CN115106053A - Composite adsorption material and preparation method and application thereof - Google Patents
Composite adsorption material and preparation method and application thereof Download PDFInfo
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- CN115106053A CN115106053A CN202110285734.9A CN202110285734A CN115106053A CN 115106053 A CN115106053 A CN 115106053A CN 202110285734 A CN202110285734 A CN 202110285734A CN 115106053 A CN115106053 A CN 115106053A
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- activated carbon
- hydrotalcite
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- 239000002131 composite material Substances 0.000 title claims abstract description 117
- 239000000463 material Substances 0.000 title claims abstract description 103
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 229
- 150000001875 compounds Chemical class 0.000 claims abstract description 73
- 239000002105 nanoparticle Substances 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims description 54
- 239000003463 adsorbent Substances 0.000 claims description 49
- 229960001545 hydrotalcite Drugs 0.000 claims description 47
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 47
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- 239000002901 radioactive waste Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- PNDPGZBMCMUPRI-HVTJNCQCSA-N 10043-66-0 Chemical compound [131I][131I] PNDPGZBMCMUPRI-HVTJNCQCSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 13
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- 239000002994 raw material Substances 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 238000009206 nuclear medicine Methods 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims description 7
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 claims description 7
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- -1 iodine anions Chemical class 0.000 abstract description 37
- 239000011630 iodine Substances 0.000 abstract description 16
- 229910052740 iodine Inorganic materials 0.000 abstract description 16
- 238000013329 compounding Methods 0.000 abstract description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 abstract 2
- 239000002354 radioactive wastewater Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 47
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000006228 supernatant Substances 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 239000006249 magnetic particle Substances 0.000 description 8
- 230000005415 magnetization Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
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- 238000000926 separation method Methods 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000011068 loading method Methods 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000000941 radioactive substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- GKLVYJBZJHMRIY-OUBTZVSYSA-N Technetium-99 Chemical compound [99Tc] GKLVYJBZJHMRIY-OUBTZVSYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229940056501 technetium 99m Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- 238000005342 ion exchange Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 206010020850 Hyperthyroidism Diseases 0.000 description 1
- 208000024770 Thyroid neoplasm Diseases 0.000 description 1
- FVFLHJZAFUCZAK-UHFFFAOYSA-N [C].[Mg].[Fe] Chemical compound [C].[Mg].[Fe] FVFLHJZAFUCZAK-UHFFFAOYSA-N 0.000 description 1
- XKPSNDTZAMTUGM-UHFFFAOYSA-N [C].[Mg].[Mn] Chemical compound [C].[Mg].[Mn] XKPSNDTZAMTUGM-UHFFFAOYSA-N 0.000 description 1
- RZWKIKCJUYJECQ-UHFFFAOYSA-N [Ni].[Fe].[C] Chemical compound [Ni].[Fe].[C] RZWKIKCJUYJECQ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
Abstract
The invention discloses a composite adsorption material, a preparation method and application thereof, mainly comprising active carbon and magnetic Fe 3 O 4 The nano particles and the hydrotalcite-like compound are compounded. The composite adsorbing material is prepared by compounding magnetic activated carbon and hydrotalcite-like compound, wherein the activated carbon has a developed pore structure, large specific surface area and Fe 3 O 4 The nano-particles have excellent magnetic properties, and the hydrotalcite-like compound has better adsorption performance on iodine anions. The composite adsorption material can be used for adsorption treatment of iodine anion radioactive wastewater, has high iodine anion removal efficiency, can be recycled under an external magnetic field, and can be reused.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a composite adsorbing material compounded by magnetic activated carbon and a hydrotalcite-like compound, and a preparation method and application thereof.
Background
Iodine-131 is the most widely used radionuclide in nuclear medicine, mainly used for the treatment of thyroid cancer and hyperthyroidism. As the number of patients treated with iodine-131 nuclides has increased year by year, the discharge of iodine-containing radioactive waste liquid has also increased year by year, making iodine-131 the most interesting and urgent nuclide in nuclear medicine radioactive waste liquid.
At present, the radioactive waste liquid of nuclear medicine mainly contains two radionuclides, i.e. iodine-131 and technetium-99 m, which mainly emit beta rays, wherein the half-life of technetium-99 m is 6.02 hours, and the half-life of iodine-131 is 8.02 days, and the radioactive waste liquid of nuclear medicine is generally treated by a storage decay method, namely: the radioactive waste liquid of nuclear medicine is statically placed in a decay tank, the standing time is not less than 10 half-lives of the radioactive nuclides (the radioactive waste liquid containing iodine-131 and technetium-99 m at least needs to be stood for 80 days by the radioactive nuclide with the longest half-life, generally stood for about 3 months), so that the radioactive nuclides naturally decay in the decay tank until the radioactive activity concentration of the radioactive waste liquid meets the national relevant standard (the national management limit values are that the total alpha radioactive activity concentration is less than or equal to 1Bq/L and the total beta radioactive activity concentration is less than or equal to 10Bq/L), and then the radioactive waste liquid is discharged.
Due to the increasing discharge of iodine-131-containing radioactive waste liquid and the long time consuming of the storage decay method, the discharge of radioactive waste liquid may exceed the treatment capacity of the decay tank, for example, if a large amount of radioactive waste liquid cannot be sufficiently treated and discharged due to insufficient standing time, the radioactive substances contained in the discharged waste liquid may cause safety risks to the environment and living beings.
At present, methods or means including chemical precipitation, ion exchange, adsorption, membrane separation, biological adsorbent and the like are used at home and abroad to remove iodine-131 in radioactive waste liquid. The adsorption method is a competitive method in the field of environmental management (particularly in the field of sewage treatment), and has the advantages of simple process, low energy consumption, micro pollution, high efficiency, reproducibility and the like, for example, the adsorption treatment of the activated carbon for common wastewater has the advantages of low cost, easy implementation in large-scale water bodies and the like, but the adsorption method is used for removing iodine-131 in radioactive waste liquid and has lower efficiency; natural inorganic materials can also be used as adsorbents for adsorption processes, but most of them require chemical modification, and their production processes are complicated. The nano-adsorption material can also be used as an adsorbent, but has poor structural stability, is difficult to fill a separation column and is difficult to separate from a water body.
