Synthetic method of active antimony sulfide for gaseous radioactive iodine adsorption

Abstract

A synthesis method of active antimony sulfide for gaseous radioactive iodine adsorption comprises the following steps: S1, mixing inorganic compound powder A, macrocyclic polyamine B and sulfur powder, putting the mixture into a container, and adding deionized water to obtain a mixture; s2, carrying out ultrasonic treatment on the mixture treated in the step S1, putting the mixture into a drying oven, and reacting for a certain time; and S3, after the reaction is finished, cooling to room temperature, filtering a product, and respectively washing with deionized water, a reagent G and a reagent F to obtain the three-dimensional framework active inorganic antimony sulfide. Through solvothermal reaction, the organic amine structure guiding effect is combined with ultrasonic vibration, the accumulation mode of the anion layer is directly influenced, then layered or open-frame crystals are formed, finally, a three-dimensional metal frame structure is formed, and the iodine adsorption saturation capacity is high.

Description

Technical Field

[0001] This invention relates to the field of waste treatment technology, specifically to a method for synthesizing active antimony sulfide for the adsorption of gaseous radioactive iodine. Background Technology

[0002] Nuclear energy, as a high-energy-density and low-carbon energy source, plays a crucial role in meeting growing energy demands and reducing greenhouse gas emissions. However, the recycling of nuclear fuel generates volatile radioactive pollutants, among which radioactive iodine poses particular environmental and biological risks. The most concerning of these is… 129 I, is a compound with a very long half-life (1.57 × 10⁻⁶). 7 The fission products of nuclear waste gas (Nuclear Waste Gas) have high mobility and bioaccumulation potential, making efficient capture of them from nuclear waste gas streams an important research topic.

[0003] In the field of closed-loop nuclear fuel processing, solid-phase adsorption technology has gradually become the mainstream approach for radioactive iodine capture due to its ease of operation and flexible system design. Silver-coated silica gel and silver-based zeolite materials exhibit good capture capabilities in both static and dynamic conditions, but their cost is relatively high. Therefore, developing novel iodine adsorbent materials that combine high adsorption capacity, good stability, and low cost is of great significance for promoting the sustainable development of nuclear energy.

[0004] In solid-phase adsorption material systems, covalent organic frameworks (COFs) have been widely used in iodine adsorption due to their tunable framework and high specific surface area. However, they still face challenges such as poor framework stability and high raw material costs. Metal sulfides are a class of materials containing electron-rich elements and metal ions, exhibiting a strong affinity for iodine molecules (I₂). Many metal components can be used to construct metal sulfides, such as transition metals and main group metals. Simultaneously, organic amines in the material act as structure-directing agents, both adjusting the material's structure and serving as adsorption sites for iodine.

[0005] This application proposes the use of macrocyclic polyamines as template agents to synthesize metal sulfide-organic amine hybrid materials in combination with Sb₂S₃. The synthesized materials possess three-dimensional structural properties, which are beneficial for the mass transfer of iodine molecules and are expected to improve the adsorption rate. Simultaneously, the S₂S₃ in the framework... 2- It can undergo a redox reaction with I2 to generate I. - Then I - Further interaction with exposed Sb 3+ It combines to generate SbI3, thereby achieving the purpose of iodine fixation. Summary of the Invention

[0006] The purpose of this invention is to provide a method for synthesizing active antimony sulfide for the adsorption of gaseous radioactive iodine, thereby adsorbing gaseous radioactive iodine.

[0007] The technical solution of the present invention is as follows: A method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine, comprising the following steps:

[0008] S1: Mix inorganic compound powder A, macrocyclic polyamine B and sulfur powder, place them in a container, add deionized water to obtain a mixture;

[0009] S2: The mixture treated by S1 is ultrasonicated and then placed in an oven for a certain period of time.

[0010] S3: After the reaction is completed and cooled to room temperature, the product is filtered and washed with deionized water, reagent G and reagent F respectively to obtain three-dimensional framework active inorganic antimony sulfide.

[0011] In S1, the inorganic compound powder A is Sb2S3 or Sb4S7.

[0012] The macrocyclic polyamine B is 1,4,8,11-tetraazacyclotetradecane or 1,4,7,10-tetraazacyclotetradecane.

