CN115557943A - Functionalized amine ionic liquid for adsorbing radioactive iodine and preparation method thereof - Google Patents
Functionalized amine ionic liquid for adsorbing radioactive iodine and preparation method thereof Download PDFInfo
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- CN115557943A CN115557943A CN202211156885.5A CN202211156885A CN115557943A CN 115557943 A CN115557943 A CN 115557943A CN 202211156885 A CN202211156885 A CN 202211156885A CN 115557943 A CN115557943 A CN 115557943A
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- radioactive iodine
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 67
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 54
- 239000011630 iodine Substances 0.000 title claims abstract description 54
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 40
- 150000001412 amines Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 amine compound Chemical class 0.000 claims abstract description 64
- 238000001179 sorption measurement Methods 0.000 claims abstract description 50
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 30
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 92
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000006184 cosolvent Substances 0.000 claims description 30
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 15
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 15
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 12
- 239000012264 purified product Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000012629 purifying agent Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- LCFNGTOKBVGQNC-UHFFFAOYSA-N 1-azabicyclo[2.2.2]octan-4-ylmethanamine Chemical compound C1CN2CCC1(CN)CC2 LCFNGTOKBVGQNC-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- 229960004011 methenamine Drugs 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CEMKLAOKVLRABO-UHFFFAOYSA-N 1-azabicyclo[2.2.2]octane-4-carbonitrile Chemical compound C1CN2CCC1(C#N)CC2 CEMKLAOKVLRABO-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 230000006866 deterioration Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000007655 standard test method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002901 radioactive waste Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
- C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a functionalized amine ionic liquid for adsorbing radioactive iodine and a preparation method thereof. According to the invention, the amine compound with methyl iodide adsorption function is modified into the functionalized amine ionic liquid through quaternary amination reaction, and the volatility of the functionalized amine compound is reduced on the premise of keeping the excellent iodine removal performance of the functionalized amine compound, so that the problems of quick deterioration of the adsorption performance and reduction of the effective service life of an iodine adsorber under the condition of slightly high temperature caused by the volatility of the active adsorption material (TEDA) are solved.
Description
Technical Field
The invention belongs to the technical field of nuclear air purification, and particularly relates to a functionalized amine ionic liquid for adsorbing radioactive iodine and a preparation method thereof.
Background
With the rapid development of the nuclear energy industry in China, the amount of radioactive waste generated and accumulated is more and more, and the effective control and treatment of the radioactive waste also become the key of the sustainable development of nuclear energy. During the operation of nuclear reactors, a plurality of gaseous fission products are inevitably generated, wherein isotopes (131I, 129I) of radioactive iodine are easy to diffuse, dissolve in water and enrich on the thyroid gland of a human body, and are considered as radioactive pollutants with the greatest harm. Aiming at the removal of radioactive iodine, the most studied and widely applied technology at home and abroad is the activated carbon solid adsorption technology. However, activated carbon is very sensitive to changes of external environments (relative humidity, temperature and the like), and at present, the iodine-removing adsorption material is usually obtained by impregnating other active components to modify the surface functional groups and the micro-pore structure of the activated carbon so as to improve the selectivity and the strength of adsorption. Therefore, the selection of the impregnant is very important for the iodine removal performance and the service life of the iodine removal adsorbing material.
