CN109865312A - It is a kind of based on rubidium extraction amino and 18 hat six ethers modification Magnetic solid phases extractant preparation method - Google Patents
It is a kind of based on rubidium extraction amino and 18 hat six ethers modification Magnetic solid phases extractant preparation method Download PDFInfo
- Publication number
- CN109865312A CN109865312A CN201910216237.6A CN201910216237A CN109865312A CN 109865312 A CN109865312 A CN 109865312A CN 201910216237 A CN201910216237 A CN 201910216237A CN 109865312 A CN109865312 A CN 109865312A
- Authority
- CN
- China
- Prior art keywords
- hat
- rubidium
- reaction
- magnetic
- ethers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Compounds Of Iron (AREA)
Abstract
The invention discloses the preparation methods of a kind of amino based on rubidium extraction and the Magnetic solid phases extractant of 18 hat six ethers modifications, the preparation method is preced with six ethers as reaction raw materials using ferroso-ferric oxide as magnetic kernel, using aminopropyl triethoxysilane, 4- carboxyl benzo 18.The present invention enhances the selectivity to rubidium hydrated ion using the synergistic effect of 18 hat six ethers and amino；Utilize the magnetism of ferroso-ferric oxide, achieve the purpose that conveniently and efficiently to separate rubidium ion from the complex matrices containing a large amount of alkali metal plasmas under externally-applied magnetic field, rubidium in aqueous solution is separated and is enriched with using prepared solid extracting agent, shortens time for sample pretreatment；To the enrichment times of rubidium ion up to 100 times or more, and extractant is preferable to the selectivity of rubidium, K+、Na+Equal interfering ions almost can be removed all, eliminate background interference, only can be detected rubidium content with conventional atomic absorption method, detection accuracy greatly improves.
Description
Technical field
The present invention relates to the magnetic extractant technical field of a new generation, specially a kind of amino and 18 based on rubidium extraction
It is preced with the preparation method of the Magnetic solid phases extractant of six ethers modification.
Background technique
In analytical chemistry, sample pre-treatments are a particularly significant steps, account for about the 60% of entire analysis time with
On, rubidium belongs to rare precious metal, though China's reserves are big, and it is small in sample substrate content, if it is desired to rubidium resources development and utilization, it is first
It first needs to solve the problems, such as that rubidium accurately detects, detection at present is the problem is that often contain a large amount of K in the aqueous solution containing rubidium
+、Na+、Ca2+、Mg2+The background of plasma, the detection means such as conventional atomic absorption spectrphotometry and inductively coupled plasma is dry
It disturbs big, it is difficult to directly detect, need a set of effective sample-pretreating method, conventional Sample Pretreatment Technique is liquid liquid
Abstraction technique takes a long time, and needs to consume a large amount of organic solutions, is unfavorable for environmentally protective.
Magnetic solid phases abstraction technique isolation technics is a kind of preferable isolation technics of prospect, and principle is by the function of selectivity
Energy group, using functional group selective absorption object, recycles externally-applied magnetic field that will adsorb target in conjunction with magnetic substrate
The Magnetic solid phases extractant of object is separated from complex matrices, and object desorption finally can reach separation and concentration object
Purpose, to achieve the purpose that accurately to analyze, 18 six ether rings of hat have good selectivity to rubidium, can use its size row
Resistance principle covers rubidium hydrated ion in ring, and amino and rubidium hydrated ion have molecule hydrogen bond action, and two kinds of active forces are mutually assisted
Together, rubidium can be enable to act on quickly with extractant, recycles Magnetic Isolation principle, that is, be convenient to rubidium ion from ambient water sample
It is conveniently separated in equal complex matrices, after a small amount of elution, can reach the purpose of enrichment, and then reach sample pre-treatments
Purify the purpose of concentration.
Summary of the invention
The purpose of the present invention is to provide a kind of amino based on rubidium extraction and the Magnetic solid phases extractions of 18 hat six ethers modifications
The preparation method for taking agent solves the problems, such as that existing liquid-liquid extraction techniques selectivity is not strong.
