CN105363425A - Magnetic cesium ion adsorbent and preparation method therefor - Google Patents
Magnetic cesium ion adsorbent and preparation method therefor Download PDFInfo
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Abstract
The present invention discloses a preparation method for a magnetic cesium ion adsorbent. The preparation method comprises the steps of: A, coating carboxylated silicon dioxide on the surface of ferroferric oxide to obtain coated ferroferric oxide; B, mixing the coated ferroferric oxide with an aminated crownether derivative to obtain a first mixture; C, placing the first mixture and a condensation agent in a first solvent to be stirred, and performing a reaction at 50-90 DEG C for 2-4 h to obtain a second mixture, wherein the first solvent can dissolve the aminated crownether derivative and the condensation agent; and D, solid-liquid separating the second mixture to obtain a first solid phase, and washing and drying the first solid phase to obtain a magnetic cesium ion adsorbent. The present invention also discloses a magnetic cesium ion adsorbent obtained by the preparation method. The adsorbent has good cesium ion adsorption selectivity, and retains stable adsorption performance after using in repeated adsorption-desorption cycles. The magnetic cesium ion adsorbent disclosed by the present invention can be applied to adsorbing and separating the cesium ion from systems such as radioactive waste and ionic competition systems.
Description
Technical field
The invention belongs to composite functional material technical field, specifically, relate to a kind of magnetic cesium ion adsorbent and preparation method thereof.
Background technology
Cs in China salt lake
+aboundresources, research is Extraction and separation Cs from salt lake how
+meaning is very great.At present for Cs
+separation and extraction, mainly contain the precipitation method, ion-exchange and solvent extraction.The precipitation method are mainly applicable to extract Cs from rock forming mineral resource
+, as extracted Cs from carnallite, lepidolite, pollucite
+, but the method belongs to intermittent operation, and step is complicated, and labour intensity is large, Separation of Solid and Liquid operating difficulties.Ion-exchange has that operating procedure is simple, machinery, heat and irradiation stability are strong and to Cs
+there is the advantage such as selective of highly significant, but inorganic ion exchanger has higher solubility in water, and organic ion exchanger is large to the exchange potential of high valence ion, has very large interference when high valence ion coexists, and is difficult to obtained satisfied chromatographic column.At Cs
+separating and extracting process in, a kind of isolation technics that solvent extraction is that Recent study is more, application is comparatively wide, makes fast progress, Solvent Extraction Separation extracts Cs
+extractant used mainly comprises the reagent such as crown ether, calixarenes, dipicrylamine and derivative thereof, and therefore solvent extraction exists that extractant price is higher, consumption is more, reclaims the problems such as the large and portion of reagent of loss is toxic.
Summary of the invention
For solving above-mentioned prior art Problems existing, the invention provides a kind of magnetic cesium ion adsorbent and preparation method thereof, first magnetic cesium ion adsorbent of the present invention forms coated ferriferrous oxide by carboxylated coated with silica on the surface of tri-iron tetroxide, then coated ferriferrous oxide surface being had a carboxyl by amidation combines with amination crown ether derivative, define stable chemical bond, therefore magnetic cesium ion adsorbent of the present invention in use its structure and stable in properties, repeatedly recycling in process and can keep good suction-operated to cesium ion all the time.
In order to reach foregoing invention object, present invention employs following technical scheme:
A preparation method for magnetic cesium ion adsorbent, comprises step: A, by the surface of carboxylated coated with silica at tri-iron tetroxide, obtain coated ferriferrous oxide; B, described coated ferriferrous oxide to be mixed with amination crown ether derivative, obtain the first mixture; C, described first mixture and condensing agent are placed in the first solvent stir, and react 2h ~ 4h at 50 DEG C ~ 90 DEG C, obtain the second mixture; Wherein, described first solvent is for dissolving described amination crown ether derivative and described condensing agent; D, Separation of Solid and Liquid is carried out to described second mixture, obtain the first solid phase, clean and dry described first solid phase, obtaining magnetic cesium ion adsorbent.
