CN113171749B - Magnetic adsorbent for removing uranium plutonium nuclide, preparation method and application - Google Patents

Magnetic adsorbent for removing uranium plutonium nuclide, preparation method and application Download PDF

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CN113171749B
CN113171749B CN202110279471.0A CN202110279471A CN113171749B CN 113171749 B CN113171749 B CN 113171749B CN 202110279471 A CN202110279471 A CN 202110279471A CN 113171749 B CN113171749 B CN 113171749B
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magnetic adsorbent
uranium
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uranium plutonium
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CN113171749A (en
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杨爱丽
王志军
张晓阳
武俊红
杨鹏
朱玉宽
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002Solid 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
    • B01J20/28009Magnetic properties
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/12Processing by absorption; by adsorption; by ion-exchange
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00Energy generation of nuclear origin
    • Y02E30/30Nuclear fission reactors

Abstract

The invention discloses a magnetic adsorbent for removing uranium plutonium nuclide, which is prepared from hydrothermal carbon microspheres GC, graphene oxide GO and ferroferric oxide Fe 3 O 4 Compounding to form magnetic adsorbent GO/Fe 3 O 4 The GC has carboxyl, the GO has hydroxyl, the carboxyl on the GC is connected with the hydroxyl on the GO through a covalent bond, and the Fe 3 O 4 Distributed on the surface of GO; comprises the following components in parts by weight: 1 part of hydrothermal carbon microsphere GC, 1-2 parts of graphene oxide GO and Fe ferroferric oxide 3 O 4 1-2 parts. And a preparation method and application of the magnetic adsorbent. By adopting the magnetic adsorbent for removing the uranium plutonium nuclide, the preparation method and the application, the magnetic adsorbent has good adsorption effect on the uranium plutonium nuclide, is high in adsorption efficiency, and is convenient to separate from waste liquid.

Description

Magnetic adsorbent for removing uranium plutonium nuclide, preparation method and application
Technical Field
The invention relates to a magnetic adsorbent for removing uranium plutonium nuclide, a preparation method and application, and belongs to the technical field of nuclear waste liquid treatment.
Background
Uranium and plutonium are main components of nuclear fuels, are indispensable raw materials for nuclear energy development and utilization, occupy important positions in various fields such as nuclear energy power generation, national defense and military industry, radiation medical treatment, agricultural food and geological exploration, and have important research and application values. In the nuclear industry, a large amount of radioactive waste liquid is generated, and the nuclide uranium and plutonium are one of main components, so that how to efficiently remove the nuclide uranium and the nuclide plutonium and reduce the wastewater treatment cost as much as possible is one of the hot spots. The method for removing the uranium and plutonium from the radioactive wastewater is the adsorption technology which is the most widely applied method at present, has the characteristics of simplicity and convenience in operation, low cost, high efficiency, environmental friendliness and the like, and the selection and preparation of the novel economic and efficient adsorption material are key links in the technology.
The carbon material has important research significance as an adsorption separation material with good thermal stability, radiation resistance and acid-base tolerance. The hydrothermal carbon (HTC) material is a semi-carbonized substance prepared from monosaccharide or polysaccharide substances in a closed system at a certain temperature (170-350 ℃) and pressure by taking water as a reaction medium, and has wide carbon source sources, such as glucose, fructose, sucrose, starch, cellulose and other sugar substances, and has wide application prospects in the adsorption and separation technology of radionuclide-containing water bodies because the material has the advantages of environmental friendliness, low price, easiness in obtaining, simple preparation process and the like and contains active functional groups on the surface.
However, when HTC is used as an adsorbent for adsorbing and separating uranium and plutonium in radioactive wastewater, inherent defects such as insufficient number of oxygen-containing functional groups on the surface, single category, specific selective uranium adsorption, poor separation performance and the like still exist, so that a novel functional hydrothermal carbon material with specific selective adsorption and excellent performance for uranium and plutonium in wastewater needs to be prepared by means of surface grafting modification, functional group functionalization and the like, and has important guiding significance for providing theoretical basis for research and development of the functional hydrothermal carbon material with high performance, treatment of uranium and plutonium pollution in radioactive wastewater, uranium and plutonium resource recycling technology and sustainable development and application of nuclear energy nuclear power plant.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides the magnetic adsorbent for removing the uranium plutonium nuclide, the preparation method and the application.