Disclosure of Invention
Aiming at the technical defects in the prior art, the invention provides a composite adsorbing material for effectively removing iodine-131 in radioactive waste liquid of nuclear medicine, which mainly comprises activated carbon and magnetic Fe 3 O 4 The granular solid compounded by the nano particles and the hydrotalcite-like compound comprises the following components in percentage by mass:
activated carbon: 16.67 to 35.71 percent of the total weight of the mixture,
magnetic Fe 3 O 4 Nanoparticles: 16.67 to 35.71 percent of the total weight of the mixture,
hydrotalcite-like compound: 28.57 to 66.67 percent.
Comprises the following components in percentage by mass:
activated carbon: 22.22 to 23.22 percent of,
magnetic Fe 3 O 4 Nano-particles: 22.22 to 23.22 percent of the total weight of the mixture,
hydrotalcite-like compound: 54.00 to 55.00 percent.
The hydrotalcite-like compound includes but is not limited to one or more of magnesium aluminum hydrotalcite-like compound, magnesium iron hydrotalcite-like compound, magnesium manganese hydrotalcite-like compound and nickel iron hydrotalcite-like compound.
The hydrotalcite-like compound and magnetic Fe 3 O 4 The nano particles are attached to the surface and in the pores of the activated carbon.
The hydrotalcite-like compound is magnesium-aluminum hydrotalcite, magnesium-iron hydrotalcite or magnesium-manganese hydrotalcite, and the composite adsorption material comprises the following raw materials in percentage by mass:
activated carbon: 6.91% -16.55%, 100-300 mesh, preferably 200 mesh;
FeCl 3 ·6H 2 o: 14.90% -35.60%; and
FeCl 2 : 5.52% -13.16%; for preparing magnetic Fe 3 O 4 A nanoparticle;
MgCl 2 ·6H 2 o: 26.97% -56.08%; and
AlCl 3 ·6H 2 7.89 to 16.57 percent of O; used for preparing magnesium-aluminum hydrotalcite;
or activated carbon: 6.76% -16.32%, 100-300 mesh, preferably 200 mesh;
FeCl 3 ·6H 2 o: 14.92% -35.60%; and
FeCl 2 : 5.41% -13.05%; for preparing magnetic Fe 3 O 4 A nanoparticle;
MgCl 2 ·6H 2 o: 26.54% -54.98%; and
FeCl 3 ·6H 2 8.81 to 18.27 percent of O; used for preparing magnesium iron hydrotalcite;
or activated carbon: 7.29 to 16.92 percent, 100 to 300 meshes, preferably 200 meshes;
FeCl 3 ·6H 2 o: 15.75% -35.54%; and
FeCl 2 : 5.83% -13.53%; for preparing magnetic Fe 3 O 4 A nanoparticle;
MgCl 2 ·6H 2 o: 27.52% -59.31%; and
MnCl 3 ·4H 2 o: 5.48% -11.81%; used for preparing magnesium-manganese hydrotalcite;
preferably, the method comprises the following steps:
activated carbon: 9.23 to 10.23 percent of the total weight of the mixture,
FeCl 3 ·6H 2 O：20.51％-21.51％，
FeCl 2 ：7.28％-8.28％，
MgCl 2 ·6H 2 o: 47.00-48.00%, and
AlCl 3 ·6H 2 O：13.50-14.50％；
or activated carbon: 9.04 to 10.04 percent of the total weight of the mixture,
FeCl 3 ·6H 2 O：20.10％-21.10％，
FeCl 2 ：7.13％-8.13％，
MgCl 2 ·6H 2 o: 46.06-47.06%, and
FeCl 3 ·6H 2 O：14.97-15.97％；
or activated carbon: 9.70 to 10.70 percent of the total weight of the mixture,
FeCl 3 ·6H 2 O：21.54％-22.54％，
FeCl 2 ：7.66％-8.66％，
MgCl 2 ·6H 2 o: 49.29-50.29%, and
MnCl 3 ·4H 2 O：9.41-10.41％。
the hydrotalcite-like compound is nickel-iron hydrotalcite-like compound, and the composite adsorption material comprises the following raw materials in percentage by mass:
activated carbon: 6.18% -15.62%, 100-300 mesh, preferably 200 mesh;
FeCl 3 ·6H 2 O：13.35％-33.75％；
FeCl 2 ：4.95％-12.50％；
FeCl 3 ·6H 2 o: 8.45% -16.72%; and
NiCl 2 ·6H 2 O：29.71％-58.79％；
preferably, the method comprises the following steps:
activated carbon: 8.36% -9.36%, 100-300 mesh, preferably 200 mesh;
FeCl 3 ·6H 2 O：18.64％-19.64％；
FeCl 2 ：6.59％-7.59％；
FeCl 3 ·6H 2 o: 13.87 to 14.87 percent; and
NiCl 2 ·6H 2 O：50.07-51.07％。
in a second aspect, the invention provides a preparation method of the composite adsorption material, which is prepared from the raw materials and sequentially comprises the following steps:
(1) dispersing the activated carbon in water to form an activated carbon dispersion liquid;
(2) adding FeCl into the active carbon dispersion liquid 3 ·6H 2 O、FeCl 2 And a baseObtaining magnetic activated carbon;
(3) adding magnetic active carbon into the solution of the synthetic hydrotalcite-like compound, and adding NaOH and Na 2 CO 3 Regulating the pH value of the solution to 10-11 to obtain a magnetic activated carbon-hydrotalcite-like compound; the solution for synthesizing the hydrotalcite-like compound is MgCl-containing 2 ·6H 2 O and AlCl 3 Or a solution containing MgCl 2 ·6H 2 O and FeCl 3 ·6H 2 Solutions of O, or containing MgCl 2 ·6H 2 O and MnCl 3 ·4H 2 Solutions of O, or containing FeCl 3 ·6H 2 O and NiCl 2 ·6H 2 A solution of O;
(4) and roasting the magnetic activated carbon-hydrotalcite-like compound to obtain the composite adsorbing material.
The step (2) is specifically as follows:
adding FeCl into the activated carbon dispersion liquid 3 ·6H 2 O and FeCl 2 In N, at 2 Under protection and stirring, when the temperature is heated to 80-85 ℃, adding excessive alkali liquor to carry out in-situ precipitation reaction, and when no more solid is generated, separating the solid from the reaction liquid by using a permanent magnet to obtain the magnetic activated carbon.
The step (3) is specifically as follows:
adding magnetic activated carbon into the solution of the synthetic hydrotalcite-like compound under the stirring of 600-1000rpm, and then adding the solution containing NaOH and Na 2 CO 3 Performing in-situ precipitation reaction until the pH value of the reaction solution is 10-11, aging for 12h when the solid in the reaction solution is not increased any more, and separating the solid from the reaction solution by using a permanent magnet to obtain the magnetic activated carbon-hydrotalcite-like compound.