Further, the concrete grammar of described steps A comprises: described tri-iron tetroxide is placed in the second solvent, and adds amination silane coupler in described second solvent, obtains the 3rd mixture; Wherein, described second solvent is for dissolving described amination silane coupler; Described 3rd mixture is stirred at 50 DEG C ~ 80 DEG C and hot reflux at least 12h, obtain 4 mixture; Separation of Solid and Liquid is carried out to described 4 mixture, obtains second solid phase, clean described second solid phase; Described second solid phase is placed in the 3rd solvent, and adds acid anhydrides in described 3rd solvent, and stir at least 18h, obtain the 5th mixture; Wherein, described 3rd solvent is for dissolving described acid anhydrides; Carry out Separation of Solid and Liquid to described 5th mixture, obtain the 3rd solid phase, cleaning is dry described 3rd solid phase also, obtains described coated ferriferrous oxide.
Further, the ratio of described tri-iron tetroxide, described amination silane coupler and described acid anhydrides is 8g ~ 50g:3mL ~ 7mL:4g ~ 9g.
Further, described amination silane coupler is selected from any one in 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane.
Further, in described step B, the mass ratio of described coated ferriferrous oxide and described amination crown ether derivative is 30 ~ 50:1.
Further, described amination crown ether derivative be selected from that 2-aminomethyl-1,2 8-is preced with-6, any one also in-18-hat-6 of the amino benzo-18-hat-6 of 4-, 4-ADP.
Further, in described step C, the ratio of described first mixture and described condensing agent is 800g:2.5mol ~ 3.5mol.
Further, described condensing agent is selected from 1-hydroxyl-7-azo BTA, I-hydroxybenzotriazole, N, any one in N '-carbonyl dimidazoles, or the mixture being 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride that amount of substance is equal and N-hydroxy-succinamide.
Further, described first solvent is selected from any one in oxolane, n-hexane, dimethyl sulfoxide (DMSO); Described second solvent be selected from n-hexyl alcohol, n-hexane, toluene any one; Described 3rd solvent is oxolane.
Another object of the present invention is also to provide a kind of magnetic cesium ion adsorbent, described magnetic cesium ion adsorbent comprises the coated ferriferrous oxide formed by carboxylated coated with silica tri-iron tetroxide, and is connected to the amination crown ether derivative on described coated ferriferrous oxide by amidation condensation.
Further, described amination crown ether derivative be selected from that 2-aminomethyl-1,2 8-is preced with-6, any one also in-18-hat-6 of the amino benzo-18-hat-6 of 4-, 4-ADP.
The present invention is first at the Surface coating carboxylated silica of tri-iron tetroxide, form coated ferriferrous oxide, then using coated ferriferrous oxide and amination crown ether derivative as reactant, by amidation therebetween, prepare the magnetic cesium ion adsorbent of structure and stable in properties.Magnetic cesium ion adsorbent according to the present invention not only has stronger cesium ion adsorptive selectivity, and its structure and stable in properties, and change hardly in the process of repeatedly Reusability, its adsorption capacity is without obvious reduction.In addition, utilize the magnetic of coated ferriferrous oxide, after adsorbed cesium ion from containing the solution of cesium ion, Separation of Solid and Liquid fast can be realized; Meanwhile, in the process of preparation, Magnetic Isolation can be adopted equally to carry out Separation of Solid and Liquid fast, improve preparation efficiency.Magnetic cesium ion adsorbent of the present invention can be applicable to adsorbing separation cesium ion from the polyion competition system of such as level radioactive nuclear waste, similar salt lake bittern.
Detailed description of the invention
Below, embodiments of the invention will be described in detail.But, the present invention can be implemented in many different forms, and the present invention should not be interpreted as being limited to the specific embodiment of setting forth here.On the contrary, provide these embodiments to be to explain principle of the present invention and practical application thereof, thus enable others skilled in the art understand various embodiment of the present invention and be suitable for the various amendments of certain expected application.
Although will be appreciated that and term " first ", " second " etc. can be used here to describe various element, these elements should by the restriction of these terms.These terms are only for separating an element and another element region.
Present embodiments provide a kind of magnetic cesium ion adsorbent, it comprises the coated ferriferrous oxide formed by carboxylated coated with silica tri-iron tetroxide, and is preced with-6 by the 2-aminomethyl-1,2 8-that amidation is connected with described coated ferriferrous oxide condensation.