In the current ventilation system of a nuclear power station, an iodine adsorber uses an iodine removal adsorption material obtained by impregnating activated carbon with triethylene diamine (TEDA) and potassium iodide (KI) to adsorb radioactive iodine, wherein TEDA can generate strong chemical adsorption with radioactive methyl iodine through coordination bond action so as to fix iodine isotope, has excellent iodine removal performance and is the most main impregnant component in the iodine removal adsorption material of active nuclear facilities. However, TEDA has the problems of low ignition point and volatility, and is easy to sublimate into gas at room temperature, which causes the adsorption performance of the iodine adsorber to be rapidly deteriorated and the effective service life to be reduced when the iodine adsorber is operated at a slightly high temperature, thereby causing the operation cost of nuclear facilities and the increase of the amount of solid waste. At present, the problems of large waste volume and high disposal difficulty of iodine adsorbers in many nuclear power bases in China are highlighted. In addition, the TEDA loading of the activated carbon can reduce the ignition point of the activated carbon, and increase the use risk of the iodine adsorber.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a functionalized amine ionic liquid for adsorbing radioactive iodine and a preparation method thereof, which can reduce the volatility of a functionalized amine compound on the premise of keeping the excellent iodine removal performance of the functionalized amine compound, and solve the problems of quick deterioration of the adsorption performance and reduction of the effective service life of an iodine adsorber caused by the volatility of an active adsorption material (TEDA) under the condition of slightly high temperature.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a functionalized amine ionic liquid for adsorbing radioactive iodine comprises the following steps:
s1, weighing reactants and a cosolvent: weighing amine compounds and halogenated alkyl compounds with methyl iodide adsorption function according to the set molar ratio of the amine compounds to the halogenated alkyl compounds, and weighing a cosolvent;
s2, dissolving reactants by adopting a cosolvent, uniformly stirring, and then filling into a reaction container: dissolving the amine compound and the halogenated alkyl compound with the methyl iodide adsorption function in the cosolvent to obtain a mixture, uniformly stirring the mixture, and filling the mixture into a reaction container;
s3, quaternization reaction: under the set reaction conditions, after the amine compound and the halogenated alkyl compound with the methyl iodide adsorption function react in the reaction vessel, obtaining an initial product;
s4, purification: dissolving the initial product by using a cosolvent to obtain an initial product solution, adding a purifying agent into the initial product solution to obtain a mixture, and performing suction filtration on the mixture to obtain a purified product;
s5, drying: and drying the purified product under the set drying condition to obtain the functionalized amine ionic liquid.
Further, the amine compound having a methyl iodide adsorption function is one selected from triethylene diamine, hexamethylenetetramine, 4-aminomethyl quinuclidine, 4-cyanoquinuclidine, N-dimethyl-p-phenylenediamine, tetramethylethylenediamine and hexamethylenediamine;
the halogenated alkyl compound is selected from one of halogenated methyl, halogenated ethyl, halogenated propyl, halogenated butyl, halogenated pentyl, halogenated hexyl, halogenated heptyl, halogenated octyl, halogenated decyl, halogenated dodecyl, halogenated tetradecyl and halogenated hexadecyl compounds.
Further, the cosolvent is selected from one of ethanol and glycol.
Further, the molar ratio of the amine compound to the haloalkyl compound is 1.
Furthermore, the volume ratio of the cosolvent to the reaction vessel is 0.1-0.3.
Further, the set reaction conditions include: the reaction temperature is 60-300 ℃; the reaction time is 5-30 h.
Further, the purifying agent is selected from one of ethanol, ethyl acetate and acetone;
the mass ratio of the purifying agent to the initial product is 1-50.
Further, the set drying conditions include: drying under vacuum condition, wherein the drying temperature is 30-200 ℃; the drying time is 8-72 h.
The invention also provides a functionalized amine ionic liquid for adsorbing radioactive iodine, which is obtained by taking an amine compound and a halogenated alkyl compound with methyl iodide adsorption functions as reactants based on the preparation method of the functionalized amine ionic liquid for adsorbing radioactive iodine.
Further, the amine compound having a methyl iodide adsorption function is one selected from triethylene diamine, hexamethylenetetramine, 4-aminomethyl quinuclidine and 4-cyanoquinuclidine.
The invention has the following beneficial effects: by adopting the functionalized amine ionic liquid for adsorbing radioactive iodine and the preparation method thereof, provided by the invention, the amine compound with a methyl iodide adsorption function can be modified into the functionalized amine ionic liquid through a quaternization reaction, and the volatility of the functionalized amine compound is reduced on the premise of keeping the excellent iodine removal performance of the functionalized amine compound, so that the problems that the adsorption performance of an iodine adsorber is rapidly deteriorated and the effective service life of the iodine adsorber is reduced under the condition of slightly high temperature caused by the volatility of the TEDA serving as an active adsorption material impregnant are solved.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a functionalized amine ionic liquid for adsorbing radioactive iodine according to an embodiment of the present invention.
Fig. 2 is a test result of the removal efficiency of radioactive methyl iodide after the TEDA monocationic ionic liquid provided by the embodiment 1 of the invention is immobilized on activated carbon fibers.
Fig. 3a is a thermogravimetric analysis test result chart of TEDA provided in example 1 of the present invention.
FIG. 3b is a thermogravimetric analysis test result chart of the TEDA single cation ionic liquid provided by the embodiment 1 of the invention.
FIG. 4 is a graph of the monthly loss rate of TEDA monocationic ionic liquid at 50 ℃ as provided in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are further clearly and completely described below with reference to the accompanying drawings and examples, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments, and all other embodiments that can be obtained by a person skilled in the art without making creative efforts based on the examples in the present invention belong to the protection scope of the present invention.
