CN114669279B - Preparation and application of bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material - Google Patents
Preparation and application of bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material Download PDFInfo
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Abstract
The invention discloses preparation and application of a bismuth-based plant tannin@collagen fiber hydrothermal carbon efficient iodine-immobilized vapor material, which comprises the following steps: crosslinking and solidifying the activated collagen fibers and the vegetable tannin aldehyde solution, and drying; adding the prepared material and bismuth nitrate pentahydrate into ethylene glycol, performing ultrasonic reaction, adding Vc-absolute ethyl alcohol solution, then placing into a hydrothermal reaction kettle for reaction, cooling to room temperature, and filtering; and adding sodium borohydride-absolute ethyl alcohol solution into the filtered material, standing for reduction, filtering and drying to obtain the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material. Through effective immobilization of plant tannin, bismuth ions are effectively combined on collagen fibers, a layer of granular matters is covered on the collagen fibers, the property is stable, the immobilization performance on iodine vapor is good, the stable chemical iodine immobilization amount is high, and the iodine is mainly obtained by BiI after being captured 3 The compound exists in a form which is not easy to volatilize, thus being beneficial to the stable storage and treatment of the radioactive gaseous iodine.
Description
Technical Field
The invention belongs to the environment-friendly field of radioactive gaseous iodine adsorption and immobilization in the environment by biomass leather waste materials, and particularly relates to a preparation method and application of a bismuth-based plant tannin@collagen fiber hydrothermal carbon efficient immobilization iodine vapor material.
Background
Collagen fiber is the most abundant renewable natural polymer material in nature, and is widely applied to leather industry. In the animal skin raw material processing process of China, about 140 ten thousand tons of leather waste are produced each year, most of the waste is difficult to reuse, waste of raw material resources is caused, and serious pollution is caused to the environment. The carboxyl, amino and hydroxyl in the collagen fiber have stronger induction adsorption effect on iodine molecules, and provide a large number of active sites for effective adsorption of iodine. However, due to the supercoiled structure between the collagen fiber molecules, an inter-chain hydrogen bond structure exists between active groups, resulting in shielding of active binding sites, thereby reducing the adsorption capacity of iodine. How to reuse leather waste resources has been a hot spot of concern to researchers. Researches show that after the leather waste is subjected to treatments such as cleaning, alkali treatment, dehydration and the like by a conventional method, the leather waste can be converted into collagen fibers with stronger hydrophilicity, but the collagen fibers are not dissolved in water, are in a dispersed state after swelling in water, have good biocompatibility, can be subjected to biodegradation treatment easily in the later stage, and cannot pollute the environment.
With the continuous increase of global energy demand, nuclear energy has attracted global attention due to the characteristics of safety, high efficiency, cleanliness, low cost, low-temperature gaseous emissions and the like. Currently, more than 400 nuclear power plants are built in 31 countries and regions worldwide, the generated energy accounts for approximately 11.5% of the generated energy worldwide, and 23 to 100% of the generated energy is expected to increase in 2030. However, the most prominent problem in nuclear power plant operation is the large amount of radioactive waste generated during spent fuel treatment, mainly including C-14, I-129, I-131, cs-134, cs-137, co-60, sr-90, ce-144, kr-85 and Xe-13. During the nitric acid treatment of spent fuel, most of the substances are further oxidized into volatile I 2 94-99% of I 2 ( 129 I and 131 i) In gaseous form from the solution. 131 The half-life of I is short (8.02 days), and the I does not cause long-term harm to the environment 129 The half-life of I is longer (1.57×10 7 Years), greater toxicity in the environment, and longer duration. Because of the high fluidity and volatility of radioiodine, it is easily accumulated and diffused in the atmosphere and can be concentrated in organisms via inhaled gas or food chain, resulting in thyroid diseases and even cancer. During the occurrence of nuclear leakage accidents of the Chernobeli and the Fudao, a large amount of radioactive iodine is generated in the air, and the radioactive iodine cannot be effectively removed in time, thus the serious threat to human health is formed. Thus, radioactivity is effectively captured and immobilizedIodine vapor has become one of the hot spot problems of global concern.