To achieve the above object, the invention provides the following technical scheme: a kind of amino and 18 hats six based on rubidium extraction
The preparation method of the Magnetic solid phases extractant of ether modification, the preparation method is using ferroso-ferric oxide as magnetic kernel, with aminopropyl three
It is reaction raw materials, 1- ethyl-(3- dimethylaminopropyl) carbodiimide salt that Ethoxysilane, 4- carboxyl benzo 18, which are preced with six ethers,
Hydrochlorate (EDC) is catalyst, by the magnetic Nano material for carrying out reaction synthesizing amino and 18 hat six ethers modifications in aqueous solution
Material, then using sodium cyanoborohydride as reducing agent, be primary amine by the unstable imine reduction of generation, synthesize the amino that can be stabilized
And 18 hat six ethers modification Magnetic solid phases extractant.
Preferably, kernel is ferroso-ferric oxide, outer cladding 3- aminopropyl triethoxysilane, and in its surface modification ten
Eight six ethers of hat.
Preferably, comprising the following steps:
(1) solvent-thermal method prepares magnetic Fe3O4Nano particle:
Weigh the anhydrous FeCl of 1.89g3, it is placed in 250mL flask, 70mL ethylene glycol is added, places it in magnetic agitation
Room temperature stir about 30min to anhydrous FeCl on device3Dissolution is then added 4.8g anhydrous sodium acetate into solution, continues stirring extremely
Solution clarification, is transferred to ptfe autoclave for reaction solution, is placed in baking oven, and oven temperature is gradually increased to 200 DEG C, and
Isothermal reaction 10h removes reaction product after being after reaction cooled to room temperature tetrafluoroethene reaction kettle, successively with pure water,
For several times, supersound washing for several times, then is placed in 50 DEG C of drying in vacuum oven to ethanol washing, obtains black Fe3O4Nano particle；
(2) magnetic Nano material Fe3O4@SiO2-NH2Preparation:
By 3- aminopropyl silicic acid triethyl, deionized water, ethyl alcohol, (212: 212: 1700 is single for 1: 1: 8 ratio by volume
Position: microlitre), it is added in 25mL eggplant formula flask, is monitored after mixing with acidometer, it will with the NaOH stock solution of 0.1mol/L
Reaction solution pH is adjusted to 9.0 or so, and reaction is hydrolyzed in stirring at normal temperature 4h on magnetic stirring apparatus, after the reaction was completed, continuously adds
0.1gFe3O4(Fe3O4And 5mL ethyl alcohol it is 1 with the mass ratio of 3- aminopropyl triethoxysilane: 2), loads onto reflux condensing tube, and
In one absorbent cotton of nozzle plug, reaction unit is put into heat collecting type constant-temperature heating magnetic stirring apparatus and carries out oil bath heating, and by
80 DEG C are gradually warming up to, 2h is reacted, after the reaction was completed, by product Fe3O4@SiO2-NH2Successively for several times with pure water, ethanol washing, surpass
Sound washs for several times, then is placed in 50 DEG C of drying in vacuum oven, spare；
The modification of (3) 4 '-carboxyl phendioxin 8- hat 6- ether:
Weigh 0.1gFe3O4@SiO2-NH2, it is added in 250mL three-necked bottle, then weigh 0.1gEDC, is dissolved in 50mLpH=5
PBS solution in, which is added in three-necked bottle, three-necked bottle is connect with reflux condensing tube, remaining two mouthfuls with anti-mouth plug
It stoppers, then three-necked bottle is put into heat collecting type constant-temperature heating magnetic stirring apparatus, oil bath heating is carried out to it after letting nitrogen in and deoxidizing 20min,
Temperature is gradually promoted to 55 DEG C, activates 3h, when activation, weighs 0.05g4 '-carboxyl phendioxin 8- hat 6- ether, is dissolved in 5mLpH=
In 5 PBS solution, this solution syringe will be injected in three-necked bottle after to be activated, reaction for 24 hours, after reaction, adds
Enter 0.05g sodium cyanoborohydride the reaction was continued 4h, finally produces reaction product, successively for several times with pure water, ethanol washing, ultrasound
Washing for several times, then is placed in 50 DEG C of drying in vacuum oven, until final product amino and the magnetic Nano of 18- hat 6- ether modification
Solid extracting agent.
