CN106636671B - A method of utilizing sulfone bridge cup [4] aromatics seperation strontium, rubidium - Google Patents
A method of utilizing sulfone bridge cup [4] aromatics seperation strontium, rubidium Download PDFInfo
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- CN106636671B CN106636671B CN201611205828.6A CN201611205828A CN106636671B CN 106636671 B CN106636671 B CN 106636671B CN 201611205828 A CN201611205828 A CN 201611205828A CN 106636671 B CN106636671 B CN 106636671B
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- rubidium
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- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 73
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052701 rubidium Inorganic materials 0.000 title claims abstract description 61
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000008346 aqueous phase Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 77
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- 229920005989 resin Polymers 0.000 claims description 55
- 229960001701 chloroform Drugs 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 40
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 claims description 39
- 238000002390 rotary evaporation Methods 0.000 claims description 36
- 150000003457 sulfones Chemical class 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000010355 oscillation Effects 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000003480 eluent Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 2
- 238000005372 isotope separation Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000805 composite resin Substances 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 125000003118 aryl group Chemical group 0.000 description 15
- 238000007789 sealing Methods 0.000 description 13
- 229910001427 strontium ion Inorganic materials 0.000 description 12
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 11
- QHYZICICAOBWPZ-UHFFFAOYSA-N O=S(=O)=S(=O)=O Chemical compound O=S(=O)=S(=O)=O QHYZICICAOBWPZ-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 6
- 229910001419 rubidium ion Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- NCCSSGKUIKYAJD-UHFFFAOYSA-N rubidium(1+) Chemical compound [Rb+] NCCSSGKUIKYAJD-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000005258 radioactive decay Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of methods using sulfone bridge cup [4] aromatics seperation strontium, rubidium, belong to isotopic separation technical field of purification.The method comprises the following steps: first sulfone bridge cup [4] aromatic hydrocarbons is supported on the inert carrier of activation, then composite material is put into the aqueous phase solution containing strontium and rubidium and carries out adsorbing separation, and eluted the strontium adsorbed on composite material with acid solution, thus the strontium solution after being separated.Sulfone bridge cup [4] aromatic hydrocarbons used in the present invention has excellent separating effect to strontium, rubidium；And this method stability is good, strong operability, and sulfone bridge cup [4] aromatic hydrocarbons composite material may be reused, and it is at low cost.
Description
Technical Field
The invention relates to a method for separating strontium and rubidium by utilizing sulfone bridged calix [4] arene, belonging to the technical field of isotope separation and purification.
Background
The isotope geology chronology is one of the isotope geology branches, and utilizes the radioactive decay law of the natural world to research and determine the formation times of various geologic bodiesThe method of isotopic timing of (1). The application of strontium isotopes in isotope measurement is of great significance.87Sr/86The Sr record can be used to trace back the date of marine sediments, to assess formation discontinuity time, to trace back food production locations, etc.
The strontium isotope analysis requires a high standard of relative standard deviation due to87The nature of Rb and87sr is close, it will interfere87Sr, and two elements often coexist, so that the two elements need to be effectively separated.
The Sr specific resin of Dowex, Bio Rad and Eichrom company can separate strontium and rubidium, but all of the materials need to be imported from foreign countries and are expensive. And when the Sr special-effect resin is used for separating strontium ions and rubidium ions, the volume of an analysis object and a special treatment environment need to be limited, so that the operation is inconvenient, the repeated utilization rate is low, and the separation effect difference is large, so that the analysis and detection cost is high, and the operability is not strong.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for separating strontium and rubidium by utilizing sulfone-bridged calix [4] arene, wherein the sulfone-bridged calix [4] arene adopted by the method has excellent separation effect on the strontium and the rubidium; the method has the advantages of good stability, strong operability and low cost.