In recent years, numerous researches show that the bismuth-based loaded material can rapidly capture iodine simple substances, and has the characteristics of low cost, easy synthesis of the material, low toxicity, high adsorption capacity and the like compared with other materials (silver doped zeolite materials, MOFs materials and the like) for capturing iodine vapor. Bismuth-based material is converted into BiI after absorbing iodine vapor 3 And BiOI, has good thermodynamic stability, and even BiI 3 And the BiOI is more stable in a strong-reducibility groundwater environment than the AgI which is reported to be most effective in absorbing iodine at present, and is a novel high-efficiency solidification adsorbent for iodine. Bismuth-containing group adsorbent Material pair I 2 、I - And IO (input/output) 3 - Exhibits adsorption properties superior to those of current commercial silver-loaded zeolites. Compared with silver-based materials, the bismuth-based material has the advantages of wide source, low price, stable property and no pollution to the environment, and is a better candidate precursor material.
Plant polyphenol is a renewable plant resource commonly existing in nature, contains rich phenolic hydroxyl structures, has a strong chelation effect on metal ions, and also has a certain induction adsorption effect on iodine. Many researchers fix the plant tannin on water insoluble matrixes such as cellulose, filter membrane and the like, can realize effective adsorption of heavy metal ions in solution, and can also be used as an effective load material of bismuth ions.
Disclosure of Invention
Aiming at the technical defects, the invention provides the bismuth-based collagen fiber material which has the advantages of low cost, no secondary pollution to the environment, stable property, difficult volatilization after iodine is captured, natural biodegradation, no toxicity and no harm. According to the invention, by combining the characteristics of the collagen fiber, after the biomass raw material is subjected to alkali treatment, more hydroxyl and amino groups are exposed in the collagen fiber, and meanwhile, more polyphenol structures can be introduced by the immobilized energy of the plant tannin, so that the bismuth ion loading and iodine capturing are facilitated; the added Vc can effectively prevent bismuth ions from being oxidized in the process of preparing the hydrothermal carbon, and meanwhile, the added sodium borohydride solution further reduces bismuth in an oxidized state into zero-valent bismuth. The immobilization adsorption of iodine vapor mainly comprises the reaction of zero-valent bismuth and iodine to generate stableBiI of (F) 3 And a part of BiOI products, and the physical adsorption quantity is lower.
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing a bismuth-based vegetable tannin @ collagen fiber hydrothermal charcoal high-efficiency iodine-immobilized vapor material, comprising the steps of:
step one, cross-linking and solidifying activated collagen fibers and plant tannins in aldehyde solution with a certain concentration, and drying;
adding the material prepared in the first step and bismuth nitrate pentahydrate into ethylene glycol, performing ultrasonic reaction, adding Vc-absolute ethyl alcohol solution, then placing the mixture into a hydrothermal reaction kettle for reaction, cooling to room temperature, and filtering;
and thirdly, adding the filtered material into a sodium borohydride-absolute ethyl alcohol solution, standing for reduction, filtering and drying to obtain the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material.
Preferably, the preparation method of the activated collagen fiber comprises the following steps: adding collagen fibers into deionized water, ultrasonically cleaning for 4-6 hours to be neutral, filtering, and drying in a vacuum drying oven; crushing the dried collagen fibers to 30-100 meshes by using a crusher, dissolving the crushed collagen fibers in deionized water, adding alkali to adjust the pH of the solution, ultrasonically cleaning the solution for 1-3 hours by using the deionized water, filtering the solution, and drying the solution in a vacuum drying oven for later use.
Preferably, the temperature of the ultrasonic cleaning is room temperature to 70 ℃, and the temperature of the ultrasonic cleaning is room temperature to 70 ℃ after the ultrasonic cleaning is dried in a vacuum drying oven; the collagen fiber is animal skin which is not tanned, and is subjected to washing, alkali treatment and dehydration treatment according to a conventional method, and then is crushed by a crusher to obtain granular substances with the particle size of 10-80 meshes; the ultrasonic cleaning frequency is 40-60 kHz, and the power is 800-1000W; the alkali is one or more of potassium hydroxide, sodium hydroxide, ammonium hydroxide and sodium carbonate; the pH of the solution is adjusted to 8-14.