The technical scheme adopted by the invention is as follows:
a magnetic adsorbent for removing uranium plutonium nuclide is prepared from hydrothermal carbon microspheres GC, graphene oxide GO and ferroferric oxide Fe 3 O 4 Compounding to form magnetic adsorbent GO/Fe 3 O 4 The GC has carboxyl, the GO has hydroxyl, the carboxyl on the GC is connected with the hydroxyl on the GO through a covalent bond, and the Fe 3 O 4 Distributed on the surface of GO.
In the invention, the hydrothermal carbon microsphere GC has carboxyl through carboxylation modification, can be compounded with hydroxylated graphene oxide under the action of a covalent bond, and is made of Fe 3 O 4 Carrying out magnetization modification. The graphene oxide GO has good adsorption capacity on uranium plutonium nuclide, the adsorption capacity of the hydrothermal carbon microsphere GC on the uranium plutonium nuclide is greatly enhanced after the hydrothermal carbon microsphere GC is subjected to carboxylation modification, and the adsorption capacity and the adsorption efficiency on the uranium plutonium nuclide can be further enhanced through the compounding of GO and GC; after the magnetic modification, the adsorbent can be conveniently and magnetically separated from the nuclear waste liquid.
A magnetic adsorbent for removing uranium plutonium species, comprising, in parts by weight: 1 part of hydrothermal carbon microsphere GC, 1-2 parts of graphene oxide GO and Fe ferroferric oxide 3 O 4 1-2 parts; GC. GO and Fe 3 O 4 Proportionally compounding to form magnetic adsorbent GO/Fe 3 O 4 /GC。
In the invention, by controlling the proportion of each component, on the basis of ensuring the solid-liquid separation effect, better adsorption effect and adsorption efficiency are obtained.
Preferably, the paint comprises the following components in parts by weight: 1 part of hydrothermal carbon microsphere GC, 1-2 parts of graphene oxide GO and Fe ferroferric oxide 3 O 4 1.4-1.6 parts.
Preferably, the hydrothermal carbon microspheres are carboxylated modified products of glucose obtained by hydrothermal synthesis and burning treatment.
In the scheme, glucose is used as a carbon source, and is modified through hydrothermal synthesis reaction and high-temperature burning treatment to obtain the carboxylated modified hydrothermal carbon microsphere GC of glucose, carboxyl groups are compounded with hydroxyl groups of graphene oxide, and the carboxylated modified hydrothermal carbon microsphere GC has rich oxygen-containing functional groups, so that the uranium plutonium adsorption effect and the uranium plutonium adsorption efficiency are improved.
Glucose is hydrothermally synthesized and burned to obtain carboxylic modified hydrothermal carbon microsphere GC, the carboxylic modified hydrothermal carbon microsphere GC is compounded with GO in ultrasonic waves, and finally, divalent iron salt and alkaline solution are added to carry out magnetization modification on the carboxylic modified hydrothermal carbon microsphere GC to obtain the magnetic adsorbent GO/Fe 3 O 4 /GC。
A method of making a magnetic adsorbent for removing uranium plutonium species, comprising the steps of:
step a: performing hydrothermal carbon microsphere GC and graphene oxide GO mixing according to the ratio of 1: 1-2, dispersing in deionized water and carrying out ultrasonic treatment for 2.5-3.5h to obtain a first solution;
step b: dripping an alkaline solution into the first solution, and adjusting the pH value to 10-12 to obtain a second solution;
step c: adding ferrous salt to the second solution in proportion to make Fe 3 O 4 Continuing stirring until the reaction is finished when GC is 1-2:1, washing and drying the precipitate to obtain a magnetic adsorbent GO/Fe 3 O 4 /GC。
Preferably, the step a is carried out by preparing GC: proportionally placing deionized water and glucose into a reaction kettle to react for 22-26h at the temperature of 180 ℃ and 220 ℃; and (3) after cooling, filtering, washing and vacuum drying, burning the product for 4-6h at the temperature of 300-400 ℃ to obtain the hydrothermal carbon microsphere GC.
