阅读说明：本技术 一种用于去除铀的甘草基复合物及其制备方法和应用 (Glycyrrhiza-based compound for removing uranium and preparation method and application thereof ) 是由 段涛 王泽儒 曹亚兰 程敬开 朱琳 于 2021-07-26 设计创作，主要内容包括：本发明提出了一种用于去除铀的甘草基复合物,所述用于去除铀的甘草基复合物包括甘草粉末及Fe-(2)O-(3)的负载于甘草粉末上的Fe-(2)O-(3),所述Fe-(2)O-(3)包覆于甘草粉末上,所述Fe-(2)O-(3)为α-Fe-(2)O-(3),由于Fe-(2)O-(3)的较快的吸附平衡时间,从而使甘草基复合物可以在短时间内与六价铀快速反应,进而使用于去除铀的甘草基复合物对铀具有较高的去除率,且在模拟人体环境下对铀有很较高的选择性,同时,本发明还提出了一种用于去除铀的甘草基复合物的制备方法,且上述用于去除铀的甘草基复合物的制备方法简单且环保无污染。(The invention provides a licorice-based compound for removing uranium, which comprises licorice powder and Fe 2 O 3 Fe supported on licorice powder 2 O 3 Said Fe 2 O 3 Coating the powder of radix Glycyrrhizae with Fe 2 O 3 Is alpha-Fe 2 O 3 Due to Fe 2 O 3 The adsorption equilibrium time is short, so that the liquorice-based compound can quickly react with hexavalent uranium in a short time, and the liquorice-based compound is used for removing uraniumThe method has high uranium removal rate and high uranium selectivity under a simulated human body environment, and meanwhile, the invention also provides a preparation method of the licorice-based compound for removing uranium, and the preparation method of the licorice-based compound for removing uranium is simple, environment-friendly and pollution-free.)

1. A licorice-based composition for uranium removal, comprising: the licorice-based compound for removing uranium comprises licorice powder and Fe₂O₃Fe supported on the licorice powder₂O₃Said Fe₂O₃Coating the radix Glycyrrhizae powder.

2. A licorice-based composition for uranium removal according to claim 1, wherein: said Fe₂O₃Is alpha-Fe₂O₃。

3. A method for preparing a licorice-based composition for uranium removal according to claims 1 to 2, wherein: the preparation method of the licorice-based compound for removing uranium comprises the following steps:

stirring and grinding liquorice into liquorice powder in a grinding machine;

FeCl is added₃Fully dissolving in ethanol, adding NaOH, stirring at room temperature for 1h to obtain a yellow brown suspension, and adding FeCl₃Continuously stirring the liquorice powder according to a certain mass ratio until the liquorice powder and the suspension are uniformly mixed to prepare a mixed solution;

and transferring the mixed solution into a high-pressure reaction kettle, reacting for a certain time at a certain temperature, filtering, washing and drying at 60 ℃ for 24 hours after the reaction is finished to obtain the licorice-based compound for removing uranium.

4. A method of preparing a licorice-based composition for uranium removal as claimed in claim 3, wherein: stirring and grinding liquorice into liquorice powder in a grinding machine, and specifically, screening the liquorice powder to obtain the liquorice powder with different meshes and liquorice slag for later use.

5. A method of preparing a licorice-based composition for uranium removal as claimed in claim 4, wherein: the mesh number of the sieve is 80.5-200 meshes.

6. A method of preparing a licorice-based composition for uranium removal as claimed in claim 3, wherein: the FeCl is₃Fully dissolved in ethanol, specifically, 0.565g to 2.26g of FeCl₃Fully dissolving in 80-100 mL of ethanol.

7. A method of preparing a licorice-based composition for uranium removal as claimed in claim 3, wherein: the mass of the added NaOH is 0.4 g-1.6 g.

8. A method of preparing a licorice-based composition for uranium removal as claimed in claim 3, wherein: the licorice powder and the FeCl₃The mass ratio of (A) to (B) is 0.5 to 2.

9. A method of preparing a licorice-based composition for uranium removal as claimed in claim 3, wherein: the temperature is 140-160 ℃, and the time is 1-3 h.

