CN113231035A - Preparation method and application of functionalized magnetic adsorption material - Google Patents
Preparation method and application of functionalized magnetic adsorption material Download PDFInfo
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- CN113231035A CN113231035A CN202110497912.4A CN202110497912A CN113231035A CN 113231035 A CN113231035 A CN 113231035A CN 202110497912 A CN202110497912 A CN 202110497912A CN 113231035 A CN113231035 A CN 113231035A
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- 239000000463 material Substances 0.000 title claims abstract description 159
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 238000005406 washing Methods 0.000 claims abstract description 28
- -1 2, 5-dihydroxy phenyl diethyl phosphonate Chemical compound 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 22
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000003463 adsorbent Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- DSVLXQCZRHZRFD-UHFFFAOYSA-N 2-diethoxyphosphorylbenzene-1,4-diol Chemical compound CCOP(=O)(OCC)C1=CC(O)=CC=C1O DSVLXQCZRHZRFD-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 description 25
- 239000002245 particle Substances 0.000 description 25
- 239000010452 phosphate Substances 0.000 description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 25
- 238000007885 magnetic separation Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 11
- 238000005119 centrifugation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- VBWSWBQVYDBVGA-NAHFVJFTSA-N uranium-234;uranium-235;uranium-238 Chemical compound [234U].[235U].[238U] VBWSWBQVYDBVGA-NAHFVJFTSA-N 0.000 description 2
- BBSVRDUHJHUMHD-UHFFFAOYSA-N CCOP(C(C=C(C(P(O)(O)=O)=C1)O)=C1O)(O)=O Chemical compound CCOP(C(C=C(C(P(O)(O)=O)=C1)O)=C1O)(O)=O BBSVRDUHJHUMHD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
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Abstract
The invention discloses a preparation method of a functionalized magnetic adsorption material, which is characterized by comprising the following steps: adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and/or 2, 5-dihydroxy phenyl diethyl phosphonate into a solvent A, adding nano ferroferric oxide, and reacting at a certain temperature to obtain a reacted material; and cooling, filtering and separating the reacted materials, washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material. The functional magnetic adsorption material prepared by the invention is of a porous structure, is formed by sparsely accumulating spherical particles and has rich functional groups such as hydroxyl, phosphorus oxygen and the like; the functional magnetic adsorption material prepared by the method has the advantages of simple synthesis, low cost, good selectivity, large adsorption capacity, convenience in collection after adsorption and the like, can be practically used for adsorbing, enriching or removing uranium in an aqueous solution, and has strong practicability.
Description
Technical Field
The invention belongs to the adsorption, enrichment or treatment of radioactive uranium element, and relates to a preparation method and application of a functionalized magnetic adsorption material. The functional magnetic adsorption material (or called phosphate functionalized nano ferroferric oxide particle adsorption material) prepared by the invention is particularly suitable for adsorption, enrichment or removal of radioactive uranium element in aqueous solution.
Background
The nuclear energy is one of the most important clean energy sources in the 21 st century, has high energy and has higher energy supply stability than hydroelectric power, thermal power and wind power; the carbon emission is less than that of hydroelectric power and wind power, the service life is longer, and the like.
The uranium resources existing on the land of China are not abundant, but the storage capacity of the uranium elements is related to the sustainable development of the nuclear power of China. The total amount of uranium resources in seawater in the world reaches 45 hundred million tons, which is more than 1000 times of the mineral reserves of uranium resources found on land, and is considered to be the future of nuclear power, but the concentration of uranium elements in seawater is lower, the environment is more complex, and the extraction difficulty is higher.
In the prior art, various methods for obtaining uranium resources from an aqueous solution exist, such as an electrodeposition method, a biological treatment method, a chemical precipitation method, an adsorption method and the like. Wherein: the adsorption method is the most effective uranium adsorption, enrichment or removal method and has the advantages of simple use method, low cost, high treatment efficiency and the like.
Currently, although nanomaterials (carbon-based composite, metal oxide and nanocarbon) exhibit excellent adsorption ability, their high dispersibility in aqueous solutions makes them difficult to separate from the matrix, which also limits their application in practical water bodies.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method and application of a functionalized magnetic adsorption material (or called phosphate functionalized nano ferroferric oxide particle adsorption material). The functional magnetic adsorption material prepared by the invention can realize adsorption, enrichment or removal of uranium in an aqueous solution.