The purpose of the invention is realized by the following technical scheme:
a method for separating strontium and rubidium by utilizing sulfone bridged calix [4] arene comprises the following specific steps:
step 1, mixing sulfone calix [4] arene, an activated inert carrier and a solvent, magnetically stirring for not less than 12 hours, and then removing the solvent by rotary evaporation;
adding the substance obtained after rotary evaporation into a solvent, and repeating the stirring and rotary evaporation operation in the step 1 for 1-2 times; adding the substance obtained by the last rotary evaporation into a solvent, uniformly mixing, filtering and drying to obtain the sulfone calix [4] arene composite material;
step 3, adding the sulfone calix [4] arene composite material into an aqueous phase solution containing strontium and rubidium, then oscillating for 5 min-9 h in a constant-temperature water bath oscillator, filtering after oscillation is finished, eluting the filtered sulfone calix [4] arene composite material by using an acid solution, wherein the eluent is a strontium-containing solution;
the structural formula of the sulfone bridged calix [4] arene is shown as follows:
wherein R is C8H17Or SO3Na；
The solvent is trichloromethane or ultrapure water;
the constant temperature oscillation temperature is 10-40 ℃, and preferably 20-30 ℃;
the inert carrier is XAD-2 resin, XAD-4 resin, XAD-7 resin, XAD-8 resin, XAD-16 resin, D101 resin, D201 resin, D202 resin, D301 resin, D307 resin or D311 resin.
The pH value of the water phase solution containing strontium and rubidium is preferably 6-8.
The concentration of strontium and rubidium in the water phase solution containing strontium and rubidium is 0.1-20 mg/L, preferably 1-20 mg/L.
In step 1, the mass ratio of the sulfone bridged calix [4] arene to the inert carrier is preferably 1: 3.
In the step 3, the acid solution is preferably hydrochloric acid aqueous solution, sulfuric acid aqueous solution or nitric acid aqueous solution, and the acid concentration in the eluent is 0.5-8 mol/L, preferably 6 mol/L.
And (3) washing the sulfone calix [4] arene composite material eluted in the step (3) with deionized water, and drying to obtain the material for separating strontium and rubidium for recycling.
Has the advantages that:
the sulfone bridge calix [4] arene in the method has excellent separation effect on strontium and rubidium, and the selectivity coefficient of strontium on rubidium is as high as 11000; and the sulfone bridge calix [4] arene composite material can be reused, so that the cost is greatly reduced. The separation method provided by the invention has the advantages of good stability and strong operability.
Detailed Description
The present invention will be further described with reference to the following embodiments.
In the following examples:
an atomic emission spectrometer: agilent technologies (China) Inc., model number MP-AES 4100.
A constant-temperature water bath oscillator: the model of the gold jar is SHZ-82.
XAD series resins: beijing technologies, Inc.
D series resin: beijing technologies, Inc.
Method for activating XAD series resin: placing XAD series resin at 250cm3Immersing a single-mouth flask in methanol, sealing, stirring for 24 hours by a magnetic force, and performing suction filtration; after repeating the above stirring and suction filtration operations 3 times, the XAD series resin was vacuum-dried at 85 ℃ for 24 hours to obtain an activated XAD series resin, which was placed in a dryer for use.
D series resin activation method: placing D series resin at 250cm3Cleaning a single-neck flask with 0.5% nitric acid aqueous solution, excessive ultrapure water and 1.0% sodium hydroxide aqueous solution in sequence, and finally adjusting the mixture to be neutral with ultrapure water; repeating the above washing step for 3 times, drying the D series resin at 45 deg.C to obtain activated D series resin, andplacing in a polyethylene container for standby.
The calculation method of the selectivity coefficient comprises the following steps:
(1) first, the amount of adsorption q is calculatede：
Wherein q ise-equilibrium adsorption, mg/g;
c0the initial solubility of the ionic solution, i.e. the concentration of strontium or rubidium in the aqueous solution before separation in example step 2, mg/L;
ce-equilibrium concentration, i.e. concentration of strontium or rubidium in the aqueous solution after separation in example step 2, mg/L;
v — volume of ionic solution, i.e. volume of aqueous phase solution separated in step 2 of example, L;
m is the mass of adsorbent, i.e. of the sulfone bridged calix [4] arene composite used in example step 2, g;
(2) then, selectivity coefficients α are calculatedSr/Rb：
Wherein,is the partition ratio of the metal ions.
