CN114522667A - Preparation and application of bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas - Google Patents
Preparation and application of bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas, which comprises the following steps: dissolving polymethylsilsesquioxane in an organic solvent, adding a nitric acid solution, stirring, adding bismuth salt, performing ultrasonic treatment, stirring to form a precursor solution, and performing electrostatic spinning to obtain a fibrous membrane; the fiber membrane is carbonized and reduced in inert atmosphere to obtain the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas, the adsorbent comprises a silica carbon fiber membrane carrier and a metal bismuth elementary substance adsorbent loaded on the carrier, chemical adsorption sites are provided for adsorption and separation of radioactive gaseous iodine, the adsorption capacity of the adsorbent is high, and the adsorbent can be efficiently used for separation and recovery of the radioactive gaseous iodine. Compared with other powder adsorbents, the material has a macroscopic morphological structure and extremely high thermal stability, and has potential application prospects in capture, fixation, storage and other aspects of radioactive gaseous iodine in nuclear power stations and spent fuel reprocessing plants.
Description
Technical Field
The invention relates to the technical field of nuclear fuel post-treatment, in particular to preparation and application of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
Background
Nuclear power is an ideal clean energy source, but various gaseous radioactive isotopes can be generated in the processes of nuclear power operation and spent fuel aftertreatment. Wherein129I is235Fission products of U, due to their long half-life (1.6X 10)7Year), high content and high toxicity, and has the characteristics of easy volatilization, strong liquidity and the like. UOxWhen spent fuel is dissolved in boiling nitric acid solution, most of CsI is oxidized into volatile radioactive I2(129I、131I) If the drug is released into the environment, metabolic disturbance and mental retardation of a human body can be caused, and the risk of diseases such as thyroid cancer is increased, the drug needs to be purified.
Solid adsorption is one of effective methods for capturing volatile pollutants, and is a method mainly adopted for adsorbing and separating radioactive iodine in the industry at present due to simple operation and low maintenance and operation cost. Commonly used adsorbents are zeolites, activated carbon, activated alumina, aerogels, Layered Double Hydroxides (LDHs), Porous Organic Polymers (POPs), metal-organic frameworks (MOFs), and the like. The activated carbon has high iodine adsorption capacity due to the porous structure and high specific surface area, but the application of the activated carbon in high-temperature tail gas treatment of a post-treatment plant is limited due to the low ignition point of the activated carbon. Silver-loaded zeolites (AgX, AgZ, etc.) are the most commonly used iodine-adsorbing materials, and achieve a high iodine-adsorbing capacity by forming a chemisorption mechanism of insoluble AgI.
However, the toxicity and high cost of silver limit its practical engineering applications. To minimize these drawbacks, it is necessary to develop an iodine adsorbent material that is environmentally friendly and cost effective.
In recent years, bismuth-based materials have become an emerging adsorbent for iodine. The bismuth-loaded porous material can rapidly capture gaseous iodine, and has the characteristics of low cost, easy synthesis of materials, low toxicity, high adsorption capacity and the like compared with other functional materials (such as silver-doped zeolite, MOFs materials and the like). Solidified phase BiI of bismuth-based material3And Bi5O7I has good thermodynamic stability and is a novel and efficient solidified body of iodine.
Iodine gas adsorbents prepared in the prior art all utilize a physical adsorption mechanism and a chemical adsorption mechanism containing metal bismuth, but the thermal stability of the iodine gas adsorbents is not good, iodine gas is easy to continuously overflow at high temperature after adsorption, secondary pollution is caused, and the adsorption capacity is relatively low, so that bismuth-based composite materials for adsorbing iodine gas need to be further researched and are used for improving the adsorption capacity, the thermal stability and the like of the adsorbents.
Disclosure of Invention
In view of the above technical problems, the present invention needs to provide a bismuth-based composite nanofiber material for removing radioactive iodine gas, which has good thermal stability, easy separation and recovery, high adsorption capacity and short adsorption time, and a preparation method thereof.