Ionic Liquids (Ionic Liquids) are composed of organic cations and polyatomic organic or inorganic anions, are in a liquid state at or near room temperature, are also called room-temperature molten salts, and have the advantages of stable physicochemical properties, difficult volatilization, adjustable structure, no toxicity, difficult combustion and explosion and the like.
In order to solve the problem that the TEDA (carbon dioxide) as the nuclear-grade activated carbon impregnant is volatile, the inventor develops a functional amine compound with low volatility and high ignition point based on the advantages of ionic liquid, and the functional amine compound is used as an impregnant of an iodine removal and adsorption material. The embodiment of the invention provides a novel method for radioactive iodine adsorption, which introduces an 'ionic liquid' concept into the field of preparation of iodine removal adsorption materials: amine compounds with methyl iodide adsorption function are modified into functional amine ionic liquid through quaternization reaction, the volatility of the amine compounds is reduced on the premise of keeping the excellent iodine removal performance of the functional amine compounds, and the amine compounds are used for replacing an active iodine adsorption material impregnant TEDA. And on the basis, a preparation method of the functionalized amine ionic liquid is provided to achieve the aims of high adsorption capacity, long service life and minimized solid waste of the iodine-removing adsorption material of the nuclear facility.
As shown in fig. 1, the present embodiment provides a method for preparing a functionalized amine ionic liquid for adsorbing radioactive iodine, the method for preparing a functionalized amine ionic liquid by quaternizing an amine compound having a methyl iodide adsorbing function, the method comprising the steps of:
s1, weighing reactants and a cosolvent: weighing an amine compound and a halogenated alkyl compound with a methyl iodide adsorption function according to a set molar ratio of the amine compound to the halogenated alkyl compound, and weighing a cosolvent;
optionally, the amine compound having a methyl iodide adsorption function is selected from one of triethylene diamine (TEDA), hexamethylenetetramine (HMTA), 4-aminomethyl quinuclidine, 4-cyanoquinuclidine, N-dimethyl-p-phenylenediamine, tetramethylethylenediamine and hexamethylenediamine.
In an alternative embodiment, the amine compound with methyl iodide adsorption function is an amine compound with a cage structure, and is selected from one of triethylene diamine, hexamethylene tetramine, 4-aminomethyl quinuclidine and 4-cyanoquinuclidine.
Optionally, the halogenated alkyl compound is selected from one of halogenated methyl, halogenated ethyl, halogenated propyl, halogenated butyl, halogenated pentyl, halogenated hexyl, halogenated heptyl, halogenated octyl, halogenated decyl, halogenated dodecyl, halogenated tetradecyl and halogenated hexadecyl compounds.
Optionally, the cosolvent is selected from one or a combination of two of ethanol and ethylene glycol.
Optionally, the set molar ratio of the amine compound with methyl iodide adsorption function to the haloalkyl compound is 1.
S2, dissolving reactants by adopting a cosolvent, uniformly stirring, and then filling into a reaction container: dissolving the amine compound and the halogenated alkyl compound with the methyl iodide adsorption function in the cosolvent to obtain a mixture, uniformly stirring the mixture, and filling the mixture into a reaction vessel;
optionally, the volume ratio of the cosolvent to the reaction vessel is 0.1-0.3.
Optionally, the reaction vessel comprises, but is not limited to, a polytetrafluoroethylene autoclave.
S3, quaternization reaction: under the set reaction conditions, after the amine compound and the halogenated alkyl compound with the methyl iodide adsorption function react in the reaction vessel, obtaining an initial product;
optionally, the set reaction conditions include: the reaction temperature is 60-300 ℃; the reaction time is 5-30 h.
S4, purification: dissolving the initial product by using a cosolvent to obtain an initial product solution, adding a purifying agent into the initial product solution to obtain a mixture, and performing suction filtration on the mixture to obtain a purified product;
optionally, the purifying agent is selected from one or a combination of several of ethanol, ethyl acetate and acetone.
Optionally, the mass ratio of the purifying agent to the initial product is 1-50.
Optionally, one of a 0.1 μm organic filter membrane, a 0.2 μm organic filter membrane and a 0.3 μm organic filter membrane is used in the suction filtration.
S5, drying: and drying the purified product under the set drying condition to obtain the functionalized amine ionic liquid.
Optionally, the set drying conditions include: drying under vacuum condition, wherein the drying temperature is 30-200 ℃; the drying time is 8-72 h.
