the year two thousand twenty, China's operation nuclear power installation is up to 58,000,000 kilowatts,
Build 30,000,000 kilowatts.However, nuclear fuel can all generate a large amount of radioactive liquid waste during circulation and post-processing, wherein by force
The sliver nucleic and actinium series nucleic of heat release all constitute human lives and ecological environment potentially hazardous.Therefore, research and development green
The new separation technology of environmental protection realizes the Selective Separation of sliver, actinium series nucleic, sustainable use and environmental protection to resource
All there is important strategic importance.
The a member of palladium as platinum group metal, the content in the earth's crust are only about 10-6, but its brilliant physicochemical property, it is extensive
Applied to the fields such as shape selective catalysis and automotive components manufacture.Continue however, the limited resource provision of nature is difficult to meet people
The demand of growth.In recent years, the sliver palladium in high-level waste gradually causes everybody concern.According to the literature, power reactor
Spentnuclear fuel is up to 1000t in the sliver palladium total amount that the year two thousand thirty accumulates, and will largely alleviate current palladium resource supply and demand and lose
The status of tune.Secondly, in 6 kinds of isotopes of sliver palladium, the Pd107 that only content is 17% be have it is radioactive and maximum
Ray energy there was only 35Kev, be a kind of weaker β ray, can be applied in many industrial materials.In addition, sliver palladium is in height
Easily formed single-phase during putting the final glass solidification of waste, this will be greatly reduced the stability of glass solidified body, easily causes and puts
The leakage of injectivity waste.Therefore, the Selective Separation for studying sliver palladium all has in the fields such as hydrometallurgy and nuclear fuel post-processing
There is important directive significance.
Currently, mainly there is the separation method of sliver palladium in nitric acid medium: ion-exchange, solvent extraction and absorption method.
In comparison, the secondary liquid waste that absorption method is generated by it is few, the advantage that easy to operate, cost of material is low and separative efficiency is high, by by
Gradually be applied to high-level waste in low concentration sliver palladium enrichment with separate.Tsinghua University successively reports amidized dicyclohexyl
18 hat six ethers (Gang Ye, et al.Separation and Purification Technology.2013,106,38-
46) and amidized calixarenes crown ether (Gang Ye, et al.Chemical Engineering Journal.2013,232,
319-326) separation of the mesoporous silicon oxide modified to sliver palladium in nitric acid medium, and achieve comparatively ideal result.But
Mesoporous material nuclear fuel post-processing put by force, peracid under the conditions of separation then become problem.In addition, conventional solid abstraction technique
Sorbent material, if mesoporous silicon, carbon nanotube, organometallic skeletal structure chromatographic column filler separate nucleic during,
Also the excessive problem of the resistance to mass tranfer because caused by increasing column pressure can be faced, these all limit its answering in actual industrial
With.
Nitrogen heterocyclic ring carboxylic acid derivates are a kind of saturation macrocycle molecules containing multiple C, N, O atom, and N atom is in ring
High degree of symmetry distribution, the carboxyl arm being close to can provide multiple O, N atoms simultaneously and participate in transition metal, a part huge sum of money on the outside of ring
Belong to the coordination model construction with rare metal, be widely used in nuclear-magnetism development and put in the medical domains such as medicine label.But so far
Until, about nitrogen heterocyclic ring carboxylic acid derivates in the coordination situation more particularly to high-level waste of noble metal sliver palladium it is quick
Separation then has not been reported.In addition, presence of the nitrogen heterocyclic ring carboxylic acid derivates because of carboxyl and N atom, soluble in nitric acid environment
It is lost, needs to be modified in solid phase material surface, to realize the adsorbing separation to metal ion.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of magnetic adsorbent and preparation method thereof in nitric acid medium
The recycling of palladium.
A kind of magnetic adsorbent is with Fe3O4Magnetic nanoparticle is core, SiO2To protect shell, nitrogen heterocyclic ring carboxylic
Acid derivative is modified in the core-shell structure magnetic adsorbent of shell outer rim；Contain in the ring skeleton of the nitrogen heterocyclic ring carboxylic acid derivates
There is N atom, the N atom in ring skeleton is connected with carboxyl arm, and the carboxyl arm is located at outside ring.