The preparation method specifically comprises the following steps:
(1) dispersing activated carbon in water to form an activated carbon dispersion liquid, and dispersing 0.25g of activated carbon in every 100mL of water;
(2) adding FeCl into the activated carbon dispersion liquid obtained in the step (1) 3 ·6H 2 O and FeCl 2 In N at 2 Stirring under protection, heating to 80-85 deg.C, adding excessive alkali solution for in-situ precipitation reactionWhen no more solid is generated, separating the solid from the reaction liquid by using a permanent magnet, wherein the solid is the magnetic activated carbon;
(3) adding magnetic activated carbon into the solution A under the stirring of 600-1000rpm, and then adding NaOH and Na 2 CO 3 Performing in-situ precipitation reaction until the pH value of the reaction solution is 10-11, aging for 12h when the solid in the reaction solution is not increased any more, and separating the solid from the reaction solution by using a permanent magnet, wherein the solid is a magnetic activated carbon-hydrotalcite-like compound; the solution A is MgCl with the concentration of 4.06g/L-20.30g/L 2 ·6H 2 O and 1.20-6.00 g/L AlCl 3 Or contains from 4.06g/L to 20.30g/L of MgCl 2 ·6H 2 O and 1.35g/L-6.75g/L FeCl 3 ·6H 2 O solution, or MgCl solution containing 4.06-20.30 g/L 2 ·6H 2 O and 8.09g/L-4.05g/L MnCl 3 ·4H 2 O or FeCl containing 1.35g/L to 6.75g/L 3 ·6H 2 O and 4.75g/L-23.77g/L NiCl 2 ·6H 2 A solution of O;
(4) and (4) placing the magnetic activated carbon-hydrotalcite-like compound obtained in the step (3) in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, roasting for 4-5 hours, grinding and sieving to obtain the composite adsorbing material.
In a third aspect, the invention provides an application of the composite adsorbing material in preparation of an adsorbent for iodine-131 in radioactive waste liquid of nuclear medicine.
The composite adsorbing material provided by the invention takes activated carbon as a matrix, and magnetic Fe is loaded on the surface and in the pores of the matrix by a chemical coprecipitation method 3 O 4 The nano particles and the hydrotalcite-like compound realize the compounding of the magnetic substance, the active carbon and the hydrotalcite-like compound; wherein, the hydrotalcite-like compound has better adsorption performance on iodine-131, and can effectively remove the iodine-131 in the radioactive waste liquid; the activated carbon has a developed pore structure and a huge specific surface area, can load a large amount of hydrotalcite-like compounds, and increases the adsorption capacity of the composite adsorption material on iodine-131 by increasing the loading capacity of the hydrotalcite-like compounds so as to enhance the effect of removing iodine-131; magnetic Fe 3 O 4 The nanoparticles haveThe composite adsorbing material has excellent magnetic performance, and is convenient to separate from radioactive waste liquid. The composite adsorbing material can be used for adsorption treatment of iodine-131-containing radioactive waste liquid, is high in treatment efficiency (adsorption can be completed within 6 hours in the third experiment), can remarkably reduce the content of iodine-131 in the radioactive waste liquid (the adsorption efficiency can reach 86% in the third experiment), can be separated from the radioactive waste liquid under an external magnetic field, can be recycled (at least 5 times in the fourth experiment), has the advantages of easiness in preparation (such as easiness in control of reaction conditions, simplicity in operation, low cost), good adsorption performance, good stability, no secondary pollution and the like, and has good use value and wide application prospect.
When the composite adsorption material is used as an adsorbent for radioactive waste liquid, the radioactive waste liquid is adsorbed by the composite adsorption material before being discharged to a decay tank, so that the concentration of the total radioactivity in the radioactive waste liquid is greatly reduced, and then the radioactive waste liquid is discharged to the decay tank, and the radioactive waste liquid can be discharged without standing or the standing time is far less than 3 months (about 13 days), so that the treatment load of the decay tank is effectively relieved. The composite adsorption material adsorbing iodine-131 is recovered under an external magnetic field, then treated by a storage decay method in a centralized manner, after standing for 10 half-life periods, adsorbed iodine ions (the concentration of radioactivity reaches the emission standard) are eluted, the eluent is directly discharged, and the composite adsorption material is recycled.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the magnetic activated carbon obtained in step (2) of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the composite adsorbent of example 1;
FIG. 3 is a graph showing magnetization curves of the magnetic activated carbon and the composite adsorbent of example 1;
FIG. 4 is a graph showing the kinetics of adsorption of iodide ions by the composite adsorbent material of example 1;
FIG. 5 is a bar graph showing the reuse performance of the composite adsorbent material of example 1;
fig. 6 is a bar graph showing the structural stability of the composite adsorbent of example 1.
Detailed Description
The invention provides a composite adsorbing material which mainly comprises active carbon and magnetic Fe 3 O 4 The nano-particles and the hydrotalcite-like compound are compounded, wherein:
the active carbon as a carbon material has a developed pore structure, a huge specific surface area and a strong adsorption capacity, and compared with graphene oxide and an organic polymer, the active carbon has stable chemical properties, high mechanical strength, acid resistance, alkali resistance, heat resistance, insolubility in water and organic solvents, and can be regenerated after being used inefficiently, so that the active carbon is widely applied to the fields of environmental protection, chemical engineering, food processing, hydrometallurgy, drug refinement, military chemical protection (such as gas masks) and the like. However, the activated carbon has low adsorption capacity and poor selectivity, and is not easy to recover, so that the application of the activated carbon in related fields is limited. In order to overcome these defects of activated carbon in recent years, many studies have been made to compound activated carbon with other materials, for example, magnetic activated carbon obtained by compounding activated carbon with magnetic particles, so as to improve the recovery performance of activated carbon. In view of the potential safety hazard of radioactive waste liquid, the use of magnetic activated carbon with low adsorption capacity and poor selectivity for the adsorption of iodine-131 in radioactive waste liquid has not been reported.