Examples 1 to 7
Step 1. bridge 0.5g p-tert-octyl sulfone [4]]Aromatic hydrocarbons and 1.5g of activated XAD-7 resin were added to 250cm3Single portAdding 100ml of trichloromethane solution into the flask, sealing the flask, magnetically stirring for 24 hours, and removing trichloromethane by rotary evaporation; adding the substance obtained after the first rotary evaporation into 100ml of trichloromethane solution, magnetically stirring for 24 hours, and then, removing trichloromethane by rotary evaporation; adding the substance obtained after the second rotary evaporation into 100ml of chloroform solution, uniformly stirring by magnetic force, filtering, placing the filtered solid substance in a vacuum drying oven, and drying at 85 ℃ for 24h to obtain white powdery p-tert-octyl sulfone bridge cup [4]]An arene-XAD-7 resin composite;
step 2, numbering 7 50mL centrifuge tubes as 1, 2, 3, 4, 5, 6 and 7 in sequence, and respectively adding 0.01g of p-tert-octyl sulfone bridge cup [4] into each centrifuge tube]Aromatic hydrocarbon-XAD-7 resin composite material and 10mL of aqueous phase solution with the concentration of both strontium and rubidium being 20mg/L, and then 0.1mol/L of HNO3Sequentially adjusting the pH value of the solution in 7 centrifugal tubes from small to large to 2, 3, 4, 5, 6, 7 and 8 according to the number by using the solution and 0.1mol/L NaOH solution, sealing the centrifugal tubes, then placing the centrifugal tubes in a constant-temperature water bath oscillator at 25 ℃ for oscillation for 8 hours, filtering after oscillation is finished, and then using 6mol/L HNO3P-tert-octyl sulfone bridge cup (4) obtained by solution elution and filtration]The aromatic hydrocarbon-XAD-7 resin composite material, wherein the eluent is the solution containing strontium obtained after separation; the eluted p-tert-octyl sulfone is bridged to a cup [4]]The arene-XAD-7 resin composite material is washed by deionized water and dried, and can be repeatedly used for separating strontium and rubidium.
Testing Rb in filtrate obtained by filtering after oscillation in the step 2 by using an atomic emission spectrometer+And Sr2+And then the selectivity coefficient is obtained. The selectivity coefficients of strontium to rubidium in the centrifugal tubes numbered 1, 2, 3, 4, 5, 6 and 7 are calculated to be 332.36, 886.46, 1898.56, 5863.71, 8806.67, 10962.36 and 10056.64 in sequence.
In the embodiment, p-tert-octyl sulfone calix [4] arene and XAD-7 resin are replaced by sulfonyl sulfone calix [4] arene and D201 resin, chloroform is replaced by ultrapure water, other conditions are not changed, the sulfonyl sulfone calix [4] arene-D201 resin composite material is used for separating aqueous phase solutions containing strontium and rubidium and having pH values of 2, 3, 4, 5, 6, 7 and 8 respectively, and accordingly, the selectivity coefficients of strontium to rubidium are 200.12, 652.11, 1578.55, 4112.33, 6555.12, 8744.69 and 7955.49 in sequence.
