CN111151216B - Preparation method and application of boron nitride block adsorbent for treating iodine vapor pollutants - Google Patents
Preparation method and application of boron nitride block adsorbent for treating iodine vapor pollutants Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a boron nitride block adsorbent for treating iodine vapor pollutants. The method comprises the following steps: adding boric acid and melamine into deionized water to prepare a precursor solution; pouring a solution of metal ions while stirring; then carrying out ultrasonic treatment in an ultrasonic instrument until floccules are completely separated out, and obtaining a precursor containing metal ions; sealing the precursor, freezing for 1-24h in a low-temperature environment, taking out, immediately putting into a freeze dryer for freeze drying, and finally performing heat treatment at 900-1500 ℃ to obtain a product; the metal ion compound is AgNO 3 、CuCl 2 ·2H 2 O or MnCl 2 . The material obtained by the invention not only has larger adsorption capacity to iodine vapor, but also is not easy to cause environmental pollution because of the blocky shape, and can be recycled after adsorption is finished.
Description
Technical Field
The invention relates to the field of boron nitride nano material ecological environment protection, in particular to a preparation method of a foamy boron nitride block adsorbent formed by metal ion in-situ induction and application of the foamy boron nitride block adsorbent in the aspect of treating iodine vapor pollutants.
Background
In the modern times, global energy consumption is continuously increasing, and fossil fuels are continuously decreasing, and the search for other alternative energy sources becomes one of the most urgent tasks for human survival at present. The nuclear energy is a representative new energy source and has the advantages of high efficiency, low cost and the like. However, the negative impact of nuclear energy sources is not negligible. Nuclear fuels are prone to produce radioactive contaminants (e.g., iodine, tritium, krypton, etc.) that can cause significant biological and environmental damage. In nuclear fuel wastes, most of the iodide ions are oxidized into iodine molecules by nitric acid or nitrous acid and then released in the form of vapor. Especially, the element I-129 is one of the greatest safety hazards of the nuclear industry because the element I-129 has strong volatility and long half-life (about 150 ten thousand years), and is easy to be enriched in thyroid gland to influence biological metabolism and other factors. On the contrary, iodine is a beneficial element from other aspects, and has important application in the aspects of new energy, materials, biological medicine and the like. In these applications, the storage and release of iodine are usually involved, and therefore, the capture, storage and controlled release of volatile iodine becomes an urgent problem to be solved.
As a commonly used method of remediating environmental pollutants, adsorption is considered to be the most effective method of capturing and storing iodine vapor at present. The existing mature porous adsorption materials comprise zeolite, activated carbon, metal organic frameworks, porous organic polymers and the like. For example, pham et al synthesized zeolite materials, but their synthesis time was long and required a long period of high temperature treatment, increasing the complexity of experimental material synthesis (t.c.t.pham, s.docao, i.c.hwang, energ.environ.sci.,2015,9, 1050-1062). Chien et al synthesized activated carbon using bamboo as a raw material, but the limitation of its adsorption performance was greatly aggravated by the fact that the material itself was powdery and needed to be impregnated on a carrier (C.C. Chien, Y.P. Huang, W.C. Wang, J.H. Chao, Y.Y. Wei, clean-SoilairWater,2015,39, 103-108.). Janeta et al have a great disadvantage that the porous silsesquioxane organic framework is prepared by condensing aminopropyl silsesquioxane cage-like compounds and selected multi-topic aldehydes, the preparation process is complex, organic matters are easy to undergo redox reaction with adsorbed substances, and high temperature resistance cannot be achieved (M.Janeta, W.Bury, S.Szafert, ACSAppl.Mater.interfaces,2018, 2319964-19973). Further comprehensive research on the above materials shows that most adsorbents do not have high thermal stability and chemical inertness due to their own limitations on specific properties, and thus are difficult to serve in severe environments such as high temperature, acidity, strong oxidation properties, and flammability and humidity.