Preferably, the vegetable tannin is any one of gallotannins, myricetin, ellagitannin and condensed tannins; the time of the crosslinking and curing is 1-24 hours, the temperature is 0-80 ℃, the crosslinking and curing are carried out in a constant temperature shaking table, and the shaking amplitude of the constant temperature shaking table is 100-150 rpm; the mass ratio of the activated collagen fiber to the vegetable tannin is 0.1-10:1; the aldehyde solution is formaldehyde solution or glutaraldehyde solution with the concentration of 0.1-20wt%; the mass-volume ratio of the total mass of the activated collagen fibers and the vegetable tannin to the aldehyde solution is 5g to 50mL.
Preferably, the cross-linking and curing are carried out in a microwave and ultrasonic integrated reactor, the temperature of the co-processing is 65-85 ℃ and the time is 30-45 min; the microwave power of the cooperative treatment is 800-1200W, the ultrasonic power is 800-1200W, and the ultrasonic frequency is 35-45 KHz.
Preferably, in the second step, the mass ratio of the material prepared in the first step to bismuth nitrate pentahydrate is 0.1-35:1; the mass volume ratio of the material prepared in the first step to the glycol is 3g to 30mL, and the ultrasonic reaction time is 2-5 hours; the power of the ultrasonic reaction is 800-1200W, and the frequency is 40-60 KHz.
Preferably, in the second step, the mass volume ratio of the material prepared in the first step to the Vc-absolute ethanol solution is 3g:30mL, and the concentration of the Vc-absolute ethanol solution is 0.005-0.02 g/mL; the hydrothermal reaction kettle is lined with polytetrafluoroethylene, the reaction temperature is 60-300 ℃, and the reaction time is 1-12 hours.
Preferably, in the second step, before the mixture is placed in a hydrothermal reaction kettle to react, three-frequency ultrasound is applied and stirred for 15-30 min, the three-frequency ultrasound is applied in an alternating manner, and the process of applying in the alternating manner is as follows: treating at 35-45 KHz for 30-60 s, 140-160 KHz for 30-90 s, and 80-110 KHz for 30-60 s; the power of the three-frequency ultrasonic wave is 1000-1500W.
Preferably, in the third step, the concentration of the sodium borohydride-absolute ethanol solution is 0.01-20mol/L; the mass volume ratio of the material prepared in the first step to the sodium borohydride-absolute ethyl alcohol solution is 3g to 30mL; the standing reduction time is 2-12 h.
The invention also provides an application of the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material prepared by the preparation method in removal of radioactive iodine.
The invention at least comprises the following beneficial effects:
(1) The effective immobilization of the plant tannin promotes bismuth ions to be effectively combined on the collagen fiber, and the collagen fiber is covered with a layer of granular matters, so that the property is stable, the immobilization performance on iodine vapor is better, the stable chemical iodine immobilization amount is higher, and is far higher than that of the currently reported biomass material, and the bismuth is mainly taken as BiI after being captured 3 The compound exists in a form which is not easy to volatilize, thus being beneficial to the stable storage and treatment of the radioactive gaseous iodine.
(2) The raw materials used in the invention are waste materials and natural plant resources generated by leather scraps, the problem of environmental pollution is solved, the source is abundant, the price is low, and the natural organisms in the later stage are easier to degrade.
(3) The preparation process is environment-friendly, and secondary pollution to the environment in the preparation process is avoided.