The hydrotalcite-like compound is composed of divalent and trivalent metal ions and belongs to hydroxyl composite metal oxides. The hydrotalcite-like compound has a unique layered structure, interlaminar anions have interchangeability, the anion exchange capacity is high (the charge density of the anions determines the exchange capacity), and the hydrotalcite-like compound has the advantages of simple synthesis, low cost and the like, and can be widely applied to the field of environmental management as an adsorbent. If the layered hydrotalcite-like compound such as Mg/Al, Zn/Al and the like is synthesized by a hydrothermal method or a coprecipitation method, anions in a water body can be removed by ion exchange, and the removal principle is as follows: the hydrotalcite-like compound has a memory effect, interlayer water and interlayer anions are lost after roasting, and an original layered structure disappears to form a metal oxide solid solution; after the solid solution adsorbs anions in water, the layered structure can be recovered, and pollutants existing in the form of anions in the water body can be effectively removed by utilizing the characteristic. However, the hydrotalcite-like compound is in a powder state, is difficult to separate from a water body, and is not easily applied to a separation column. Similarly, in view of the potential safety hazard of radioactive waste liquid, the hydrotalcite-like compound having radioactive substances adsorbed thereon is not easily separated from the waste liquid, which results in radioactive substances remaining in the waste liquid, i.e., radioactive substances in the radioactive waste liquid cannot be effectively removed, and thus the situation of treatment overload in a decay tank cannot be improved.
The hydrotalcite-like compound can be divided into magnesium-aluminum hydrotalcite, magnesium-iron hydrotalcite, magnesium-manganese hydrotalcite, nickel-iron hydrotalcite and the like according to the types of metal ions, the hydrotalcite-like compounds containing different metal ions have different adsorption selectivity on anions, and the magnesium-aluminum hydrotalcite, the magnesium-iron hydrotalcite, the magnesium-manganese hydrotalcite and the nickel-iron hydrotalcite can be used for adsorbing iodine ions after screening.
The magnetic separation technology is a separation and concentration technology combining magnetic particles and an adsorbent, the magnetic particles are used as a carrier loaded adsorbent, the magnetic separation technology has the advantages of high selectivity, simplicity and convenience in operation, low cost, less generated secondary waste and the like, and the problem that the powdery adsorbent is difficult to separate in the actual application process is solved. However, few reports have been made on the removal of iodide ions by using hydrotalcite-like compounds as adsorbents in combination with magnetic particles. Only in one study of the Korean academy of science and technology will be magnetic Fe 3 O 4 Nano composite adsorption material (code number is Fe) obtained by directly compounding nano particles and magnesium-aluminum hydrotalcite 3 O 4 @ CLDH) was used for iodine adsorption, magnetic Fe was used in this study 3 O 4 The nano particles are used as a carrier to load the magnesium-aluminum hydrotalcite adsorbent. The specific surface area of the support determines the amount of adsorbent that can be loaded, and the amount of adsorbent loaded determines the adsorption capacity of the composite adsorbent material. Magnetic Fe in the nano composite adsorption material 3 O 4 The specific surface area of the nanoparticles was 76.4m 2 (ii)/g, the loading of the adsorbent is 40% (by mass fraction), Fe due to magnetism 3 O 4 The specific surface area of the nano particles is small, so that the loading capacity of the nano particles to the adsorbent is small, and the adsorption capacity of the nano composite adsorption material is influenced finally. In addition, when the pH value of the solution containing the iodide ions is less than 5, the hydrotalcite-like compound of the nano-composite adsorption material is partially dissolved in the solution with the pH value, and the structure is unstable, so that the adsorption capacity of the composite adsorption material to iodine is obviously reduced.
The invention provides a composite adsorbing material which comprises the following components in percentage by mass:
activated carbon: 16.67 to 35.71 percent of the total weight of the mixture,
magnetic Fe 3 O 4 Nanoparticles: 16.67 to 35.71 percent of the total weight of the mixture,
hydrotalcite-like compound: 28.57% -66.67%;
preferably, the method comprises the following steps:
activated carbon: 22.22 to 23.22 percent of the total weight of the mixture,
magnetic Fe 3 O 4 Nano-particles: 22.22 to 23.22 percent of the total weight of the mixture,
hydrotalcite-like compound: 54.00 to 55.00 percent.
The raw materials for preparing the composite adsorbing material, taking magnesium-aluminum hydrotalcite as an example, comprise the following components in percentage by mass:
activated carbon: 6.91% -16.55%, 100-300 mesh, preferably 200 mesh;
FeCl 3 ·6H 2 O：14.90％-35.60％；
FeCl 2 ：5.52％-13.16％；
MgCl 2 ·6H 2 o: 26.97% -56.08%; and
AlCl 3 ·6H 2 O 7.89％-16.57％；
preferably, the method comprises the following steps:
activated carbon: 9.23 to 10.23 percent of the total weight of the mixture,
FeCl 3 ·6H 2 O：20.51％-21.51％，
FeCl 2 ：7.28％-8.28％，
MgCl 2 ·6H 2 o: 47.00-48.00%, and
AlCl 3 ·6H 2 O：13.50-14.50％。
the invention also provides a method for preparing the composite adsorbing material by using the raw materials, taking magnesium-aluminum hydrotalcite as an example, and comprising the following steps:
(1) soaking the activated carbon in deionized water, then placing the activated carbon in an ultrasonic cleaning machine for ultrasonic dispersion for 20min, centrifuging the activated carbon at 4000 rpm for 30min after dispersion, removing supernatant, and adding the deionized water into the precipitate; the above washing process of dispersing, centrifuging, discarding the supernatant, and adding deionized water to the precipitate was repeated 3 times. Ultrasonically dispersing the cleaned activated carbon in deionized water to obtain an activated carbon dispersion liquid; the dosage ratio of the active carbon to the deionized water is as follows: 0.25 of activated carbon is dispersed in each 100mL of water;
(2) adding FeCl into the activated carbon dispersion liquid obtained in the step (1) 3 ·6H 2 O and FeCl 2 In N at 2 Stirring under protection, heating to 80-85 deg.C, rapidly adding excessive alkali solution (such as ammonia water) for in-situ precipitation reaction to obtain magnetic Fe 3 O 4 The nano-particles, the reaction equation is shown in formula 1,
Fe 3+ +2Fe 2+ +8OH - →Fe 3 O 4 +4H 2 o formula 1
Reaction to produce magnetic Fe 3 O 4 Magnetic Fe while being nano-sized 3 O 4 The nanoparticles adhere to the surface and pores of the activated carbon and the reaction is terminated when no more solids are produced. Pouring the reaction liquid into a conical flask, placing the conical flask on a permanent magnet, and settling the solid in the reaction liquid at the bottom of the conical flask; removing supernatant after the supernatant is clear and colorless, adding deionized water into the precipitate, repeating the above cleaning process on a permanent magnet, settling, and removing supernatant for 3 times to obtain precipitate, and drying the precipitate to obtain black powdered magnetic activated carbon (loaded with magnetic Fe) 3 O 4 Nano-particulate activated carbon).
