CN117299068B - Preparation method of copper-based carbon silicon material and application of copper-based carbon silicon material in adsorption of radioactive iodine - Google Patents
Preparation method of copper-based carbon silicon material and application of copper-based carbon silicon material in adsorption of radioactive iodine Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 120
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 100
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 42
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 34
- 239000011630 iodine Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 title abstract description 34
- 239000012876 carrier material Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 39
- 241000209094 Oryza Species 0.000 claims abstract description 38
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 38
- 235000009566 rice Nutrition 0.000 claims abstract description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002153 silicon-carbon composite material Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 229910009111 xH2 O Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 238000002715 modification method Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 42
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002901 radioactive waste Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0251—Compounds of Si, Ge, Sn, Pb
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- G21F9/02—Treating gases
-
- 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
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Abstract
The invention discloses a preparation method of a copper-based carbon silicon material and application thereof in adsorbing radioactive iodine, comprising the following steps: firstly, rice hulls are used as raw materials to prepare a carbon-silicon carrier material; and secondly, selecting a copper source, adopting a hydrothermal reduction method, taking ethylene glycol as an additive, and taking a carbon-silicon carrier material as a carrier to prepare the copper-based carbon-silicon composite material. The method takes the cheap rice hulls as silicon and carbon sources, copper nitrate as a copper source, adopts a hydrothermal reduction method to simply and efficiently synthesize the copper-based carbon-silicon composite material (Cu@CSI), and results show that the preparation method of the copper-based carbon-silicon material prepared by the preparation method of the copper-based carbon-silicon material provided by the invention has extremely high adsorption capacity on iodine gas, and provides a new material and a new method for radioactive gaseous iodine treatment.
Description
Technical Field
The invention belongs to the technical field of materials and radioactive waste treatment, and particularly relates to a preparation method of a copper-based carbon-silicon material and application of the copper-based carbon-silicon material in adsorbing radioactive iodine.
Background
A large amount of radioactive waste gas can be generated in the nuclear power operation and post-treatment process of spent fuel, so that the environmental safety and the human health are seriously threatened, and the nuclear power safety is a main problem. Wherein 129 I is an important volatile fission product, has the characteristics of long half-life (1.52×10 7 years), high toxicity, easiness in migration and diffusion in the environment and the like, and the problems of potential radiation hazard and biotoxicity caused by long-term accumulation are not negligible. Therefore, the trapping and the treatment of the radioactive gaseous iodine are important to the guarantee of nuclear safety in China.
The radioactive iodine gas has strong diffusion capability in any medium due to strong volatility, and is one of the radioactive waste gases which are acknowledged to be difficult to treat. At present, the treatment method of radioactive gaseous iodine mainly comprises wet washing and solid-phase adsorption. Among them, the solid-phase adsorption method is one of the important effective methods for trapping radioactive gaseous iodine. The main challenge faced by solid phase adsorption is the design and preparation of efficient adsorbents. Silver-based materials are considered to be good radioactive iodine adsorbents, and show certain advantages in adsorption capacity and stability, but the high cost, toxicity and the like of the silver-based materials greatly limit the practical application of the silver-based materials. In addition, most of the existing adsorbents have the problems of low adsorption quantity, high cost and the like. Based on the method, the novel iodine adsorbent with low development cost and good adsorption performance is a good strategy for realizing efficient treatment of radioactive gaseous iodine, and has important significance for enhancing sustainable development of nuclear energy.
The rice hulls are the leftovers in the rice production process and usually account for 20% of the mass of the rice, but most of the rice hulls are burnt due to low nutritive value, wide sources, large yield and low price, so that air pollution is caused, and resources are wasted greatly. As the rice hulls contain a large amount of SiO 2 and are in a network state in cellulose and lignin, the mechanical strength is better, and porous structures are easy to form on the surfaces of the rice hulls through means such as pyrolysis carbonization, chemical modification and the like. The biomass charcoal prepared from rice hulls has a special pore structure, large specific surface area, and rich-COOH, -OH and other organic functional groups on the surface, and is easy to functionalize or graft. Rice hulls are an inexpensive raw material for preparing carbon-silicon carrier materials.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing a copper-based carbon-silicon material, comprising the steps of:
Firstly, rice hulls are used as raw materials to prepare a carbon-silicon carrier material;
And secondly, selecting a copper source, adopting a hydrothermal reduction method, taking ethylene glycol as an additive, and taking a carbon-silicon carrier material as a carrier to prepare the copper-based carbon-silicon composite material.