Further, the nitrogen heterocyclic ring carboxylic acid derivates be Isosorbide-5-Nitrae, 7- 7-triazacyclononane-Isosorbide-5-Nitrae, 7- triacetic acid, Isosorbide-5-Nitrae,
7,10- tetraazacyclododecanand -1,4,7,10- tetraacethyl, 1,4,8,11- tetraazacyclododecane tetradecane -1,4,8,11- tetraacethyl,
1,4,7,10,13- five-nitrogen heterocyclic pentadecane -1,4,7,10,13- pentaacetic acid or 1,4,7,10,13,16- hexanitrogen heterocycle octadecane -
Six acetic acid of 1,4,7,10,13,16-.
A kind of preparation method of above-mentioned magnetic adsorbent, comprising the following steps:
(1) nitrogen heterocyclic ring carboxylic acid derivates are dissolved in the biological buffer solutions that pH is 5.2~5.6, under nitrogen protection,
Catalyst EDCHCl and NHS is added, is stirred to react 1h at room temperature, prepares the activated intermediate of nitrogen heterocyclic ring carboxylic acid derivates；
(2) magnetic microsphere of amino functional is added into above-mentioned reaction solution, after ultrasonic disperse, the temperature of control system and
Reaction time to amidation process terminates, and after magnet separates product, alternately washs number with 0.1mol/L HCl solution, second alcohol and water
Secondary, core-shell structure magnetic adsorbent is made in 45 DEG C of vacuum drying 12h；The magnetic microsphere of the amino functional is with Fe3O4Magnetic
Property nano particle be core, SiO2To protect shell, contain terminal amino group structure on shell.
In the reaction system of step (1), catalyst EDC need to be added in every activation 1mmol nitrogen heterocyclic ring carboxylic acid derivates
The amount of HCl is 9.95~40.05mmol, and the molar ratio of EDCHCl and NHS additional amount is (2~2.5): 1.
In the reaction system of step (1), the biological buffer solutions are the morpholino b acid aqueous solution of 1.0mol/L, are added
Amount be 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 additional amount of the amino functional is that 0.45~0.55g is every
1mmol nitrogen heterocyclic ring carboxylic acid derivates.
The reaction system of step (2), control reaction first at 25 ± 0.2 DEG C are stirred to react 8h, after be adjusted to 4 ± 0.2 DEG C
12~16h of lower standing.
A kind of recycling of magnetic adsorbent to palladium in nitric acid medium is added to after the magnetic adsorbent is vacuum dried
In the nitric acid solution of palladium, after ultrasonic 5min, vibrated with 200r/min to adsorption equilibrium under 25 ± 0.2 DEG C of constant temperature.
The nitric acid solution of the palladium, nitric acid acidity are 0.01~5.0mol/L, and the concentration of palladium is 48~52mg/L.
The nitric acid solution of palladium described in every processing 10mL, the magnetic absorption dosage of addition are 0.09~0.11g.
A kind of recycling of magnetic adsorbent to palladium in nitric acid medium is added to after the magnetic adsorbent is vacuum dried
In high activity liquid waste analog material liquid, after ultrasonic 5min, is vibrated with 200r/min to absorption and put down under 25 ± 0.2 DEG C of constant temperature
Weighing apparatus；In the 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, corresponding mass concentration are 48~52mg/L.
High activity liquid waste analog material liquid described in every processing 10mL, the magnetic absorption dosage of addition are 0.1~0.15g.
The palladium of the magnetic adsorbent adsorption, it is molten using the nitric acid of 5% thiocarbamide under 25 ± 0.2 DEG C of constant temperature
Liquid desorption, realizes and is recycled.
Absorption principle: the O atom of multiple N atoms and carboxyl arm on nitrogen heterocyclic ring carboxylic acid derivates ring, energy and palladium are in nitre
Stable complex compound is constructed in acid medium, the sequestering power of other sliver nucleic is limited by ring cavity size, N atom and carboxylic
Base arm O atom Protonation effect influences and the limitation of the freedom degree on solid phase material surface, more difficult in nitric acid medium to be formed accordingly
Complex structure, therefore to the palladium in nitric acid medium have Selective recognition and separating property.