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas, comprising the steps of:
dissolving polymethylsilsesquioxane in an organic solvent, stirring until the polymethylsilsesquioxane is dissolved, adding a nitric acid solution, stirring, adding bismuth salt, performing ultrasonic treatment for 20-50 min, and continuously stirring for 0.5-6 h to form a precursor solution;
step two, performing electrostatic spinning on the precursor solution to obtain a fiber membrane;
and step three, carrying out carbonization reduction on the fiber film in an inert atmosphere to obtain a composite fiber film, namely the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
Preferably, in the first step, the organic solvent is any one of tetrahydrofuran, dimethylformamide, isopropanol, and a mixed solvent of tetrahydrofuran and dimethylformamide.
Preferably, in the first step, the mass ratio of the bismuth salt to the polymethylsilsesquioxane to the organic solvent is 0.2-0.6: 2-4: 2. within the proportion range, the bismuth salt and the MK resin can be completely dissolved in the solvent, and the viscosity of the precursor spinning solution within the proportion range is just suitable for electrostatic spinning; the MK resin has good spinnability after hydrolysis reaction under the action of nitric acid, the hydrolysis time is preferably 0.5-6 h, the viscosity is too low after the hydrolysis time is too short, beaded defective fibers are easy to form, the viscosity is too high due to too long hydrolysis time, and continuous and stable fibers are not easy to form; when the concentration of the current precursor spinning solution is too high, continuous and uniform fibers cannot be spun, and when the concentration is too low, microspheres can be obtained; therefore, the contents of MK resin and bismuth salt and the hydrolysis time are very important for electrospinning, and the content of bismuth salt is increased as much as possible under the condition that MK resin can be electrospun, thereby providing more adsorption sites.
Preferably, in the first step, the concentration of the nitric acid solution is 0.5-1.5 wt%; the mass volume ratio of the bismuth salt to the nitric acid solution is 0.5-1 g:30 mu L.
Preferably, in the first step, the bismuth salt is any one of bismuth nitrate, bismuth acetate, bismuth nitrate or bismuth oxalate and hydrates thereof; the power of the ultrasonic wave is 300-400W, and the ultrasonic frequency is 45-65 KHz.
Preferably, in the second step, the parameters of electrostatic spinning are as follows: a needle head: 20-30 stainless steel needles; spinning voltage: 6-20 KV; electrode distance: 5-20 cm; rate of syringe pump advancement: 0.01-0.1 mL/min; ambient temperature: 5-20 ℃; ambient humidity: 30 to 80 percent. The filaments obtained within the range are uniform and can provide uniform attachment points for bismuth salt; only when the critical voltage is reached, the electric field force can overcome the surface tension of the polymer liquid drop, the polymer solution can be sprayed out from the Taylor cone to form jet flow, and fibers are formed under the further drawing of the electric field force; increasing the voltage, wherein the diameter of the fiber is reduced firstly and then increased, but the defective fiber with a beaded structure is formed when the voltage is too high; and the flow rate is also an important process parameter influencing the jet flow speed and the material exchange speed, and stable and uniform fibers can be formed only if the spinning voltage and the propelling speed of the injection pump reach a certain correlation. But also the temperature and humidity of the environment affects the viscosity of the spinning solution and the solvent rate and thus also the formation of constant fibres.
Preferably, in the third step, the inert atmosphere is argon-hydrogen mixed atmosphere; parameters of the carbonization reduction are as follows; the temperature rising speed is 2-10 ℃/min, the carbonization and reduction temperature is 700-900 ℃, and the heat preservation time is 1-3 h. When the temperature rise rate is too slow, carbonization time is too long, and when the temperature rise rate is too fast, mechanical properties of the carbon fibers are reduced. The carbonization temperature is controlled to be 700-900 ℃, carbon fibers with stable performance can be well prepared, and meanwhile bismuth ions can be completely reduced to simple substance bismuth in the temperature range.