First tri-iron tetroxide is undertaken coated by carboxylated silica by the magnetic cesium ion adsorbent of the present embodiment, define coated ferriferrous oxide, the carboxyl then on coated ferriferrous oxide surface and 2-aminomethyl-1,2 8-are preced with and carry out amidation between the amino on-6 and condensation is formed.
Below the preparation method of the magnetic cesium ion adsorbent to the present embodiment is described in detail.
In step one, prepare tri-iron tetroxide.
First the ferrous sulfate of 5mmol being dissolved in 100mL volume ratio is in the mixed solution of ethanol/water/oleic acid of 1:1:1; Then add 3gNaOH wherein, pour into after stirring in 150mL hydrothermal reaction kettle, be heated to 180 DEG C, and be incubated 12h, obtain the 6th mixture; Finally be cooled to after room temperature (about 25 DEG C) until hydrothermal reaction kettle, described 6th mixture is after ethanol and washed with de-ionized water twice, and magnetic Separation of Solid and Liquid, the dry 6h of gained solid phase at 60 DEG C, obtains tri-iron tetroxide.
The concrete grammar cleaning the 6th mixture is: first cleaned in ethanol by the 6th mixture ultrasonic disperse, and magnetic Separation of Solid and Liquid, repeat twice; Then the 6th mixture ultrasonic disperse through ethanol purge is cleaned in deionized water, and magnetic Separation of Solid and Liquid, repeat twice.Described Magnetic Isolation can utilize magnet to be fitted in the bottom of the container of splendid attire the 6th mixture, and wherein solid precipitation relies on the magnetic force of magnet to keep motionless to container bottom, and liquid phase is directly poured out by the top of this container.
In step 2, get the tri-iron tetroxide that 8g step one obtains and be placed in 500mL n-hexane, and add 4mL3-aminopropyl triethoxysilane wherein, obtain the 3rd mixture.
In step 3, the 3rd mixture is stirred 12h at 50 DEG C, obtains 4 mixture; Described 4 mixture, through magnetic Separation of Solid and Liquid, obtains second solid phase; Preferably, described second solid phase is cleaned each three times with ethanol and oxolane respectively.
In step 4, be added in 200mL oxolane by described second solid phase, and add 4g succinic anhydride wherein, under room temperature, (25 DEG C) stir 18h, obtain the 5th mixture, and the 5th mixture described in Magnetic Isolation, obtain the 3rd solid phase; Clean described 3rd solid phase twice successively by DMF, ethanol and deionized water respectively again, and at 40 DEG C dry described 3rd solid phase, obtain coated ferriferrous oxide.
In step 5, coated ferriferrous oxide step 4 obtained and 2-aminomethyl-1,2 8-are preced with-6 and are 50:1 according to mass ratio ratio mixes, and obtain the first mixture.
In step 6, the first mixture described in 8g and 0.03mol1-hydroxyl-7-azo BTA are placed in 300mL oxolane, stir and hot reflux at 50 DEG C, reaction 2h, obtains the second mixture.
Oxolane is as a kind of solvent, and its boiling point is 65 DEG C ~ 66 DEG C, and the 2-aminomethyl-1,2 8-played in dissolving first mixture is preced with the effect of-6; Meanwhile, because above-mentioned heating-up temperature is close to the boiling point of oxolane, therefore in order to prevent oxolane from volatilizing, have employed condensation reflux unit.
In step 7, centrifugation second mixture, obtains the first solid phase, and described first solid phase obtains described magnetic cesium ion adsorbent through cleaning-drying.
The concrete grammar described first solid phase being carried out to cleaning-drying process is: the first solid phase ultrasonic disperse first above-mentioned centrifugation obtained cleans in deionized water, and Magnetic Isolation, in triplicate; Then the first solid phase ultrasonic disperse through washed with de-ionized water is cleaned in absolute ethyl alcohol, and Magnetic Isolation, in triplicate; Finally dry 12h at 40 DEG C.