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. 1a is an SEM image of a vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material bt@acf HC prepared in comparative example 1; fig. 1b is an SEM image of the bismuth-based vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material Bi-bt @ acf HC prepared in example 2; FIG. 1c shows Bi-BT@ACF HC-I after adsorbing iodine by the bismuth-based vegetable tannin@collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in example 2 2 SEM images of (a);
fig. 2a is a PXRD graph of the vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material bt@acf HC prepared in comparative example 1 before and after iodine adsorption; fig. 2b is a PXRD graph of the bismuth-based vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material prepared in example 2 before and after iodine adsorption;
FIG. 3 shows Bi-BT@ACF HC and Bi-BT@ACF HC-I 2 XPS total profile of (b);
FIG. 4 shows Bi-BT@ACF HC and Bi-BT@ACF HC-I 2 XPS (Bi 4 f);
FIG. 5 shows Bi-BT@ACF HC and Bi-BT@ACF HC-I 2 XPS graph (I3 d);
FIG. 6 is a graph showing the effect of chemical and physical iodine fixation on the material prepared according to the present invention;
FIG. 7 is a graph showing the effect of chemical and physical iodine fixation on the material prepared according to the present invention.
The specific embodiment is as follows:
the present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of a bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material comprises the following steps:
step one, cross-linking and solidifying 4g of activated collagen fibers and 1g of waxberry tannin in 50mL of glutaraldehyde solution with the concentration of 10wt%, and drying; the time of the crosslinking and curing is 4 hours, the temperature is 45 ℃, the crosslinking and curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125rpm;
adding 3g of the material prepared in the first step and 0.1g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, performing ultrasonic reaction for 3h (the power of ultrasonic reaction is 800W, the frequency is 45 KHz), then adding 30mL of Vc-absolute ethanol solution with the concentration of 0.01g/mL, placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 160 ℃, cooling to room temperature, and filtering;
adding 30mL of sodium borohydride-absolute ethyl alcohol solution with the concentration of 0.3mol/L into the filtered material in the step II, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material;
the preparation method of the activated collagen fiber comprises the following steps: cleaning animal skin without tanning treatment, alkali treatment, dewatering treatment by conventional method, and pulverizing by pulverizer to obtain granular collagen fiber with particle diameter of 30 mesh; adding collagen fibers into deionized water, ultrasonically cleaning for 5 hours to neutrality, filtering, and drying in a vacuum drying oven; crushing 5g of dried collagen fibers to 50 meshes by using a crusher, dissolving the crushed collagen fibers in 500mL of deionized water, adding sodium hydroxide to adjust the pH of the solution to 13, carrying out ultrasonic treatment for 2 hours, cleaning by using the deionized water, filtering, and drying in a vacuum drying oven for later use; the ultrasonic cleaning temperature and the vacuum drying temperature are controlled at 35 ℃; the ultrasonic cleaning frequency is 45kHz and the power is 800W;
example 2:
a preparation method of a bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material comprises the following steps:
step one, cross-linking and solidifying 4g of activated collagen fibers and 1g of waxberry tannin in 50mL of glutaraldehyde solution with the concentration of 10wt%, and drying; the time of the crosslinking and curing is 4 hours, the temperature is 45 ℃, the crosslinking and curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125rpm;
adding 3g of the material prepared in the first step and 0.5g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, performing ultrasonic reaction for 3h (the power of ultrasonic reaction is 800W, the frequency is 45 KHz), then adding 30mL of Vc-absolute ethanol solution with the concentration of 0.01g/mL, placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 160 ℃, cooling to room temperature, and filtering;
adding 30mL of sodium borohydride-absolute ethyl alcohol solution with the concentration of 0.3mol/L into the filtered material in the step II, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material (Bi-BT@ACF HC);
the preparation method of the activated collagen fibers is described in example 1;
example 3:
a preparation method of a bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material comprises the following steps:
step one, cross-linking and solidifying 4g of activated collagen fibers and 1g of waxberry tannin in 50mL of glutaraldehyde solution with the concentration of 10wt%, and drying; the time of the crosslinking and curing is 4 hours, the temperature is 45 ℃, the crosslinking and curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125rpm;