(3) The MgCl is reacted with 2 ·6H 2 O and AlCl 3 ·6H 2 Dissolving O in deionized water to obtain MgCl 2 ·6H 2 O and AlCl 3 ·6H 2 The solution with the O concentration of 4.06g/L-20.30g/L and 1.20g/L-6.00g/L is marked as solution A; mixing NaOH and Na 2 CO 3 Dissolving in deionized water to obtain NaOH and Na 2 CO 3 (e.g., the concentrations are 12.00g/L and 15.90g/L respectively), and the mixed solution is marked as solution B;
(4) adding the magnetic activated carbon obtained in the step (2) into the solution A obtained in the step (3) under the stirring of 600-1000rpm, then dropwise adding the solution B obtained in the step (3) until the pH of the reaction solution is 10-11, carrying out in-situ precipitation reaction to generate the magnesium-aluminum hydrotalcite, wherein the reaction formula is shown as 2,
6Mg 2+ +2Al 3+ +16OH - +CO 3 2- +4H 2 O→Mg 6 A1 2 (OH) 16 CO 3 ·4H 2 o formula 2
While magnesium-aluminum hydrotalcite is generated by reaction, magnetic Fe 3 O 4 The nano particles are attached to the surface and in the pores of the active carbon, and the reaction is finished when the solid in the reaction solution is not increased any more; and aging for 12h, pouring the reaction liquid into a conical flask, placing the conical flask on a permanent magnet, settling the solid in the reaction liquid at the bottom of the conical flask, discarding the supernatant, adding deionized water into the precipitate, repeating the cleaning process of placing the mixture on the permanent magnet, settling and discarding the supernatant for 3 times to obtain a precipitate, and drying and grinding the precipitate to obtain the magnetic activated carbon-magnesium-aluminum hydrotalcite composite (namely the magnetic activated carbon loaded with magnesium-aluminum hydrotalcite).
And then placing the magnetic activated carbon-magnesium-aluminum hydrotalcite composite in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, roasting at the temperature for 4-5 hours, and grinding and sieving to obtain the composite adsorption material compounded by the magnetic activated carbon-magnesium-aluminum hydrotalcite. The particle size of the final composite adsorption material depends on the mesh number of the sieve, the larger the mesh number is, the smaller the particle size of the final composite adsorption material is, and the smaller the mesh number is, the larger the particle size of the final composite adsorption material is.
When preparing magnetWhen the composite adsorption material compounded by the active carbon-magnesium iron hydrotalcite, the composite adsorption material compounded by the magnetic active carbon-magnesium manganese hydrotalcite, or the composite adsorption material compounded by the magnetic active carbon-nickel iron hydrotalcite is adopted, other steps are not changed, and only the MgCl in the step (3) is needed 2 ·6H 2 O and AlCl 3 ·6H 2 Replacement of O by MgCl respectively 2 ·6H 2 O and FeCl 3 ·6H 2 O、MgCl 2 ·6H 2 O and MnCl 3 ·4H 2 O, or FeCl 3 ·6H 2 O and NiCl 2 ·6H 2 And (4) O.
The present invention will be described more specifically and further illustrated with reference to specific examples, which are by no means intended to limit the scope of the present invention.
Example 1:
placing the four-mouth bottle in a constant-temperature water bath kettle, adding 100ml of deionized water and 0.25g of active carbon when the water temperature is 60 ℃, stirring at the rotating speed of 150rpm under the protection of nitrogen, adding 0.54g of FeCl when the water temperature is increased to 80 DEG C 3 ·6H 2 O and 0.2g FeCl 2 Increasing the nitrogen ventilation amount, increasing the rotation speed to 180rpm, adding 2ml of ammonia water, then reducing the rotation speed to 150rpm, stirring for 30min, performing solid-liquid separation on reaction liquid by using a permanent magnet, discarding supernatant, washing precipitates with deionized water for several times to obtain magnetic activated carbon, and placing the magnetic activated carbon in the deionized water for storage.
0.41g of MgCl was weighed 2 ·6H 2 O and 0.12g AlCl 3 ·6H 2 Dissolving O in 100mL of deionized water to obtain a solution A; 0.4g NaOH and 0.53g Na were weighed out 2 CO 3 Dissolving in 100mL of deionized water to obtain a solution B; adding 0.6g of magnetic activated carbon into the three-necked bottle filled with the solution A, placing the three-necked bottle in a constant-temperature water bath kettle at a rotating speed of 150rpm, stirring, and dropwise adding the solution B when the water temperature is 60 ℃ until the pH value of a reaction solution is between 10 and 11, and reacting for 5 hours; standing and aging for 12h after the reaction is finished, performing solid-liquid separation on the reaction liquid by using a permanent magnet, discarding the supernatant, washing the precipitate with deionized water for a plurality of times, putting the obtained precipitate into an oven, drying at 60 ℃, and grinding to obtain the magnetic activated carbon-magnesium-aluminum hydrotalcite composite。
And (3) placing the magnetic activated carbon-magnesium-aluminum hydrotalcite composite in a muffle furnace, roasting at 500 ℃ for 4h at the heating rate of 5 ℃/min, grinding, and sieving with a 200-mesh sieve to obtain the composite adsorbing material compounded by the magnetic activated carbon-magnesium-aluminum hydrotalcite. Through identification (see experiment I), the composite adsorbing material is granular solid and comprises 22.73 wt% of active carbon and magnetic Fe by mass percentage 3 O 4 22.73 wt% of nano particles and 54.54 wt% of magnesium-aluminum hydrotalcite, and placing the mixture in a dryer for storage.
Example 2:
the composite adsorbing material compounded by the magnetic activated carbon-magnesium-aluminum hydrotalcite is obtained by the method of the embodiment 1, and the adding amount of the raw materials is only adjusted, so that the composite adsorbing material comprises 35.71 wt% of activated carbon and magnetic Fe according to the mass percentage 3 O 4 35.71 wt% of nano particles and 28.58 wt% of magnesium-aluminum hydrotalcite.