Preferably, in the step one, the process after adding the bismuth salt is replaced by: adding the feed liquid added with the bismuth salt into a microwave and ultrasonic integrated reactor, and simultaneously starting microwaves and ultrasonic waves for synergistic treatment for 90-120 min; the microwave power of the synergistic treatment is 300-500W, the ultrasonic power is 300-400W, and the ultrasonic frequency is 45-65 KHz; the treatment temperature is 40-45 ℃.
The invention also provides a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas, which is prepared according to the preparation method.
The invention also provides application of the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas, which is prepared according to the preparation method, in adsorption of gaseous iodine. The material has very high adsorption capacity to gaseous iodine and good thermal stability, and can be stabilized to more than 800 ℃ in inert atmosphere.
The electrostatic spinning is a technology widely applied to fiber preparation, the diameter of the prepared fiber can reach several nanometers to several micrometers, and the nano-micron fiber with high porosity and large specific surface area can be prepared. The bismuth-based composite nanofiber material is prepared by mixing and dissolving bismuth salt and polymethylsilsesquioxane (MK resin) in an organic solvent to form a precursor spinning solution, then obtaining a fiber film through an electrostatic spinning process, and finally forming the bismuth-based composite nanofiber material which takes silica-carbon fiber as a framework and uniformly loads metal bismuth elementary substances on the surface and in a three-dimensional network space through a high-temperature carbonization reduction process.
The invention at least comprises the following beneficial effects:
(1) compared with other bismuth agent materials, the novel bismuth-based nanofiber composite membrane material disclosed by the invention is an inorganic macroscopic adsorption material, has good thermal stability, cannot be oxidized at high temperature, and has potential application value in related fields of adsorbing radioactive iodine gas and the like.
(2) The novel bismuth-based nanofiber composite membrane material has the following advantages as an adsorbent in the aspect of adsorbing radioactive iodine gas: the material has good thermal stability, and the loaded metal bismuth monomer can form BiI with iodine gas3The product has stable solidification phase and good thermodynamic stability, and is a novel and efficient iodine solidification body.
(3) The adsorbent comprises a silica carbon fiber membrane carrier and a metal bismuth elementary substance adsorbent loaded on the carrier, provides a chemical adsorption site for adsorption and separation of radioactive gaseous iodine, has high adsorption capacity, and can be efficiently used for separation and recovery of the radioactive gaseous iodine. And compared with other powder adsorbents, the material has a macroscopic morphological structure and extremely high thermal stability, and has potential application prospects in capture, fixation, storage and other aspects of radioactive gaseous iodine in nuclear power stations and spent fuel post-treatment plants.
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.
Description of the drawings:
fig. 1 is an SEM image of the bismuth-based nanofiber composite film materials of example 1(a), example 2(b), example 3(c) and corresponding application example 1(d, e, f);
FIG. 2 is an XRD pattern of the bismuth-based nanofiber composite film material of example 1;
FIG. 3 is an XRD pattern of a bismuth-based nanofiber composite film material of application example 1;
FIG. 4 is a graph showing the adsorption kinetics of iodine gas for the novel bismuth-based nanofiber composite membrane materials prepared in examples 1, 2 and 3;
FIG. 5 is a graph showing the adsorption kinetics of iodine gas for the novel bismuth-based nanofiber composite membrane materials prepared in examples 1 and 4;
FIG. 6 is a graph showing the adsorption kinetics of iodine gas for the novel bismuth-based nanofiber composite membrane materials prepared in examples 2 and 5;
FIG. 7 is a graph showing the adsorption kinetics of iodine gas for the novel bismuth-based nanofiber composite membrane materials prepared in examples 3 and 6;
FIG. 8 is a TGA curve of the novel bismuth-based nanofiber composite membrane material of example 1 and application example 1;
fig. 9 is an isothermal adsorption curve of the novel bismuth-based nanofiber composite membrane materials prepared in example 1, example 2 and example 3 at different iodine gas concentrations.
The specific implementation mode is as follows:
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 starting materials polymethylsilsesquioxane (MK resin) used in the following examples were purchased from Wacker chemical Co., Ltd, Germany, and bismuth nitrate pentahydrate, nitric acid and tetrahydrofuran were purchased from Aladdin chemical Co., Ltd, and were used without further purification.