10. Use of a licorice-based composition according to claims 1-2 for uranium removal, wherein: the licorice-based compound for removing uranium can adsorb uranium in human body.

Technical Field

The invention relates to a Chinese herbal medicine-based compound, in particular to a liquorice-based compound for removing uranium and a preparation method and application thereof.

Background

With the rapid development of nuclear power industry, the nuclear safety problem brought by the nuclear power industry becomes more and more prominent, and due to frequent nuclear accidents, the nuclear safety protection is highly emphasized.

The Su Unichernobilel nuclear accident and the Japanese Fukushima nuclear accident are two nuclear accidents with the most serious harm and the widest spread in history, and release a large amount of radioactive nuclides to the environment. The radionuclides such as uranium, thorium, plutonium and the like have long half-life period, and once being introduced into a human body, the radionuclides with strong radioactivity and high metal chemical toxicity can generate internal irradiation and chemical damage to tissues and organs of the human body, and cause tissue lesion over time. The most abundant radionuclide generated by these nuclear accidents is uranium, which is an actinide and is a very important nuclear fuel. Natural uranium exists in natural soils and rocks and is derived from radioactive isotopes²³⁴U(0.005％)、²³⁵U(0.720％)、²³⁸U (99.27%) in the material remaining after the natural uranium has been concentrated²³⁵Uranium with a lower U content than natural uranium is called depleted uranium and is a main raw material for preparing nuclear weapons such as dirty bombs and depleted uranium bombs. A large amount of depleted uranium dust can be generated after the depleted uranium bomb explodes, can be absorbed by local residents and soldiers in battle in a large amount, and meanwhile, uranium is introduced into the body in a wound or ingestion mode, deposited in the body and generates internal irradiation and toxic damage. Causing joint myalgia and low immunity of soldiers in battle and local residents, and greatly increasing the proportion of diseases such as cancers, tumors, renal failure, uremia and the like.

The most effective medical treatment currently used is chemochelation therapy (abbreviated as "nuclide excretion"): the medicament which can be effectively chelated with the radionuclide is taken, and the medicament promotes the excretion of the ligand and competes with human protein, phosphate and the like to chelate the radionuclide to form a stable soluble complex, so that the excretion speed of the radionuclide through urine, feces and the like is increased, and the acute radiation injury, chemical toxicity and long-term irradiation effect of the radionuclide in a human body are reduced. However, the research of radionuclide chelators has been slow in three decades, and no chelator or excretion promoter having good biocompatibility and high efficiency for chelating radionuclides is available.

Disclosure of Invention

In view of the above technical problems, the present invention needs to provide a glycyrrhiza based composite for uranium removal, which has strong removing ability and high biocompatibility, and a preparation method and an application thereof.

A licorice-based composition for uranium removal, the licorice-based composition for uranium removal comprising licorice powder and Fe₂O₃Fe supported on licorice powder₂O₃Said Fe₂O₃Is coated on Glycyrrhrizae radix powder.

Further, said Fe₂O₃Is alpha-Fe₂O₃。

A preparation method of a licorice-based compound for removing uranium comprises the following steps:

stirring and grinding liquorice into liquorice powder in a grinding machine;

FeCl is added₃Fully dissolving in ethanol, adding NaOH, stirring at room temperature for 1h to obtain yellow brown suspension, adding FeCl₃Continuously stirring the liquorice powder in a certain mass ratio until the liquorice powder and the suspension are uniformly mixed to prepare a mixed solution;

and transferring the mixed solution into a high-pressure reaction kettle, reacting for a certain time at a certain temperature, filtering, washing and drying at 60 ℃ for 24 hours after the reaction is finished to obtain the licorice-based compound for removing uranium.

Further, stirring and grinding the liquorice into liquorice powder in a grinding machine, and specifically, screening the liquorice powder to obtain the liquorice powder with different meshes and liquorice slag for later use.

Furthermore, the mesh number of the screen is 80.5-200 meshes.

Further, the method comprises the step of adding FeCl₃Fully dissolved in ethanol, specifically, 0.565g to 2.26g of FeCl₃Fully dissolving in 80-100 mL of ethanol.

Further, licorice powder and FeCl₃The mass ratio of (A) to (B) is 0.5 to 2.