Preferably, in the first step, the specific method for preparing the carbon-silicon carrier material by using rice hulls as raw materials comprises the following steps:
s11, soaking rice hulls in an HCl solution to remove impurities;
S12, washing the soaked rice hulls with deionized water and drying;
and S13, placing the purified rice hulls in a tube furnace to be sintered in the N 2 atmosphere, and obtaining the carbon-silicon carrier material.
Preferably, in the step S11, the mass volume ratio of the rice husk to the HCl solution is 1-20 g:10-30 mL.
Preferably, in S11, the concentration of the HCl solution is 0.5 to 1M, and the soaking time is 12 to 48 hours.
Preferably, in S13, the sintering temperature of the rice hulls in the tube furnace is 500-900 ℃ and the sintering time is 1-6 h.
Preferably, the specific method of the second step includes:
S21, dissolving copper nitrate Cu (NO 3)2·xH2 O in ethanol, and fully stirring to obtain a blue solution I;
s22, adding a carbon-silicon carrier material into the solution I to form a solution II;
s23, adding glycol into the solution II, and stirring for a certain time to form a mixture;
s24, transferring the mixture into a hydrothermal reaction kettle, and performing hydrothermal treatment for a certain time;
and S25, finally, fully washing the copper-based carbon-silicon composite material by ethanol and deionized water.
Preferably, the mass volume ratio of the copper nitrate Cu (NO 3)2·xH2 O, ethanol, glycol and carbon silicon carrier material is 0-1.5 g:10-20 mL:6-12 mL:0.9-120 g).
Preferably, in S23, the stirring time is 1 to 8 hours.
Preferably, in S24, the hydrothermal temperature is 120-200 ℃ and the hydrothermal time is 2-8 h.
The capability of the copper-based carbon-silicon composite material prepared by taking the carbon-silicon carrier material as a raw material for capturing gaseous iodine also has a lifting space, and in order to improve the capability of the copper-based carbon-silicon composite material for capturing gaseous iodine, the carbon-silicon carrier material in the first step is replaced by a modified carbon-silicon carrier material, and the modification method of the modified carbon-silicon carrier material comprises the following steps:
Pouring a carbon-silicon carrier material into a reaction container, adding dimethylbenzene and sodium methacrylate into the reaction container, introducing nitrogen, heating to 90-130 ℃ under the nitrogen atmosphere, stirring for reaction for 8-10 h, performing solid-liquid separation after the reaction, washing with deionized water for multiple times, and performing vacuum freeze-drying to obtain solid powder A, wherein the temperature of vacuum freeze-drying is-60 to-30 ℃, the vacuum degree of vacuum freeze-drying is 1.1-2.5 Pa, and the vacuum freeze-drying time is 1-4 h;
and B, adding the solid powder A into polytetrafluoroethylene emulsion, stirring to obtain mixed slurry, adding a polydimethyldiallyl ammonium chloride aqueous solution into the mixed slurry, performing ultrasonic dispersion at a frequency of 25-80 kHz for 30-60 min, standing for 2-4 h, performing solid-liquid separation to obtain solid powder B, washing with deionized water for multiple times, and drying at 80-120 ℃ to obtain the modified carbon silicon carrier material, wherein the mass fraction of the polydimethyldiallyl ammonium chloride aqueous solution is 5-13%.