Preferably, the step a is carried out by preparing GC: 50-70 parts of ionized water and 5-7 parts of glucose are placed in a reaction kettle to react for 22-26h at the temperature of 180 ℃ and 220 ℃; and (3) cooling, filtering, washing with deionized water, drying at 50-70 ℃ in vacuum, and then burning at 300-400 ℃ for 4-6h to obtain the hydrothermal carbon microsphere GC.
Preferably, step a adopts a Hummers method to prepare GO: according to the weight portion, 3-5 portions of graphite and 1-3 portions of NaNO are mixed 3 And 80-100 parts of H 2 SO 4 Mixing in ice bath, slowly adding 10-14 parts of KMnO while stirring 4 Controlling the adding speed to ensure that the temperature of the reaction solution is not higher than 20 ℃; removing ice bath, raising the temperature of the solution to about 30-40 ℃, keeping the temperature for 25-35min, slowly adding 160-200 parts of water, stirring for 25-35min, adding 300-400 parts of 0.05 wt% H 2 O 2 The solution is reacted; and centrifuging, washing and vacuum drying to obtain the graphene oxide GO.
Preferably, the ferrous salt is one or more of ferrous sulfate, ferrous chloride and ferrous nitrate.
Preferably, the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water.
The method also comprises the application of a magnetic adsorbent for removing uranium plutonium nuclide, wherein the magnetic adsorbent is used for removing the uranium plutonium nuclide in the nuclear waste liquid, adjusting the pH value of the nuclear waste liquid to be 5-6, and adding a magnetic adsorbent GO/Fe 3 O 4 and/GC, the magnetic adsorbent achieves a good uranium adsorption effect within 30min, and magnetic separation is carried out after adsorption is completed.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the adsorption effect on uranium and plutonium nuclides is good, the maximum removal rate of uranium nucleins reaches more than 99.5%, and the maximum removal rate of plutonium nuclides reaches more than 95%;
2. the adsorption efficiency on uranium plutonium nuclides is high, and the optimal adsorption effect can be achieved within 30 min;
3. the magnetic separation of the adsorbent from the nuclear waste liquid is easy.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is GO/Fe 3 O 4 A schematic structural diagram of/GC;
FIG. 2 is GO/Fe 3 O 4 A preparation process diagram of/GC;
FIG. 3 is a graph of the effect of pH on the effectiveness of the sorbent to remove uranium plutonium;
FIG. 4 is a graph of the adsorption effect versus adsorption time;
FIG. 5 is GO/Fe 3 O 4 And the treatment effects of the/GC and the GC on the nuclear waste liquid in actual production of different batches of nuclear industries are compared.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
A method of making a magnetic adsorbent for removing uranium plutonium species, comprising the steps of:
step a: dispersing 0.25g of GC and 0.25g of GO in 100ml of deionized water, and carrying out ultrasonic treatment for 3 hours to obtain a first solution;
step b: dripping 30% ammonia water into the first solution until the pH value is 11 to obtain a second solution;
step c: to the second solution was slowly added 1.26g of FeSO 4 ·7H 2 Continuously magnetically stirring the O until the reaction is finished, and washing and drying the O after magnetic separation to obtain the magnetic adsorbent GO/Fe 3 O 4 /GC。
Wherein the preparation process of GC is as follows: putting 60ml of ionized water and 6g of glucose into a reaction kettle to react for 24 hours at 180 ℃; and cooling, filtering and washing the product with deionized water until the filtrate is colorless, drying the product in vacuum at 60 ℃, and then burning the dried product at 300 ℃ for 5 hours to obtain powdery hydrothermal carbon microspheres GC.
The preparation process of GO comprises the following steps: 4g of graphite and 2g of NaNO 3 And 92g H 2 SO 4 Mixing in ice bath, adding 12g KMnO slowly while stirring 4 Controlling the adding speed to ensure that the temperature of the reaction solution is not higher than 20 ℃; removing ice bath to raise the temperature of the solution to about 35 deg.CStanding for 30min, slowly adding 184ml water, stirring for 30min, adding 340ml H with concentration of 0.05 wt% 2 O 2 The solution is reacted; and centrifuging the obtained brown product, washing with 10% HCl and deionized water, and vacuum drying at 40 ℃ to obtain graphene oxide GO.