Example 1:
a preparation method of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas comprises the following steps:
dissolving 6g of polymethylsilsesquioxane in 4g of tetrahydrofuran, stirring for 1h until the polymethylsilsesquioxane is dissolved, adding 30uL of 1 wt% nitric acid solution, stirring for 10min, adding 1g of bismuth nitrate pentahydrate, performing ultrasonic treatment for 30min, and continuously stirring for 3h to form a precursor solution;
step two, carrying out electrostatic spinning on the precursor solution (the spinning parameters are that a needle head is a 25-grade stainless steel needle head, the spinning voltage is 12KV, the electrode distance is 15cm, the propelling speed of an injection pump is 0.08mL/min, the environmental temperature is 18 ℃ and the environmental humidity is 40 percent) to obtain a fiber membrane;
and thirdly, heating the fiber film to 800 ℃ at a speed of 3 ℃/min in an argon-hydrogen mixed atmosphere, and calcining for 2 hours to obtain the bismuth-based nanofiber composite film with the metal bismuth elementary substance loading of 10%, namely the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
Example 2:
a preparation method of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas comprises the following steps:
dissolving 6g of polymethylsilsesquioxane in 4g of tetrahydrofuran, stirring for 1h until the polymethylsilsesquioxane is dissolved, adding 30uL of 1 wt% nitric acid solution, stirring for 10min, adding 0.8g of bismuth nitrate pentahydrate, performing ultrasonic treatment for 30min, and continuously stirring for 3h to form a precursor solution;
step two, performing electrostatic spinning on the precursor solution (the spinning parameters are that a needle head is a No. 25 stainless steel needle head, the spinning voltage is 12KV, the electrode distance is 15cm, the propelling speed of an injection pump is 0.08mL/min, the environmental temperature is 18 ℃, and the environmental humidity is 40%) to obtain a fiber membrane;
and step three, heating the fiber film to 800 ℃ at the speed of 3 ℃/min in argon-hydrogen mixed atmosphere, and calcining for 2 hours to obtain the bismuth-based nanofiber composite film with the metal bismuth elementary substance loading of 8%, namely the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
Example 3:
a preparation method of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas comprises the following steps:
step one, dissolving 6g of polymethylsilsesquioxane in 4g of tetrahydrofuran, stirring for 1h until the polymethylsilsesquioxane is dissolved, adding 30uL of 1 wt% nitric acid solution, stirring for 10min, then adding 0.5g of bismuth nitrate pentahydrate, performing ultrasonic treatment for 30min, and continuing stirring for 3h to form a precursor solution;
step two, carrying out electrostatic spinning on the precursor solution (the spinning parameters are that a needle head is a 25-grade stainless steel needle head, the spinning voltage is 12KV, the electrode distance is 15cm, the propelling speed of an injection pump is 0.08mL/min, the environmental temperature is 18 ℃ and the environmental humidity is 40 percent) to obtain a fiber membrane;
and step three, heating the fiber film to 800 ℃ at the speed of 3 ℃/min in argon-hydrogen mixed atmosphere, and calcining for 2 hours to obtain the bismuth-based nanofiber composite film with the metal bismuth elementary substance loading of 5%, namely the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
Example 4:
a preparation method of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas comprises the following steps:
dissolving 6g of polymethylsilsesquioxane in 4g of tetrahydrofuran, stirring for 1h until the polymethylsilsesquioxane is dissolved, adding 30uL of 1 wt% nitric acid solution, stirring for 10min, then adding 1g of bismuth nitrate pentahydrate, adding the feed liquid into a microwave and ultrasonic integrated reactor, and simultaneously starting microwaves and ultrasonic waves for synergistic treatment for 120 min; the microwave power of the cooperative treatment is 300W, the ultrasonic power is 300W, and the ultrasonic frequency is 45 KHz; the processing temperature is 40 ℃, and precursor solution is formed;
step two, carrying out electrostatic spinning on the precursor solution (the spinning parameters are that a needle head is a 25-grade stainless steel needle head, the spinning voltage is 12KV, the electrode distance is 15cm, the propelling speed of an injection pump is 0.08mL/min, the environmental temperature is 18 ℃ and the environmental humidity is 40 percent) to obtain a fiber membrane;