Hexagonal Boron Nitride (BN) is a material with superior thermal stability, hydrophobicity, chemical inertness, high specific surface area and pore volume, and has attracted much attention in recent years. Wherein, nitrogen atoms and boron atoms form a covalent bond to form a BN hexagonal structure. Since the nitrogen atom has pi bonds in the vicinity, BN layers can be bonded by van der waals force. And the porous BN nano-fibers are assembled in a crossing way to obtain a macroscopic foam block. After metal ions are added, lewis acid-base interaction between the iodine vapor and the porous BN is enhanced, and the adsorption capacity of the BN to the iodine vapor is improved, so that the BN-based iodine adsorbent can be used as a high-efficiency iodine adsorbent.
Disclosure of Invention
The invention provides a preparation method of a foam block adsorbent assembled by BN (boron nitride) nano fibers generated by metal ion in-situ induction, aiming at the defects that most of the existing iodine vapor adsorbents are low in thermal stability, weak in chemical inertness, difficult to serve in severe environments such as acidity, strong oxidizing property, flammability and the like, low in adsorption quantity, difficult to recycle and the like. According to the method, metal ions are added in the process of synthesizing the BN precursor, and the BN fiber is thinned and controlled at a nanometer level through the in-situ induction effect generated by complexing or oxidation reduction of the metal ions and the BN precursor, so that the porosity and the specific surface area are greatly increased, the organization structure of porous BN is optimized and designed, and the iodine adsorption effect is improved. The material obtained by the invention not only has larger adsorption capacity to iodine vapor, but also is not easy to cause environmental pollution because of the blocky shape, and can be recycled after adsorption is finished.
The technical scheme of the invention is as follows:
a method of making a boron nitride bulk sorbent for treating iodine vapor contaminants, the method comprising the steps of:
(1) Dissolving a metal ion compound in deionized water to prepare a metal ion solution for later use;
wherein in the metal ion compound, the metal ion is Ag + 、Cu 2+ Or Mn 2+ (ii) a The anion being NO 3 - Or Cl - (ii) a The concentration of metal ions in the solution is 0.001-0.005mol/L;
(2) Adding boric acid and melamine into deionized water, and continuously stirring for 1-4 h on a constant-temperature stirrer at 70-99 ℃ to prepare a precursor solution;
wherein, the concentration of the melamine and the boric acid is 0.01 to 0.02g per milliliter of water; the mass ratio of boric acid to melamine is 2;
(3) Stirring the precursor solution at normal temperature, and pouring the solution of the metal ions prepared in the step (1) while stirring; then continuously stirring for 3-6min;
wherein the volume ratio is precursor solution: metal ion solution =245 to 240:5 to 10;
(4) Putting the solution obtained in the step (3) into an ultrasonic instrument which is cooled to 5-20 ℃ in advance for ultrasonic treatment for 1-6 h until floccules are separated out, and obtaining a precursor containing metal ions;
wherein, the ultrasonic frequency is 20-100KHz, and the power is 30-350W;
(5) Sealing the precursor, freezing for 1-24h in a low-temperature environment, taking out, and immediately putting into a freeze dryer for freeze drying for 4-10 days; and then putting the precursor into a tube furnace, carrying out heat treatment for 1-5h at the temperature of 900-1500 ℃ in the protective atmosphere of nitrogen, changing the protective atmosphere into ammonia gas, continuing the heat treatment for 1-5h at the same flow rate and temperature, and finally cooling to room temperature to obtain the boron nitride bulk adsorbent containing metal particles.
Wherein the freezing temperature is-30 ℃ to-10 ℃, and the cold drying temperature is-50 ℃ to-24 ℃; the flow rate of the protective gas is 60-100mL/min;
the diameter range of the BN nano-fiber is 100-800nm.
The metal ion compound is AgNO 3 、CuCl 2 ·2H 2 O or MnCl 2 。
The protective atmosphere is nitrogen and ammonia.
