CN106749162A - A kind of modified crown ether material and its synthetic method for adsorption uranium - Google Patents

A kind of modified crown ether material and its synthetic method for adsorption uranium Download PDF

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Publication number
CN106749162A
CN106749162A CN201611132204.6A CN201611132204A CN106749162A CN 106749162 A CN106749162 A CN 106749162A CN 201611132204 A CN201611132204 A CN 201611132204A CN 106749162 A CN106749162 A CN 106749162A
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crown ether
uranium
modified
crown
benzo
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谢磊
王慧娟
王劲松
周芬芬
刘迎九
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University of South China
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University of South China
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a kind of modified crown ether material and its synthetic method for adsorption uranium, it is related to uranium absorption field of material technology, the synthetic method is with benzo-crown ether as reaction raw materials, reacted by multi-step chemical and aldoxime group is derived on the phenyl ring of crown ether, so as to prepare the group modified crown ether material of aldoxime.Synthetic material of the invention has excellent absorption property to uranium, it is adaptable to the treatment of uranium-containing waste water, can provide new optional approach for the recovery of low content uranium in the extraction of uranium in uranium resources in China and waste water.

Description

A kind of modified crown ether material and its synthetic method for adsorption uranium
Technical field
The present invention relates to uranium absorption field of material technology, more particularly to a kind of modified crown ether material for adsorption uranium and its Synthetic method.
Background technology
Nuclear energy is one of important energy source that the mankind use, and greenhouse gas emission, gas are increasingly paid attention in current international community Under the situation that time warms, actively push forward Construction of Nuclear Electricity, be an important policies of China's energy construction.
In each link that nuclear energy is develop and useedd, the radioactivity for producing therefrom（Uranium-bearing, thorium etc.）The species of waste water and Quantity is more and more, and the potential threat to human health and natural ecological environment is on the rise.Additionally, a large amount of waste liquids and waste water In low content uranium but cannot fully reclaim.In order to improve the treatment effeciency of radioactive wastewater, promote Uranium clean manufacturing And environmental protection, exploitation uranium is processed to have great importance with separation and recovery new technology, new material.
Crown ether as first generation supermolecule main block compound, with hydrophobic external skeletal, but with it is hydrophilic can be with The inner chamber of metal ion bonding.The complex of stabilization can be formed with many kinds of metal ions, and the big ring in different cavity footpath is modified There is certain coordination selectivity to different metal ions afterwards, therefore can optionally carry out separation of metal ions, in molecule （Ion）The numerous areas such as identification, ion transmission, separation and recovery show wide application prospect.
Oxime is the class material containing-CNOH groups in molecule, with preferable metal complex performance, with uranyl ion With strong coordination, the separation based on the material modified preparation of oximido and its for URANIUM IN SEAWATER in recent years takes with enrichment process Some positive achievements in research were obtained, but there is no open source literature or the relevant report for introducing that group containing oximido is modified to crown ether.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of synthetic method of the modified crown ether material for adsorption uranium, The synthetic method step is simple and convenient to operate, and crown ether greatly improved to uranium by introducing group containing oximido on the side arm of crown ether The selectivity of acyl ion coordination.
In order to solve the above-mentioned technical problem, the present invention uses following scheme：A kind of modified crown ether material for adsorption uranium Synthetic method, comprise the following steps：
（1）With HCHO and HCL as chloromethylation reagents, with ZnCl2Or H3PO4It is catalyst, benzo-crown ether and chloromethylation reagents In 60-90oReaction 4-8 hours in C temperature ranges, filtering obtains product 1；
（2）Hexa is dissolved in water, with CHCl3It is catalyst, in 20-50oIn C temperature ranges, product 1 is added simultaneously Reaction 3-6 hours, cooling, obtains product 2 after filtering；
（3）Hydroxylamine hydrochloride is dissolved in water, then is charged with NaHCO3To clarifying, it is subsequently added into product 2 and volume fraction is 95% ethanol, is heated to reflux 2-3 hours under the conditions of oil bath, then stops heating, and decompression boils off ethanol, after crystallisation by cooling The modified crown ether material of the crystal for arriving as aldoxime.
Further, the benzo-crown ether is selected from Benzo-18-crown-6, phendioxin 5- crown ether -5, dibenzo -18- hats Ether -6, the one kind in dibenzo -15- crown ethers -5.