The content of the invention is as follows: a method for preparing a functionalized magnetic adsorption material (namely a phosphate functionalized nano ferroferric oxide particle adsorption material) is characterized by comprising the following steps:
a. adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and/or 2, 5-dihydroxy phenyl diethyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at a certain temperature to obtain a reacted material;
b. and (3) cooling, filtering and separating the reacted materials (preferably by centrifugation or magnetic separation), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
The invention relates to a preparation method of a functionalized magnetic adsorption material, which is characterized by comprising the following steps:
a. adding ethyl 2, 5-dihydroxy-1, 4-benzene diphosphonate and diethyl 2, 5-dihydroxyphenyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at 30-150 ℃ for 2-30 hours to obtain a reacted material;
the molar ratio of the dosages of the ferroferric oxide, the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and the 2, 5-dihydroxy phenyl phosphonic acid diethyl ester is 1: 0.1-5;
b. and (3) cooling the reacted materials, filtering and separating (preferably by centrifugation or magnetic separation), washing the solid with a solvent B (washing to remove impurities such as organic matters, inorganic matters and the like in pores of the adsorbing material), and drying to obtain the functionalized magnetic adsorbing material (namely the phosphate functionalized nano ferroferric oxide particle adsorbing material).
The preparation method of the functionalized magnetic adsorption material is characterized by further comprising the following steps:
a. adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at the temperature of 30-150 ℃ for 2-30 hours to obtain a reacted material;
the molar ratio of the ferroferric oxide to the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester is 1: 0.1-5;
b. and (3) cooling, filtering and separating the reacted materials (preferably by centrifugation or magnetic separation), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
The preparation method of the functionalized magnetic adsorption material is characterized by further comprising the following steps:
a. adding diethyl 2, 5-dihydroxyphenylphosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at the temperature of 30-150 ℃ for 2-30 hours to obtain a reacted material;
the molar ratio of the dosage of the ferroferric oxide to the dosage of the diethyl 2, 5-dihydroxyphenyl phosphonate is 1: 0.1-5;
b. and (3) cooling, filtering and separating the reacted materials (preferably by centrifugation or magnetic separation), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
The invention comprises the following steps: in the step a, the reaction is carried out for 2 to 30 hours at a temperature of 30 to 150 ℃, preferably for 8 to 10 hours at a temperature of 70 to 90 ℃.
The invention comprises the following steps: the solvent A in the step a can be any one or a mixture of more than two of toluene, pentane, dichloromethane, N-dimethylformamide, acetonitrile, acetone, diethyl ether and cyclohexane.
The invention comprises the following steps: the solvent B in the step B can be any one or a mixture of more than two of ethyl acetate, methanol, ethanol and water.
The invention comprises the following steps: the reaction in step a is preferably carried out under magnetic stirring or ultrasonic oscillation.
The invention comprises the following steps: and c, the prepared functional magnetic adsorption material in the step b is used for adsorbing, enriching or removing uranium in the aqueous solution.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) according to the invention, the adsorbing material is prepared by directly reacting the phenolic hydroxyl groups of ethyl 2, 5-dihydroxy-1, 4-benzenediphosphonate and diethyl 2, 5-dihydroxyphenylphosphonate with the surface of ferroferric oxide, namely the functionalized magnetic adsorbing material (namely phosphate functionalized nano ferroferric oxide particle adsorbing material) is prepared in one step, and the prepared functionalized magnetic adsorbing material is of a porous structure, is formed by sparsely accumulating spherical particles and has rich functional groups such as hydroxyl, phosphorus oxygen and the like; the method has the advantages of simple synthesis, low cost, good selectivity, large adsorption capacity, convenience for collection after adsorption and the like, and can be practically used for adsorption, enrichment or removal of uranium in an aqueous solution;
(2) uranium adsorption performance research shows that: in aqueous solution, the functionalized magnetic adsorption material (phosphate functionalized nano ferroferric oxide particle adsorption material) prepared by the invention has the optimal adsorption capacity at the pH of 5, and the uranium adsorption capacity is as high as 200 mg g- 1 The material has good uranyl ion selectivity and more excellent comprehensive performance compared with other nano adsorption materials; the initial concentration was 50mg L-1When the ions of copper, potassium, zinc and uranium are multiple, the adsorption quantity of the functional magnetic adsorption material prepared by the invention to uranium reaches 117mg g-1The amount of the adsorbed other ions was about 20mg g-1. The results fully show that the functionalized magnetic adsorption material provided by the invention has high adsorption capacity and selectivity on uranyl ions;
(3) the preparation process is simple and low in cost; the functionalized magnetic adsorption material provided by the invention has good practical value and strong practicability.