Compared with prior art, beneficial effects of the present invention are as follows:
1, the kernel of extractant of the present invention is ferroso-ferric oxide super-paramagnetism nano particle, and particle has superparamagnetism,
It can easily be separated from complex matrices under externally-applied magnetic field, microparticle surfaces have modified the functions such as amino and 18 six ethers of hat
Group can be acted on, selective absorption rubidium water using the molecule Hyarogen-bonding of functional group and the size exclusion of ring molecule
Ion is closed, is the comparatively ideal solid phase extraction material for rubidium extraction.
2, extractant of the present invention is in synthesis step, takes synthesis in water system, and a large amount of existing amino of mating surface increases
The strong hydrophilicity of extractant, makes the rubidium ion in aqueous phase system be easy to be adsorbed.
3, the Magnetic solid phases extractant prepared by the present invention reaches 216mg/g to the adsorption capacity of rubidium ion, and can contain
There is selective absorption rubidium ion in the solution of the alkali metal ions such as potassium, sodium, excludes the interference of common ion.
4, the present invention is desorbing agent using hydrochloric acid, the rate of recovery of rubidium ion can be made to reach 102%, the rate of recovery is higher.
Detailed description of the invention
Fig. 1 is the process of Magnetic solid phases extractant prepared by the present invention and the extraction process to Rb+；
Fig. 2 is the transmission electron microscope picture of Magnetic solid phases extractant prepared by the present invention；
Fig. 3 is the infrared spectrogram of Magnetic solid phases extractant prepared by the present invention；
Fig. 4 is Fe of the present invention3O4The XRD spectrum of the solid extracting agent of kernel and Modified with Crown Ether；
Fig. 5 is standard Fe3O4XRD standard diagram.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Please refer to Fig. 1-5, a kind of system of the Magnetic solid phases extractant of the amino based on rubidium extraction and 18 hat six ethers modifications
Preparation Method, the preparation method are preced with using ferroso-ferric oxide as magnetic kernel with aminopropyl triethoxysilane, 4- carboxyl benzo 18
Six ethers are reaction raw materials, and 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride (EDC) is catalyst, by water
Carried out in solution reaction synthesizing amino and 18 hat six ethers modification magnetic Nano material, then with sodium cyanoborohydride be reduction
The unstable imine reduction of generation is primary amine by agent, and the magnetism for synthesizing the amino that can be stabilized and 18 hat six ethers modifications is solid
Phase extractant.
Embodiment 1
It is a kind of based on rubidium extraction amino and 18 hat six ethers modification Magnetic solid phases extractant preparation method, including with
Lower step: (1) solvent-thermal method prepares magnetic Fe3O4Nano particle: the anhydrous FeCl of 1.89g is weighed3, it is placed in 250mL flask, adds
Enter 70mL ethylene glycol, places it in room temperature stir about 30min to anhydrous FeCl on magnetic stirring apparatus3Dissolution is then added
4.8g anhydrous sodium acetate continues stirring to solution and clarifies, reaction solution is transferred to ptfe autoclave, is placed in baking into solution
In case, oven temperature is gradually increased to 200 DEG C, and isothermal reaction 10h, is after reaction cooled to tetrafluoroethene reaction kettle
After room temperature, reaction product is removed, successively for several times with pure water, ethanol washing, supersound washing for several times, then is placed in vacuum oven
50 DEG C of drying, obtain black Fe3O4Nano particle；(2) magnetic Nano material Fe3O4@SiO2-NH2Preparation: by 3- aminopropyl silicon
Triethylenetetraminehexaacetic acid ester, deionized water, ethyl alcohol, 1: 1: 8 ratio (212: 212: 1700 units: microlitre), is added to 25mL by volume
It in eggplant formula flask, is monitored after mixing with acidometer, reaction solution pH is adjusted to by 9.0 left sides with the NaOH stock solution of 0.1mol/L