The boron nitride block adsorbent for treating iodine vapor pollutants is applied to adsorption and storage of iodine vapor.
The invention has the substantive characteristics that:
in the patent (publication No. CN 106495109A) entitled "preparation method of foamed boron nitride bulk material", which is only preparation of BN bulk material, the present subject group has great limitation in practical application. The invention not only has the innovative operation of adding metal ions in the material preparation process (and finds out the mechanism that the metal ions generate the metal ion in-situ induction effect through the complexation or oxidation-reduction reaction with BN precursor), but also has the application of iodine adsorption performance and the creative discovery of the semiconductor properties of the material in the adsorption process. The operation steps are further optimized according to the application of iodine vapor adsorption, so that the specific components, the tissue structure, the specific surface area, the pore size distribution and the like of the materials in the synthesized foamed boron nitride block material are more suitable for adsorption and storage of iodine vapor.
The invention adopts an ultrasonic-assisted method, and constructs a foamy BN block which can be used for adsorbing iodine vapor by BN nano-fibers generated by metal ion in-situ induction. Firstly, dissolving raw materials in an aqueous solution to obtain a stable precursor solution, then pouring a solution containing metal ions prepared in advance into the stable precursor solution, and accelerating the generation of the precursor by using the formed stable new ions. The growth and collapse dynamic process generated by the cavitation of the low-temperature ultrasound is beneficial to the growth of the superfine fiber. The superfine fibers are mutually wound and crystallized under the assistance of ultrasound, block-shaped solid is obtained by freezing and pumping, and finally, the foam-shaped BN block is obtained by high-temperature heat treatment under the protective atmosphere. Wherein the selection of different metal ions and different protective gases can influence the adsorption effect on the iodine vapor.
The invention has the following beneficial effects:
1. the product obtained by the invention is a foamy solid assembled by BN nano-fibers generated by in-situ induction of metal ions.
2. The diameter of the fiber is 100-800nm, and the fiber contains slit-shaped pores and through holes.
3. The BN foam obtained by the invention has good stability in harsh environments such as high temperature, acidity, strong oxidizing property, flammability and the like, and can effectively adsorb iodine molecules in a steam state.
4. The product obtained by the invention can be recycled, the energy consumption and the production cost are reduced, the method is efficient, safe and reliable, the yield is high, and the method is suitable for mass production.
5. Experiments show that the BN foam block prepared by the method has semiconductor properties when an iodine adsorption experiment is carried out at high temperature, namely the conductivity is rapidly increased and approaches a certain balance value after iodine adsorption, and the conductivity is also rapidly decreased along with the reduction of the temperature after the iodine adsorption is finished. The property widens the thought for the preparation of high-temperature semiconductor materials in the future.
6. At present, the adsorption performance of most iodine adsorption materials is limited to be 1-5 times of the mass of the materials, the adsorption capacity of the adsorbent is more than 10 times, and the adsorption effect is remarkably improved compared with that of a common iodine adsorbent. The maximum adsorption amount of the BN foam-like block to iodine vapor without addition of metal ions and with addition of different metal ions is as follows:
| adsorbent and process for producing the same | BN foam | Ag @ BN foam | Cu @ BN foam | Mn @ BN foam |
| Maximum adsorption capacity | 210.2％ | 2234.1％ | 1739.7％ | 2807.9％ |
7. The innovative discovery of the invention lies in the creative discovery in the experimental process that the BN bulk adsorbent has semiconductor properties, namely greatly reduced resistance and conductive properties in the high-temperature iodine absorption process (see the curve shown in the figure 5I-t obtained in example 8), which is in sharp contrast to the BN material which is an insulating material.
Drawings
Fig. 1 is a graph showing the characterization and iodine adsorption performance test results of BN foam generated by in-situ induction of metal Ag ions prepared in example 1. Wherein, FIG. 1a is a macro-topography optical photograph; FIGS. 1b and 1c are scanning electron microscope images at different magnifications; FIG. 1d shows the result of adsorption of iodine vapor.