The absorption property of magnetic cesium ion adsorbent to cesium ion that the present embodiment prepares is tested.Particularly, being placed in the magnetic cesium ion adsorbent of the present embodiment containing cesium ion concentration is the cesium nitrate aqueous solution of 200mg/L, finds that the adsorption capacity of the magnetic cesium ion adsorbent of the present embodiment is 11.8mg/g; That is, the magnetic cesium ion adsorbent of every gram of the present embodiment can adsorb the cesium ion of 11.8mg, and adsorption capacity is in good level; Meanwhile, the magnetic cesium ion adsorbent of the present embodiment is carried out the circulation experiment of adsorption-desorption, after the above-mentioned circulation of 15 times, the quality of described magnetic cesium ion adsorbent remains more than 99% of Theoretical Mass, illustrate and recycle in process at adsorption-desorption, almost do not occur acid-soluble erosion phenomenon; That is, in the operating process of pickling desorption, this magnetic cesium ion sorbent structure is stablized, almost not by acid-soluble eating away.In addition, thermogravimetric analysis (TG/DSC) is carried out to magnetic cesium ion adsorbent now, find now by amidation be connected to quantity that 2-aminomethyl-1,2 8-on coated ferriferrous oxide is preced with-6 be initially synthesize time quantity 96%; That is, through the adsorption-desorption cycle of 15 times, described magnetic cesium ion adsorbent has 4% to cause partial loss because of reasons such as structure collapses, gradually molten damage, therefore magnetic cesium ion sorbent structure and the stable in properties of the present embodiment is said, in the process of recycled for multiple times, lose less, absorption property is without obvious reduction.
The magnetic cesium ion adsorbent of the present embodiment comprises the magnetic coated ferriferrous oxide of tool, therefore not only in the process of preparation, Separation of Solid and Liquid operation can adopt Magnetic Isolation, accelerate Separation of Solid and Liquid speed, and utilize the magnetic cesium ion adsorbent of the present embodiment from containing cesium ion solution adsorbed cesium ion after, Magnetic Isolation also can be utilized to be adsorbed with the magnetic cesium ion adsorbent of cesium ion and to be carried out Separation of Solid and Liquid fast by adsorbent solution, not only shorten the speed utilizing magnetic cesium ion adsorbent separating cesium ions, magnetic can also be utilized to carry out the recovery of this magnetic cesium ion adsorbent, reduce the loss and waste.Simultaneously, the magnetic cesium ion adsorbent of the present embodiment has 2-aminomethyl-1,2 8-and is preced with-6, it belongs to a kind of amination crown ether derivative, has higher selective, also help its selective absorption cesium ion from the environment containing multiple interfering ion to cesium ion; Therefore, the magnetic cesium ion adsorbent of the present embodiment can be used for removing the cesium ion in level radioactive nuclear waste, or for adsorbing and extracting cesium ion in the competition system that coexists from multiple alkali metal such as such as salt lakes.
Embodiment 2
In the description of embodiment 2, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 2 is with the difference of embodiment 1, the amino benzo-18-hat-6 of 4-that the magnetic cesium ion adsorbent in embodiment 2 is comprised coated ferriferrous oxide and is connected on described coated ferriferrous oxide by amidation condensation.
First tri-iron tetroxide is undertaken coated by carboxylated silica by the magnetic cesium ion adsorbent of the present embodiment, define coated ferriferrous oxide, the amino benzo-18-of the carboxyl then on coated ferriferrous oxide surface and 4-is preced with and carries out amidation between the amino on-6 and condensation is formed.
The difference of the preparation method in the preparation method of the magnetic cesium ion adsorbent of the present embodiment and embodiment 1 is, in step one, first the ferrous nitrate of 5mmol being dissolved in 100mL volume ratio is in the mixed solution of ethanol/water/oleic acid of 1:1:1; Then add 8gNaOH wherein, pour into after stirring in 150mL hydrothermal reaction kettle, be heated to 220 DEG C, and be incubated 24h, obtain the 6th mixture; Finally be cooled to after room temperature until hydrothermal reaction kettle, described 6th mixture is after second alcohol and water cleaning twice, and Magnetic Isolation, the dry 6h of gained solid phase at 60 DEG C, obtains tri-iron tetroxide.