The right side, reaction is hydrolyzed in stirring at normal temperature 4h on magnetic stirring apparatus, after the reaction was completed, continuously adds 0.1gFe3O4(Fe3O4With 3-
And 5mL ethyl alcohol the mass ratio of aminopropyl triethoxysilane is 1: 2), loading onto reflux condensing tube, and in one degreasing of nozzle plug
Reaction unit is put into heat collecting type constant-temperature heating magnetic stirring apparatus and carries out oil bath heating by cotton, and is gradually heated to 80 DEG C, reaction
2h, after the reaction was completed, by product Fe3O4@SiO2-NH2Successively for several times with pure water, ethanol washing, supersound washing for several times, then is placed in
50 DEG C of drying, spare in vacuum oven；The modification of (3) 4 '-carboxyl phendioxin 8- hat 6- ether: 0.1gFe is weighed3O4@SiO2-
NH2, it is added in 250mL three-necked bottle, then weigh 0.1gEDC, is dissolved in the PBS solution of 50mLpH=5, which is added to
In three-necked bottle, three-necked bottle is connect with reflux condensing tube, remaining two mouthfuls are stoppered with anti-mouth plug, then three-necked bottle is put into heat collecting type perseverance
Temperature heats magnetic stirring apparatus, carries out oil bath heating to it after letting nitrogen in and deoxidizing 20min, and temperature is gradually promoted to 55 DEG C, activates 3h,
When activation, 0.05g4 '-carboxyl phendioxin 8- hat 6- ether is weighed, is dissolved in the PBS solution of 5mLpH=5, it will after to be activated
This solution will be injected in three-necked bottle with syringe, and for 24 hours, after reaction, 0.05g sodium cyanoborohydride is added, and the reaction was continued for reaction
4h finally produces reaction product, and successively for several times with pure water, ethanol washing, supersound washing for several times, then is placed in vacuum oven
50 DEG C of drying, until final product amino and the magnetic nano solid extracting agent of 18- hat 6- ether modification.
Obtained amino and the Magnetic solid phases extractant of 18 hat six ethers modifications, transmission electron microscope is as shown in Fig. 2, by attached
Fig. 2 it is found that the present invention it is preparation-obtained be spheric granules that average grain diameter is about 150 nanometers, can be significantly from figure
Out, the part of black is Fe among particle3O4Kernel, and the shallower part of exterior color is the clad of silica, element point
The results are shown in Table 1 for analysis, can also be seen that the presence of Si element in elemental analysis table, then as Cr, Cu element detected
Be TEM detection experiment pretreatment process in be added as needed, so, the characterization result of TEM, which further explains, to be contained
Silicon dioxide layer has successfully been coated on Fe 3 O 4 magnetic kernel.
The surface-element of Magnetic solid phases extractant prepared by 1 present invention of table analyzes result
Obtained amino and the Magnetic solid phases extractant of 18 hat six ethers modifications, infrared spectrogram is as shown in Fig. 3, attached
Two curves in Fig. 3 respectively correspond the Fe that this experiment is prepared3O4Kernel and amino and 4 '-carboxyl phendioxin 8- are preced with 6-
The infrared spectroscopy of product after ether modification, by comparison it can be seen that in product infrared spectrogram, in 3540cm-1~3180cm-1
Place, there are two absorption band, that is, 3521.8cm of point-1And 3455.2cm-1, this belongs to-NH2Contraction absorption of vibrations band, this explanation
Fe3O4- NH has successfully been modified outside kernel2；And in 1667.4cm-1Place, product there are vibration absorption peak, can belong to-
NH2Characteristic absorption peak, illustrate Fe3O4@SiO2-NH2Amidation process occurs with 4 '-carboxyl phendioxin 8- hat 6- ether, and
It successfully modifies in Fe3O4Outside kernel；In 1650-1500cm-1Between several small absorption peaks can then belong to phenyl ring spy
Peak and water peak are levied, can also illustrate that 4 '-carboxyl phendioxin 8- hat 6- ether is successfully modified on solid extracting agent；?
568.7cm-1The absorption peak at place illustrates the presence of Fe, so, by infrared spectrum characterization result can find out experiment prepare kernel and
The success of coating decoration.