The invention has the benefit that
1) amidation process that the present invention is catalyzed by EDCHCl and NHS arrives the modification of nitrogen heterocyclic ring carboxylic acid derivates
The SiO of magnetic composite microsphere2Shell outer rim is prepared for the novel magnetic adsorbent with core-shell structure, and preparation process energy consumption
It is low, easy to operate, using the small biological buffer of low toxicity, environmental pollution as reaction dissolvent, avoid conventional adsorbent preparation
The consumption of organic solvent in the process reduces operating cost, economic and environment-friendly, it is easy to accomplish amplification production.
2) the nitrogen heterocyclic ring carboxylic acid derivates of magnetic adsorbent surface modification prepared by the present invention, in wider concentration of nitric acid
It is big to palladium adsorption capacity, the rate of adsorption is fast in range, and under the interference of a variety of high activity liquid waste sliver nucleic, palladium is shown
Splendid Selective Separation ability, and the palladium of adsorbent surface absorption can be eluted with the nitric acid solution of 5% thiocarbamide, be conducive to circulation
It uses.
3) magnetic adsorbent of the bright preparation of we has good superparamagnetism energy, is easy under external magnetic fields point
From, the period being separated by solid-liquid separation in Solid Phase Extraction is shortened, the operation suitable for putting by force, under low sour extreme condition, at low cost, separation effect
Rate is high.
Detailed description of the invention
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 derivative spectrogram of the X-ray of magnetic nanoparticle；Fig. 2 (b) is amino functional in embodiment 1
The derivative spectrogram of the X-ray of magnetic microsphere；Fig. 2 (c) is the derivative spectrogram of X-ray of magnetic adsorbent in embodiment 1；
Fig. 3 is magnetic adsorbent to the adsorption rate of palladium and the curve graph of concentration of nitric acid.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.It is emphasized that following the description
It is only exemplary, the range and its application being not intended to be limiting of the invention.
A kind of embodiment 1: preparation method of magnetic adsorbent, comprising the following steps:
(1) by 1.0mmol nitrogen heterocyclic ring carboxylic acid derivates Cyclen -1,4,7,10- tetraacethyl
(DOTA) it is dissolved in 50mL morpholino b acid biological buffer solutions, adjusting pH buffering section is 5.4~5.5, under nitrogen protection,
Catalyst 25.0mmol EDCHCl and 10mmol NHS is added, is stirred to react 1h at room temperature, it is derivative to prepare nitrogen heterocyclic ring carboxylic acid
The activated intermediate of object DOTA.
(2) into above-mentioned reaction solution be added 0.5g amino functional magnetic microsphere (magnetic microsphere of amino functional
Preparation refers to related document Wang Xiangke, et al.Chemical Engineering Journal.2014,235,275-
283), after ultrasonic disperse, first at a temperature of 25 ± 0.2 DEG C, 8h is reacted under the action of mechanical stirring, is cooled to 4 ± 0.2 DEG C
Stand 12h.After magnet separates product, with 0.1mol/L HCl, second alcohol and water, alternately washing for several times, is dried in vacuo 12h at 45 DEG C,
Required core-shell structure magnetic adsorbent is made.
Fig. 1 (a) is the transmission electron microscope photo of the magnetic microsphere of amino functional, can obviously observe core
Fe3O4(the deeper black portions of color) partial size is 300nm or so, SiO2Shell (the shallower grey parts of color) with a thickness of
20nm or so.Fig. 1 (b) is the transmission electron microscope photo of magnetic adsorbent, and original shell pattern and thickness is not bright
Aobvious variation, illustrates that nitrogen heterocyclic ring carboxylic acid derivates are mainly modified in SiO2The edge of shell.
Fig. 2 (a) is Fe3O4The derivative spectrogram of the X-ray of magnetic nanoparticle, corresponding crystal face are respectively (111), (220),
(311), (400), (422), (511), (440) belong to standard Fe3O4The centroid cubic crystal system of card；Fig. 2 (b) is amino functional
The derivative spectrogram of the X-ray of the magnetic microsphere of change, Fig. 2 (c) are the derivative spectrogram of X-ray of magnetic adsorbent, it can be seen that amino
The modification of functionalization and organic molecule nitrogen heterocyclic ring carboxylic acid derivates, all without changing original Fe3O4Crystalline structure.