In step 2, get the tri-iron tetroxide that 15g step one obtains and be placed in 500mL n-hexane, and add 7mL3-aminopropyl triethoxysilane wherein, obtain the 3rd mixture.
In step 3, the 3rd mixture is stirred 20h at 80 DEG C, obtains 4 mixture; Described 4 mixture, through Magnetic Isolation, obtains second solid phase; Preferably, described second solid phase is cleaned each three times with ethanol and oxolane respectively.
In step 4, be added in 200mL oxolane by described second solid phase, and add 9g succinic anhydride wherein, under room temperature, (25 DEG C) stir 24h, obtain the 5th mixture, and the 5th mixture described in Magnetic Isolation, obtain the 3rd solid phase; Clean described 3rd solid phase twice successively by DMF, ethanol and deionized water respectively again, and at 40 DEG C dry described 3rd solid phase, obtain coated ferriferrous oxide.
In step 5, amino to coated ferriferrous oxide and 4-benzo-18-is preced with-6 and is 30:1 according to mass ratio ratio mixes, obtain the first mixture.
In step 6, the first mixture described in 8g and 0.03mol1-hydroxybenzotriazole are placed in 400mL oxolane, stir and hot reflux at 80 DEG C, reaction 4h, obtains the second mixture.
Oxolane is as a kind of solvent, and its boiling point is 65 DEG C ~ 66 DEG C, plays the effect of dissolving the amino benzo-18-hat-6 of 4-and I-hydroxybenzotriazole; Meanwhile, because above-mentioned heating-up temperature has exceeded the boiling point of oxolane, therefore in order to prevent oxolane from volatilizing, have employed condensation reflux unit.
All the other steps, with reference to described in embodiment 1, have prepared magnetic cesium ion adsorbent.
The absorption property of magnetic cesium ion adsorbent to cesium ion that the present embodiment prepares is tested.Particularly, being placed in the magnetic cesium ion adsorbent of the present embodiment containing cesium ion concentration is the cesium nitrate aqueous solution of 200mg/L, finds that the adsorption capacity of the magnetic cesium ion adsorbent of the present embodiment is 12.6mg/g; That is, the magnetic cesium ion adsorbent of every gram of the present embodiment can adsorb the cesium ion of 12.6mg, and adsorption capacity level is in well; Meanwhile, the magnetic cesium ion adsorbent of the present embodiment is carried out the circulation experiment of adsorption-desorption, after the above-mentioned circulation of 15 times, the quality of described magnetic cesium ion adsorbent remains more than 99% of Theoretical Mass, illustrate and recycle in process at adsorption-desorption, almost do not occur acid-soluble erosion phenomenon; That is, in the operating process of pickling desorption, this magnetic cesium ion sorbent structure is stablized, almost not by acid-soluble eating away.In addition, thermogravimetric analysis (TG/DSC) is carried out to magnetic cesium ion adsorbent now, find that the quantity being now connected to the amino benzo-18-hat-6 of 4-on coated ferriferrous oxide by amidation is 97% of quantity when initially synthesizing; That is, through the adsorption-desorption cycle of 15 times, described magnetic cesium ion adsorbent has 3% to cause partial loss because of reasons such as structure collapses, gradually molten damage, therefore magnetic cesium ion sorbent structure and the stable in properties of the present embodiment is said, in the process of recycled for multiple times, lose less, absorption property is without obvious reduction.
The magnetic cesium ion adsorbent of the present embodiment comprises the magnetic coated ferriferrous oxide of tool, therefore not only in the process of preparation, Magnetic Isolation can be adopted in Separation of Solid and Liquid operation, accelerate Separation of Solid and Liquid speed, and utilize the magnetic cesium ion adsorbent of the present embodiment from containing cesium ion solution adsorbed cesium ion after, Magnetic Isolation also can be utilized to be adsorbed with the magnetic cesium ion adsorbent of cesium ion and to be carried out Separation of Solid and Liquid fast by adsorbent solution, not only shorten the speed utilizing magnetic cesium ion adsorbent separating cesium ions, magnetic can also be utilized to carry out the recovery of this magnetic cesium ion adsorbent, reduce the loss and waste.Simultaneously, the magnetic cesium ion adsorbent of the present embodiment has the amino benzo-18-hat-6 of 4-, it belongs to a kind of amination crown ether derivative, has higher selective, also help its selective absorption cesium ion from the environment containing multiple interfering ion to cesium ion; Therefore, the magnetic cesium ion adsorbent of the present embodiment can be used for removing the cesium ion in level radioactive nuclear waste, or for adsorbing and extracting cesium ion in the competition system that coexists from multiple alkali metal such as such as salt lakes.