and step three, heating the fiber film to 800 ℃ at the speed of 3 ℃/min in argon-hydrogen mixed atmosphere, and calcining for 2 hours to obtain the bismuth-based nanofiber composite film with the metal bismuth elementary substance loading of 10%, namely the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
Example 5:
a preparation method of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas comprises the following steps:
dissolving 6g of polymethylsilsesquioxane in 4g of tetrahydrofuran, stirring for 1h until the polymethylsilsesquioxane is dissolved, adding 30uL of 1 wt% nitric acid solution, stirring for 10min, adding 0.8g of bismuth nitrate pentahydrate, adding the feed liquid into a microwave and ultrasonic integrated reactor, and simultaneously starting microwaves and ultrasonic waves for synergistic treatment for 120 min; the microwave power of the cooperative treatment is 300W, the ultrasonic power is 300W, and the ultrasonic frequency is 45 KHz; the processing temperature is 40 ℃, and precursor solution is formed;
step two, carrying out electrostatic spinning on the precursor solution (the spinning parameters are that a needle head is a 25-grade stainless steel needle head, the spinning voltage is 12KV, the electrode distance is 15cm, the propelling speed of an injection pump is 0.08mL/min, the environmental temperature is 18 ℃ and the environmental humidity is 40 percent) to obtain a fiber membrane;
and step three, heating the fiber film to 800 ℃ at the speed of 3 ℃/min in argon-hydrogen mixed atmosphere, and calcining for 2 hours to obtain the bismuth-based nanofiber composite film with the metal bismuth elementary substance loading of 8%, namely the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
Example 5:
a preparation method of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas comprises the following steps:
dissolving 6g of polymethylsilsesquioxane in 4g of tetrahydrofuran, stirring for 1h until the polymethylsilsesquioxane is dissolved, adding 30uL of 1 wt% nitric acid solution, stirring for 10min, adding 0.5g of bismuth nitrate pentahydrate, adding the feed liquid into a microwave and ultrasonic integrated reactor, and simultaneously starting microwaves and ultrasonic waves for synergistic treatment for 120 min; the microwave power of the cooperative treatment is 300W, the ultrasonic power is 300W, and the ultrasonic frequency is 45 KHz; the processing temperature is 40 ℃, and precursor solution is formed;
step two, carrying out electrostatic spinning on the precursor solution (the spinning parameters are that a needle head is a 25-grade stainless steel needle head, the spinning voltage is 12KV, the electrode distance is 15cm, the propelling speed of an injection pump is 0.08mL/min, the environmental temperature is 18 ℃ and the environmental humidity is 40 percent) to obtain a fiber membrane;
and step three, heating the fiber film to 800 ℃ at the speed of 3 ℃/min in argon-hydrogen mixed atmosphere, and calcining for 2 hours to obtain the bismuth-based nanofiber composite film with the metal bismuth elementary substance loading of 5%, namely the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
Application example 1:
in order to test the adsorption performance of the bismuth-based nanofiber composite membrane material obtained above as an adsorbent on iodine gas. Adsorption experiments were performed under static conditions (75 ℃ and ambient pressure) with 0.3g of iodine and 0.03g of the adsorbents prepared in example 1, example 2 and example 3 placed in the bottom of a 30mL glass bottle and conical filter paper, respectively, and sealed (i.e., iodine placed in the glass bottle, adsorbent placed in the conical filter paper, and conical filter paper on top of the glass bottle). Their iodine adsorption capacity was then calculated by weighing the mass change of the adsorbents after different reaction times. Calculated according to the formula:
iodine adsorption capacity ═ (mass after reaction-mass before reaction)/mass before reaction;
to determine that the increase in mass of the adsorbent in the experimental results was due to adsorption, rather than reaction with air to form oxides, a blank control experiment was performed. Similarly, the adsorbent prepared in example 1 was placed in an air apparatus containing no iodine, and the final mass was measured under the same conditions.