Further, the temperature is 140-160 ℃, and the time is 1-3 h.

Application of a licorice-based compound for removing uranium is disclosed, wherein the licorice-based compound for removing uranium can be used for carrying out adsorption treatment on uranium in a human body.

The licorice-based compound for removing uranium is prepared by coating Fe on the surface of licorice by a solvothermal method₂O₃Due to Fe₂O₃The quick adsorption balance time, thereby the liquorice-based compound can rapidly react with hexavalent uranium in a short time, and then the liquorice-based compound used for removing uranium has higher removal rate to uranium, and has higher selectivity to uranium under the simulated human environment. Meanwhile, the preparation method of the licorice-based compound for removing uranium is simple, environment-friendly and pollution-free.

Drawings

FIG. 1 is a scanning electron microscope image of the field emission of the licorice-based composition for uranium removal of the present invention.

Fig. 2 is a flow chart of a method for preparing a licorice-based composition for uranium removal according to the present invention.

FIG. 3 shows a licorice-based composition, licorice powder and alpha-Fe for uranium removal according to the present invention₂O₃An infrared spectrum of (1).

FIG. 4 is an adsorption isotherm diagram of a licorice-based composite for uranium removal, alpha-Fe, prepared in examples 1-3 of the present invention₂O₃The adsorption isotherm diagram of (a) and the adsorption isotherm diagram of licorice powder;

FIG. 5 is a schematic drawing of a licorice-based composition for uranium removal according to the present invention;

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The licorice-based composite for removing uranium and the preparation method thereof provided by the invention are further described in detail with reference to the accompanying drawings and embodiments.

A licorice-based composition for uranium removal comprises licorice powder and Fe₂O₃Fe supported on licorice powder₂O₃In this example, Fe₂O₃Coating with licorice powder, Fe₂O₃Is alpha-Fe₂O₃. FIG. 1 is a field emission scanning electron micrograph of a licorice-based composite for uranium removal. As can be seen from FIG. 1, Fe₂O₃Successfully loaded on the licorice powder, the uniform distribution of Fe, O and C elements can be seen through the element distribution, which shows that Fe₂O₃Uniformly coating the Glycyrrhrizae radix powder.

As shown in fig. 2, a method for preparing a licorice-based compound for removing uranium includes the following steps:

s101: stirring and grinding liquorice into liquorice powder in a grinding machine;

in this embodiment, the licorice powder is sieved to obtain licorice powder with different meshes and licorice slag for subsequent use. The mesh number of the screen is 80.5-200 meshes.

S102: FeCl is added₃Fully dissolving in ethanol, adding NaOH, stirring at room temperature for 1h to obtain yellow brown suspension, adding FeCl₃Continuously stirring the liquorice powder in a certain mass ratio until the liquorice powder and the suspension are uniformly mixed to prepare a mixed solution;

in this example, 0.565 g-2.26 g FeCl was added₃Fully dissolved in 80-100 mL of ethanol, added with 0.4-1.6 g of NaOH, and licorice powder and FeCl₃The mass ratio of (A) to (B) is 0.5-2;

s103: and transferring the mixed solution into a high-pressure reaction kettle, reacting for a certain time at a certain temperature, filtering, washing and drying at 60 ℃ for 24 hours after the reaction is finished to obtain the licorice-based compound for removing uranium.

In the embodiment, the temperature is 140-160 ℃, and the reaction time is 1-3 h.

Example 1:

stirring and grinding liquorice into liquorice powder in a grinding machine, and sieving the liquorice powder by a sieve of 80 meshes; 0.565g FeCl₃Fully dissolving in 80mL ethanol, adding 0.4g NaOH, stirring at room temperature for 0.5h to obtain a yellow brown suspension, adding 1.13g Glycyrrhrizae radix powder, and continuously stirring until the Glycyrrhrizae radix powder and the suspension are uniformly mixed to obtain a mixed solution; and transferring the mixed solution into a high-pressure reaction kettle, reacting for 1h at 140 ℃, filtering, washing and drying for 24h at 60 ℃ after the reaction is finished to obtain the licorice-based compound for removing uranium.