Preferably, in the step A, the mass volume ratio of the carbon-silicon carrier material, the dimethylbenzene and the sodium methacrylate is 2-20 g:20-150 mL:1-15 mg;
In the step B, the mass volume ratio of the solid powder to the polytetrafluoroethylene emulsion to the polydimethyldiallyl ammonium chloride solution is 1-10 mg/30-250 mL/20-200 mL.
The application of the copper-based carbon-silicon material is that the copper-based carbon-silicon material is applied to the trapping of radioactive iodine.
The invention at least comprises the following beneficial effects:
1. the cost is low: copper is far cheaper than silver. In addition, inexpensive Carbon Silicon (CSi) carrier materials can be obtained by a simple low-temperature sintering method using inexpensive rice hulls as raw materials. Therefore, the Cu@CSI material disclosed by the invention is far lower in cost than silver-based adsorption materials and other similar materials.
2. The iodine adsorption amount is large: the iodine adsorption amount of the copper-based carbon-silicon composite (Cu@CSI) material prepared by the method is up to 840+/-68 mg/g, which is far higher than that of a silver-based material with high price.
3. The operation is simple and efficient: rice husk is used as raw material, and Carbon Silicon (CSI) carrier material is obtained after simple sintering. The simple hydrothermal reduction method is adopted, copper nitrate is used as a copper source, and the copper-based carbon-silicon composite (Cu@CSI) material can be simply and efficiently synthesized.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an XRD pattern of the copper-based carbon-silicon materials prepared in examples 1 and 2, the CSI material prepared in comparative example 1, and the copper-based material prepared in comparative example 2;
FIG. 2 is an XRD pattern of the 50% Cu@CSI material prepared in example 2 before and after adsorption of iodine;
FIG. 3 shows the adsorption amounts of iodine at different temperatures of the copper-based carbon-silicon materials prepared in examples 1 and 2, the CSI material prepared in comparative example 1, and the copper-based material prepared in comparative example 2;
Fig. 4 shows the adsorption amounts of iodine at different temperatures for the copper-based carbon-silicon materials prepared in example 1, example 2 and example 3, the CSi material prepared in comparative example 1 and the copper-based material prepared in comparative example 2.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
The embodiment provides a preparation method of a copper-based carbon silicon material, which comprises the following steps:
step one, taking rice hulls as raw materials to prepare a carbon-silicon carrier material, which specifically comprises the following steps:
S11, placing 100g of rice hulls in 1500mL of 1M HCl solution for soaking for 24 hours to remove impurities;
S12, washing the soaked rice hulls with deionized water and drying;
S13, placing the purified rice hulls in a tube furnace, and sintering at 600 ℃ for 2 hours in an atmosphere of N 2 to obtain a carbon-silicon carrier material;
selecting a copper source, adopting a hydrothermal reduction method, taking ethylene glycol as an additive, taking a carbon-silicon carrier material as a carrier, and preparing the copper-based carbon-silicon composite material, wherein the preparation method specifically comprises the following steps of:
s21, dissolving 0.885g of copper nitrate Cu (NO 3)2·xH2 O in 16mL of ethanol, and fully stirring to obtain a blue solution I;
s22, adding 95g of carbon-silicon carrier material into the solution I to form a solution II;
S23, adding 8mL of ethylene glycol into the solution II, and stirring for a certain time to form a mixture;
s24, transferring the mixture into a hydrothermal reaction kettle, and performing hydrothermal treatment for 4 hours at 160 ℃;
And S25, finally, fully washing the copper-based carbon-silicon composite material by ethanol and deionized water to obtain the copper-based carbon-silicon composite material, wherein the copper-based carbon-silicon composite material is marked as 30% Cu@CSI.