adding 3g of the material prepared in the step one and 1g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, performing ultrasonic reaction for 3h (the power of ultrasonic reaction is 800W, the frequency is 45 KHz), then adding 30mL of Vc-absolute ethanol solution with the concentration of 0.01g/mL, placing into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 160 ℃, cooling to room temperature, and filtering;
adding 30mL of sodium borohydride-absolute ethyl alcohol solution with the concentration of 0.3mol/L into the filtered material in the step II, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material;
the preparation method of the activated collagen fibers is described in example 1;
example 4:
a preparation method of a bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material comprises the following steps:
step one, cross-linking and solidifying 4g of activated collagen fibers and 1g of waxberry tannin in 50mL of glutaraldehyde solution with the concentration of 10wt%, and drying; the time of the crosslinking and curing is 4 hours, the temperature is 45 ℃, the crosslinking and curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125rpm;
adding 3g of the material prepared in the first step and 5g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, performing ultrasonic reaction for 3h (the power of ultrasonic reaction is 800W, the frequency is 45 KHz), then adding 30mL of Vc-absolute ethanol solution with the concentration of 0.01g/mL, placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 160 ℃, cooling to room temperature, and filtering;
adding 30mL of sodium borohydride-absolute ethyl alcohol solution with the concentration of 0.3mol/L into the filtered material in the step II, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material;
the preparation method of the activated collagen fibers is described in example 1;
comparative example 1:
step one, cross-linking and solidifying 4g of activated collagen fibers and 1g of waxberry tannin in 50mL of glutaraldehyde solution with the concentration of 10wt%, and drying; the time of the crosslinking and curing is 4 hours, the temperature is 45 ℃, the crosslinking and curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125rpm;
adding 3g of the material prepared in the step one into 30mL of ethylene glycol, performing ultrasonic reaction for 3h (the power of ultrasonic reaction is 800W, the frequency is 45 KHz), adding 30mL of Vc-absolute ethyl alcohol solution with the concentration of 0.01g/mL, placing the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 160 ℃, cooling to room temperature, and filtering;
adding 30mL of sodium borohydride-absolute ethyl alcohol solution with the concentration of 0.3mol/L into the filtered material in the step II, standing and reducing for 6 hours, filtering and drying to obtain the high-efficiency solid-supported iodine vapor material (BT@ACF HC) of the plant tannin@collagen fiber hydrothermal carbon;
the preparation method of the activated collagen fibers is described in example 1;
example 5:
a preparation method of a bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material comprises the following steps:
step one, cross-linking and solidifying 4g of activated collagen fibers and 1g of waxberry tannin in 50mL of glutaraldehyde solution with the concentration of 10wt%, and drying; the cross-linking curing adopts the cooperative treatment in a microwave and ultrasonic integrated reactor, the temperature of the cooperative treatment is 70 ℃ and the time is 30min; the microwave power of the cooperative treatment is 1200W, the ultrasonic power is 800W, and the ultrasonic frequency is 45KHz;
adding 3g of the material prepared in the first step and 0.5g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, performing ultrasonic reaction for 3h (the power of ultrasonic reaction is 800W, the frequency is 45 KHz), then adding 30mL of Vc-absolute ethanol solution with the concentration of 0.01g/mL, placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 160 ℃, cooling to room temperature, and filtering;
adding 30mL of sodium borohydride-absolute ethyl alcohol solution with the concentration of 0.3mol/L into the filtered material in the step II, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material;
the preparation method of the activated collagen fibers is described in example 1;
example 6:
a preparation method of a bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material comprises the following steps:
step one, cross-linking and solidifying 4g of activated collagen fibers and 1g of waxberry tannin in 50mL of glutaraldehyde solution with the concentration of 10wt%, and drying; the cross-linking curing adopts the cooperative treatment in a microwave and ultrasonic integrated reactor, the temperature of the cooperative treatment is 70 ℃ and the time is 30min; the microwave power of the cooperative treatment is 1200W, the ultrasonic power is 800W, and the ultrasonic frequency is 45KHz;