In this embodiment, in the functionalized amine ionic liquid for adsorbing radioactive iodine and the preparation method thereof provided in embodiments 1 to 3, the structure of the functionalized amine ionic liquid is designed according to the principle of radioactive iodine adsorption, and the functionalized amine ionic liquid (novel iodine removal impregnant) is obtained by using the amine compound and the haloalkyl compound having the methyl iodine adsorption function as reactants and adopting the preparation method of the functionalized amine ionic liquid for adsorbing radioactive iodine to replace the existing iodine removal impregnant TEDA.
Taking example 1 as an example, the functionalized amine ionic liquid is TEDA ionic liquid obtained by modifying TEDA through quaternization reaction. In order to realize the removal function of the functionalized amine ionic liquid on radioactive iodine, the constructed TEDA ionic liquid is the TEDA single-cation ionic liquid, and the structural formula of the TEDA single-cation ionic liquid is shown as the following formula.
When the TEDA monocationic ionic liquid is prepared based on the preparation method of the TEDA monocationic ionic liquid described in example 1, one nitrogen atom in the TEDA is controlled to be converted into ammonium ion N through a coordinate bond synthesized through quaternization reaction + So that it is converted into ionic liquid, thereby obtainingTo reduce the volatile effect of TEDA; the other nitrogen atom remains so that the TEDA monocationic ionic liquid retains the function of removing radioactive methyl iodide. Furthermore, the results of the adsorption test showed conversion to ammonium ion N + The nitrogen atoms still have certain function of generating chemical adsorption by the complex reaction with methyl iodide.
The iodine removing principle of the active iodine removing impregnant TEDA is as follows:
the iodine removal principle after the TEDA is converted into the TEDA monocationic ionic liquid through quaternization is as follows:
example 1
The preparation method of the TEDA single-cation ionic liquid (TEDAILs system) comprises the following steps:
s11, weighing reactants and a cosolvent: weighing 6g of triethylene diamine, 10g of chloro n-butane and 5g of ethanol by using a weighing balance;
s12, filling the weighed reactants and cosolvent into a beaker, uniformly mixing the reactants and the cosolvent through magnetic stirring, and filling the mixture into a polytetrafluoroethylene high-pressure reaction kettle;
s13, placing the polytetrafluoroethylene high-pressure reaction kettle at 120 ℃, setting the reaction time to be 18h, and naturally cooling to room temperature after the reaction is finished to obtain an initial product;
s14, dissolving the initial product by adopting 25g of ethanol to obtain an initial product solution, adding 10g of ethyl acetate into the initial product solution to obtain a mixture, and performing suction filtration treatment on the mixture for 3 times to obtain a purified product;
s15, standing and drying the purified product at 100 ℃ for 24 hours to obtain the TEDA single cation ionic liquid.
Referring to the requirements of the standard test method of ASTM D3803-1991 (2014) nuclear grade activated carbon for the adsorption material standard radioactive iodine adsorption performance test, after the TEDA single cation ionic liquid (TEDAILs system) obtained in example 1 is immobilized on the Activated Carbon Fiber (ACF), the removal efficiency of radioactive methyl iodine reaches 99.94% under the conditions of 30 ℃, 40% relative humidity and 4.8m/min of linear velocity of airflow passing through the material, as shown in FIG. 2.
The thermogravimetric analysis results of the TEDA monocationic ionic liquid (TEDAILs system) obtained in example 1 are shown in fig. 3b, the thermogravimetric analysis results of TEDA are shown in fig. 3a, and the thermal stability of the TEDAILs system and TEDA can be found by comparing the thermal stability of the TEDAILs system with that of the TEDA in fig. 3a and 3 b: TEDA decomposes almost completely at 126 ℃ with the fastest decomposition speed of 29.45%. Min -1 The TEDAILs system is completely decomposed at 362 ℃, and the thermal stability is improved by about 187% compared with the TEDA, thereby verifying that the TEDAILs system can solve the problem of easy volatility of the TEDA.
In addition, this embodiment also tests the monthly loss rate at 50 ℃ of the TEDAILs system obtained in example 1, and the results are shown in fig. 4. After the TEDAILs system is immobilized on the activated carbon fiber, the monthly loss rate under the condition of 50 ℃ is 2.756 percent (mass percentage); the monthly loss rate of the tedalils system after immobilization on activated carbon was significantly reduced compared to the monthly loss rate (16.9%) of TEDA after immobilization on activated carbon.