Used as another aspect of the present invention, the present invention also provides a kind of modified crown ether material for adsorption uranium, and this is modified Crown ether material is connected to an aldoxime group based on benzo-crown ether on one end phenyl ring of the benzo-crown ether（--CHNOH）. The modified crown ether material can be obtained by above method synthesis.
The present invention changes from uranyl ion coordination configuration, design synthesis conformation separation, the aldoxime base of coordination configuration matching Property benzo-crown ether, the crown ether derivative obtained by the above method is coordinated to uranyl ion has strong selectivity, due in crown ether Side arm on introduce group containing oximido, one side oximido has strong coordination ability to uranium, and another aspect oximido function side arm is increased The chain length and bonding size of crown ether side arm, both factors are greatly improved the selectivity that crown ether is coordinated to uranyl ion（I.e. Serve effect of the one-plus-one more than two）, and from above-mentioned preparation process it can also be seen that the synthetic method that the present invention is provided is walked Suddenly it is simple and convenient to operate, so as to ensure that the stability and reliability of preparation process, is adapted to industrialized production and application.
Specific embodiment
Improvements of the invention are more clearly understood that for the ease of those skilled in the art, below by 4 embodiments To be further described to the present invention.
Embodiment 1
（1）With HCHO and HCL as chloromethylation reagents, with H3PO4It is catalyst, Benzo-18-crown-6 and chloromethylation reagents In 60-90oReaction 4-8 hours in C temperature ranges, filtering obtains product 1；
（2）Hexa is dissolved in water, with CHCl3It is catalyst, maintenance reaction temperature 20-50oC, adds product 1 simultaneously Reaction 3-6 hours, cooling, obtains product 2 after filtering；
（3）Hydroxylamine hydrochloride is dissolved in water, then is charged with NaHCO3To clarifying, it is subsequently added into product 2 and volume fraction is 95% ethanol, is heated to reflux 2-3 hours under the conditions of oil bath, then stops heating, and decompression boils off ethanol, then crystallisation by cooling is obtained To crystal, the crystal is the modified crown ether material of aldoxime（Aldoxime is modified Benzo-18-crown-6）.
To probe into the present embodiment gained crystal to uranium adsorption selectivity, applicant is attached from Hengyang, Hunan Province uranium tailings pond 100ml natural water samples are taken near pool, 100mg crystals are added, 200rpm vibrations 24h, skill is detected with ICP-MS at room temperature The concentration of Na, Mg, K, Ca, Mn, Fe, Al, Zn and U in the front and rear solution of art measurement absorption, the ability of selective absorption is by selection Coefficient and breadth coefficient represent that wherein breadth coefficient is：
,
V is liquor capacity in formula, and M is crystal quality, C0It is solution initial ion concentration, CeIon is dense during for adsorption equilibrium Degree；Selection COEFFICIENT K is quotient of the uranium breadth coefficient divided by other ion distribution coefficients.
Through calculating, the crystal that the present embodiment is prepared is 169mg/g to the adsorbance of uranium.
Table 1 lists the breadth coefficient that the crystal adsorbs various ions, and table 2 lists crystal absorption uranium ion phase For the selection COEFFICIENT K for adsorbing other ions, wherein, breadth coefficient is bigger, illustrates that this kind of ion is adsorbed material（Crystal） The ability of absorption is bigger, and selects COEFFICIENT K bigger, then representing uranium ion compared to other ions there is more preferable selective absorption to imitate Really.
Embodiment 2
（1）With HCHO and HCL as chloromethylation reagents, with ZnCl2It is catalyst, dibenzo-18-crown-6 (DB18C6) is tried with chloromethylation Agent is in 60-90oReaction 4-8 hours in C temperature ranges, filtering obtains product 1；
（2）Hexa is dissolved in water, with CHCl3It is catalyst, maintenance reaction temperature 20-50oC, adds product 1 simultaneously Reaction 3-6 hours, cooling, obtains product 2 after filtering；
（3）Hydroxylamine hydrochloride is dissolved in water, then is charged with NaHCO3To clarifying, it is subsequently added into product 2 and volume fraction is 95% ethanol, is heated to reflux 2-3 hours under the conditions of oil bath, then stops heating, and decompression boils off ethanol, then crystallisation by cooling is obtained To crystal, the crystal is the modified crown ether material of aldoxime（Aldoxime is modified dibenzo-18-crown-6 (DB18C6)）.
To probe into the present embodiment gained crystal to uranium adsorption selectivity, applicant is attached from Hengyang, Hunan Province uranium tailings pond 100ml natural water samples are taken near pool, 100mg crystals are added, 200rpm vibrations 24h, skill is detected with ICP-MS at room temperature The concentration of Na, Mg, K, Ca, Mn, Fe, Al, Zn and U in the front and rear solution of art measurement absorption, the ability of selective absorption is by selection Coefficient and breadth coefficient represent that wherein breadth coefficient is：
,
V is liquor capacity in formula, and M is crystal quality, C0It is solution initial ion concentration, CeIon is dense during for adsorption equilibrium Degree；Selection COEFFICIENT K is quotient of the uranium breadth coefficient divided by other ion distribution coefficients.