Magnetic adsorbent GO/Fe obtained in the embodiment 3 O 4 in/GC, GO is Fe 3 O 4 Wherein GC is 1:1.4:1, carboxyl on GC is connected with hydroxyl on GO through covalent bond, Fe 3 O 4 Distributed on the surface of GO.
Example 2
Based on embodiment 1, the present embodiment is different from embodiment 1 in that: by adjusting the raw material addition ratio, the magnetic adsorbent GO/Fe obtained in the embodiment 3 O 4 in/GC, GO is Fe 3 O 4 :GC=1:1:1。
Example 3
Based on embodiment 1, the present embodiment is different from embodiment 1 in that: by adjusting the raw material addition ratio, the magnetic adsorbent GO/Fe obtained in the embodiment 3 O 4 in/GC, GO is Fe 3 O 4 :GC=1:2:1。
Example 4
Based on embodiment 1, the present embodiment is different from embodiment 1 in that: by adjusting the raw material addition ratio, the magnetic adsorbent GO/Fe obtained in the embodiment 3 O 4 in/GC, GO is Fe 3 O 4 :GC=1:1.5:1。
Example 5
Based on embodiment 1, the present embodiment is different from embodiment 1 in that: by adjusting the raw material addition ratio, the magnetic adsorbent GO/Fe obtained in the embodiment 3 O 4 in/GC, GO is Fe 3 O 4 :GC=1:1.6:1。
Example 6
Based on embodiment 1, the present embodiment is different from embodiment 1 in that: by adjusting the raw material addition ratio, the magnetic adsorbent GO/Fe obtained in this example 3 O 4 in/GC, GO is Fe 3 O 4 :GC=1:1.4:2。
The magnetic adsorbent obtained in the above embodiment is subjected to an adsorption performance test, 20mL of uranium plutonium solution with a certain initial concentration is measured and placed in a conical flask, the pH value is adjusted to a desired value by HCl or NaOH solution, a certain amount of adsorbent is added, the mixture is placed in a shaking table for oscillation adsorption and filtration, the uranium plutonium concentration in the filtrate is measured by using a trace uranium analyzer and a low background alpha measuring instrument, and the uranium plutonium removal rate R (%) is calculated by using formula (1).
R=[(c0-ct)/c0]×100% (1)
In the formula: c0 and ct (mg/L) are the initial concentration of uranium plutonium and the concentration at the adsorption time t, respectively.
As shown in figure 3, the magnetic adsorbent GO/Fe prepared by the invention 3 O 4 A graph of the change of the uranium plutonium nuclide removal rate of the/GC and the GC in a certain time under different pH values, wherein the curves in the graph are GO/Fe from top to bottom respectively 3 O 4 Removal rate curve of/GC to uranium, GO/Fe 3 O 4 A plutonium removal rate curve by GC, a uranium removal rate curve by GC, and a plutonium removal rate curve by GC. It can be seen that the pH value of the solution has obvious influence on the effect of removing uranium plutonium, the effect of removing uranium plutonium is obviously improved along with the increase of the pH value, and GO/Fe is added when the pH values respectively reach 5.0-6.0 3 O 4 The maximum adsorption effect is achieved by the aid of the/GC and the GC respectively, the maximum uranium removal rate is 96.25% and 63.21%, and the maximum plutonium removal rate is 94.44% and 68.70%. The results show that GO/Fe 3 O 4 The adsorption effect of the/GC is obviously higher than that of the GC, wherein GO/Fe 3 O 4 The PH value of the optimal uranium removal rate of the/GC is 5.0, the PH value of the optimal plutonium removal rate of the/GC is 6.0, and the GO/Fe is comprehensively obtained 3 O 4 The pH value of the optimum uranium plutonium removal rate of/GC is 5.0-6.0, and the optimum uranium plutonium removal rate of the/GC has good uranium plutonium nuclide removal rate at the pH value of 5.0-6.0.