Embodiment 2: recycling of the resulting magnetic adsorbent of embodiment 1 to palladium in nitric acid medium
Pipetting nitric acid acidity is the 50mg/L palladium solution 10mL of 0.01mol/L in conical flask, and it is resulting that embodiment 1 is added
After magnetic adsorbent 0.1g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.Magnet separation
After adsorbent, supernatant liquor is taken out, with the mass concentration of Atomic Absorption Spectrometry wherein palladium, is calculated according to adsorption equilibrium formula
The adsorbent is at this time to the adsorption rate E=99.8% of palladium out.
Embodiment 3: recycling of the resulting magnetic adsorbent of embodiment 1 to palladium in nitric acid medium
Pipetting nitric acid acidity is the 50mg/L palladium solution 10mL of 0.1mol/L in conical flask, and it is resulting that embodiment 1 is added
After magnetic adsorbent 0.1g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.Magnet separation
After adsorbent, supernatant liquor is taken out, with the mass concentration of Atomic Absorption Spectrometry wherein palladium, is calculated according to adsorption equilibrium formula
The adsorbent is at this time to the adsorption rate E=98.2% of palladium out.
Embodiment 4: recycling of the resulting magnetic adsorbent of embodiment 1 to palladium in nitric acid medium
Pipetting nitric acid acidity is the 50mg/L palladium solution 10mL of 0.5mol/L in conical flask, and it is resulting that embodiment 1 is added
After magnetic adsorbent 0.1g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.Magnet separation
After adsorbent, supernatant liquor is taken out, with the mass concentration of Atomic Absorption Spectrometry wherein palladium, is calculated according to adsorption equilibrium formula
The adsorbent is at this time to the adsorption rate E=90.3% of palladium out.Embodiment 5: the resulting magnetic adsorbent of embodiment 1 is to nitric acid medium
The recycling of middle palladium
Pipetting nitric acid acidity is the 50mg/L palladium solution 10mL of 1.0mol/L in conical flask, and it is resulting that embodiment 1 is added
After magnetic adsorbent 0.1g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.Magnet separation
After adsorbent, supernatant liquor is taken out, with the mass concentration of Atomic Absorption Spectrometry wherein palladium, is calculated according to adsorption equilibrium formula
The adsorbent is at this time to the adsorption rate E=76.7% of palladium out.Embodiment 6: the resulting magnetic adsorbent of embodiment 1 is to nitric acid medium
The recycling of middle palladium
Pipetting nitric acid acidity is the 50mg/L palladium solution 10mL of 2.0mol/L in conical flask, and it is resulting that embodiment 1 is added
After magnetic adsorbent 0.1g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.Magnet separation
After adsorbent, supernatant liquor is taken out, with the mass concentration of Atomic Absorption Spectrometry wherein palladium, is calculated according to adsorption equilibrium formula
The adsorbent is at this time to the adsorption rate E=66.1% of palladium out.Embodiment 7: the resulting magnetic adsorbent of embodiment 1 is to nitric acid medium
The recycling of middle palladium
Pipetting nitric acid acidity is the 50mg/L palladium solution 10mL of 3.0mol/L in conical flask, and it is resulting that embodiment 1 is added
After magnetic adsorbent 0.1g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.Magnet separation
After adsorbent, supernatant liquor is taken out, with the mass concentration of Atomic Absorption Spectrometry wherein palladium, is calculated according to adsorption equilibrium formula
The adsorbent is at this time to the adsorption rate E=60.7% of palladium out.Embodiment 8: the resulting magnetic adsorbent of embodiment 1 is to nitric acid medium
The recycling of middle palladium
Pipetting nitric acid acidity is the 50mg/L palladium solution 10mL of 4.0mol/L in conical flask, and it is resulting that embodiment 1 is added
After magnetic adsorbent 0.1g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.Magnet separation
After adsorbent, supernatant liquor is taken out, with the mass concentration of Atomic Absorption Spectrometry wherein palladium, is calculated according to adsorption equilibrium formula
The adsorbent is at this time to the adsorption rate E=53.1% of palladium out.Embodiment 9: the resulting magnetic adsorbent of embodiment 1 is to nitric acid medium
The recycling of middle palladium
Pipetting nitric acid acidity is the 50mg/L palladium solution 10mL of 5.0mol/L in conical flask, and it is resulting that embodiment 1 is added
After magnetic adsorbent 0.1g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.Magnet separation
After adsorbent, supernatant liquor is taken out, with the mass concentration of Atomic Absorption Spectrometry wherein palladium, is calculated according to adsorption equilibrium formula
The adsorbent is at this time to the adsorption rate E=50.3% of palladium out.