Fig. 2 is a graph showing the characterization and iodine adsorption performance test results of BN pure foam prepared in example 7 without adding any metal ion. FIG. 2a is a macro topography optical photograph; FIGS. 2b and 2c are scanning electron microscope images at different magnifications; FIG. 1d shows the result of adsorption of iodine vapor. .
Fig. 3 is a graph showing the characterization and iodine adsorption performance test results of BN foam generated by in-situ induction of metallic Cu ions prepared in example 8. FIG. 3a is a macro topography optical photograph; FIGS. 3b and 3c are scanning electron microscope images at different magnifications; FIG. 3d shows the result of adsorption of iodine vapor.
Fig. 4 is a graph showing the characterization and iodine adsorption performance test results of BN foam generated by in-situ induction of metal Mn ions prepared in example 9. FIG. 4a is a macro topography optical photograph; FIGS. 4b and 4c are scanning electron microscope images at different magnifications; FIG. 4d shows the result of adsorption of iodine vapor.
Fig. 5 is the I-t plot of the BN foam blocks generated by in situ induction of metallic Cu ions in example 8 at the end of the iodine adsorption and iodine adsorption experiments.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, in which the high temperature furnace used in the examples is a known apparatus.
Example 1
(1) 0.424g of AgNO 3 Dissolving the mixture in 5mL of deionized water to prepare a metal ion solution with the concentration of 0.0025mol/L for later use.
(2) Mixing boric acid and melamine in a 250mL beaker, and adding 245mL deionized water to prepare a precursor solution, wherein each milliliter of water contains 0.018g of melamine and 0.0126g of boric acid; the mass ratio of boric acid to melamine is 3;
(3) And (3) putting the precursor solution in the step (2) into a constant-temperature stirrer at 90 ℃ and stirring for 2h to completely dissolve the boric acid and the melamine.
(4) 245mL of the solution obtained in step (3) was transferred to room temperature and stirred, and 5mL of the metal ion-containing solution prepared in step (1) was poured while stirring. Stirring for 3min.
(5) And (5) transferring the beaker in the step (4) to an ultrasonic instrument which is cooled to 10 ℃ in advance, and carrying out ultrasonic treatment for 4 hours at the power of 45KHz,350W and 50% until white floccules are completely separated out, so as to obtain a precursor containing metal ions.
(6) Sealing the precursor, transferring to-24 deg.C environment, freezing for 12 hr, taking out, and immediately freezing and vacuum drying in-40 deg.C freeze drier for 6 days. And after the internal water is completely pumped out, putting the precursor into a tube furnace, carrying out heat treatment for 2h at the temperature of 1100 ℃ in the nitrogen atmosphere with the flow rate of 100ml/min, and then changing the atmosphere into ammonia gas to continue heat treatment for 2h at the same gas flow rate and temperature. And after the heat treatment is finished, the foam adsorbent assembled by BN nano-fibers generated by in-situ induction of metal ions is obtained.
(7) 10mg of the prepared adsorbent was added to a closed vessel containing 20g of elemental iodine, and the closed vessel was transferred to an environment at a temperature of 107 ℃. After adsorption for 10min,30min,1h,2h,3h,4h,5h,6h,8h,20h,22h,24h and 26h, the closed container is cooled to room temperature, and the mass of the adsorbent is respectively weighed to determine the adsorption amount of the adsorbent to iodine vapor.