Example 3:
the composite adsorbing material compounded by the magnetic activated carbon-magnesium-aluminum hydrotalcite is obtained by the method of the embodiment 1, and the adding amount of the raw materials is only adjusted, so that the composite adsorbing material comprises 16.67 wt% of activated carbon and magnetic Fe according to the mass percentage 3 O 4 16.67 wt% of nano particles and 66.66 wt% of magnesium-aluminum hydrotalcite.
Comparative example 1:
the composite adsorbing material compounded by the magnetic activated carbon-magnesium-aluminum hydrotalcite is obtained by the method of the embodiment 1, and the adding amount of the raw materials is only adjusted, so that the composite adsorbing material comprises 52.63 wt% of activated carbon and magnetic Fe by mass percent 3 O 4 26.31 wt% of nano particles and 21.06 wt% of magnesium-aluminum hydrotalcite. The proportion of the activated carbon in the composite adsorbing material is too large, so that the composite adsorbing material is weak in magnetism and is not easy to separate from a water body.
Experiment one:
the magnetic activated carbon and the composite adsorbing material obtained in example 1 to 3 were used as samples, and the microstructure thereof was observed by a vacuum sputtering method, specifically: the sample is placed on a sample stage at a distance of about 10-15cm from the evaporation source, and is sprayed with gold (10kv, 60s) under rotary motion, and the sprayed layer is observed under a Scanning Electron Microscope (SEM) after being uniform. The results of the magnetic activated carbon and the composite adsorbent obtained in example 1 are shown in fig. 1 and 2, respectively.
FIG. 1 is a photograph showing that in the magnetic activated carbon, a large number of ferroferric oxide particles are distributed on the surface and in the pores of the activated carbon and Fe 3 O 4 The particles are in nanometer level, which shows that the active carbon is loaded with magnetic Fe 3 O 4 Nanoparticles, namely: magnetic Fe 3 O 4 The nanoparticles were successfully attached to the surface and pores of the activated carbon, indicating magnetic Fe 3 O 4 The nano particles and the active carbon are successfully compounded.
The photograph in fig. 2 shows that in the composite adsorbing material, the hydrotalcite-like compound is in a sheet shape and is embedded in the surface and pores of the magnetic activated carbon, that is: the magnetic active carbon is loaded with hydrotalcite-like compound; magnetic Fe 3 O 4 The nanoparticles and the hydrotalcite-like compound are successfully attached to the surface and the pores of the activated carbon, which shows that the magnetic Fe 3 O 4 The nanometer particles, the hydrotalcite-like compound and the active carbon are successfully compounded.
The specific surface area of the magnetic activated carbon and the composite adsorbing material obtained in example 1 was analyzed by a physical adsorption apparatus to obtain a magnetic activated carbon having a specific surface area of 430.64m 2 The specific surface area of the composite adsorbing material loaded with the magnesium-aluminum hydrotalcite is 102.12m 2 (ii) in terms of/g. Compared with the magnetic activated carbon, the more the specific surface area of the composite adsorbing material is reduced, which indicates that more hydrotalcite-like compounds are loaded on the surface and in the pores of the magnetic activated carbon, and the 76% reduction of the specific surface area of the composite adsorbing material obtained in example 1 compared with the magnetic activated carbon indicates that a large amount of magnesium-aluminum hydrotalcite is successfully loaded on the surface and in the pores of the magnetic activated carbon, so that it can be further inferred that the composite adsorbing material of the present invention contains such a large amount of hydrotalcite-like compounds, which can exert a high-efficiency adsorption effect on iodine-131.
Experiment two:
the magnetic activated carbon and the composite adsorbing material obtained in the example 1-3 were used as a sample, and the saturation magnetization of the sample was characterized by a Vibration Sample Magnetometer (VSM), specifically: after accurately weighing the mass of the sample, wrapping the sample by using a white plastic film, folding and wrapping the outside of the white plastic film by using weighing paper to form a sheet shape, and finally placing the sheet shape in a vibration sample magnetometer to measure the saturation magnetization of the sample. The results of taking the magnetic activated carbon and the composite adsorbent obtained in example 1 as an example are shown in fig. 3.
The results in FIG. 3 show that the saturation magnetization of the magnetic activated carbon was 31.47emu/g, and that the saturation magnetization of the magnetic activated carbon loaded with the magnesium-aluminum hydrotalcite (i.e., the composite adsorbent in example 1) was 12.58 emu/g. Compared with the magnetic activated carbon, the more the saturation magnetization of the composite adsorbing material is reduced, which indicates that the more magnesium-aluminum hydrotalcite is loaded on the surface and in the pores of the magnetic activated carbon, the 60% reduction in the saturation magnetization of the composite adsorbing material obtained in example 1 is compared with the magnetic activated carbon, which indicates that a large amount of magnesium-aluminum hydrotalcite is successfully attached to the surface and in the pores of the magnetic activated carbon, and it can be further inferred that the composite adsorbing material of the present invention contains such a large amount of hydrotalcite-like compounds, which can exert a high-efficient adsorption effect on iodine-131.
Although the saturation magnetization of the composite adsorbent of example 1 is greatly reduced compared to the magnetic activated carbon, it is still maintained at 10emu/g or more, which shows that the composite adsorbent of the present invention can still use permanent magnet for magnetic separation, so that the separation is easy and the recovery is easy.
Experiment three:
10mL of KI solution having a concentration of 10. mu.g/L was measured and placed in a 25mL Erlenmeyer flask, and the composite adsorbent obtained in example 1-3 was added thereto so that the final concentration of the composite adsorbent was 2 mg/mL. Stirring at room temperature and 150rpm to make the composite adsorbing material fully adsorb iodide ions, and sampling at 1h, 2h, 3h, 4h, 5h, 6h and 7h after adsorption begins respectively. After the sample is separated by the permanent magnet, supernatant fluid is taken, the concentration of iodine ions in the supernatant fluid is measured by an inductively coupled plasma mass spectrometer (ICP-MS), the adsorption capacity is calculated, and a kinetic curve is drawn by taking time as a horizontal coordinate and the adsorption capacity as a vertical coordinate (the drawing process is referred to the section of ' chemical dynamics basis ' of physical chemistry ' of the book of the Sudoku et al). The results of taking the composite adsorbent obtained in example 1 as an example are shown in fig. 4.