Drawings
FIG. 1 is an infrared spectrum of a functionalized magnetic adsorbent material prepared in example 2 of the present invention, which shows that the functionalized magnetic adsorbent material has abundant phosphorus oxide groups;
FIG. 2 is a transmission electron microscope image of a functionalized magnetic adsorbing material prepared in example 2 of the present invention, wherein the transmission electron microscope image shows that ferroferric oxide nanospheres of the functionalized magnetic adsorbing material are aggregated together;
FIG. 3 shows the pore size distribution and specific surface area of the functionalized magnetic adsorbent prepared in example 2 of the present invention; nitrogen adsorption and desorption experiments show that the specific surface area of the functionalized magnetic adsorption material is 8.31m2 g-1；
FIG. 4 is a thermogram of a functionalized magnetic adsorbent material prepared in example 2 of the present invention, showing an organic compound content of about 10%;
FIG. 5 is a graph of adsorption capacities of uranium in solutions with different pH values of the functionalized magnetic adsorption material prepared in example 2 of the present invention; the figure shows that the functionalized magnetic adsorbent material has the best adsorption capacity at the pH of 5, and the adsorption capacity of the adsorbent material reaches 200 mg g-1；
FIG. 6 is a graph of the adsorption amount of the functionalized magnetic adsorbent obtained in example 2 of the present invention as a function of time, showing that the adsorption equilibrium time is about 6 hours;
FIG. 7 is a drawing showing selective adsorption of uranium in a multi-metal cation solution by a functionalized magnetic adsorbent material prepared by the present invention and the examples.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Example 1:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 0.01mol of 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester into 25 mL of solvent A toluene (dissolving), adding 0.005 mol of nano ferroferric oxide (powder), and reacting for 10 hours under the condition of a temperature of 80 ℃ by magnetic stirring to obtain a reacted material;
b. and (3) cooling the reacted materials, filtering and separating (centrifugal or magnetic separation is available), washing the solid with a solvent B (ethyl acetate is used for centrifugal washing for 10 times), and drying to obtain the functionalized magnetic adsorbing material (namely the phosphate functionalized nano ferroferric oxide particle adsorbing material).
And (3) performance testing:
(1) the functionalized magnetic adsorbent prepared in example 1 was added to a pre-prepared solution having a concentration of 50mg L-1And uranyl ion solution with pH of 5, placing in a rotary oscillator, rotating at 30 deg.C for 10 hr, and measuring the adsorption amount of about 200 mg g-1；
(2) Preparing a solution containing copper ions, potassium ions, magnesium ions, manganese ions and uranyl ions at a concentration of 50mg L-1The mixed uranium solution is vibrated for 12 hours at 30 ℃ in a rotary oscillator, and after test and calculation, the adsorption quantity of uranium is measured to be 117mg g-1。
Example 2:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 0.01mol of 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and 0.01mol of 2, 5-dihydroxy phenyl diethyl phosphonate into 60 mL of solvent A N, dissolving in N-dimethylformamide, adding 0.01mol of nano ferroferric oxide (powder), and reacting at 30 ℃ for 5 hours to obtain a reacted material;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with solvent B ethanol (centrifugal washing is carried out for 5 times), and drying to obtain the functionalized magnetic adsorbing material (namely the phosphate functionalized nano ferroferric oxide particle adsorbing material).
And (3) performance testing:
the functionalized magnetic adsorbent prepared in example 2 was added to a pre-prepared solution having a concentration of 50mg L-1And uranyl ion solution with pH of 2-8, placing in a rotary oscillator, rotating at 30 deg.C for 20 hr, centrifuging, and measuring and calculating to obtain the optimum adsorption amount at pH of 5. The performance test condition is referred to the attached drawings and the description of the attached drawings.
Example 3:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 0.01mol of diethyl 2, 5-dihydroxyphenylphosphonate into 30 ml of pentane solvent A (for dissolving), adding 0.01mol of nano ferroferric oxide (powder), and reacting at 120 ℃ for 15 hours to obtain a reacted material;
b. and (3) cooling the reacted materials, filtering and separating (centrifugal or magnetic separation is available), washing the solid with a solvent B (ethyl acetate is used for centrifugal washing for 5 times, and then water is used for centrifugal washing for 5 times), and drying to obtain the functionalized magnetic adsorbing material (namely the phosphate functionalized nano ferroferric oxide particle adsorbing material).