Characterization analysis of the iodine adsorbent prepared in example 1, example 2 and example 3 and the adsorbed material in experimental example 1 gave SEM graph shown in fig. 1, XRD graph shown in fig. 2 and fig. 3, adsorption kinetics graph shown in fig. 4, and TGA thermogravimetric graph shown in fig. 5, respectively.
As shown in fig. 1(a-c), the diameter of the composite fiber (examples 1-3) successfully prepared by the electrostatic spinning process is 800nm-2 μm, the elemental metal bismuth particles are uniformly distributed on the surface of the fiber, and the uniform loading of the elemental metal bismuth particles on the silica-carbon nanofiber provides a large number of active sites, so that the iodine adsorption performance of the adsorbent is further improved. FIG. 1(d-f) shows the surface morphology of the fiber after iodine gas adsorption in application example 1 (examples 1 to 3), and it can be seen from the graph that the small particles on the fiber become white small balls after adsorption; the bismuth loaded on the silica-alumina carbon fiber is an effective iodine adsorption site, so that the adsorption of iodine can be effectively realized, the adsorption mechanism of the material can be obtained, and a new stable phase bismuth iodide chemical adsorption and partial physical adsorption are generated mainly through the reaction of simple substance bismuth and iodine gas.
As shown in fig. 2, the XRD curves of the bismuth-based nanofiber composite film materials of example 3 and application example 1 (after adsorption of iodine to the bismuth-based nanofiber composite film material corresponding to example 3) show that the diffraction peak on the curves is Bi (ICDD PDF No.85-1330), which proves the existence of the metal bismuth simple substance in the material; after adsorption, the diffraction peak on the curve shown in FIG. 3 was changed to BiI3(ICDD PDF No. 48-1795). The material is proved to successfully load the metal bismuth simple substance, and the adsorption mechanism of the material is that the simple substance bismuth reacts with iodine gas to generate a new stable phase bismuth iodide.
As shown in fig. 4, the adsorption rate of the bismuth-based nanofiber composite membrane materials prepared in examples 1, 2 and 3 to iodine gas is high, and the saturated adsorption capacity can be reached in about 120 min. The maximum adsorption capacity of the bismuth-based nanofiber composite membrane materials with different loading amounts in the three embodiments is 176mg/g, 448mg/g and 515.2mg/g respectively. And remained stable in the blank for 10h in an environment without iodine vapor, indicating that it did not react with air. Example 1 the bismuth-based nanofiber composite membrane with the metal bismuth simple substance loading of 10% has the best adsorption performance, and the maximum adsorption capacity can reach 515.2 mg/g.
As shown in fig. 5 to 7, the bismuth-based nanofiber composite membrane materials prepared in examples 4, 5, and 6 have a better effect of adsorbing iodine gas, because the spinnability of the precursor solution is improved and the components are mixed more uniformly after the bismuth-based nanofiber composite membrane materials are treated in the microwave and ultrasonic integrated reactor, the prepared bismuth-based nanofiber composite membrane materials have a better effect of adsorbing iodine gas.
As shown in fig. 8, when the temperature was increased to 800 ℃, the quality of the bismuth-based nanofiber composite membrane material prepared in example 1 was slightly decreased, but only decreased by 1.88%, and the quality of application example 1 (after the bismuth-based nanofiber composite membrane material corresponding to example 1 adsorbed iodine) was lost by 47.12%. By comparative analysis, the weight loss can be attributed to the following three components: 1.88% is due to adsorption of water in the air or to a small decomposition of the adsorbent itself: 32.98 percent of the iodine molecules which are physically adsorbed volatilize, and the curve begins to decline from about 75 ℃; the remaining 12.26% is BiI due to chemisorption3Decomposition at 127-800 deg.C. Therefore, it can be seen that the bismuth-based nanofiber composite membrane material prepared in example 1 has excellent thermal stability, does not decompose at 800 ℃, and has better stability than other iodine gas adsorbents.