Embodiment 3
In the description of embodiment 3, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 3 is with the difference of embodiment 1, and the magnetic cesium ion adsorbent in embodiment 3 is comprised coated ferriferrous oxide and is connected to the 4-ADP also-18-hat-6 on described coated ferriferrous oxide by amidation.
First tri-iron tetroxide is undertaken coated by carboxylated silica by the magnetic cesium ion adsorbent of the present embodiment, define coated ferriferrous oxide, carry out amidation between the carboxyl then on coated ferriferrous oxide surface and the 4-ADP amino that also-18-is preced with on-6 and condensation is formed.
The difference of the preparation method in the preparation method of the magnetic cesium ion adsorbent of the present embodiment and embodiment 1 is, in step one, first the potassium ferrocyanide of 15mmol being dissolved in 100mL volume ratio is in the mixed solution of ethanol/water/oleic acid of 1:1:1; Then add 8gNaOH wherein, pour into after stirring in 150mL hydrothermal reaction kettle, be heated to 220 DEG C, and be incubated 24h, obtain the 6th mixture; Finally be cooled to after room temperature until hydrothermal reaction kettle, described 6th mixture is after second alcohol and water cleaning twice, and Magnetic Isolation, the dry 6h of gained solid phase at 60 DEG C, obtains tri-iron tetroxide.
In step 2, get the tri-iron tetroxide that 15g step one obtains and be placed in 500mL toluene, and add 7mL3-aminopropyl triethoxysilane wherein, obtain the 3rd mixture.
In step 3, the 3rd mixture is stirred 20h at 80 DEG C, obtains 4 mixture; Described 4 mixture, through Magnetic Isolation, obtains second solid phase; Preferably, described second solid phase is cleaned each three times with ethanol and oxolane respectively.
In step 4, be added in 200mL oxolane by described second solid phase, and add 9g succinic anhydride wherein, under room temperature, (25 DEG C) stir 24h, obtain the 5th mixture, and the 5th mixture described in Magnetic Isolation, obtain the 3rd solid phase; Clean described 3rd solid phase twice successively by DMF, ethanol and deionized water respectively again, and at 40 DEG C dry described 3rd solid phase, obtain coated ferriferrous oxide.
In step 5, by coated ferriferrous oxide and 4-ADP also-18-be preced with-6 and be 30:1 according to mass ratio ratio mixes, obtain the first mixture.
In step 6, the first mixture described in 8g and 0.03molN, N '-carbonyl dimidazoles are placed in 400mL oxolane, stir and hot reflux at 80 DEG C, reaction 4h, obtains the second mixture.
Oxolane is as a kind of solvent, and its boiling point is 65 DEG C ~ 66 DEG C, plays the effect of dissolving 4-ADP also-18-hat-6 and N, N '-carbonyl dimidazoles; Meanwhile, because above-mentioned heating-up temperature has exceeded the boiling point of oxolane, therefore in order to prevent oxolane from volatilizing, have employed condensation reflux unit.
All the other steps, with reference to described in embodiment 1, have prepared magnetic cesium ion adsorbent.