Fig. 3 is adsorption rate E and concentration of nitric acid C (HNO of the magnetic adsorbent to palladium in nitric acid medium3) curve graph, it is magnetic
Adsorbent has a stronger absorption property to palladium within the scope of the concentration of nitric acid of 0.01~5.0mol/L, adsorption rate be 50% with
On, and adsorption rate is lower with the raising of concentration of nitric acid, concentration of nitric acid is lower than 1.0mol/L, adsorption rate of the magnetic adsorbent to palladium
It is 76% or more；Concentration of nitric acid is lower than 0.5mol/L, and magnetic adsorbent is 90% or more to the adsorption rate of palladium；Concentration of nitric acid is lower than
0.1mol/L, magnetic adsorbent are 98% or more to the adsorption rate of palladium；Concentration of nitric acid is 0.01mol/L, and magnetic adsorbent is to palladium
Adsorption rate up to 99.8%；This is primarily due under high concentration of nitric acid, and the O atom of N atom and carboxyl arm in ring can protonate
Effect, so as to cause H+With the adsorption site on palladium competitive adsorbate surface.
Embodiment 10: magnetic adsorbent recycles
Parsing agent of the nitric acid solution of 5% thiocarbamide as palladium is selected, wherein concentration of nitric acid is 0.5mol/L.By embodiment 4
In reach the magnetic adsorbent after adsorption equilibrium, after magnet separation, be washed with deionized 4-5 times, to remove residual non-adsorbed
Palladium nitric acid solution, after 60 DEG C of vacuum dry 12h, be transferred in conical flask, and the nitric acid solution of 5% thiocarbamide is added, 25
2h is vibrated with 200r/min in ± 0.2 DEG C of constant temperature air bath, after being centrifugated solid, supernatant sample is taken out, uses Atomic absorption
The mass concentration of spectroscopic assay palladium.Calculating the eluting rate that palladium is accumulative at this time according to adsorption equilibrium formula is 92%.As shown in table 1,
After magnetic adsorbent round-robin 4 times, to the absorption property of palladium without being substantially reduced.
Table 1
Embodiment 11: recycling of the resulting magnetic adsorbent of embodiment 1 to palladium in nitric acid medium
Pipetting nitric acid acidity is the high activity liquid waste sliver radionuclide solution 10mL of 1.0mol/L in conical flask, and embodiment is added
After 1 resulting magnetic adsorbent 0.15g, ultrasonic 5min, in 25 ± 0.2 DEG C of constant temperature air baths for 24 hours with 200r/min oscillation.
After magnet separating adsorbent, remaining clear liquid is taken out, measures each sliver nucleic with inductively-coupled plasma spectrometer (ICP-OES)
The mass concentration of K, Cs, Sr, Ba, Cd, Ni, Nd, Cr, Ru, Fe, Pd calculate the adsorbent at this time according to adsorption equilibrium formula
Adsorption rate to palladium is 93.1%, and the adsorption rate of other sliver nucleic is 5% hereinafter, concrete outcome is shown in Table 2.
Table 2
Claims (11)
1. a kind of magnetic adsorbent recycling nitric acid medium in palladium application, which is characterized in that the magnetic adsorbent be with
Fe3O4Magnetic nanoparticle is core, SiO2To protect shell, nitrogen heterocyclic ring carboxylic acid derivates are modified in the nucleocapsid of shell outer rim
Structure magnetic adsorbent；Contain N atom, N atom and carboxylic in ring skeleton in the ring skeleton of the nitrogen heterocyclic ring carboxylic acid derivates
Base arm is connected, and the carboxyl arm is located at outside ring；
The nitrogen heterocyclic ring carboxylic acid derivates are 1,4,7- 7-triazacyclononane -1,4,7- triacetic acid, 1,4,7,10- tetraazacyclododecane
Dodecane -1,4,7,10- tetraacethyl, 1,4,8,11- tetraazacyclododecane tetradecane -1,4,8,11- tetraacethyl, 1,4,7,10,13- five
Azepine cyclopentadecane -1,4,7,10,13- pentaacetic acid or 1,4,7,10,13,16- hexanitrogen heterocycle octadecane -1,4,7,10,13,
Six acetic acid of 16-；
The magnetic adsorbent has Selective recognition and separating property to the palladium in nitric acid medium, and the nitric acid for Recover palladium is molten
Palladium in liquid, wherein concentration of nitric acid is 0.01 ~ 5.0 mol/L, and the concentration of palladium is 48 ~ 52 mg/L；Can be used for recycling height put it is useless
Palladium in liquid analog material liquid, wherein concentration of nitric acid be 0.9 ~ 1.1 mol/L, sliver nucleic include K, Cs, Sr, Ba, Cd, Ni, Nd,
Cr, Ru, Fe, Pd, corresponding mass concentration are 48 ~ 52 mg/L.