Attached drawing 4 is Magnetic solid phases extractant and Fe prepared by the present invention3O4X-ray diffractogram, attached drawing 5 is Fe3O4's
Standard X-ray diffraction figure, Fe3O4It with stronger superparamagnetism, is more convenient for separating, therefore is not intended in material preparation process
Fe3O4It is converted into Fe2O3, attached drawing 4 by with Fe3O4The comparison of XRD standard diagram, it is found that use prepared by the present invention
Make the Fe of magnetic kernel3O4Measured XRD characterization map and Fe3O4Standard XRD pattern, the angle and peak height of diffraction maximum are uniform
It causes, and by by final product and Fe3O4The XRD characterization map of magnetic kernel is compared, it can be seen that the angle of diffraction maximum
It is also consistent with peak height, illustrate the present invention in coated Si O2-NH2When and modification 4 '-carboxyl phendioxin 8- hat 6- ether when do not make
Fe3O4It is converted into Fe2O3, prepared material is apparently also black from the appearance, rather than Fe2O3Distinctive rust red,
This point can be proved from side, illustrate in material preparation process, Fe3O4It is not oxidized to Fe2O3。
Embodiment 2
It is a kind of based on rubidium extraction amino and 18 hat six ethers modification Magnetic solid phases extractant preparation method, selectivity
Rare precious metal rubidium ion in adsorption aqueous solution, comprising the following steps: (1) prepare stock solution: compound concentration is 1.5mol/L's
Hydrochloric acid solution；The buffer that pH=13 is prepared with ammonium hydroxide and ammonium chloride, is accurately pipetted the rubidium standard specimen of 10mg/mL, is with pH respectively
13 ammonium hydroxide ammonium chloride buffer, it is configured to the mark of 0.5mg/mL, 1.0mg/mL, 2.5mg/mL, 5mg/mL, 7.5mg/mL
Calibration curve solution of the quasi- solution as atomic absorption method；(2) it prepares interfering ion stock solution: being distinguished with potassium chloride and sodium chloride
Preparing ion concentration is containing Na+20g/L and containing the stock solution of K+14g/L；(3) solid extracting agent activation step: system is accurately weighed
Standby Magnetic solid phases extractant 20mg activates 30min with 5mL ammonium hydroxide-ammonium chloride buffer solution (pH=13), with externally-applied magnetic field point
From extractant and solution, and discard supernatant liquid；(4) Solid Phase Extraction loading step: by the activated solid extracting agent of step 3,
It is separately added into the standard solution of 1mL (a) step preparation, K+, Na+ interfering ion stock solution that each 1mL (b) step is prepared, then divides
Not Jia Ru (a) step prepare 7mLpH be 13 ammonium hydroxide-ammonium chloride buffer, ultrasonic 5min, vortex 3min, stand Magneto separate,
Collect supernatant；(5) Solid Phase Extraction rinsing step: accurately pipetting 1mL1.5mol/l hydrochloric acid and be added in magnetic solid phase extraction agent, whirlpool
90s is revolved, is repeated 3 times, the ammonium hydroxide ammonium chloride buffer that 1mLpH is 13 is accurately pipetted and is added in magnetic solid phase extraction agent, be vortexed
90s is repeated 3 times, then is accurately pipetted 1mL ultrapure water and eluted, and vortex 90s is repeated 3 times, and collects supernatant every time, is merged
The supernatant eluted every time；(6) elution step: accurately pipetting 1mL concentrated hydrochloric acid and eluted, and collects supernatant；(7) after introduction of the sample
Supernatant in and eluent in be separately added into 100ug rubidium standard specimen, be settled to 50mL volumetric flask；(8) with aas determination
Rubidium content in all samples；(9) Magnetic solid phases extractant prepared by the present invention is measured to the saturation of rubidium using Rubidium Standard liquid
The method of adsorbance are as follows: total amount containing rubidium is added in activated 50mg solid extracting agent as the Rubidium Standard solution of 12mg, then plus
Enter ammonium hydroxide-ammonium chloride buffer that the pH of (a) step preparation is 13, total volume about 10mL, ultrasonic 5min, vortex 3min are stood
Magneto separate collects supernatant；(10) step (5)~(8) are repeated.
The obtained sample of each step is measured using atomic absorption spectrophotometer, maximum saturation adsorbance is
216mg/g, as shown in table 2 to the detection calculated result of rubidium extraction process in Rubidium Standard liquid and interfering ion aqueous solution:
Mean concentration of 2 rubidium ion of table in Solid Phase Extraction respectively walks
In addition, the experimental results showed that, there is interfering ion K+Loading total amount is 14mg/mL, Na+When for 20mg/mL, loading
K in supernatant afterwards+Concentration is 13.5mg/mL, Na+It is practically free of in eluent after eluting several times for 15.2mg/mL
K+And Na+, illustrate to remove most interfering ions by loading, elution and elution step, then will with a small amount of concentrated hydrochloric acid
Adsorbent dissolution can reach separation, enrichment and the effect for eliminating interference.