Example 2
The embodiment provides a preparation method of a copper-based carbon silicon material, which comprises the following steps:
step one, taking rice hulls as raw materials to prepare a carbon-silicon carrier material, which specifically comprises the following steps:
S11, placing 100g of rice hulls in 1500mL of 1M HCl solution for soaking for 24 hours to remove impurities;
S12, washing the soaked rice hulls with deionized water and drying;
S13, placing the purified rice hulls in a tube furnace, and sintering at 600 ℃ for 2 hours in an atmosphere of N 2 to obtain a carbon-silicon carrier material;
selecting a copper source, adopting a hydrothermal reduction method, taking ethylene glycol as an additive, taking a carbon-silicon carrier material as a carrier, and preparing the copper-based carbon-silicon composite material, wherein the preparation method specifically comprises the following steps of:
S21, 1.476g of copper nitrate Cu (NO 3)2·xH2 O is dissolved in 16mL of ethanol, and the mixture is fully stirred to obtain a blue solution I;
S22, adding 117.5g of carbon-silicon carrier material into the solution I to form a solution II;
S23, adding 8mL of ethylene glycol into the solution II, and stirring for a certain time to form a mixture;
s24, transferring the mixture into a hydrothermal reaction kettle, and performing hydrothermal treatment for 4 hours at 160 ℃;
And S25, finally, fully washing the copper-based carbon-silicon composite material by ethanol and deionized water to obtain the copper-based carbon-silicon composite material, wherein the copper-based carbon-silicon composite material is marked as 50% Cu@CSI.
Example 3
The copper-based carbon-silicon composite material prepared by taking the carbon-silicon carrier material as a raw material also has a lifting space for the trapping capacity of gaseous iodine, in order to improve the trapping capacity of the copper-based carbon-silicon composite material for gaseous iodine, the carbon-silicon carrier material in the first embodiment is replaced by a modified carbon-silicon carrier material, and other preparation methods and parameters are the same as those in embodiment 2, and the modification method of the modified carbon-silicon carrier material comprises the following steps:
Pouring 10g of carbon-silicon carrier material into a reaction container, adding 80mL of dimethylbenzene and 10mg of sodium methacrylate into the reaction container, introducing nitrogen, heating to 110 ℃ under the nitrogen atmosphere, stirring for reaction for 8 hours, performing solid-liquid separation after the reaction, washing with deionized water for multiple times, and performing vacuum freeze-drying to obtain solid powder A, wherein the temperature of vacuum freeze-drying is-30 ℃, the vacuum degree of vacuum freeze-drying is 1.1Pa, and the vacuum freeze-drying time is 2 hours;
And B, adding 5g of solid powder A into 250mL of polytetrafluoroethylene emulsion, stirring to obtain mixed slurry, adding 150mL of polydimethyldiallyl ammonium chloride aqueous solution with mass fraction of 8%, ultrasonically dispersing at a frequency of 40kHz for 30min, standing for 2h, performing solid-liquid separation to obtain solid powder B, washing with deionized water for multiple times, and drying at 90 ℃ to obtain the modified carbon silicon carrier material.
The copper-based carbon-silicon material prepared in this example was recorded as 50% Cu@CSI-1.
Example 4
This example provides a method for preparing a copper-based carbon-silicon material, which differs from example 2 in that a modified carbon-silicon carrier material is used instead of a carbon-silicon carrier material, and the remaining process parameters are the same as example 2.
The modification method of the modified carbon silicon carrier material comprises the following steps:
step A, pouring 20g of carbon-silicon carrier material into a reaction container, adding 150mL of dimethylbenzene and 15mg of sodium methacrylate into the reaction container, introducing nitrogen, heating to 120 ℃ under the nitrogen atmosphere, stirring and reacting for 8 hours, finishing solid-liquid separation, washing with deionized water for multiple times, and vacuum freeze-drying to obtain solid powder A, wherein the vacuum freeze-drying temperature is-60 ℃, the vacuum degree of vacuum freeze-drying is 2.1Pa, and the vacuum freeze-drying time is 4 hours;
And B, adding 10g of solid powder A into 250mL of polytetrafluoroethylene emulsion, stirring to obtain mixed slurry, adding 200mL of polydimethyldiallyl ammonium chloride aqueous solution with the mass fraction of 10%, performing ultrasonic dispersion at the frequency of 80kHz for 60min, standing for 4h, performing solid-liquid separation to obtain solid powder B, washing with deionized water for multiple times, and drying at the temperature of 100 ℃ to obtain the modified carbon silicon carrier material.