adding 3g of the material prepared in the first step and 0.5g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, performing ultrasonic reaction for 3h (the power of ultrasonic reaction is 800W, the frequency is 45 KHz), then adding 30mL of Vc-absolute ethyl alcohol solution with the concentration of 0.01g/mL, applying three-frequency ultrasonic to the mixed material, stirring for 20min, then placing the mixed material into a hydrothermal reaction kettle with a polytetrafluoroethylene lining for reaction at 160 ℃ for 12h, cooling to room temperature, and filtering; the three-frequency ultrasonic wave is applied in an alternating mode, and the process of applying in the alternating mode is as follows: processing at 35KHz for 60s, 145KHz for 90s, and 90KHz for 60s; the power of the three-frequency ultrasonic wave is 1200W;
adding 30mL of sodium borohydride-absolute ethyl alcohol solution with the concentration of 0.3mol/L into the filtered material in the step II, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material;
the preparation method of the activated collagen fibers is described in example 1;
fig. 1a is an SEM image of a vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material bt@acf HC prepared in comparative example 1; fig. 1b is an SEM image of the bismuth-based vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material Bi-bt @ acf HC prepared in example 2; drawing of the figure1c is Bi-BT@ACF HC-I after adsorbing iodine by the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in example 2 2 SEM images of (a);
fig. 2a is a PXRD graph of the vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material bt@acf HC prepared in comparative example 1 before and after iodine adsorption; the results show that the BT@ACF HC is amorphous before and after capturing iodine, no characteristic diffraction peak of crystal iodine appears, and no absorption vibration peak of crystal iodine is near 731cm < -1 >, which shows that the capturing of the iodine by the BT@ACF HC is not the deposition of iodine crystals on the surface of the material, but the capturing of the iodine after acting with an active site. Fig. 2b is a PXRD graph of the bismuth-based vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material prepared in example 2 before and after iodine adsorption; the Bi-BT@ACF HC material has typical diffraction characteristic peaks which indicate that a crystal structure is generated in the material, and the diffraction peaks are found to be attributed to Bi0 (PDF No. 44-1246) at 22.5, 27.2, 38.0, 39.6, 44.6, 48.7, 56.1, 62.2 and 64.50 by standard card comparison. While Bi-BT@ACF HC-I 2 The diffraction peaks of the curves are obviously changed, which shows that after iodine is captured by Bi-BT@ACFHC, the crystal structure is changed, the diffraction peak originally attributed to Bi0 disappears, and new diffraction characteristic peaks appear, and the diffraction peaks are found in 12.8, 14.2, 16.0, 27.0, 35.3, 41.5, 43.7, 46.2, 50.2, 53.0, 55.6, 58.3, 63.8, 67.1, 69.5, 71.8 and 72.80 to be attributed to BiI 3 (PDF No. 48-1795) shows that BiI is produced after the simple substance bismuth reacts with iodine 3 And (3) phase (C). The reaction mechanism of bismuth metal to capture iodine is mainly Bi0 and I 2 After chemical reaction, biI is generated 3 The phase fixes the iodine.
XPS characterization was used to study the valence state changes of the elements, further revealing the interaction between Bi-BT@ACF HC and iodine. FIG. 3 shows Bi-BT@ACF HC and Bi-BT@ACF HC-I 2 XPS total profile of (b); FIG. 4 shows Bi-BT@ACF HC and Bi-BT@ACF HC-I 2 XPS (Bi 4 f); FIG. 5 shows Bi-BT@ACF HC and Bi-BT@ACF HC-I 2 XPS graph (I3 d); bi-BT@ACF HC and Bi-BT@ACF HC-I 2 Peaks at 159.2eV and 164.5eV correspond to Bi4f7/2 and Bi4f5/2 characteristic peaks respectively, which shows that the material successfully carries bismuth. After capturing iodine by Bi-BT@ACF HC, new peaks at 619.4eV and 630.9eV correspond to I3 respectivelyd5/2 and I3d3/2 characteristic peaks indicate that iodine is adsorbed on Bi-BT@ACFHC. The Bi4f spectrum of Bi-BT@ACF HC is decomposed into two sets of overlapping peaks, bi3+ (164.2 eV and 158.8 eV) and Bi0 (163.5 eV and 158.2 eV), respectively, indicating that the immobilized Bi3+ portion of the material is reduced to Bi0. After iodine is captured by Bi-BT@ACF HC, the Bi4f spectrum of the HC has only one group of overlapped peaks, which are characteristic peaks of Bi3+ (164.5 eV and 159.1 eV), so that Bi3+ substances are generated after the Bi0 reacts with the iodine. Further analysis of the spectral peak information combined with iodine shows that the I3d spectrum of Bi-BT@ACFHC-I2 is mainly decomposed into two groups of overlapped peaks, I2 (631.4 eV and 619.7 eV) and I-or I3- (630.8 eV and 619.3 eV) respectively, which shows that iodine vapor and Bi-BT@ACFHC are in contact with each other to generate I-and I3-type substances. The combination of Bi4f spectrum information is presumed to be probably caused by the reaction of Bi0 and I2 to generate a BiI3 phase, so that the characterization analysis result of PXRD is further verified; by combining the results, it is speculated that the capturing of Bi-BT@ACF HC to iodine is mainly that Bi0 and I2 are chemically reacted to generate BiI3 phase, and meanwhile, part of iodine is combined with active groups in the material to lead to the capture of iodine molecules after polarization, so that the capturing of Bi-BT@ACF HC to iodine is mainly based on chemical adsorption and is accompanied by physical adsorption.