Application example 2:
in order to explore the iodine gas adsorption performance of the bismuth-based nanofiber composite membrane material under different concentrations, a series of isothermal adsorption experiments are also carried out. 0.1g of the bismuth-based nanofiber composite membrane materials prepared in the embodiment 1, the embodiment 2 and the embodiment 3 are respectively taken, iodine simple substances with different qualities are added to obtain iodine contents with different concentrations, and then the influence of different iodine concentrations on the adsorption of iodine gas by the materials is experimentally researched at 75 ℃. Similarly, the iodine capturing performance of the bismuth-based nanofiber composite membrane material is calculated by weighing the mass change of the bismuth-based nanofiber composite membrane material after 4 hours of adsorption, and the result is shown in fig. 9, and the result shows that the bismuth-based nanofiber composite membrane material can also have better adsorption performance on iodine gas under the condition of different iodine concentrations.
While embodiments of the invention have been described above, it is not intended to be limited to the details shown, described and illustrated herein, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed, and to such extent that such modifications are readily available to those skilled in the art, and it is not intended to be limited to the details shown and described herein without departing from the general concept as defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas is characterized by comprising the following steps:
dissolving polymethylsilsesquioxane in an organic solvent, stirring until the polymethylsilsesquioxane is dissolved, adding a nitric acid solution, stirring, adding bismuth salt, performing ultrasonic treatment for 20-50 min, and continuously stirring for 0.5-6 h to form a precursor solution;
step two, performing electrostatic spinning on the precursor solution to obtain a fiber membrane;
and step three, carrying out carbonization reduction on the fiber film in an inert atmosphere to obtain a composite fiber film, namely the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas.
2. The method of preparing a bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas as claimed in claim 1, wherein in the first step, the organic solvent is any one of tetrahydrofuran, dimethylformamide, isopropanol, and a mixed solvent of tetrahydrofuran and dimethylformamide.
3. The preparation method of the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas as claimed in claim 1, wherein in the first step, the mass ratio of the bismuth salt, the polymethylsilsesquioxane and the organic solvent is 0.2-0.6: 2-4: 2.
4. the preparation method of the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas according to claim 1, wherein in the first step, the concentration of the nitric acid solution is 0.5-1.5 wt%; the mass volume ratio of the bismuth salt to the nitric acid solution is 0.5-1 g:30 mu L.
5. The preparation method of the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas as claimed in claim 1, wherein in the first step, the bismuth salt is any one of bismuth nitrate, bismuth acetate, bismuth nitrate or bismuth oxalate and hydrates thereof; the power of the ultrasonic wave is 300-400W, and the ultrasonic frequency is 45-65 KHz.
6. The method for preparing the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas as claimed in claim 1, wherein in the second step, the parameters of electrospinning are as follows: a needle head: 20-30 stainless steel needles; spinning voltage: 6-20 KV; electrode distance: 5-20 cm; rate of syringe pump advancement: 0.01-0.1 mL/min; ambient temperature: 5-20 ℃; ambient humidity: 30 to 80 percent.
7. The method for preparing the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas according to claim 1, wherein in the third step, the inert atmosphere is argon-hydrogen mixed atmosphere; parameters of the carbonization reduction are as follows; the temperature rising speed is 2-10 ℃/min, the carbonization and reduction temperature is 700-900 ℃, and the heat preservation time is 1-3 h.
8. The method for preparing the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas as claimed in claim 1, wherein in the step one, the process after adding the bismuth salt is replaced by: adding the feed liquid added with the bismuth salt into a microwave and ultrasonic integrated reactor, and simultaneously starting microwaves and ultrasonic waves for synergistic treatment for 90-120 min; the microwave power of the synergistic treatment is 300-500W, the ultrasonic power is 300-400W, and the ultrasonic frequency is 45-65 KHz; the treatment temperature is 40-45 ℃.
9. A bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas, prepared according to the preparation method of any one of claims 1 to 8.
10. The application of the bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas, prepared by the preparation method according to any one of claims 1 to 8, in adsorption of gaseous iodine.
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