GO/Fe 3 O 4 The optimal adsorption conditions for the initial concentration of 10mg/L uranium solution by/GC are: the pH value is 5, the adding amount is 0.15g/L, the adsorption time is 30min, the maximum uranium removal rate reaches more than 99.5 percent, and the maximum adsorption amount can reach 350 mg/g; the maximum removal rate of the nuclide plutonium in plutonium wastewater with an initial concentration of 20Bq/L was 95.07%.
As shown in FIG. 4, the magnetic adsorbent prepared by the present inventionGO/Fe 3 O 4 The graph shows the change of the removal rate of uranium plutonium nuclide by the aid of the/GC and the GC under different adsorption times, and the curves in the graph are respectively GO/Fe from top to bottom 3 O 4 A uranium removal rate curve of/GC, a uranium removal rate curve of GC, and GO/Fe 3 O 4 A plutonium removal rate curve by GC and a plutonium removal rate curve by GC. It can be seen that the adsorption time is on GO/Fe 3 O 4 The effect of uranium plutonium removal effect of/GC and GC is also more remarkable, compared with GO/Fe 3 O 4 the/GC can achieve a good uranium removing effect in a short time (within 30 min), and the uranium removing rate can reach 98.60%. GC is low in uranium removal rate, good adsorption effect can be achieved after more than 24 hours, the uranium removal rate can reach 97.08%, and GO/Fe 3 O 4 The uranium nuclein removal efficiency by/GC is faster. GO/Fe 3 O 4 The efficiency of removal of plutonium species by/GC and GC is slower, requiring more adsorption time, but GO/Fe 3 O 4 The adsorption effect and the adsorption efficiency of the/GC are still better than those of the GC, and GO/Fe is still better than that of the GC at 24h 3 O 4 The maximum plutonium removal rates of the/GC and GC were 95.07% and 77.07%, respectively.
As shown in FIG. 4, the magnetic adsorbent GO/Fe prepared by the invention 3 O 4 The comparative graph of the treatment effect of the GC and the GC on the actual production waste liquid of different batches of the nuclear industry is shown. It can be seen that for the initial uranium concentration C 0 0.3-3 mg/L of actual production wastewater sample, GO/Fe 3 O 4 The time required for achieving the optimal treatment effect by the GC and the GC is respectively 30min and 24h, and the treatment effect of the GO/Fe3O4/GC is superior to that of the GC; and GO/Fe 3 O 4 the/GC has good magnetism, and can realize simple, convenient and quick solid-liquid separation after adsorption.
For different Fe in the examples 3 O 4 Content of (2) ensuring magnetic adsorbent GO/Fe 3 O 4 the/GC has good adsorption performance and good magnetism, and can realize rapid magnetic separation. In the invention, GO is Fe 3 O 4 GC is 1-2:1-2:1, namely equivalent to Fe 3 O 4 The mass fraction of (A) is 25-50%; when Fe 3 O 4 When the mass fraction of (A) is less than 25%, the magnetic properties of the adsorbent are less favorable for the adsorbentSolid-liquid separation; when Fe 3 O 4 When the mass fraction of (B) is more than 50%, excessive Fe 3 O 4 Will occupy more active adsorption sites to make GO/Fe 3 O 4 The adsorption performance of/GC is lowered. In the invention, GO is Fe 3 O 4 GC-1: 2:1-2:1 can satisfy both adsorption performance and magnetic separation, and further, GO: Fe 3 O 4 When GC is 1-2:1.4-1.6:1, the adsorption performance and the magnetic separation effect are better.
Magnetic adsorbent GO/Fe prepared by the invention 3 O 4 the/GC has the characteristics of good stability, excellent adsorption performance, easy solid-liquid separation and the like. The preparation method is simple and feasible, economic and environment-friendly, the obtained product has strong magnetism, and the uranium plutonium loaded product is very easy to separate from a liquid phase, so that the treatment efficiency of the nuclear waste liquid is greatly improved.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.

Claims (10)

1. A magnetic adsorbent for removing uranium plutonium species, characterized by: the magnetic adsorbent is used for removing uranium plutonium nuclide in nuclear waste liquid, and is prepared from hydrothermal carbon microspheres GC, graphene oxide GO and ferroferric oxide Fe 3 O 4 Compounding to form magnetic adsorbent GO/Fe 3 O 4 The GC has carboxyl, the GO has hydroxyl, the carboxyl on the GC is connected with the hydroxyl on the GO through a covalent bond, and the Fe 3 O 4 Distributed on the surface of GO.