The invention adopts the radioactive iodine simple substance to replace the radioactive iodine simple substance for carrying out the iodine fixation experiment. Firstly, placing excessive iodine simple substance at the bottom of a 250mL serum bottle, taking 100mg bismuth-based plant tannin@collagen fiber hydrothermal carbon material (respectively prepared in examples 1-6 and comparative example 1) and commercially available pure bismuth powder (99.99%, 200 meshes, shanghai Michelin Biochemical technology Co., ltd.) to be placed in filter paper folded into a funnel shape, placing the filter paper in a serum bottle mouth, screwing a bottle cap, sealing the bottle cap by a sealing film, placing the serum bottle in a 200 ℃ oven, absorbing for 6 hours, taking out from the oven, cooling to room temperature, measuring the content of iodine vapor absorbed by the bismuth-based plant tannin@collagen fiber hydrothermal carbon according to a weight method, carrying out three absorption experiments on each absorption material in parallel, and taking an average value. After the material after iodine is captured is processed for 6 hours in an oven at 119 ℃, weighing again, and calculating stable chemical iodine fixing amount according to the loss of front and rear mass; wherein the bismuth-based plant tannin@collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in example 2 is expressed as Bi-BT@ACF HC-I after iodine adsorption 2 The method comprises the steps of carrying out a first treatment on the surface of the The vegetable tannin@collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in comparative example 1 is expressed as (BT@ACF HC-I after iodine adsorption 2 )；
Fig. 6 shows the iodine adsorption effects of examples 1 to 4, comparative example 1 and pure bismuth powder, and it can be seen from the graph that the material prepared by the invention has better immobilization performance on iodine vapor and higher stable chemical iodine fixation amount; fig. 7 shows the iodine adsorption effects of examples 2 and 5 to 6, and it can be seen from the figures that the chemical iodine fixation amount of the materials prepared in examples 5 to 6 is significantly improved, because the crosslinking solidification effect is improved by using the cavitation of ultrasonic waves and the high-speed oscillation principle of microwaves through the reaction in the microwave and ultrasonic integrated reactor, the chemical iodine fixation amount of the materials is further improved, and meanwhile, the mixing uniformity degree of each material is further improved by using multi-frequency ultrasonic waves, so that the oxidation of bismuth ions in the process of preparing the hydrothermal carbon can be effectively prevented, and the chemical iodine fixation amount is further improved.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (8)
1. The preparation method of the bismuth-based vegetable tannin@collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material is characterized by comprising the following steps of:
step one, cross-linking and solidifying activated collagen fibers and plant tannins in aldehyde solution with a certain concentration, and drying;
adding the material prepared in the first step and bismuth nitrate pentahydrate into ethylene glycol, performing ultrasonic reaction, adding Vc-absolute ethyl alcohol solution, then placing the mixture into a hydrothermal reaction kettle for reaction, cooling to room temperature, and filtering;
adding sodium borohydride-absolute ethyl alcohol solution into the material filtered in the step II, standing for reduction, filtering, and drying to obtain the bismuth-based vegetable tannin@collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material;
the vegetable tannin is any one of gallotannin, myricetin or ellagitannin; the mass ratio of the activated collagen fibers to the vegetable tannin is 0.1-10:1; the aldehyde solution is formaldehyde solution or glutaraldehyde solution with the concentration of 0.1-20wt%; the mass-volume ratio of the total mass of the activated collagen fibers and the vegetable tannin to the aldehyde solution is 5g to 50mL;
the cross-linking curing is carried out in a microwave and ultrasonic integrated reactor, the temperature of the co-processing is 65-85 ℃ and the time is 30-45 min; the microwave power of the cooperative treatment is 800-1200W, the ultrasonic power is 800-1200W, and the ultrasonic frequency is 35-45 KHz.