Example 2
The preparation method of the HMTA monocationic ionic liquid (TEDAILs system) comprises the following steps:
s21, weighing reactants and a cosolvent: weighing 6g of HMTA, 21g of chloro-n-hexylalkane and 6g of ethanol by using a weighing balance;
s22, filling the weighed reactants and cosolvent into a beaker, uniformly mixing the reactants and the cosolvent through magnetic stirring, and filling the mixture into a polytetrafluoroethylene high-pressure reaction kettle;
s23, placing the polytetrafluoroethylene high-pressure reaction kettle at the temperature of 110 ℃, setting the reaction time to be 14h, and naturally cooling to room temperature after the reaction is finished to obtain an initial product;
s24, dissolving the initial product by adopting 50g of ethanol to obtain an initial product solution, adding 200g of ethyl acetate into the initial product solution to obtain a mixture, and performing suction filtration treatment on the mixture for 3 times to obtain a purified product;
s25, standing and drying the purified product at 60 ℃ for 12h to obtain the HMTA single cation ionic liquid.
Referring to the requirements of standard radioactive iodine adsorption performance experiments of adsorption materials in the standard test method of ASTM D3803-1991 (2014) nuclear-grade activated carbon, the removal efficiency of radioactive methyl iodide reaches 98.99% under the conditions of 30 ℃, 40% relative humidity and 4.8m/min of linear velocity of airflow passing through materials after the HMTA single-cation ionic liquid (HMTAILs system) obtained in example 2 is immobilized on a molecular sieve.
By comparing the HMTAILs system and the thermogravimetric analysis result of HMTA, the following results can be found: the HMTA monocationic ionic liquid (HMTAILs system) obtained in example 2 completely decomposed at 791 ℃ whereas HMTA decomposed substantially completely at 367 ℃, and the thermal stability of the HMTAILs system was improved by about 116% compared to HMTA.
In addition, the monthly loss rate of the HMTAILs system obtained in example 2 was 1.026% (mass percentage) at 50 ℃ after immobilization on a molecular sieve.
Example 3
The preparation method of the tetramethylethylenediamine monocationic ionic liquid comprises the following steps:
s31, weighing reactants and a cosolvent: weighing 6g of tetramethylethylenediamine, 18g of chloro-n-decanane and 20g of ethanol by using a weighing balance;
s32, filling the weighed reactants and cosolvent into a beaker, uniformly mixing the reactants and the cosolvent through magnetic stirring, and filling the mixture into a polytetrafluoroethylene high-pressure reaction kettle;
s33, placing the polytetrafluoroethylene high-pressure reaction kettle at the temperature of 90 ℃, setting the reaction time to be 8 hours, and naturally cooling to room temperature after the reaction is finished to obtain an initial product;
s34, under the heating condition, dissolving the initial product by adopting 10g of ethanol to obtain an initial product solution, adding 30g of acetone into the initial product solution to obtain a mixture, cooling the mixture for 4 hours, and performing suction filtration on the mixture for 3 times to obtain a purified product;
s35, standing and drying the purified product at the temperature of 60 ℃ for 12 hours to obtain the tetramethylethylenediamine monocationic ionic liquid.
Referring to the requirements of standard radioactive iodine adsorption performance experiments of adsorption materials in the standard test method of ASTM D3803-1991 (2014) nuclear-grade activated carbon, after the tetramethylethylenediamine monocationic ionic liquid obtained in example 3 is immobilized on the activated carbon, the removal efficiency of radioactive methyl iodine reaches 97.11% under the conditions of 30 ℃, 40% relative humidity and linear velocity of air flow passing through the material of 4.8 m/min.
By comparing the thermogravimetric analysis results of the tetramethylethylenediamine monocationic ionic liquid and the tetramethylethylenediamine, the following results can be found: the tetramethylethylenediamine monocationic ionic liquid obtained in example 3 completely decomposed at 343 ℃, while tetramethylethylenediamine decomposed substantially completely at 150 ℃, and the thermal stability of the tetramethylethylenediamine monocationic ionic liquid was improved by about 129% compared to that of tetramethylethylenediamine.