2. application according to claim 1, which is characterized in that the preparation method of the magnetic adsorbent includes following step
It is rapid:
(1) nitrogen heterocyclic ring carboxylic acid derivates are dissolved in the biological buffer solutions that pH is 5.2 ~ 5.6, under nitrogen protection, are added
Catalyst EDC HCl and NHS, are stirred to react 1 h at room temperature, prepare the activated intermediate of nitrogen heterocyclic ring carboxylic acid derivates；
(2) magnetic microsphere of amino functional is added into above-mentioned reaction solution, after ultrasonic disperse, the temperature of control system and anti-
Terminate between seasonable to amidation process, after magnet separates product, alternately washs number with 0.1 mol/L HCl solution, second alcohol and water
Secondary, core-shell structure magnetic adsorbent is made in 45 DEG C of 12 h of vacuum drying；The magnetic microsphere of the amino functional is with Fe3O4Magnetic
Property nano particle be core, SiO2To protect shell, contain terminal amino group structure on shell.
3. application according to claim 2, which is characterized in that in the reaction system of step (1), 1 mmol azepine of every activation
Big ring carboxylic acid derivates, the amount that catalyst EDC HCl need to be added is 9.95 ~ 40.05 mmol, and EDC HCl and NHS are added
The molar ratio of amount is (2 ~ 2.5): 1.
4. application according to claim 2, which is characterized in that in the reaction system of step (1), the biological buffer solutions
For the morpholino b acid aqueous solution of 1.0 mol/L, the amount of addition is that the every 1.0 mmol azepine of 45 ~ 55 mL biological buffer solutions is big
Ring carboxylic acid derivates.
5. application according to claim 2, which is characterized in that in the reaction system of step (2), the amino functional
Magnetic microsphere additional amount is the every 1 mmol nitrogen heterocyclic ring carboxylic acid derivates of 0.45 ~ 0.55 g.
6. application according to claim 2, which is characterized in that the reaction system of step (2), control reaction first 25 ±
8 h are stirred to react at 0.2 DEG C, after be adjusted at 4 ± 0.2 DEG C stand 12 ~ 16 h.
7. application according to claim 1, which is characterized in that after the magnetic adsorbent is vacuum dried, be added to palladium
Nitric acid solution in, after 5 min of ultrasound, vibrated with 200 r/min to adsorption equilibrium under 25 ± 0.2 DEG C of constant temperature.
8. application according to claim 7, which is characterized in that the nitric acid solution of palladium described in 10 mL of every processing, the magnetic of addition
Property quantity of sorbent be 0.09 ~ 0.11 g.
9. application according to claim 1, which is characterized in that after the magnetic adsorbent is vacuum dried, be added to height
In radioactive waste liquid analog material liquid, after 5 min of ultrasound, is vibrated with 200 r/min to absorption and put down under 25 ± 0.2 DEG C of constant temperature
Weighing apparatus.
10. application according to claim 9, which is characterized in that high activity liquid waste analog material liquid described in 10 mL of every processing adds
The magnetic absorption dosage entered is 0.1 ~ 0.15 g.
11. according to application described in claim 7-10 any claim, which is characterized in that inhale on the magnetic adsorbent surface
Attached palladium is desorbed under 25 ± 0.2 DEG C of constant temperature using the nitric acid solution of 5 % thiocarbamides, is realized and is recycled.
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