In use, simplifying synthesis step on ferroso-ferric oxide surface for amido modified using one-step method in aqueous phase system
Suddenly, under the catalytic action of EDC, amino and 4- carboxyl-ten eight are preced with six ethers and can be bonded under the conditions of conveniently, by amino and
18 six ethers of hat are modified simultaneously arrives ferroso-ferric oxide surface, can make solid extracting agent while have both magnetism, hydrophily, size exclusion
Property, molecule Hyarogen-bonding, the convenient selective absorption to rubidium ion in complex matrices.
The present invention will have special selective amino and 18 hat six ethers and amido modified to the hydrated ion of rubidium for the first time
Ferriferrous oxide nanometer material is bonded to together, is prepared for 18 six ethers of hat and ammonia for complicated brine systems rubidium separation and concentration
The Magnetic solid phases extractant of base modification is enhanced on the one hand using the synergistic effect of 18 hat six ethers and amino to rubidium hydrated ion
Selectivity；On the other hand, using the magnetism of ferroso-ferric oxide, reach under externally-applied magnetic field conveniently and efficiently by rubidium ion from containing
The purpose separated in the complex matrices for having a large amount of alkali metal plasmas, using prepared solid extracting agent to rubidium in aqueous solution into
Row separation and enrichment, to being detected since enrichment, whole process is only needed 3 hours or so, substantially reduces sample pre-treatments
Time；To the enrichment times of rubidium ion up to 100 times or more, and extractant is preferable to the selectivity of rubidium, K+、Na+Equal interfering ions
It almost can all remove, eliminate background interference, only can be detected rubidium content with conventional atomic absorption method, detection accuracy is big
It is big to improve.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (3)
1. the preparation method of a kind of amino based on rubidium extraction and the Magnetic solid phases extractant of 18 hat six ethers modifications, feature exist
In: the preparation method is preced with six ethers using ferroso-ferric oxide as magnetic kernel, with aminopropyl triethoxysilane, 4- carboxyl benzo 18
For reaction raw materials, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride (EDC) is catalyst, by aqueous solution
The middle magnetic Nano material for carrying out reaction synthesizing amino and 18 hat six ethers modifications, then using sodium cyanoborohydride as reducing agent, it will
The unstable imine reduction generated is primary amine, synthesizes the Magnetic solid phases extraction of the amino that can be stabilized and 18 hat six ethers modifications
Agent.
2. a kind of amino based on rubidium extraction according to claim 1 and the Magnetic solid phases extractant of 18 hat six ethers modifications
Preparation method, it is characterised in that: its kernel is ferroso-ferric oxide, outer cladding 3- aminopropyl triethoxysilane, and in its table
18 six ethers of hat of face modification.