The absorption property of magnetic cesium ion adsorbent to cesium ion that the present embodiment prepares is tested.Particularly, being placed in the magnetic cesium ion adsorbent of the present embodiment containing cesium ion concentration is the cesium nitrate aqueous solution of 200mg/L, finds that the adsorption capacity of the magnetic cesium ion adsorbent of the present embodiment is 12.1mg/g; That is, the magnetic cesium ion adsorbent of every gram of the present embodiment can adsorb the cesium ion of 12.1mg, and adsorption capacity level is in well; Meanwhile, the magnetic cesium ion adsorbent of the present embodiment is carried out the circulation experiment of adsorption-desorption, after the above-mentioned circulation of 15 times, the quality of described magnetic cesium ion adsorbent remains more than 99% of Theoretical Mass, illustrate and recycle in process at adsorption-desorption, almost do not occur acid-soluble erosion phenomenon; That is, in the operating process of pickling desorption, this magnetic cesium ion sorbent structure is stablized, almost not by acid-soluble eating away.In addition, thermogravimetric analysis (TG/DSC) is carried out to magnetic cesium ion adsorbent now, find that the quantity being now connected to the amino benzo-18-hat-6 of 4-on coated ferriferrous oxide by amidation is 97% of quantity when initially synthesizing; That is, through the adsorption-desorption cycle of 15 times, described magnetic cesium ion adsorbent has the losses such as the decomposition of 3%, therefore magnetic cesium ion sorbent structure and the stable in properties of the present embodiment is said, in the process of recycled for multiple times, lose less, absorption property is without obvious reduction.
The magnetic cesium ion adsorbent of the present embodiment comprises the magnetic coated ferriferrous oxide of tool, therefore not only in the process of preparation, Magnetic Isolation can be adopted in Separation of Solid and Liquid operation, accelerate Separation of Solid and Liquid speed, and utilize the magnetic cesium ion adsorbent of the present embodiment from containing cesium ion solution adsorbed cesium ion after, Magnetic Isolation also can be utilized to be adsorbed with the magnetic cesium ion adsorbent of cesium ion and to be carried out Separation of Solid and Liquid fast by adsorbent solution, not only shorten the speed utilizing magnetic cesium ion adsorbent separating cesium ions, magnetic can also be utilized to carry out the recovery of this magnetic cesium ion adsorbent, reduce the loss and waste.Simultaneously, the magnetic cesium ion adsorbent of the present embodiment has 4-ADP also-18-hat-6, it belongs to a kind of amination crown ether derivative, has higher selective, also help its selective absorption cesium ion from the environment containing multiple interfering ion to cesium ion; Therefore, the magnetic cesium ion adsorbent of the present embodiment can be used for removing the cesium ion in level radioactive nuclear waste, or for adsorbing and extracting cesium ion in the competition system that coexists from multiple alkali metal such as such as salt lakes.
Certainly, described first solvent in preparation method of the present invention in step 6 is not limited to the oxolane in above-described embodiment 1-3, other are as n-hexane, dimethyl sulfoxide (DMSO) equal solvent, to play the object of dissolving amination crown ether derivative and condensing agent.In addition, in the condensation course of coated ferriferrous oxide and amination crown ether derivative, condensing agent is also not limited to 1-hydroxyl-7-azo BTA, I-hydroxybenzotriazole and the N described in above-described embodiment 1-4, N '-carbonyl dimidazoles can also be wait 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride of amount of substance and the mixture of N-hydroxy-succinamide.
What deserves to be explained is, when preparing magnetic cesium ion adsorbent of the present invention, it can be arbitrary proportion between the coated ferriferrous oxide formed by carboxylated coated with silica and amination crown ether derivative, preferably, the mass ratio controlling amination tri-iron tetroxide and carboxylated crown ether derivative is 30 ~ 50:1, be excessive state to prevent coated ferriferrous oxide, and cause excessive coated ferriferrous oxide to be difficult to be separated with magnetic cesium ion adsorbent, thus affect purity and the effect of this magnetic cesium ion adsorbent.
Carboxylated coated with silica tri-iron tetroxide is adopted according to magnetic cesium ion adsorbent of the present invention, obtain coated ferriferrous oxide, and be connected by the amidation phase condensation between carboxyl with amino with amination crown ether derivative by the carboxyl on its surface, by forming new chemical bond, make the combination of coated ferriferrous oxide and carboxylated crown ether derivative more firm, thus utilizing described magnetic cesium ion adsorbent to carry out in recycling of adsorption-desorption, the corrosion loss of this magnetic cesium ion adsorbent when desorption in the process of pickling is less, this magnetic cesium ion adsorbent is made to remain good absorption property, meanwhile, utilize the magnetic of wherein coated ferriferrous oxide, can make described magnetic cesium ion adsorbent by containing cesium ion solution in adsorbed cesium ion after, can be separated with this solution fast, raising application efficiency.