Through calculating, the crystal that the present embodiment is prepared is 186mg/g to the adsorbance of uranium.
Table 1 lists the breadth coefficient that the crystal adsorbs various ions, and table 2 lists crystal absorption uranium ion phase For the selection COEFFICIENT K for adsorbing other ions, wherein, breadth coefficient is bigger, illustrates that this kind of ion is adsorbed material（Crystal） The ability of absorption is bigger, and selects COEFFICIENT K bigger, then representing uranium ion compared to other ions there is more preferable selective absorption to imitate Really.
Embodiment 3
Crown ether used by the present embodiment is phendioxin 5- crown ether -5, and preparation process is similar with embodiment 1,2, is stated to simplify, for It will not be described for specific preparation process.
To probe into the present embodiment gained crystal to uranium adsorption selectivity, applicant is attached from Hengyang, Hunan Province uranium tailings pond 100ml natural water samples are taken near pool, 100mg crystals are added, 200rpm vibrations 24h, skill is detected with ICP-MS at room temperature The concentration of Na, Mg, K, Ca, Mn, Fe, Al, Zn and U in the front and rear solution of art measurement absorption, the ability of selective absorption is by selection Coefficient and breadth coefficient represent that wherein breadth coefficient is：
,
V is liquor capacity in formula, and M is crystal quality, C0It is solution initial ion concentration, CeIon is dense during for adsorption equilibrium Degree；Selection COEFFICIENT K is quotient of the uranium breadth coefficient divided by other ion distribution coefficients.
Through calculating, the crystal that the present embodiment is prepared is 157mg/g to the adsorbance of uranium.
Table 1 lists the breadth coefficient that the crystal adsorbs various ions, and table 2 lists crystal absorption uranium ion phase For the selection COEFFICIENT K for adsorbing other ions, wherein, breadth coefficient is bigger, illustrates that this kind of ion is adsorbed material（Crystal） The ability of absorption is bigger, and selects COEFFICIENT K bigger, then representing uranium ion compared to other ions there is more preferable selective absorption to imitate Really.
Embodiment 4
Crown ether used by the present embodiment is dibenzo -15- crown ether -5, and preparation process is similar with embodiment 1,2, is stated to simplify, right In specific preparation process, it will not be described.
To probe into the present embodiment gained crystal to uranium adsorption selectivity, applicant is attached from Hengyang, Hunan Province uranium tailings pond 100ml natural water samples are taken near pool, 100mg crystals are added, 200rpm vibrations 24h, skill is detected with ICP-MS at room temperature The concentration of Na, Mg, K, Ca, Mn, Fe, Al, Zn and U in the front and rear solution of art measurement absorption, the ability of selective absorption is by selection Coefficient and breadth coefficient represent that wherein breadth coefficient is：
,
V is liquor capacity in formula, and M is crystal quality, C0It is solution initial ion concentration, CeIon is dense during for adsorption equilibrium Degree；Selection COEFFICIENT K is quotient of the uranium breadth coefficient divided by other ion distribution coefficients.
Through calculating, the crystal that the present embodiment is prepared is 175mg/g to the adsorbance of uranium.
Table 1 lists the breadth coefficient that the crystal adsorbs various ions, and table 2 lists crystal absorption uranium ion phase For the selection COEFFICIENT K for adsorbing other ions, wherein, breadth coefficient is bigger, illustrates that this kind of ion is adsorbed material（Crystal） The ability of absorption is bigger, and selects COEFFICIENT K bigger, then representing uranium ion compared to other ions there is more preferable selective absorption to imitate Really.
Table 1（Breadth coefficient D）
Metal ion Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
U 3.553 3.622 3.528 3.604
Na 0.056 0.048 0.059 0.051
Mg 0.039 0.035 0.042 0.037
K 0.027 0.025 0.029 0.027
Ca 0.035 0.037 0.034 0.039
Mn 0.030 0.031 0.034 0.032
Fe 0.143 0.137 0.149 0.132
Al 0.156 0.147 0.162 0.145
Zn 0.178 0.192 0.174 0.185
Table 2（Selection COEFFICIENT K）
Metal ion Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Na 63.446 75.458 59.797 70.667
Mg 91.103 103.486 84 97.405
K 131.593 144.88 121.655 133.481
Ca 101.514 97.892 103.765 92.410
Mn 118.433 116.129 103.765 112.625
Fe 24.846 26.438 23.678 27.303
Al 22.776 24.639 21.777 24.855
Zn 19.961 18.865 20.276 19.481
The crystal prepared in embodiment 1-4 is can be seen that from above-mentioned test result to uranyl ion coordination with extremely strong Selectivity and stronger adsorption capacity.
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can be realized with other manner, Any obvious replacement is within protection scope of the present invention on the premise of not departing from the technical program design.
In order to allow those of ordinary skill in the art more easily to understand improvements of the present invention relative to prior art, this Some descriptions of invention have been simplified, and for the sake of clarity, present specification is omitted some other elements, ability Domain those of ordinary skill should be aware that these elements for omitting also may make up present disclosure.