[0013] In S1, the inorganic compound powder A has a mass of 2-4 parts, the macrocyclic polyamine B has a mass of 1-2 parts, the sulfur powder has a mass of 0.5-2 parts, and the deionized water has a mass of 5-10 parts.

[0014] In S2, the ultrasonic time is 7 minutes per 0.1g of macrocyclic polyamine, the oven temperature is 150-165℃, and the reaction takes 7-9 days in the oven.

[0015] In S3, reagent G is any one of ethylene glycol, isopropanol, or ethanol.

[0016] Reagent F is any one of acetone, cyclohexanone, or ethyl acetate.

[0017] In step S3, the product is washed 3-5 times with deionized water, reagent G, and reagent F respectively, and then naturally dried.

[0018] In step S1, the container is placed in a polytetrafluoroethylene-lined container.

[0019] The significant advantage of this invention is that, through a solvothermal reaction, the structure-directing effect of organic amines combined with ultrasonic vibration directly affects the stacking mode of the anion layer, thereby forming layered or open-frame crystals, and finally forming a three-dimensional metal framework structure with a high iodine adsorption saturation capacity.

[0020] This invention addresses the technical shortcomings of existing radioactive iodine adsorption technologies, namely, the poor thermal stability of organic amine-modified activated carbon, the high cost of precious metal silver-based adsorbents, secondary pollution, and poor Ag-I bond stability. It innovatively studies a novel metal sulfide-organic hybrid adsorption system based on the synergistic effect of organic ligands and a low-cost antimony source. This material first adsorbs iodine molecules into the channel through electrostatic transfer interactions. Then, S2- in the framework undergoes redox interactions with I2 to generate I-. Subsequently, I- further combines with exposed Sb3+ to form SbI3, thereby achieving iodine fixation. Experimental data show that this material effectively captures iodine under conditions of iodine vapor concentration ≤10 mg / h and temperature 100℃. Cost calculations indicate that the material cost per 1g of iodine vapor adsorbed is lower than that of commercial silver zeolite. Attached Figure Description

[0021] Figure 1 PXRD pattern of the 3D-Sb2S3-framework in Example 1;

[0022] Figure 2 Dynamic iodine adsorption performance of the 3D-Sb2S3-framework in Example 1; Detailed Implementation

[0023] Many specific details are set forth in the following description to provide a full understanding of this application. However, this application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of this application; therefore, this application is not limited to the specific embodiments disclosed below.

[0024] The terminology used in one or more embodiments of this application is for the purpose of describing particular embodiments only and is not intended to limit the scope of one or more embodiments of this application. The singular forms “a,” “the,” and “the” used in one or more embodiments of this application and in the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” used in one or more embodiments of this application refers to and includes any or all possible combinations of one or more associated listed items.

[0025] It should be understood that although the terms first, second, etc., may be used to describe various information in one or more embodiments of this application, such information should not be limited to these terms. These terms are only used to distinguish information of the same type from one another. For example, first may also be referred to as second without departing from the scope of one or more embodiments of this application, and similarly, second may also be referred to as first.

[0026] The specific technical content of the present invention will now be described with reference to the accompanying drawings;

[0027] A method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine includes the following steps:

[0028] S1: Mix inorganic compound powder A, macrocyclic polyamine B and sulfur powder, and put them into a polytetrafluoroethylene-lined container of sufficient volume, and add deionized water;

[0029] Specifically, inorganic compound powder A is any one of Sb2S3, Sb4S7, or other antimony sulfide compounds;

[0030] Specifically, macrocyclic polyamine B is 1,4,8,11-tetraazacyclotetradecane or 1,4,7,10-tetraazacyclotetradecane;

[0031] Specifically, in S1, the inorganic compound powder A is 2-4 parts by mass, the macrocyclic polyamine B is 1-2 parts by mass, the sulfur powder is 0.5-2 parts by mass, and the deionized water is 5-10 parts by mass.

[0032] S2: The mixture treated by S1 is ultrasonicated to obtain a homogeneous mixture, and then the mixture is placed in an oven and reacted for a certain period of time.

[0033] Specifically, the sonication time is 7 minutes for every 0.1g of macrocyclic polyamine;

[0034] Specifically, the oven temperature is 150-165℃;

[0035] Specifically, the reaction takes 7-9 days in an oven;

[0036] S3: After the reaction is completed and cooled to room temperature, the product is filtered and washed 3-5 times with deionized water, reagent G and reagent F respectively. Finally, it is naturally dried to obtain a three-dimensional framework active inorganic antimony sulfide material.