FIG. 1a is a macroscopic optical picture of Ag @ BN foam, from which it can be seen that the adsorbent is a white foam-like block and can be cut into any shape according to the actual application requirements. FIG. 1b shows a scanned image of Ag @ BN foam, and it can be seen from the image that the adsorbent is a three-dimensional bulk structure formed by interweaving and winding nanofibers, and the fibers leave gaps to form a rich pore structure, which is also a main source of mechanical properties of the adsorbent. From FIG. 1c we can see that the internal fiber of Ag @ BN foam has large specific surface area, rich through holes and micropores, and is the main source of adsorption performance. The iodine adsorption performance and results are mainly shown in FIG. 1d, and it is understood from the graph that the adsorption amount of the adsorbent gradually increases with the increase of the adsorption time, the adsorption rate gradually decreases from 10 to 15 hours, and the adsorption capacity approaches the saturation state at about 25 hours. The maximum adsorption was 2234%.
Example 2
The BN block adsorbent obtained in the example 1 after adsorption is placed at a high temperature of 200 ℃ for iodine steam desorption treatment, the adsorption experiment is repeatedly carried out in a cycle after desorption is completed, and after 5 repeated cycles, the obtained adsorption result is similar to that of the example 1.
Example 3
The heat treatment temperature in example 1 was changed to 1050 ℃ and the other operations were the same as in example 1, and the obtained product was the same as in example 1.
Example 4
The freeze-drying time in example 1 was changed to 8 days, and the other operations were the same as in example 1, and the obtained product was the same as in example 1.
Example 5
The ultrasonic time in the example 1 is changed to 5h, the other operations are the same as the example 1, and the obtained product is the same as the example 1.
Example 6
The freezing time in example 1 was changed to 20h, and the other operations were the same as in example 1, and the obtained product was the same as in example 1.
Example 7
Unlike example 1, this example is a BN pure foam obtained without adding metal ions during the preparation, and the other operations are the same as example 1.
As can be seen from the macroscopic optical picture of BN foam shown in fig. 2a, the material obtained without addition of metal ions is also a foam-like block, white in color. From fig. 2b we can see that its internal fibers are intertwined in value, but from fig. 2c we can clearly see from comparison with fig. 1c that the BN foam without added metal ions has thicker internal fibers at the same rate. As shown in FIG. 2d, the adsorption amount of the adsorbent gradually increases with the increase of the adsorption time, the adsorption rate gradually slows down from 8 to 12 hours, and the adsorption capacity gradually approaches the saturation state around 20 hours. The maximum adsorption amount is 210%, which is far lower than the maximum adsorption amount of BN foam added with metallic silver ions.
Example 8
0.424gAgNO of example 1 3 Changed to 0.426g CuCl 2 ·2H 2 And O, connecting the block material with an electrode in the adsorption process, connecting the other end of the lead with a four-probe light source instrument (KEITHLEY, model2400series resource) capable of detecting current in real time, and obtaining an I-t curve after the adsorption is finished, wherein other operations are the same as those in the embodiment 1.
From the macroscopic optical picture of BN foam shown in fig. 3a, it can be seen that BN foam with added metallic copper ions has a pink color. From fig. 3b and fig. 3c, it can be known that the BN fibers generated by in-situ induction of metal copper ions are finer than the fibers of BN foams without metal ions, and the large metal particles on the surface are less than the BN foams with metal silver ions added, because the higher melting point of copper is not easy to dissolve and volatilize in a large amount during high temperature treatment, so that more metal ions act in the BN fibers. From fig. 3d, it can be seen that the iodine adsorption amount of the BN foam added with metal copper ions is far higher than that of the BN foam without metal ions, which reaches 1739%. Fig. 5 is an I-t curve after adsorption is completed, and it can be seen from the graph that the electric conduction capacity of the high-temperature adsorption device is close to an insulation state when the high-temperature adsorption is not started, and the electric conduction capacity is improved by about 6 orders of magnitude after a period of high-temperature adsorption, so that the potential of the high-temperature adsorption device with the high-temperature semiconductor is judged, and the thought is widened for the future high-temperature semiconductor research.
Example 9
0.424gAgNO of example 1 3 Changed to 0.314gMnCl 2 The other operations are the same as those in embodiment 1.