Examples 8 to 10
Step 1. bridge 0.5g p-tert-octyl sulfone [4]]Aromatic hydrocarbons and 1.5g of activated XAD-7 resin were added to 250cm3Adding 100ml of trichloromethane solution into the single-neck flask, sealing the single-neck flask, magnetically stirring for 24 hours, and then removing trichloromethane by rotary evaporation; adding the substance obtained after the first rotary evaporation into 100ml of trichloromethane solution, magnetically stirring for 24 hours, and then, removing trichloromethane by rotary evaporation; adding the substance obtained after the second rotary evaporation into 100ml of chloroform solution, uniformly stirring by magnetic force, filtering, placing the filtered solid substance in a vacuum drying oven, and drying at 85 ℃ for 24h to obtain white powdery p-tert-octyl sulfone bridge cup [4]]An arene-XAD-7 resin composite;
step 2, numbering 350 mL centrifuge tubes as 8, 9 and 10 in sequence, and respectively adding 0.01g p-tert-octyl sulfone bridge cup [4] into each centrifuge tube]Aromatic hydrocarbon-XAD-7 resin composite material and 10mL of aqueous phase solution with the concentration of both strontium and rubidium being 20mg/L, and then 0.1mol/L of HNO3Adjusting the pH value of the solution in 3 centrifugal tubes to 6 by using the solution and 0.1mol/L NaOH solution, sealing the centrifugal tubes, placing the 3 centrifugal tubes in a constant-temperature water bath oscillator with the temperature of 20 ℃, 30 ℃ and 40 ℃ from small to large according to the serial number, oscillating for 8 hours, filtering after oscillation is finished, and then using 2mol/L HNO3P-tert-octyl sulfone bridge cup (4) obtained by solution elution and filtration]The aromatic hydrocarbon-XAD-7 resin composite material, wherein the eluent is the solution containing strontium obtained after separation; the eluted p-tert-octyl sulfone is bridged to a cup [4]]The arene-XAD-7 resin composite material is washed by deionized water and dried, and can be repeatedly used for separating strontium and rubidium.
Testing Rb in filtrate obtained by filtering after oscillation in the step 2 by using an atomic emission spectrometer+And Sr2+And then the selectivity coefficient is obtained. Calculated and numbered as 8,9. The selectivity coefficients of strontium to rubidium in 10 centrifuge tubes were 11126.25, 9624.32, and 8350.46, respectively.
The p-tert-octyl sulfone calix [4] arene and XAD-7 resin in the embodiment are replaced by sulfonyl sulfone calix [4] arene and D201 resin, chloroform is replaced by ultrapure water, other conditions are not changed, the sulfonyl sulfone calix [4] arene-D201 resin composite material is used for carrying out oscillation separation on the water phase solution containing strontium and rubidium at the temperature of 20 ℃, 30 ℃ and 40 ℃, and accordingly, the selectivity coefficients of strontium to rubidium are 8987.55, 7553.13 and 5477.52 respectively. Examples 11 to 15
Step 1. bridge 0.5g p-tert-octyl sulfone [4]]Aromatic hydrocarbons and 1.5g of activated XAD-7 resin were added to 250cm3Adding 100ml of trichloromethane solution into the single-neck flask, sealing the single-neck flask, magnetically stirring for 24 hours, and then removing trichloromethane by rotary evaporation; adding the substance obtained after the first rotary evaporation into 100ml of trichloromethane solution, magnetically stirring for 24 hours, and then, removing trichloromethane by rotary evaporation; adding the substance obtained after the second rotary evaporation into 100ml of chloroform solution, uniformly stirring by magnetic force, filtering, placing the filtered solid substance in a vacuum drying oven, and drying at 85 ℃ for 24h to obtain white powdery p-tert-octyl sulfone bridge cup [4]]An arene-XAD-7 resin composite;
step 2, numbering 5 50mL centrifuge tubes as 11, 12, 13, 14 and 15 in sequence, and adding 0.01g p-tert-octyl sulfone bridge cup [4] into each centrifuge tube]The arene-XAD-7 resin composite material is prepared by sequentially adding 10mL of aqueous phase solution with the concentration of 0.1mg/L, 0.5mg/L, 1mg/L, 10mg/L and 15mg/L of strontium and rubidium into 5 centrifugal tubes from small to large according to the number, and then adding 0.1mol/L of HNO3Adjusting the pH value of the solution in 5 centrifugal tubes to 6 by using the solution and 0.1mol/L NaOH solution, sealing the centrifugal tubes, placing the centrifugal tubes in a constant-temperature water bath oscillator at 25 ℃ to oscillate for 8 hours, filtering after oscillation is finished, and eluting and filtering by using 7mol/L HCl solution to obtain the p-tert-octyl sulfone bridge cup [4]]The aromatic hydrocarbon-XAD-7 resin composite material, wherein the eluent is the solution containing strontium obtained after separation; the eluted p-tert-octyl sulfone is bridged to a cup [4]]The arene-XAD-7 resin composite material is washed by deionized water and dried,can be repeatedly used for separating strontium and rubidium.