In addition, the tetramethylethylenediamine monocationic ionic liquid obtained in example 3 had a monthly loss rate of 3.584% (mass percentage) at 50 ℃ after being immobilized on activated carbon.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (10)
1. A preparation method of a functionalized amine ionic liquid for adsorbing radioactive iodine is characterized by comprising the following steps:
s1, weighing reactants and a cosolvent: weighing amine compounds and halogenated alkyl compounds with methyl iodide adsorption function according to the set molar ratio of the amine compounds to the halogenated alkyl compounds, and weighing a cosolvent;
s2, dissolving the reactants by adopting a cosolvent, uniformly stirring, and then filling into a reaction container: dissolving the amine compound and the halogenated alkyl compound with the methyl iodide adsorption function in the cosolvent to obtain a mixture, uniformly stirring the mixture, and filling the mixture into a reaction container;
s3, quaternization reaction: under the set reaction conditions, after the amine compound and the halogenated alkyl compound with the methyl iodide adsorption function react in the reaction vessel, obtaining an initial product;
s4, purification: dissolving the initial product by using a cosolvent to obtain an initial product solution, adding a purifying agent into the initial product solution to obtain a mixture, and performing suction filtration on the mixture to obtain a purified product;
s5, drying: and drying the purified product under the set drying condition to obtain the functionalized amine ionic liquid.
2. The method for preparing the functionalized amine ionic liquid for adsorbing the radioactive iodine according to claim 1, wherein the amine compound having the methyl iodide adsorption function is one selected from triethylene diamine, hexamethylenetetramine, 4-aminomethyl quinuclidine, 4-cyanoquinuclidine, N-dimethyl-p-phenylenediamine, tetramethylethylenediamine and hexamethylenediamine;
the halogenated alkyl compound is selected from one of halogenated methyl, halogenated ethyl, halogenated propyl, halogenated butyl, halogenated pentyl, halogenated hexyl, halogenated heptyl, halogenated octyl, halogenated decyl, halogenated dodecyl, halogenated tetradecyl and halogenated hexadecyl compounds.
3. The method for preparing the functionalized amine ionic liquid for adsorbing the radioactive iodine according to claim 1, wherein the cosolvent is selected from one of ethanol and ethylene glycol.
4. The method for preparing the functionalized amine ionic liquid for adsorbing the radioactive iodine according to claim 1, wherein the molar ratio of the amine compound to the haloalkyl compound is set to be 1.
5. The preparation method of the functionalized amine ionic liquid for adsorbing radioactive iodine according to claim 1, wherein the volume ratio of the cosolvent to the reaction container is 0.1-0.3.
6. The method for preparing the functionalized amine ionic liquid for adsorbing the radioactive iodine according to claim 1, wherein the set reaction conditions comprise: the reaction temperature is 60-300 ℃; the reaction time is 5-30 h.
7. The method for preparing the functionalized amine ionic liquid for adsorbing the radioactive iodine according to claim 1, wherein the purifying agent is one selected from ethanol, ethyl acetate and acetone;
the mass ratio of the purifying agent to the initial product is 1-50.
8. The method for preparing the functionalized amine ionic liquid for adsorbing the radioactive iodine according to claim 1, wherein the set drying conditions comprise: drying under vacuum condition, wherein the drying temperature is 30-200 ℃; the drying time is 8-72 h.
9. A functionalized amine ionic liquid for adsorbing radioactive iodine, which is obtained by taking an amine compound and a halogenated alkyl compound with methyl iodide adsorption function as reactants based on the preparation method of the functionalized amine ionic liquid for adsorbing radioactive iodine as claimed in any one of claims 1 to 8.
10. The method for preparing the functionalized amine ionic liquid for adsorbing the radioactive iodine according to claim 9, wherein the amine compound having the methyl iodide adsorption function is one selected from triethylene diamine, hexamethylene tetramine, 4-aminomethyl quinuclidine and 4-cyanogen quinuclidine.
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| JP2017227633A (en) * | 2016-06-21 | 2017-12-28 | フタムラ化学株式会社 | Radioactive iodine adsorbent and method for manufacturing the same |
| CN111039948A (en) * | 2018-10-15 | 2020-04-21 | 中国科学院宁波材料技术与工程研究所 | Triethylene diamine diionic liquid, preparation method and application thereof |
| CN111389370A (en) * | 2020-03-20 | 2020-07-10 | 中国辐射防护研究院 | Preparation method of nuclear-grade activated carbon loaded with ionic liquid |
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| JP2017227633A (en) * | 2016-06-21 | 2017-12-28 | フタムラ化学株式会社 | Radioactive iodine adsorbent and method for manufacturing the same |
| CN111039948A (en) * | 2018-10-15 | 2020-04-21 | 中国科学院宁波材料技术与工程研究所 | Triethylene diamine diionic liquid, preparation method and application thereof |
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