From the scanning picture of fig. 4b, it can be seen that the BN foam added with manganese ions has longer internal fibers and smaller diameter. The maximum adsorption reached 2807% as shown in FIG. 4 d.
The mechanism of the invention is as follows: according to the invention, a large number of researches and experiments are carried out to draw a conclusion that compared with a BN foam block material without any metal ions, the BN foam block material with the metal ions added therein has long and thin fibers due to the in-situ induction effect of the metal ions, and the single fiber has rich hole structures, so that the mechanical property and the adsorption property of the BN foam block material are greatly improved. On the other hand, the reasonable raw material proportion and the heat treatment atmosphere ensure that the adsorbent can be prepared in a large scale.
By characterizing the samples obtained in the above examples, we can derive: by adding metal ions, the BN foam block adsorbent which is large in adsorption capacity, fine in fiber and uniform in internal appearance is prepared. In the whole process, all the steps are simple to operate without harsh test conditions, all the used equipment is common equipment in a laboratory, and no organic solvent is added except deionized water in the synthesis process, so that the pollution to the environment in the material preparation process is effectively reduced, and the safety in the material preparation process is improved. The foam has good adsorption performance to iodine. The environment-friendly synthesis method which can lead the material to be produced in batch widens the way for the mass synthesis of BN foam added with metal ions, the synthesis and application of the adsorption material and the like.
The invention is not the best known technology.
Claims (3)
1. A method of making a boron nitride bulk sorbent for treating iodine vapor contaminants, characterized in that the method comprises the steps of:
(1) Dissolving a metal ion compound in deionized water to prepare a metal ion solution for later use;
wherein, in the metal ionic compound, the metal ions are Ag \8314, cu \\8314, or Mn \8314; the anion being NO 3 \8315orCl \8315; the concentration of metal ions in the solution is 0.001-0.005mol/L;
(2) Adding boric acid and melamine into deionized water, and continuously stirring for 1 to 4 hours on a constant-temperature stirrer at the temperature of 70-99 ℃ to prepare a precursor solution;
wherein, the concentration of the melamine and the boric acid is 0.01 to 0.02g per milliliter of water; the mass ratio of boric acid to melamine is 2;
(3) Stirring the precursor solution at normal temperature, and pouring the metal ion solution prepared in the step (1) while stirring; then continuously stirring for 3-6min;
wherein the volume ratio is precursor solution: metal ion solution = 245-240: 5-10;
(4) Putting the solution in the step (3) into an ultrasonic instrument which is cooled to 5-20 ℃ in advance for ultrasonic treatment for 1-6 h until floccules are separated out, and obtaining a precursor containing metal ions;
(5) Sealing the precursor, freezing for 1-24h in a low-temperature environment, taking out, and immediately putting into a freeze dryer for freeze drying for 4-10 days; then putting the precursor into a tube furnace, carrying out heat treatment for 1-5h at 900-1500 ℃ under the protection atmosphere of nitrogen, changing the protection atmosphere into ammonia gas, continuing heat treatment for 1-5h at the same flow rate and temperature, and finally cooling to room temperature to obtain the boron nitride bulk adsorbent containing metal particles;
wherein the freezing temperature is minus 30 ℃ to minus 10 ℃, and the freezing drying temperature is minus 50 ℃ to minus 24 ℃; the flow rate of the protective gas is 60-100mL/min;
the boron nitride block is constructed by BN nano-fiber generated by in-situ induction of metal ions, and the diameter range of the BN nano-fiber is 100-800nm.
2. The preparation method of the boron nitride block adsorbent for treating iodine vapor pollutants as claimed in claim 1, characterized in that the ultrasonic frequency is 20-100KHz, and the power is 30 to 350W.
3. Use of a boron nitride bulk sorbent for the treatment of iodine vapor contaminants prepared by the method of claim 1, characterized by its use for the adsorption and storage of iodine vapor.
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