[0037] Specifically, reagent G is any one of ethylene glycol, isopropanol, or ethanol;

[0038] Specifically, reagent F is any one of acetone, cyclohexanone, or ethyl acetate;

[0039] Two specific embodiments are given below.

[0040] Example 1

[0041] 0.4 g of 1,4,8,11-tetraazacyclotetradecane and 0.90 g of Sb₂S₃ powder, along with 0.7 g of sulfur powder, were mixed in a 35 mL Teflon-lined reactor. 4 g of deionized water was then added, and the mixture was ultrasonically stirred for 30 min. The homogenized mixture was then placed in a 150 °C oven for 9 days. After the reaction was complete, impurities were removed, and the mixture was washed three times each with cyclohexanone, ethylene glycol, and deionized water, and then dried to obtain a three-dimensional, non-polar antimony sulfide compound. The successful synthesis of the product was confirmed by single-crystal X-ray diffraction (SCXRD).

[0042] Example 2

[0043] Four grams of 1,4,7,10-tetraazacyclotetradecane and nine grams of Sb₄S₇ powder, along with 0.7 grams of sulfur powder, were mixed in a 400 mL Teflon-lined reactor. 35 grams of deionized water were then added, and the mixture was ultrasonically stirred for 280 min. The homogenized mixture was then placed in a 160 °C oven for 8 days. After the reaction was complete, impurities were removed, and the mixture was washed five times each with ethanol, ethyl acetate, and deionized water, and then dried to obtain a three-dimensional, non-polar antimony sulfide compound. The successful synthesis of the product was confirmed by single-crystal X-ray diffraction (SCXRD).

[0044] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

[0045] It should be noted that, for the sake of simplicity, the foregoing method embodiments are all described as a series of actions. However, those skilled in the art should understand that this application is not limited to the described order of actions, as some steps may be performed in other orders or simultaneously according to this application. Furthermore, those skilled in the art should also understand that the embodiments described in the specification are preferred embodiments, and the actions and modules involved are not necessarily essential to this application.

[0046] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions of other embodiments.

[0047] The preferred embodiments disclosed above are merely illustrative of this application. The optional embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this application. These embodiments are selected and specifically described in this application to better explain the principles and practical applications of this application, thereby enabling those skilled in the art to better understand and utilize this application.

Claims

1. A method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine, characterized in that: Includes the following steps: S1: Mix inorganic compound powder A, macrocyclic polyamine B and sulfur powder, place them in a container, add deionized water to obtain a mixture; S2: The mixture treated by S1 is ultrasonicated and then placed in an oven for a certain period of time. S3: After the reaction is completed and cooled to room temperature, the product is filtered and washed with deionized water, reagent G and reagent F respectively to obtain three-dimensional framework active inorganic antimony sulfide.

2. The method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine according to claim 1, characterized in that: In S1, the inorganic compound powder A is Sb2S3 or Sb4S7.

3. The method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine according to claim 2, characterized in that: The macrocyclic polyamine B is 1,4,8,11-tetraazacyclotetradecane or 1,4,7,10-tetraazacyclotetradecane.

4. The method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine according to claim 1, characterized in that: In S1, the inorganic compound powder A has a mass of 2-4 parts, the macrocyclic polyamine B has a mass of 1-2 parts, the sulfur powder has a mass of 0.5-2 parts, and the deionized water has a mass of 5-10 parts.

5. The method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine according to claim 1, characterized in that: In S2, the ultrasonic time is 7 minutes per 0.1g of macrocyclic polyamine, the oven temperature is 150-165℃, and the reaction takes 7-9 days in the oven.

6. The method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine according to claim 3, characterized in that: In S3, reagent G is any one of ethylene glycol, isopropanol, or ethanol.

7. The method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine according to claim 6, characterized in that: Reagent F is any one of acetone, cyclohexanone, or ethyl acetate.

8. The method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine according to claim 1, characterized in that: In step S3, the product is washed 3-5 times with deionized water, reagent G, and reagent F respectively, and then naturally dried.

9. The method for synthesizing active antimony sulfide for adsorption of gaseous radioactive iodine according to claim 1, characterized in that: In step S1, the container is placed in a polytetrafluoroethylene-lined container.

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