Testing Rb in filtrate obtained by filtering after oscillation in the step 2 by using an atomic emission spectrometer+And Sr2+And then the selectivity coefficient is obtained. The selectivity coefficients of strontium to rubidium in the centrifugal tubes with the numbers of 11, 12, 13, 14 and 15 are calculated to be 8452.55, 9445.21, 10001.56, 11588.45 and 9956.22 in sequence.
In the embodiment, p-tert-octyl sulfone calix [4] arene and XAD-7 resin are replaced by sulfonyl sulfone calix [4] arene and D201 resin, chloroform is replaced by ultrapure water, other conditions are not changed, the sulfonyl sulfone calix [4] arene-D201 resin composite material is used for separating aqueous phase solution containing strontium and rubidium with the concentration of 0.1mg/L, 0.5mg/L, 1mg/L, 10mg/L and 15mg/L, and accordingly, the selectivity coefficient of strontium to rubidium is 6445.22, 7985.55, 8155.41, 8966.55 and 8445.22 in sequence.
Examples 16 to 21
Step 1. bridge 0.5g p-tert-octyl sulfone [4]]Aromatic hydrocarbons and 1.5g of activated XAD-7 resin were added to 250cm3Adding 100ml of trichloromethane solution into the single-neck flask, sealing the single-neck flask, magnetically stirring for 24 hours, and then removing trichloromethane by rotary evaporation; adding the substance obtained after the first rotary evaporation into 100ml of trichloromethane solution, magnetically stirring for 24 hours, and then, removing trichloromethane by rotary evaporation; adding the substance obtained after the second rotary evaporation into 100ml of chloroform solution, uniformly stirring by magnetic force, filtering, placing the filtered solid substance in a vacuum drying oven, and drying at 85 ℃ for 24h to obtain white powdery p-tert-octyl sulfone bridge cup [4]]An arene-XAD-7 resin composite;
step 2, numbering 6 centrifuge tubes of 50mL in sequence as 16, 17, 18, 19, 20 and 21, and adding 0.01g p-tert-octyl sulfone bridge cup [4] into each centrifuge tube]Aromatic hydrocarbon-XAD-7 resin composite material and 10mL of aqueous phase solution containing 20mg/L of strontium and rubidium, and then 0.1mol/L of HNO3The solution and 0.1mol/L NaOH solutionAdjusting the pH value of the solution in the 6 centrifugal tubes to 6, sealing the centrifugal tubes, placing the 6 centrifugal tubes in a constant-temperature water bath oscillator at 25 ℃ in sequence from small to large according to the number, oscillating for 5min, 10min, 20min, 60min, 480min and 540min, filtering after oscillation is finished, and then using 6mol/L HNO3P-tert-octyl sulfone bridge cup (4) obtained by solution elution and filtration]The aromatic hydrocarbon-XAD-7 resin composite material, wherein the eluent is the solution containing strontium obtained after separation; the eluted p-tert-octyl sulfone is bridged to a cup [4]]The arene-XAD-7 resin composite material is washed by deionized water and dried, and can be repeatedly used for separating strontium and rubidium.
Testing Rb in filtrate obtained by filtering after oscillation in the step 2 by using an atomic emission spectrometer+And Sr2+And then the selectivity coefficient is obtained. The calculated selectivity coefficients of strontium to rubidium in the centrifugal tubes with the numbers of 16, 17, 18, 19, 20 and 21 are 4552.23, 7001.22, 8112.23, 9665.22, 11556.12 and 11002.28 in sequence.
In the embodiment, p-tert-octyl sulfone calix [4] arene and XAD-7 resin are replaced by sulfonyl sulfone calix [4] arene and D201 resin, chloroform is replaced by ultrapure water, other conditions are not changed, the sulfonyl sulfone calix [4] arene-D201 resin composite material is used for respectively shaking and separating the water phase solution containing strontium and rubidium for 5min, 10min, 20min, 60min, 480min and 540min, and accordingly, the selectivity coefficients of strontium and rubidium are 4012.55, 6554.23, 7011.23, 7852.55, 8455.23 and 8011.56 in sequence.