And (3) performance testing:
20mg L at 1000 ml pH5-1Adding 50mg of the functionalized magnetic adsorbing material (or called phosphate functionalized nano ferroferric oxide particle adsorbing material) prepared in the embodiment 3 into the uranyl ion solution, respectively sampling 5ml of the solution after shaking for a certain time (the solution is a homogeneous system), centrifuging to obtain supernatant, and finding out through testing and calculation that the adsorption amount is gradually increased along with the increase of the adsorption time, and the adsorption reaches saturation after 6 hours.
Example 4:
a method for preparing a functionalized magnetic adsorption material (namely a phosphate functionalized nano ferroferric oxide particle adsorption material) comprises the following steps:
a. adding ethyl 2, 5-dihydroxy-1, 4-benzene diphosphonate and diethyl 2, 5-dihydroxyphenyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at a certain temperature to obtain a reacted material;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 5:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding ethyl 2, 5-dihydroxy-1, 4-benzene diphosphonate and diethyl 2, 5-dihydroxyphenyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at 30 ℃ for 30 hours to obtain a reacted material;
the molar ratio of the dosages of the ferroferric oxide, the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and the 2, 5-dihydroxy phenyl phosphonic acid diethyl ester is 1:0.1: 0.1;
b. and (3) cooling, filtering and separating the reacted materials (preferably by centrifugation or magnetic separation), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 6:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding ethyl 2, 5-dihydroxy-1, 4-benzene diphosphonate and diethyl 2, 5-dihydroxyphenyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at 150 ℃ for 2 hours to obtain a reacted material;
the molar ratio of the dosages of the ferroferric oxide, the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and the 2, 5-dihydroxy phenyl phosphonic acid diethyl ester is 1: 5: 5;
b. and (3) cooling, filtering and separating the reacted materials (preferably by centrifugation or magnetic separation), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 7:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding ethyl 2, 5-dihydroxy-1, 4-benzene diphosphonate and diethyl 2, 5-dihydroxyphenyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at 90 ℃ for 16 hours to obtain a reacted material;
the molar ratio of the dosages of the ferroferric oxide, the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and the 2, 5-dihydroxy phenyl phosphonic acid diethyl ester is 1:2.5: 2.5;
b. and (3) cooling, filtering and separating the reacted materials (preferably by centrifugation or magnetic separation), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 8:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at the temperature of 30 ℃ for 30 hours to obtain a reacted material;
the molar ratio of the ferroferric oxide to the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester is 1: 0.1;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 9:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at the temperature of 150 ℃ for 2 hours to obtain a reacted material;
the molar ratio of the ferroferric oxide to the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester is 1: 5;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 10:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at the temperature of 90 ℃ for 17 hours to obtain a reacted material;
the molar ratio of the ferroferric oxide to the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester is 1: 2.6;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 11:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 2, 5-dihydroxyphenyl diethyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at the temperature of 30 ℃ for 30 hours to obtain a reacted material;
the molar ratio of the dosage of the ferroferric oxide to the dosage of the diethyl 2, 5-dihydroxyphenyl phosphonate is 1: 0.1;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 12:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 2, 5-dihydroxyphenyl diethyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at 150 ℃ for 2 hours to obtain a reacted material;
the molar ratio of the dosage of the ferroferric oxide to the dosage of the diethyl 2, 5-dihydroxyphenyl phosphonate is 1: 5;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 13:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 2, 5-dihydroxyphenyl diethyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at the temperature of 90 ℃ for 16 hours to obtain a reacted material;
the molar ratio of the dosage of the ferroferric oxide to the dosage of the diethyl 2, 5-dihydroxyphenyl phosphonate is 1: 2.5;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 14:
a preparation method of a functionalized magnetic adsorption material comprises the following steps:
a. adding 2, 5-dihydroxyphenyl diethyl phosphonate into a solvent A (dissolving), adding nano ferroferric oxide (powder), and reacting at the temperature of 60 ℃ for 20 hours to obtain a reacted material;
the molar ratio of the ferroferric oxide to the diethyl 2, 5-dihydroxyphenyl phosphonate is 1: 4;
b. and (3) cooling, filtering and separating the reacted materials (centrifugal or magnetic separation is available), washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material (namely the phosphate functionalized nano ferroferric oxide particle adsorption material).
Example 15:
a preparation method of a functionalized magnetic adsorption material comprises the following steps of: the reaction was carried out at 70 ℃ for 10 hours, and the procedure was otherwise as described in any of examples 5 to 14, except that it was omitted.
Example 16:
a preparation method of a functionalized magnetic adsorption material comprises the following steps of: the reaction was carried out at 90 ℃ for 8 hours, and the procedure was otherwise as described in any of examples 5 to 14, except that it was omitted.