The results in fig. 4 show that the composite adsorbent of example 1 completed adsorption in 6 hours, and the adsorption efficiency was 86%. The result shows that 86% of iodine-131 can be adsorbed and removed in 6 hours when the composite adsorbing material is used as an adsorbent for radioactive waste liquid, the radioactive waste liquid after adsorption treatment is still discharged into a decay tank to be treated by a storage decay method, most radioactive iodide ions in the radioactive waste liquid are adsorbed and removed, the standing time of the radioactive waste liquid in the decay tank can be shortened to about 13 days, and compared with the treatment time of 3 months by the storage decay method, the composite adsorbing material can greatly shorten the treatment time of the iodine-131 in the radioactive waste liquid and reduce the treatment load of the decay tank. After the composite adsorbing material is recovered and treated by a storage decay method, iodide ions with radioactivity meeting the requirements are eluted from the composite adsorbing material, and the composite adsorbing material is recycled.
Experiment four:
measuring 10mL KI solution with the concentration of 10 mug/L, placing the KI solution in a 25mL conical flask, adding the composite adsorbing material obtained in the embodiment 1-3 to enable the final concentration of the composite adsorbing material to be 2mg/mL, adsorbing iodine ions at room temperature, and separating the composite adsorbing material from the solution by using a permanent magnet after adsorbing for 6 hours; then dispersing in Na with the concentration of 500mg/L 2 CO 3 Stirring the aqueous solution (as eluent) for 6h at room temperature for elution, separating by a permanent magnet, taking supernatant, measuring the concentration of iodide ions in the supernatant by using an inductively coupled plasma mass spectrometer (ICP-MS), and calculating the elution efficiency d% of the iodide ions, wherein the calculation formula is shown as formula 3,
d％＝(m de /m ad ) X 100% of formula 3
In the formula, m de (mg) represents the mass of iodide ions desorbed from the composite adsorbent, and m ad (mg) represents the total mass of iodide ions adsorbed onto the composite adsorbent material;
drying and roasting the eluted composite adsorbing material, repeating the adsorption and elution processes, and measuring and calculating the elution efficiency and the adsorption efficiency of the composite adsorbing material after each adsorption; the results are shown in fig. 5, using the composite adsorbent obtained in example 1 as an example.
After the composite adsorbing material of example 1 adsorbs iodide ions to saturation, and after the iodine ions are intensively recovered and stored for 3 months, the iodine ions are desorbed, and the elution efficiency after desorbing the iodine ions each time is 94%, that is: after the iodide ions are eluted, 94% of the iodide ions enter the eluent, the eluent can be directly discharged, and the desorbed composite adsorbing material can be recycled.
The results in fig. 5 show that the adsorption efficiency of the composite adsorbent material of example 1 still reaches 81% after repeated adsorption for 5 times, which indicates that the composite adsorbent material of the present invention has good adsorption performance, good stability, environmental friendliness, and no secondary pollution.
Experiment five:
taking 10 mu g/L KI solution, adjusting the pH value of the KI solution to 1-12 by using 0.1mol/L HCl and NaOH solutions, respectively, putting 10mL KI solutions with different pH values into 25mL conical flasks, adding the composite adsorbing material obtained in the examples 1-3 to enable the final concentration of the composite adsorbing material to be 2mg/mL, adsorbing iodine ions at room temperature for 6 hours, separating the composite adsorbing material from the solution by using a permanent magnet, measuring the concentration of the iodine ions in the supernatant by using an inductively coupled plasma mass spectrometer (ICP-MS), and calculating the adsorption efficiency. The results of plotting a bar graph with pH as the abscissa and adsorption efficiency as the ordinate and taking the composite adsorbent obtained in example 1 as an example are shown in fig. 6.
The results in FIG. 6 show that when the pH value of the KI solution is changed between 1 and 12, the change of the adsorption efficiency is small, and the composite adsorption material of the invention has better stability in a wider pH value range. When the pH value of the KI solution is increased from 1 to 9, the adsorption efficiency of the composite adsorption material is gradually increased along with the increase of the pH value; and the adsorption efficiency reaches the maximum when the pH value is 9; when pH > 9, the adsorption efficiency decreases with increasing pH, probably because of OH - And I - All are anions, competitive adsorption exists, and part of OH is - Occupy I - And the position on the composite adsorption material reduces the adsorption efficiency of the composite adsorption material to iodine ions. Composite adsorption of the inventionThe adsorption efficiency of the material under different pH values is stable, which shows that the material has stronger acid and alkali resistance and more stable structure, so that the adsorption performance of the material is more stable, and the adsorption process is controllable.
The composite adsorbing material provided by the invention is prepared by mixing magnetic Fe 3 O 4 The nano particles, the hydrotalcite-like compound and the active carbon are compounded, and the defects of small adsorption quantity, poor selectivity, difficult recovery and the like of the active carbon, difficult recovery of the hydrotalcite-like compound and easy agglomeration of magnetic particles and an adsorbent are overcome. The invention combines magnetic particles (magnetic Fe) 3 O 4 Nanoparticles) and an adsorbent (hydrotalcite-like compound) are sequentially immobilized on a carrier (activated carbon, used as a carrier for magnetic particles and an adsorbent in the present invention, not an adsorbent) having a large specific surface area, avoiding magnetic particles (magnetic Fe) 3 O 4 Nano particles) and an adsorbent (hydrotalcite-like compound), so that the stability of the composite adsorbent and the loading capacity of the hydrotalcite-like compound are improved, and the efficient adsorption effect is exerted.
The composite adsorption material is used as an adsorbent of the radioactive waste liquid of nuclear medicine, so that the content of iodine-131 in the radioactive waste liquid is greatly reduced, the standing time of the radioactive waste liquid in a decay tank is greatly reduced, even the radioactive waste liquid can be discharged without standing, and the treatment load of the decay tank is reduced. When the composite adsorption material is used as an adsorbent, the iodine-131 is easy to recover after being adsorbed, and the iodine ions are eluted after naturally decaying until the radioactivity reaches the standard after recovery, so that the iodine ions can be recycled.
The foregoing is illustrative of the preferred embodiments of the present invention and it will be appreciated by those skilled in the art that various changes and modifications may be made without departing from the principles of the invention and it is intended that such changes and modifications be considered as within the scope of the invention.
Claims (10)
1. The composite adsorbing material is characterized by mainly comprising active carbon and magnetic Fe 3 O 4 The granular solid compounded by the nano particles and the hydrotalcite-like compound comprises the following components in percentage by massThe composition is as follows:
activated carbon: 16.67 to 35.71 percent of the total weight of the mixture,
magnetic Fe 3 O 4 Nano-particles: 16.67 to 35.71 percent of the total weight of the mixture,
hydrotalcite-like compound: 28.57 to 66.67 percent.