Example 2:

stirring and grinding liquorice into liquorice powder in a grinding machine, and screening by a 150-mesh screen; 1.13g of FeCl₃Fully dissolving in 90mL of ethanol, adding 0.8g of NaOH, stirring at room temperature for a certain time for 1h to obtain a yellow brown suspension, adding 1.13g of licorice powder, and continuously stirring until the licorice powder and the suspension are uniformly mixed to obtain a mixed solution; transferring the mixed solution into a high-pressure reaction kettle, reacting for 2 hours at 150 ℃, filtering, washing and drying for 24 hours at 60 ℃ after the reaction is finished to obtain the sweet for removing uraniumA grass-based complex.

Example 3:

stirring and grinding liquorice into liquorice powder in a grinding machine, and sieving the liquorice powder with a 200-mesh sieve; 2.26g FeCl₃Fully dissolving in 100mL ethanol, adding 1.6g NaOH, stirring at room temperature for 1.5h to obtain a yellow brown suspension, adding 1.13g Glycyrrhrizae radix powder, and continuously stirring until the Glycyrrhrizae radix powder and the suspension are uniformly mixed to obtain a mixed solution; and transferring the mixed solution into a high-pressure reaction kettle, reacting for 3h at 160 ℃, filtering, washing and drying for 24h at 60 ℃ after the reaction is finished to obtain the licorice-based compound for removing uranium.

The prepared licorice-based compound for removing uranium is characterized by the invention, and is shown in figures 3-4.

FIG. 3 shows the licorice-based composition (α -Fe) for uranium removal prepared in example 2₂O₃-GL), Glycyrrhiza powder (Glycyrrhiza), and iron oxide (α -Fe)₂O₃) The infrared spectrum of (1). As can be seen from the IR spectrum, the licorice-based composite prepared in example 2 exhibited a peak of Fe-O bonds which is a characteristic vibration of iron oxide, and a blue shift was generated, indicating that Fe in the licorice-based composite is present₂O₃The Fe-O bond of (A) is more stable. Meanwhile, as can be seen from fig. 2, the glycyrrhiza based compound for removing uranium prepared in this example 2 contains methyl and phenolic hydroxyl groups, which theoretically facilitates adsorption of uranium by the glycyrrhiza based compound. Meanwhile, the liquorice is a traditional Chinese medicine in China, contains various components such as triterpenes, flavones and alkaloids, and has the functions of resisting viruses and removing free radicals. The triterpene component rich in licorice has hydroxyl and carboxyl, and the structure and functional group thereof have good chelation effect on uranium; in addition, flavonoids and phenols have more phenolic hydroxyl groups and have good chelation effect on uranium.

Fig. 4 is an adsorption isotherm of uranium by the licorice-based compound for removing uranium prepared in this example 1-3. As can be seen from FIG. 3, the maximum adsorption capacities of the glycyrrhiza-based composites for uranium removal prepared in examples 1 to 3 for U (VI) were 73mg/g, 188mg/g and 213mg/g, respectively, and the adsorption capacities were gradually increased as the loading amount of glycyrrhiza was increased.

Fig. 5 is a drawing showing the selective adsorption of ions in a simulated human environment by the glycyrrhiza based composite for uranium removal prepared in example 2. As can be seen from fig. 5, the glycyrrhiza based composite for removing uranium prepared in this example 2 has a U (vi) removal rate of 85% to 90% in the coexistence of a plurality of mixed ions simulating human body environment, which is significantly better than other ions (Ca)^{2 +}、Mg²⁺、Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺)。

The licorice-based compound for removing uranium is prepared by coating Fe on the surface of licorice by a solvothermal method₂O₃Due to Fe₂O₃The quick adsorption balance time to make licorice root base complex can react with hexavalent uranium fast in the short time, and then use in getting rid of the licorice root base complex of uranium to have higher clearance to uranium, and have very higher selectivity and adsorptivity to uranium under simulation human environment. Meanwhile, the preparation method of the licorice-based compound for removing uranium is simple, environment-friendly and pollution-free.

The embodiments of the present invention have been described in detail, but the description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. Any modification, equivalent replacement, and improvement made within the scope of the present invention shall be included in the protection scope of the present invention.