The copper-based carbon-silicon material prepared in this example was recorded as 50% Cu@CSI-2.
Comparative example 1
The comparative example provides a preparation method of a CSI material, which comprises the following steps:
step one, taking rice hulls as raw materials to prepare a carbon-silicon carrier material, which specifically comprises the following steps:
S11, placing 100g of rice hulls in 1500mL of 1M HCl solution for soaking for 24 hours to remove impurities;
S12, washing the soaked rice hulls with deionized water and drying;
S13, placing the purified rice hulls in a tube furnace, and sintering at 600 ℃ for 2 hours in an atmosphere of N 2 to obtain a carbon-silicon carrier material;
step two, taking a carbon-silicon carrier material as a raw material to prepare the CSI material, which comprises the following steps:
s21, adding 0.9g of carbon-silicon carrier material into 16mL of ethanol, and fully stirring to obtain a solution;
s22, adding 8mL of ethylene glycol into the solution, and stirring for a certain time to form a mixture;
s23, transferring the mixture into a hydrothermal reaction kettle, and performing hydrothermal treatment for 4 hours at 160 ℃;
and S24, finally, fully washing the material by ethanol and deionized water to obtain the CSI material.
Comparative example 2
The comparative example provides a method for preparing a copper-based material, comprising the following steps:
S21, dissolving 0.295g of copper nitrate Cu (NO 3)2·xH2 O in 16mL of ethanol, and fully stirring to obtain a blue solution I;
S22, adding 117.5g of carbon-silicon carrier material into the solution I to form a solution II;
S23, adding 8mL of ethylene glycol into the solution II, and stirring for a certain time to form a mixture;
s24, transferring the mixture into a hydrothermal reaction kettle, and performing hydrothermal treatment for 4 hours at 160 ℃;
And S25, finally, fully washing the copper-based material by ethanol and deionized water to obtain the copper-based material, wherein the copper-based material is marked as 10% Cu@CSI.
Comparative example 3
This comparative example provides a method for preparing a copper-based carbon-silicon material, which is different from example 2 in that a modified carbon-silicon carrier material is used instead of the carbon-silicon carrier material, and the remaining process parameters are the same as example 2.
The modification method of the modified carbon silicon material comprises the following steps:
Pouring 10g of carbon-silicon carrier material into a reaction vessel, adding 80mL of dimethylbenzene and 10mg of sodium methacrylate into the reaction vessel, introducing nitrogen, heating to 110 ℃ under the nitrogen atmosphere, stirring for reaction for 8 hours, finishing solid-liquid separation, washing with deionized water for multiple times, and vacuum freeze-drying to obtain the modified carbon-silicon carrier material, wherein the vacuum freeze-drying temperature is-30 ℃, the vacuum degree of vacuum freeze-drying is 1.1Pa, and the vacuum freeze-drying time is 2 hours.
The copper-based carbon-silicon material prepared in this example was recorded as 50% Cu@CSI-3.
Comparative example 4
This comparative example provides a method for preparing a copper-based carbon-silicon material, which is different from example 2 in that a modified carbon-silicon carrier material is used instead of the carbon-silicon carrier material, and the remaining process parameters are the same as example 2.
The modification method of the modified carbon silicon material comprises the following steps:
Adding 5g of carbon-silicon carrier material into 250mL of polytetrafluoroethylene emulsion, stirring to obtain mixed slurry, adding 150mL of polydimethyldiallyl ammonium chloride aqueous solution with mass fraction of 8%, performing ultrasonic dispersion at a frequency of 40kHz for 30min, standing for 2h, performing solid-liquid separation to obtain solid powder B, washing with deionized water for multiple times, and drying at 90 ℃ to obtain the modified carbon-silicon carrier material.
The copper-based carbon-silicon material prepared in this example was recorded as 50% Cu@CSI-4.