Example 22
Step 1. bridge 0.5g p-tert-octyl sulfone [4]]Aromatic hydrocarbons and 1.5g of activated XAD-7 resin were added to 250cm3Adding 100ml of trichloromethane solution into the single-neck flask, sealing the single-neck flask, magnetically stirring for 24 hours, and then removing trichloromethane by rotary evaporation; adding the substance obtained after the first rotary evaporation into 100ml of trichloromethane solution, magnetically stirring for 24 hours, and then, removing trichloromethane by rotary evaporation; adding the substance obtained after the second rotary evaporation into 100ml of chloroform solution, and magnetically stirring for 24hThen, performing rotary evaporation to remove trichloromethane; adding the material obtained after the third rotary evaporation into 100ml of chloroform solution, uniformly stirring by magnetic force, filtering, placing the filtered solid material in a vacuum drying oven, and drying at 85 ℃ for 24h to obtain white powdery p-tert-octyl sulfone bridge cup [4]]An arene-XAD-7 resin composite;
step 2. adding 0.01g of p-tert-butyl sulfone bridge cup [4]]arene-XAD-7 resin composite and 10mL of Mn-containing resin composite2+、Mg2 +、Ca2+、Na+、K+、Rb+、Sr2+、Ba2+、Cu2+、Nd3+、Pb2+、Cr3+、Zn2+The aqueous phase solution of (1) is added into a 50mL centrifuge tube and then 0.1mol/L HNO is added3Adjusting the pH value of the solution in the centrifugal tube to 6 by using the solution and 0.1mol/L NaOH solution, sealing the centrifugal tube, placing the centrifugal tube in a constant-temperature water bath oscillator at 25 ℃ for oscillation for 8 hours, filtering after oscillation is finished, and then using 6mol/L HNO3P-tert-octyl sulfone bridge cup (4) obtained by solution elution and filtration]The aromatic hydrocarbon-XAD-7 resin composite material, wherein the eluent is the solution containing strontium obtained after separation; the eluted p-tert-octyl sulfone is bridged to a cup [4]]The arene-XAD-7 resin composite material is washed by deionized water and dried, and can be repeatedly used for separating strontium and rubidium.
Testing Rb in filtrate obtained by filtering after oscillation in the step 2 by using an atomic emission spectrometer+And Sr2+And then the selectivity coefficient is obtained. The selectivity coefficient for strontium versus rubidium was calculated to be 11446.22.
The p-tert-octyl sulfone in this example was bridged to a cup [4]]Replacement of arene and XAD-7 resin with sulfonyl sulfone bridged cups [4]]Aromatic hydrocarbon and D201 resin, chloroform is replaced by ultrapure water, other conditions are not changed, and sulfonyl sulfone bridge cup [4] is utilized]Aromatic hydrocarbon-D201 resin composite material pair containing Mn2+、Mg2+、Ca2+、Na+、K+、Rb+、Sr2+、Ba2+、Cu2+、Nd3+、Pb2+、Cr3+And Zn2+Is carried out in aqueous solutionAnd the selectivity coefficient of strontium to rubidium is 8556.28.