2. The preparation method of the bismuth-based plant tannin@collagen fiber hydrothermal carbon efficient iodine-immobilized vapor material is characterized by comprising the following steps of: adding the collagen fibers into deionized water, ultrasonically cleaning for 4-6 hours to be neutral, filtering, and drying in a vacuum drying oven; crushing the dried collagen fibers to 30-100 meshes by using a crusher, dissolving the crushed collagen fibers in deionized water, adding alkali to adjust the pH of the solution, carrying out ultrasonic treatment for 1-3 hours, cleaning by using the deionized water, filtering, and drying in a vacuum drying oven for later use.
3. The preparation method of the bismuth-based plant tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material is characterized by comprising the steps of carrying out ultrasonic cleaning at a temperature of room temperature to 70 ℃, and drying in a vacuum drying oven at a temperature of room temperature to 70 ℃; the collagen fiber is animal skin which is not tanned, and is subjected to washing, alkali treatment and dehydration treatment according to a conventional method, and then is crushed by a crusher to obtain granular substances with the particle size of 10-80 meshes; the ultrasonic cleaning frequency is 40-60 kHz, and the power is 800-1000W; the alkali is one or more of potassium hydroxide, sodium hydroxide, ammonium hydroxide and sodium carbonate; the pH of the solution is adjusted to 8-14.
4. The preparation method of the bismuth-based plant tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material is characterized by comprising the following steps of, in the second step, preparing a material and bismuth nitrate pentahydrate in a mass ratio of 0.1-35:1; the mass volume ratio of the material prepared in the first step to the ethylene glycol is 3g to 30mL, and the ultrasonic reaction time is 2-5 hours; the power of the ultrasonic reaction is 800-1200W, and the frequency is 40-60 KHz.
5. The preparation method of the bismuth-based plant tannin@collagen fiber hydrothermal charcoal efficient immobilized iodine vapor material is characterized by comprising the following steps of, in the second step, preparing a material and Vc-absolute ethyl alcohol solution, wherein the mass volume ratio of the material prepared in the first step to the Vc-absolute ethyl alcohol solution is 3g:30mL, and the concentration of the Vc-absolute ethyl alcohol solution is 0.005-0.02 g/mL; the hydrothermal reaction kettle is lined with polytetrafluoroethylene, the reaction temperature is 60-300 ℃, and the reaction time is 1-12 hours.
6. The preparation method of the bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material according to claim 1, wherein in the second step, three-frequency ultrasound is applied to the mixed material and stirred for 15-30 min before the mixed material is placed in a hydrothermal reaction kettle for reaction, the three-frequency ultrasound is applied in an alternating mode, and the process of applying in the alternating mode is as follows: treating for 30-60 s at a frequency of 35-45 KHz, treating for 30-90 s at 140-160 KHz, and treating for 30-60 s at 80-110 KHz; the power of the three-frequency ultrasonic wave is 1000-1500W.
7. The preparation method of the bismuth-based plant tannin@collagen fiber hydrothermal charcoal high-efficiency immobilized iodine vapor material is characterized by comprising the following steps of, in the third step, the concentration of a sodium borohydride-absolute ethyl alcohol solution is 0.01-20mol/L; the mass volume ratio of the material prepared in the first step to the sodium borohydride-absolute ethyl alcohol solution is 3g to 30mL; and standing and reducing for 2-12 h.
8. The application of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency immobilized iodine vapor material prepared by the preparation method of any one of claims 1-7 in removal of radioactive iodine.
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