Iodine gas adsorption assays were performed using the copper-based carbon-silicon materials prepared in example 1 and example 2, the CSi material prepared in comparative example 1, and the copper-based material prepared in comparative example 2, respectively, by the following adsorption methods:
A. weighing a certain amount of elemental iodine and placing the elemental iodine into a corundum tank (450 ml);
B. a quantity of cu@csi material m 0 is placed in a small crucible (5 ml);
C. placing a small crucible containing Cu@CSI material into a corundum tank, and covering a cover of the corundum tank;
C. Placing the corundum tank in an oven, preserving heat for different times at different temperatures (100 ℃, 150 ℃ and 200 ℃) and testing the iodine adsorption performance of the Cu@CSI material;
D. The adsorption quantity is determined by a weighing method, the mass m t of the material after adsorption is weighed, and the calculation formula of the adsorption quantity Q (mg/g) is as follows:
Fig. 1 is an XRD pattern of the copper-based carbon-silicon materials prepared in example 1 and example 2, the CSi material prepared in comparative example 1, and the copper-based material prepared in comparative example 2. Comparing the XRD patterns of the different Cu-loaded materials, it can be seen that the characteristic diffraction peak intensities of Cu and Cu 2 O are enhanced as the Cu-loaded amount is increased. The result shows that the method can be used for successfully synthesizing the copper-based carbon silicon (Cu@CSI) material.
Fig. 2 is an XRD pattern before and after iodine adsorption of 50% cu@csi material prepared in example 2. As shown in FIG. 2, characteristic peaks of Cu and Cu 2 O can be observed in the XRD spectrum of the sample before iodine is adsorbed, and the characteristic peaks of Cu and Cu 2 O in the XRD spectrum of the material after iodine is adsorbed disappear, and a characteristic peak of CuI appears, which indicates that the adsorption of the Cu@CSI material to iodine is mainly chemical reaction, and the adsorption mechanism is that Cu and Cu 2 O chemically react with I 2 to generate CuI.
Fig. 3, 4 and the following table show the adsorption performance of copper-based carbon-silicon materials (cu@csi) with different copper loadings for iodine at different temperatures. As can be seen from FIGS. 3, 4 and the following tables, the adsorption amounts of pure CSi material to iodine at 100deg.C, 150deg.C and 200deg.C are 380+ -40, 392+ -46 and 368+ -50 mg/g, respectively; the iodine adsorption amounts of the Cu@CSI are 380+/-40, 392+/-46 and 368+/-50 mg/g respectively; iodine adsorption amounts of 30% Cu@CSI are 406+/-45, 418+/-40 and 432+/-55 mg/g respectively; iodine adsorption amounts of 50% Cu@CSI are 706+/-54, 820+/-62 and 840+/-68 mg/g respectively, and 50% Cu@CSI-1 and 50% Cu@CSI-2 using the modified carbon silicon carrier materials can reach 933+/-51 mg/g and 926+/-42 mg/g at most. The results show that the adsorption temperature and copper loading have a large influence on the iodine adsorption performance of cu@csi. The cu@csi material prepared in example 2 had an adsorption amount of up to 840±68mg/g for iodine, which was higher than that of example 1, which was much higher than that of comparative examples 1 to 4, and the copper-supported copper-based carbon silicon material prepared in examples 3 to 4 by using the modified carbon silicon support material had an adsorption amount of up to 50% of cu@csi prepared in example 2.