3. a kind of amino based on rubidium extraction according to claim 1 and the Magnetic solid phases extractant of 18 hat six ethers modifications
Preparation method, it is characterised in that: the following steps are included:
(1) solvent-thermal method prepares magnetic Fe3O4Nano particle:
Weigh the anhydrous FeCl of 1.89g3, it is placed in 250mL flask, 70mL ethylene glycol is added, places it in magnetic stirring apparatus upper chamber
Warm stir about 30min to anhydrous FeCl3Dissolution is then added 4.8g anhydrous sodium acetate into solution, it is clear to solution to continue stirring
Clearly, reaction solution is transferred to ptfe autoclave, be placed in baking oven, oven temperature is gradually increased to 200 DEG C, and constant temperature is anti-
10h is answered, after being after reaction cooled to room temperature tetrafluoroethene reaction kettle, reaction product is removed, is successively washed with pure water, ethyl alcohol
It washs for several times, supersound washing for several times, then is placed in 50 DEG C of drying in vacuum oven, obtains black Fe3O4Nano particle；
(2) magnetic Nano material Fe3O4@SiO2-NH2Preparation:
By 3- aminopropyl silicic acid triethyl, deionized water, ethyl alcohol, by volume 1: 1: 8 ratio (212: 212: 1700 units:
Microlitre), it is added in 25mL eggplant formula flask, is monitored after mixing with acidometer, it will be anti-with the NaOH stock solution of 0.1mol/L
Liquid pH is answered to be adjusted to 9.0 or so, reaction is hydrolyzed in stirring at normal temperature 4h on magnetic stirring apparatus, after the reaction was completed, continuously adds
0.1gFe3O4(Fe3O4And 5mL ethyl alcohol it is 1 with the mass ratio of 3- aminopropyl triethoxysilane: 2), loads onto reflux condensing tube, and
In one absorbent cotton of nozzle plug, reaction unit is put into heat collecting type constant-temperature heating magnetic stirring apparatus and carries out oil bath heating, and by
80 DEG C are gradually warming up to, 2h is reacted, after the reaction was completed, by product Fe3O4@SiO2-NH2Successively for several times with pure water, ethanol washing, surpass
Sound washs for several times, then is placed in 50 DEG C of drying in vacuum oven, spare；
The modification of (3) 4 '-carboxyl phendioxin 8- hat 6- ether:
Weigh 0.1gFe3O4@SiO2-NH2, it is added in 250mL three-necked bottle, then weigh 0.1gEDC, is dissolved in the PBS of 50mLpH=5
In solution, which is added in three-necked bottle, three-necked bottle is connect with reflux condensing tube, remaining two mouthfuls are stoppered with anti-mouth plug,
Three-necked bottle is put into heat collecting type constant-temperature heating magnetic stirring apparatus again, oil bath heating is carried out to it after letting nitrogen in and deoxidizing 20min, by temperature
It is gradually promoted to 55 DEG C, activates 3h, when activation, weigh 0.0594 '-carboxyl phendioxin 8- hat 6- ether, be dissolved in the PBS of 5mLpH=5
In solution, this solution syringe will be injected in three-necked bottle after to be activated, reaction for 24 hours, after reaction, is added
0.05g sodium cyanoborohydride the reaction was continued 4h, finally produces reaction product, and successively for several times with pure water, ethanol washing, ultrasound is washed
It washs for several times, then is placed in 50 DEG C of drying in vacuum oven, until the magnetic Nano of final product amino and 18- hat 6- ether modification is solid
Phase extractant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910216237.6A CN109865312A (en) | 2019-03-21 | 2019-03-21 | It is a kind of based on rubidium extraction amino and 18 hat six ethers modification Magnetic solid phases extractant preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910216237.6A CN109865312A (en) | 2019-03-21 | 2019-03-21 | It is a kind of based on rubidium extraction amino and 18 hat six ethers modification Magnetic solid phases extractant preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109865312A true CN109865312A (en) | 2019-06-11 |
Family
ID=66920999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910216237.6A Pending CN109865312A (en) | 2019-03-21 | 2019-03-21 | It is a kind of based on rubidium extraction amino and 18 hat six ethers modification Magnetic solid phases extractant preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109865312A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551894A (en) * | 2019-10-17 | 2019-12-10 | 青海民族大学 | Extraction separation system for separating rubidium ions from salt lake brine and use method thereof |
| CN110787640A (en) * | 2019-11-04 | 2020-02-14 | 陕西省膜分离技术研究院有限公司 | Separation method of Rb + and Na + based on ionic liquid polymer liquid membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070193954A1 (en) * | 2004-04-05 | 2007-08-23 | Philippe Busson | Method of preparing a separation matrix |