Claims (3)

1. a kind of modified crown ether material for adsorption uranium, it is characterised in that：The modified crown ether material based on benzo-crown ether, An aldoxime group is connected on the phenyl ring of described benzo-crown ether one end.
2. the modified crown ether material for adsorption uranium according to claim 1, it is characterised in that the benzo-crown ether choosing One kind from Benzo-18-crown-6, phendioxin 5- crown ethers -5, dibenzo-18-crown-6 (DB18C6), dibenzo -15- crown ethers -5.
3. the synthetic method of the modified crown ether material of adsorption uranium is used in claim 1 or 2, it is characterised in that including following step Suddenly：
（1）With HCHO and HCL as chloromethylation reagents, with ZnCl2Or H3PO4It is catalyst, benzo-crown ether and chloromethylation reagents In 60-90oReaction 4-8 hours in C temperature ranges, filtering obtains product 1；
（2）Hexa is dissolved in water, with CHCl3It is catalyst, in 20-50oIn C temperature ranges, add product 1 simultaneously anti- Answer 3-6 hours, cool down, product 2 is obtained after filtering；
（3）Hydroxylamine hydrochloride is dissolved in water, then is charged with NaHCO3To clarifying, it is subsequently added into product 2 and volume fraction is 95% ethanol, is heated to reflux 2-3 hours under the conditions of oil bath, then stops heating, and decompression boils off ethanol, after crystallisation by cooling The modified crown ether material of the crystal for arriving as aldoxime.
CN201611132204.6A 2016-12-09 2016-12-09 A kind of modified crown ether material and its synthetic method for adsorption uranium Pending CN106749162A (en)

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Application publication date: 20170531