Iodine adsorption performance of surface copper-based carbon silicon material (Cu@CSI)
The number of equipment and the scale of processing described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be readily apparent to those skilled in the art.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (9)
1. The preparation method of the copper-based carbon silicon material is characterized by comprising the following steps of:
Firstly, rice hulls are used as raw materials to prepare a carbon-silicon carrier material;
Selecting a copper source, adopting a hydrothermal reduction method, taking ethylene glycol as an additive, and taking a carbon-silicon carrier material as a carrier to prepare a copper-based carbon-silicon composite material;
In the first step, rice hulls are used as raw materials, and the specific method for preparing the carbon-silicon carrier material comprises the following steps:
s11, soaking rice hulls in an HCl solution to remove impurities;
S12, washing the soaked rice hulls with deionized water and drying;
S13, sintering the purified rice hulls in a tube furnace under the atmosphere of N 2 to obtain a carbon-silicon carrier material;
The carbon-silicon carrier material is modified, and the modification method comprises the following steps:
pouring a carbon-silicon carrier material into a reaction container, adding dimethylbenzene and sodium methacrylate into the reaction container, introducing nitrogen, heating to 90-130 ℃ in a nitrogen atmosphere, stirring for reaction for 8-10 hours, performing solid-liquid separation after the reaction, washing with deionized water for multiple times, and performing vacuum freeze-drying to obtain solid powder A, wherein the temperature of vacuum freeze-drying is-60 to-30 ℃, the vacuum degree of vacuum freeze-drying is 1.1-2.5 Pa, and the vacuum freeze-drying time is 1-4 hours;
Adding the solid powder A into polytetrafluoroethylene emulsion, stirring to obtain mixed slurry, adding a polydimethyldiallyl ammonium chloride aqueous solution into the mixed slurry, performing ultrasonic dispersion at a frequency of 25-80 kHz for 30-60 min, standing for 2-4 h, performing solid-liquid separation to obtain solid powder B, washing with deionized water for multiple times, and drying at 80-120 ℃ to obtain a modified carbon silicon carrier material, wherein the mass fraction of the polydimethyldiallyl ammonium chloride aqueous solution is 5-13%;
in the step A, the mass volume ratio of the carbon-silicon carrier material, the dimethylbenzene and the sodium methacrylate is 2-20 g, 20-150 mL and 1-15 mg;
In the step B, the mass volume ratio of the solid powder, the polytetrafluoroethylene emulsion and the polydimethyldiallyl ammonium chloride solution is 1-10 mg, 30-250 mL and 20-200 mL.
2. The method for preparing the copper-based carbon-silicon material according to claim 1, wherein in the step S11, the mass-volume ratio of rice husk to HCl solution is 1-20 g and 10-30 mL.
3. The method for preparing a copper-based carbon-silicon material according to claim 1, wherein in the step S11, the concentration of HCl solution is 0.5-1M, and the soaking time is 12-48 h.
4. The method for preparing a copper-based carbon-silicon material according to claim 1, wherein in the step S13, the sintering temperature of rice hulls in a tube furnace is 500-900 ℃ and the sintering time is 1-6 h.
5. The method for preparing a copper-based carbon-silicon material according to claim 1, wherein the specific method of the second step comprises:
S21, dissolving copper nitrate Cu (NO 3)2·xH2 O in ethanol, and fully stirring to obtain a blue solution I;
s22, adding a carbon-silicon carrier material into the solution I to form a solution II;
s23, adding glycol into the solution II, and stirring for a certain time to form a mixture;
s24, transferring the mixture into a hydrothermal reaction kettle, and performing hydrothermal treatment for a certain time;
and S25, finally, fully washing the copper-based carbon-silicon composite material by ethanol and deionized water.
6. The method for preparing the copper-based carbon-silicon material according to claim 5, wherein the mass-volume ratio of the copper nitrate Cu (NO 3)2· xH2 O, ethanol, ethylene glycol and carbon-silicon carrier material is 0-1.5 g, 10-20 mL, 6-12 mL and 0.9-120 g, and the mass of the copper nitrate Cu (NO 3)2·xH2 O is not equal to 0).
7. The method for preparing a copper-based carbon-silicon material according to claim 5, wherein in the step S23, the stirring time is 1-8 hours.
8. The method for preparing a copper-based carbon-silicon material according to claim 5, wherein in the step S24, the hydrothermal temperature is 120-200 ℃ and the hydrothermal time is 2-8 hours.
9. The use of a copper-based carbon-silicon material prepared by the method for preparing a copper-based carbon-silicon material according to any one of claims 1 to 5, characterized in that the copper-based carbon-silicon material is used for trapping radioactive iodine.
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