Examples 23 to 26
Step 1. 4 parts of 0.5g p-tert-octyl sulfone bridge cup [4]]Aromatic hydrocarbons were added to four 250cm containers containing 1.5g of activated XAD-2 resin, XAD-4 resin, XAD-8 resin, XAD-16 resin3In the single-neck flask, respectively adding 100ml of trichloromethane solution into four single-neck flasks, then sealing the single-neck flasks, magnetically stirring for 24 hours, and then removing trichloromethane by rotary evaporation; adding the substance obtained after the first rotary evaporation into 100ml of trichloromethane solution, magnetically stirring for 24 hours, and then, removing trichloromethane by rotary evaporation; adding the substance obtained after the second rotary evaporation into 100ml of trichloromethane solution, magnetically stirring for 24 hours, and then removing trichloromethane by rotary evaporation; adding the material obtained after the third rotary evaporation into 100ml of chloroform solution, uniformly stirring by magnetic force, filtering, placing the filtered solid material in a vacuum drying oven, and drying at 85 ℃ for 24h to respectively obtain white powdery p-tert-octyl sulfone bridge cup [4]]arene-XAD-2 resin composite material and p-tert-octyl sulfone bridge cup [4]arene-XAD-4 resin composite material and p-tert-octyl sulfone bridge cup [4]arene-XAD-8 resin composite material and p-tert-octyl sulfone bridge cup [4]An aromatic hydrocarbon-XAD-16 resin composite material.
Step 2, taking 4 50mL centrifuge tubes, and adding a p-tert-butyl sulfone bridge cup [4] into each centrifuge tube]0.01g of aromatic hydrocarbon-XAD series resin composite material and Mn2+、Mg2+、Ca2+、Na+、K+、Rb+、Sr2+、Ba2+、Cu2+、Nd3+、Pb2+、Cr3+、Zn2+10mL of aqueous phase solution with the concentration of 20mg/L, and then 0.1mol/L of HNO3Adjusting the pH value of the solution in 4 centrifugal tubes to 6 by using the solution and 0.1mol/L NaOH solution, sealing the centrifugal tubes, placing the centrifugal tubes in a constant-temperature water bath oscillator at 25 ℃ to oscillate for 8 hours, filtering after oscillation is finished, and then using 6mol/L HNO3P-tert-octyl sulfone bridge cup (4) obtained by solution elution and filtration]Aromatic hydrocarbon-XAD series resin composite materialThe material and the eluent are the solution containing strontium obtained after separation; the eluted p-tert-octyl sulfone is bridged to a cup [4]]The arene-XAD series resin composite material is washed by deionized water and dried, and can be repeatedly used for separating strontium and rubidium.
Testing Rb in filtrate obtained by filtering after oscillation in the step 2 by using an atomic emission spectrometer+And Sr2+And then the selectivity coefficient is obtained. Calculated, using a p-tert-octyl sulfone bridge cup [4]]arene-XAD-2 resin composite material and p-tert-octyl sulfone bridge cup [4]arene-XAD-4 resin composite material and p-tert-octyl sulfone bridge cup [4]arene-XAD-8 resin composite material and p-tert-octyl sulfone bridge cup [4]arene-XAD-16 resin composite material pair containing Mn2+、Mg2+、Ca2+、Na+、K+、Rb+、Sr2+、Ba2+、Cu2 +、Nd3+、Pb2+、Cr3+And Zn2+The aqueous phase solution of (a) was separated, and the selectivity coefficients of strontium to rubidium were 9523.43, 10567.26, 8563.67, and 11310.32, in this order.