2. The composite adsorption material according to claim 1, comprising the following components in percentage by mass:
activated carbon: 22.22 to 23.22 percent of the total weight of the mixture,
magnetic Fe 3 O 4 Nano-particles: 22.22 to 23.22 percent of the total weight of the mixture,
hydrotalcite-like compound: 54.00 to 55.00 percent.
3. The composite adsorbent material of claim 1 or 2, wherein the hydrotalcite-like compound comprises one or more of, but not limited to, magnesium-aluminum hydrotalcite, magnesium-iron hydrotalcite, magnesium-manganese hydrotalcite, and nickel-iron hydrotalcite.
4. The composite adsorbent material according to any one of claims 1 to 3, wherein the hydrotalcite-like compound and magnetic Fe 3 O 4 The nano particles are attached to the surface and in the pores of the activated carbon.
5. The composite adsorption material of any one of claims 1 to 4, wherein the hydrotalcite-like compound is magnesium-aluminum hydrotalcite-like compound, magnesium-iron hydrotalcite-like compound or magnesium-manganese hydrotalcite-like compound, and the raw materials of the composite adsorption material comprise, by mass:
activated carbon: 6.91 to 16.55 percent, 100 to 300 meshes, preferably 200 meshes;
FeCl 3 ·6H 2 O：14.90％-35.60％；
FeCl 2 ：5.52％-13.16％；
MgCl 2 ·6H 2 o: 26.97% -56.08%; and
AlCl 3 ·6H 2 O：7.89％-16.57％；
or
Activated carbon: 6.76 to 16.32 percent, 100 to 300 meshes, preferably 200 meshes;
FeCl 3 ·6H 2 O：14.92％-35.60％；
FeCl 2 ：5.41％-13.05％；
MgCl 2 ·6H 2 o: 26.54% -54.98%; and
FeCl 3 ·6H 2 O:8.81％-18.27％；
or
Activated carbon: 7.29 to 16.92 percent, 100 to 300 meshes, preferably 200 meshes;
FeCl 3 ·6H 2 O：15.75％-35.54％；
FeCl 2 ：5.83％-13.53％；
MgCl 2 ·6H 2 o: 27.52% -59.31%; and
MnCl 3 ·4H 2 O：5.48％-11.81％；
preferably, the method comprises the following steps:
activated carbon: 9.23 to 10.23 percent of the total weight of the mixture,
FeCl 3 ·6H 2 O：20.51％-21.51％，
FeCl 2 ：7.28％-8.28％，
MgCl 2 ·6H 2 o: 47.00-48.00%, and
AlCl 3 ·6H 2 O：13.50-14.50％；
or
Activated carbon: 9.04 to 10.04 percent of the total weight of the mixture,
FeCl 3 ·6H 2 O：20.10％-21.10％，
FeCl 2 ：7.13％-8.13％，
MgCl 2 ·6H 2 o: 46.06-47.06%, and
FeCl 3 ·6H 2 O：14.97-15.97％；
or
Activated carbon: 9.70 to 10.70 percent of the total weight of the mixture,
FeCl 3 ·6H 2 O：21.54％-22.54％，
FeCl 2 ：7.66％-8.66％，
MgCl 2 ·6H 2 o: 49.29-50.29%, and
MnCl 3 ·4H 2 O：9.41-10.41％。
6. the composite adsorption material according to any one of claims 1 to 4, wherein the hydrotalcite-like compound is a nickel-iron hydrotalcite-like compound, and the raw materials of the composite adsorption material comprise, by mass:
activated carbon: 6.18 to 15.62 percent, 100 to 300 meshes, preferably 200 meshes;
FeCl 3 ·6H 2 O：13.35％-33.75％；
FeCl 2 ：4.95％-12.50％；
FeCl 3 ·6H 2 o: 8.45% -16.72%; and
NiCl 2 ·6H 2 O：29.71％-58.79％；
preferably, the method comprises the following steps:
activated carbon: 8.36 to 9.36 percent, 100 to 300 meshes, preferably 200 meshes;
FeCl 3 ·6H 2 O：18.64％-19.64％；
FeCl 2 ：6.59％-7.59％；
FeCl 3 ·6H 2 o: 13.87 to 14.87 percent; and
NiCl 2 ·6H 2 O：50.07-51.07％。
7. a method for preparing the composite adsorption material of any one of claims 1 to 6, which is prepared from the raw materials, and sequentially comprises the following steps:
(1) dispersing the activated carbon in water to form an activated carbon dispersion liquid;
(2) adding FeCl into the active carbon dispersion liquid 3 ·6H 2 O、FeCl 2 And alkali liquor to obtain magnetic activated carbon;
(3) adding magnetic activated carbon into the solution of the synthetic hydrotalcite-like compound, and adding a catalyst containing the magnetic activated carbonNaOH and Na 2 CO 3 Adjusting the pH value of the solution to 10-11 to obtain a magnetic activated carbon-hydrotalcite like compound; the solution for synthesizing the hydrotalcite-like compound is MgCl-containing 2 And AlCl 3 Or a solution containing MgCl 2 And FeCl 3 Or a solution containing MgCl 2 And MnCl 3 Or a solution containing FeCl 3 And NiCl 2 The solution of (1);
(4) and roasting the magnetic activated carbon-hydrotalcite-like compound to obtain the composite adsorbing material.
8. The method according to claim 7, wherein the step (2) is specifically:
adding FeCl into the activated carbon dispersion liquid 3 ·6H 2 O and FeCl 2 In N at 2 Under protection and stirring, when the temperature is heated to 80-85 ℃, adding excessive alkali liquor to carry out in-situ precipitation reaction, and when no more solid is generated, separating the solid from the reaction liquid by using a permanent magnet to obtain the magnetic activated carbon.
9. The method according to claim 7 or 8, wherein the step (3) is specifically:
adding magnetic activated carbon into the solution of the synthetic hydrotalcite-like compound under the stirring of 600-1000rpm, and then adding NaOH and Na 2 CO 3 Performing in-situ precipitation reaction until the pH value of the reaction solution is 10-11, aging for 12h when the solid in the reaction solution is not increased any more, and separating the solid from the reaction solution by using a permanent magnet to obtain the magnetic activated carbon-hydrotalcite-like compound.
10. Use of the composite adsorbent material according to any one of claims 1 to 6 for preparing an adsorbent for iodine-131 from a radioactive waste liquid from nuclear medicine.
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