Example 17:
a preparation method of a functionalized magnetic adsorption material comprises the following steps of: the reaction was carried out at 80 ℃ for 9 hours, and the procedure was otherwise as described in any of examples 5 to 14, except that it was omitted.
In examples 4-17 above: the solvent A in the step a is any one or a mixture of more than two of toluene, pentane, dichloromethane, N-dimethylformamide, acetonitrile, acetone, diethyl ether and cyclohexane.
In examples 4-17 above: the solvent B in the step B is one or a mixture of more than two of ethyl acetate, methanol, ethanol and water.
In examples 4-17 above: the reaction in step a is preferably carried out under magnetic stirring or ultrasonic oscillation.
The functionalized magnetic adsorption material prepared in the step b of the embodiment 4-17 is suitable for adsorption, enrichment or removal of uranium in an aqueous solution, and has a good effect.
In the above embodiment: all the raw materials are commercially available products.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the parts by mass (by weight) may all be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, concentration, etc.) and the amounts of the components in each step are within the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above embodiments are the same as the prior art.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (10)
1. A preparation method of a functionalized magnetic adsorption material is characterized by comprising the following steps:
a. adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and/or 2, 5-dihydroxy phenyl diethyl phosphonate into a solvent A, adding nano ferroferric oxide, and reacting at a certain temperature to obtain a reacted material;
b. and cooling, filtering and separating the reacted materials, washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material.
2. The method for preparing a functionalized magnetic adsorbent material according to claim 1, comprising the steps of:
a. adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and 2, 5-dihydroxy phenyl diethyl phosphonate into a solvent A, adding nano ferroferric oxide, and reacting at the temperature of 30-150 ℃ for 2-30 hours to obtain a reacted material;
the molar ratio of the dosages of the ferroferric oxide, the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester and the 2, 5-dihydroxy phenyl phosphonic acid diethyl ester is 1: 0.1-5;
b. and cooling, filtering and separating the reacted materials, washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material.
3. The method for preparing a functionalized magnetic adsorbent material according to claim 1, comprising the steps of:
a. adding 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester into a solvent A, adding nano ferroferric oxide, and reacting at the temperature of 30-150 ℃ for 2-30 hours to obtain a reacted material;
the molar ratio of the ferroferric oxide to the 2, 5-dihydroxy-1, 4-benzene diphosphonic acid ethyl ester is 1: 0.1-5;
b. and cooling, filtering and separating the reacted materials, washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material.
4. The method for preparing a functionalized magnetic adsorbent material according to claim 1, comprising the steps of:
a. adding 2, 5-dihydroxyphenyl diethyl phosphonate into a solvent A, adding nano ferroferric oxide, and reacting at the temperature of 30-150 ℃ for 2-30 hours to obtain a reacted material;
the molar ratio of the dosage of the ferroferric oxide to the dosage of the diethyl 2, 5-dihydroxyphenyl phosphonate is 1: 0.1-5;
b. and cooling, filtering and separating the reacted materials, washing the solid with a solvent B, and drying to obtain the functionalized magnetic adsorption material.
5. A method of making a functionalized magnetic adsorbent material according to claim 1, 2, 3 or 4, wherein: in the step a, the reaction is carried out for 2-30 hours at the temperature of 30-150 ℃, and the reaction is carried out for 8-10 hours at the temperature of 70-90 ℃.
6. A method of making a functionalized magnetic adsorbent material according to claim 1, 2, 3 or 4, wherein: the solvent A in the step a is any one or a mixture of more than two of toluene, pentane, dichloromethane, N-dimethylformamide, acetonitrile, acetone, diethyl ether and cyclohexane.
7. A method of making a functionalized magnetic adsorbent material according to claim 1, 2, 3 or 4, wherein: the solvent B in the step B is one or a mixture of more than two of ethyl acetate, methanol, ethanol and water.
8. A method of making a functionalized magnetic adsorbent material according to claim 1, 2, 3 or 4, wherein: the reaction in the step a is carried out under magnetic stirring or ultrasonic oscillation.
9. A method of making a functionalized magnetic adsorbent material according to claim 1, 2, 3 or 4, wherein: and c, the prepared functional magnetic adsorption material in the step b is used for adsorbing, enriching or removing uranium in the aqueous solution.
10. The method of claim 5, wherein the functionalized magnetic adsorbent material is prepared by: and c, the prepared functional magnetic adsorption material in the step b is used for adsorbing, enriching or removing uranium in the aqueous solution.
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