| CN101053827A (en) * | 2007-05-10 | 2007-10-17 | 复旦大学 | Surface fixing metal ions magnetic microspheres and its preparation method and application |
| KR20120031724A (en) * | 2010-09-27 | 2012-04-04 | 한국세라믹기술원 | Hydrohpobic and functional groups modified silica coated magnetic nanoparticles and a seperation method of protein using thereof |
| CN107335403A (en) * | 2017-06-29 | 2017-11-10 | 上海工程技术大学 | Load magnetic core-shell nano composite material, its preparation method and the application of nickel particle |
-
2019
- 2019-03-21 CN CN201910216237.6A patent/CN109865312A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070193954A1 (en) * | 2004-04-05 | 2007-08-23 | Philippe Busson | Method of preparing a separation matrix |
| CN101053827A (en) * | 2007-05-10 | 2007-10-17 | 复旦大学 | Surface fixing metal ions magnetic microspheres and its preparation method and application |
| KR20120031724A (en) * | 2010-09-27 | 2012-04-04 | 한국세라믹기술원 | Hydrohpobic and functional groups modified silica coated magnetic nanoparticles and a seperation method of protein using thereof |
| CN107335403A (en) * | 2017-06-29 | 2017-11-10 | 上海工程技术大学 | Load magnetic core-shell nano composite material, its preparation method and the application of nickel particle |
Non-Patent Citations (1)
| Title |
|---|
| 刘霍: "针对铷离子的功能化磁性固相萃取剂的制备", 《中国优秀硕士学位论文全文库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551894A (en) * | 2019-10-17 | 2019-12-10 | 青海民族大学 | Extraction separation system for separating rubidium ions from salt lake brine and use method thereof |
| CN110787640A (en) * | 2019-11-04 | 2020-02-14 | 陕西省膜分离技术研究院有限公司 | Separation method of Rb + and Na + based on ionic liquid polymer liquid membrane |
| CN110787640B (en) * | 2019-11-04 | 2021-11-23 | 陕西省膜分离技术研究院有限公司 | Liquid film pair Rb based on ionic liquid polymer+And Na+Of (2) a separation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109261128B (en) | Boric acid type magnetic COFs material, preparation method and application thereof | |
| CN105879842B (en) | A kind of magnetism PAFs solid extracting agents and its preparation method and application | |
| Khoddami et al. | A new magnetic ion-imprinted polymer as a highly selective sorbent for determination of cobalt in biological and environmental samples | |
| CN105413659B (en) | A kind of bionical adsorbent of magnetism and its application in the acid uranium-containing waste water of processing | |
| CN106582543B (en) | Chiral MOF- magnetic graphenes functional material and its preparation method and application | |
| CN110385116A (en) | A kind of magnetic nanometer composite material and its preparation and application | |
| CN105709690A (en) | Adsorbent capable of preferentially adsorbing gold and preparing method and application thereof | |
| CN109865312A (en) | It is a kind of based on rubidium extraction amino and 18 hat six ethers modification Magnetic solid phases extractant preparation method | |
| CN103268797B (en) | A kind of hydrophilic magnetic mesoporous microballoon and preparation method thereof and application | |
| CN108502964B (en) | A kind of preparation method of magnetic nanometer composite material | |
| CN108417337B (en) | Nickelized magnetic microsphere and preparation method and application thereof | |
| CN110496608A (en) | A kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101 and its preparation method and application | |
| CN109626367A (en) | Graphene composite material, preparation method and applications | |
| CN105771904B (en) | A kind of magnetic adsorbent and preparation method thereof and the recycling to palladium in nitric acid medium | |
| CN110152632A (en) | A kind of magnetic COF-TpPa and its preparation method and application for being enriched with amides pesticide | |
| CN107551987A (en) | A kind of magnetic adsorbent and its production and use | |
| CN105486791A (en) | Fe3O4@SiO2@G magnetic adsorbent and method for detecting 16 anti-staling agents in vegetable by using same | |
| CN110314669A (en) | A kind of magnetic COF-TbPa and its preparation method and application for being enriched with triazole pesticide | |
| CN102516822B (en) | Surface-functionalized Fe3O4 nanoparticles as well as preparation method and application thereof | |
| CN107652377A (en) | The preparation method of the chelating resin of polyfunctional group modification | |
| CA3109058C (en) | Benzeneboronic acid solid-phase extraction column packing and preparation method thereof | |
| CN108586660A (en) | The preparation method of TNT magnetic molecularly imprinted polymer microballoons | |
| CN109806841A (en) | Basic amino acid modified silica-gel material and its preparation method and application | |
| CN108928880A (en) | A kind of processing method of the waste water containing radioactive element | |
| CN107286189B (en) | A kind of organic-inorganic hybrid material and preparation method thereof handling heavy metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190611 |
|
| RJ01 | Rejection of invention patent application after publication |