Although illustrate and describe the present invention with reference to specific embodiment, but it should be appreciated by those skilled in the art that: when not departing from the spirit and scope of the present invention by claim and equivalents thereof, the various changes in form and details can be carried out at this.
Claims (11)
1. a preparation method for magnetic cesium ion adsorbent, is characterized in that, comprises step:
A, by the surface of carboxylated coated with silica at tri-iron tetroxide, obtain coated ferriferrous oxide;
B, described coated ferriferrous oxide to be mixed with amination crown ether derivative, obtain the first mixture;
C, described first mixture and condensing agent are placed in the first solvent stir, and react 2h ~ 4h at 50 DEG C ~ 90 DEG C, obtain the second mixture; Wherein, described first solvent is for dissolving described amination crown ether derivative and described condensing agent;
D, Separation of Solid and Liquid is carried out to described second mixture, obtain the first solid phase, clean and dry described first solid phase, obtaining magnetic cesium ion adsorbent.
2. preparation method according to claim 1, is characterized in that, the concrete grammar of described steps A comprises:
Described tri-iron tetroxide is placed in the second solvent, and adds amination silane coupler in described second solvent, obtain the 3rd mixture; Wherein, described second solvent is for dissolving described amination silane coupler;
Described 3rd mixture is stirred at 50 DEG C ~ 80 DEG C and hot reflux at least 12h, obtain 4 mixture;
Separation of Solid and Liquid is carried out to described 4 mixture, obtains second solid phase, clean described second solid phase;
Described second solid phase is placed in the 3rd solvent, then adds acid anhydrides in described 3rd solvent, and stir at least 18h, obtain the 5th mixture; Wherein, described 3rd solvent is for dissolving described acid anhydrides;
Carry out Separation of Solid and Liquid to described 5th mixture, obtain the 3rd solid phase, cleaning is dry described 3rd solid phase also, obtains described coated ferriferrous oxide.
3. preparation method according to claim 2, is characterized in that, the ratio of described tri-iron tetroxide, described amination silane coupler and described acid anhydrides is 8g ~ 50g:3mL ~ 7mL:4g ~ 9g.
4. preparation method according to claim 3, is characterized in that, described amination silane coupler be selected from 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane any one.
5., according to the arbitrary described preparation method of Claims 1-4, it is characterized in that, in described step B, the mass ratio of described coated ferriferrous oxide and described amination crown ether derivative is 30 ~ 50:1.
6. preparation method according to claim 5, is characterized in that, described amination crown ether derivative is selected from that 2-aminomethyl-1,2 8-is preced with-6, any one also in-18-hat-6 of the amino benzo-18-hat-6 of 4-, 4-ADP.
7. preparation method according to claim 5, is characterized in that, in described step C, the ratio of described first mixture and described condensing agent is 800g:2.5mol ~ 3.5mol.
8. preparation method according to claim 7, it is characterized in that, described condensing agent is selected from 1-hydroxyl-7-azo BTA, I-hydroxybenzotriazole, N, any one in N '-carbonyl dimidazoles, or the mixture being 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride that amount of substance is equal and N-hydroxy-succinamide.
9. preparation method according to claim 2, is characterized in that, described first solvent be selected from oxolane, n-hexane, dimethyl sulfoxide (DMSO) any one; Described second solvent be selected from n-hexyl alcohol, n-hexane, toluene any one; Described 3rd solvent is oxolane.
10. a magnetic cesium ion adsorbent, it is characterized in that, described magnetic cesium ion adsorbent comprises the coated ferriferrous oxide formed by carboxylated coated with silica tri-iron tetroxide, and is connected to the amination crown ether derivative on described coated ferriferrous oxide by amidation condensation.
11. magnetic cesium ion adsorbents according to claim 10, is characterized in that, described amination crown ether derivative is selected from that 2-aminomethyl-1,2 8-is preced with-6, any one also in-18-hat-6 of the amino benzo-18-hat-6 of 4-, 4-ADP.
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