2. A magnetic adsorbent for the removal of uranium plutonium species as defined in claim 1, wherein: comprises the following components in parts by weight: 1 part of hydrothermal carbon microsphere GC, 1-2 parts of graphene oxide GO and Fe ferroferric oxide 3 O 4 1-2 parts; GC. GO and Fe 3 O 4 Proportionally compounding to form magnetic adsorbent GO/Fe 3 O 4 /GC。
3. A magnetic adsorbent for the removal of uranium plutonium species according to claim 1 or 2, characterized in that: the hydrothermal carbon microsphere is a carboxylated modified substance obtained by carrying out hydrothermal synthesis and firing treatment on glucose.
4. Method for the preparation of a magnetic adsorbent for the removal of uranium plutonium species as defined in claim 1, wherein: glucose is hydrothermally synthesized and burned to obtain carboxylation modified hydrothermal carbon microsphere GC, the carboxylation modified hydrothermal carbon microsphere GC is compounded with GO in ultrasonic waves, and finally, ferrous salt and alkaline solution are added to carry out magnetization modification on the composite to obtain a magnetic adsorbent GO/Fe 3 O 4 /GC。
5. Method for the preparation of a magnetic adsorbent for the removal of uranium plutonium species according to claim 4, characterized in that: the method comprises the following steps:
step a: performing hydrothermal carbon microsphere GC and graphene oxide GO treatment according to the ratio of 1: 1-2 parts by weight of the first solution are dispersed in deionized water and subjected to ultrasonic treatment for 2.5-3.5 hours to obtain a first solution;
step b: dripping alkaline solution into the first solution, and adjusting the pH value to 10-12 to obtain a second solution;
step c: adding ferrous salt into the second solution according to the mass part ratio to enable Fe 3 O 4 Continuing stirring until the reaction is finished when GC is 1-2:1, washing and drying the precipitate to obtain a magnetic adsorbent GO/Fe 3 O 4 /GC。
6. Method for the preparation of a magnetic adsorbent for the removal of uranium plutonium species according to claim 5, characterized in that: and (b) preparing GC by adopting a hydrothermal method in the step a: proportionally placing deionized water and glucose into a reaction kettle to react for 22-26h at the temperature of 180 ℃ and 220 ℃; and (3) after cooling, filtering, washing and vacuum drying, burning the product for 4-6h at the temperature of 300-400 ℃ to obtain the hydrothermal carbon microsphere GC.
7. Method for the preparation of a magnetic adsorbent for the removal of uranium plutonium species according to claim 5, characterized in that: in step aGO is prepared by a Hummers method: according to the weight portion, 3-5 portions of graphite and 1-3 portions of NaNO are mixed 3 And 80-100 parts of H 2 SO 4 Mixing in ice bath, slowly adding 10-14 parts of KMnO while stirring 4 Controlling the adding speed to ensure that the temperature of the reaction solution is not higher than 20 ℃; removing ice bath, raising the temperature of the solution to 30-40 ℃, keeping the temperature for 25-35min, slowly adding 160-200 parts of water, stirring for 25-35min, adding 300-400 parts of 0.05 wt% H 2 O 2 The solution is reacted; and centrifuging, washing and vacuum drying to obtain the graphene oxide GO.
8. Method for the preparation of a magnetic adsorbent for the removal of uranium plutonium species according to claim 4 or 5, characterized in that: the ferrous salt is one or more of ferrous sulfate, ferrous chloride and ferrous nitrate.
9. Method for the preparation of a magnetic adsorbent for the removal of uranium plutonium species according to claim 4 or 5, characterized in that: the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water.
10. Use of a magnetic adsorbent for removing uranium plutonium species, according to claim 1, for removing uranium plutonium species from nuclear effluents, characterized in that: adjusting pH of the nuclear waste liquid to 5-6, and adding magnetic adsorbent GO/Fe 3 O 4 and/GC, the magnetic adsorbent achieves a good uranium adsorption effect within 30min, and magnetic separation is carried out after adsorption is completed.
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