The p-tert-octyl sulfone in this example was bridged to a cup [4]]Replacement of arene and XAD series resins with sulfonyl sulfone bridged cups [4]]Aromatic hydrocarbon and D series (D101, D202, D301, D307, D311) resin, chloroform was replaced with ultrapure water, and sulfonyl sulfone bridge [4] was used under otherwise unchanged conditions]Aromatic hydrocarbon-D101 resin composite material and sulfonyl sulfone bridge cup [4]]arene-D202 resin composite material and sulfonyl sulfone bridge cup [4]]Aromatic hydrocarbon-D301 resin composite material and sulfonyl sulfone bridge cup [4]]arene-D307 resin composite material and sulfonyl sulfone bridge cup [4]]Aromatic hydrocarbon-D311 resin composite material containing Mn2+、Mg2+、Ca2+、Na+、K+、Rb+、Sr2+、Ba2+、Cu2 +、Nd3+、Pb2+、Cr3+And Zn2+The aqueous phase solution of (a) was separated and accordingly the selectivity coefficients for strontium over rubidium were 7642.31, 9652.46, 12353.49, 9642.36, 10028.77 in that order.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for separating strontium and rubidium by utilizing sulfone bridged calix [4] arene is characterized by comprising the following steps: the method comprises the following specific steps:
step 1, mixing sulfone calix [4] arene, an activated inert carrier and a solvent, magnetically stirring for not less than 12 hours, and then removing the solvent by rotary evaporation;
adding the substance obtained after rotary evaporation into a solvent, and repeating the stirring and rotary evaporation operation in the step 1 for 1-2 times; adding the substance obtained by the last rotary evaporation into a solvent, uniformly mixing, filtering and drying to obtain the sulfone calix [4] arene composite material;
step 3, adding the sulfone calix [4] arene composite material into an aqueous phase solution containing strontium and rubidium, then oscillating for 5 min-9 h in a constant-temperature water bath oscillator, filtering after oscillation is finished, eluting the filtered sulfone calix [4] arene composite material by using an acid solution, wherein the eluent is a strontium-containing solution;
the structural formula of the sulfone bridged calix [4] arene is shown as follows:
wherein R is C8H17Or SO3Na；
The solvent is trichloromethane or ultrapure water;
the constant temperature oscillation temperature is 10-40 ℃;
the inert carrier is XAD-2 resin, XAD-4 resin, XAD-7 resin, XAD-8 resin, XAD-16 resin, D101 resin, D201 resin, D202 resin, D301 resin, D307 resin or D311 resin.
2. The method for separating strontium and rubidium by using sulfone bridged calix [4] arene, according to claim 1, characterized in that: the temperature of constant temperature oscillation is 20-30 ℃.
3. The method for separating strontium and rubidium by using sulfone bridged calix [4] arene, according to claim 1, characterized in that: the pH value of the water phase solution containing strontium and rubidium is 6-8.
4. The method for separating strontium and rubidium by using sulfone bridged calix [4] arene, according to claim 1, characterized in that: the concentration of strontium and the concentration of rubidium in the water phase solution containing strontium and rubidium are respectively 0.1 mg/L-20 mg/L.
5. The method for separating strontium and rubidium by using sulfone bridged calix [4] arene, according to claim 4, characterized in that: in the water phase solution containing strontium and rubidium, the concentration of strontium and rubidium is 1 mg/L-20 mg/L.
6. The method for separating strontium and rubidium by using sulfone bridged calix [4] arene, according to claim 1, characterized in that: in the step 1, the mass ratio of the sulfone calix [4] arene to the inert carrier is 1: 3.
7. The method for separating strontium and rubidium by using sulfone bridged calix [4] arene, according to claim 1, characterized in that: in the step 3, the acid solution is hydrochloric acid aqueous solution, sulfuric acid aqueous solution or nitric acid aqueous solution, and the acid concentration in the eluent is 0.5-8 mol/L.
8. The method for separating strontium and rubidium by using sulfone bridged calix [4] arene, according to claim 7, characterized in that: the concentration of the acid in the eluent is 6 mol/L.
9. The method for separating strontium and rubidium by using sulfone bridged calix [4] arene, according to claim 1, characterized in that: and (3) washing the sulfone calix [4] arene composite material eluted in the step (3) with deionized water, and drying to obtain the material for separating strontium and rubidium for recycling.
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| CN1400322A (en) * | 2002-09-05 | 2003-03-05 | 北京矿冶研究总院 | Method for separating platinum, palladium and iridium |
Non-Patent Citations (2)
| Title |
|---|
| "Extration Property of p-tert-Butylsulfonylcalix[4]arene Possessing Irradiation Stability towards Cesium(Ⅰ) and Strontium(Ⅱ)";Cong liu et al.;《Applied Sciences》;20160728;第6卷(第212期);第1-15页 |
| "Removal of Nd（Ⅲ）、Sr（Ⅱ）and Rb（Ⅰ）Ions from Aqueous Solution by Thiacalixarene-Functionalized Graphene Oxide Composite as an Adsorbent";Peng Zhang et al.;《Journal of chemical & engineering》;20160914;第61卷;第3679-3691页 |
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