CN114669279A - Preparation and application of bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material - Google Patents
Preparation and application of bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material Download PDFInfo
- Publication number
- CN114669279A CN114669279A CN202210380147.2A CN202210380147A CN114669279A CN 114669279 A CN114669279 A CN 114669279A CN 202210380147 A CN202210380147 A CN 202210380147A CN 114669279 A CN114669279 A CN 114669279A
- Authority
- CN
- China
- Prior art keywords
- iodine
- bismuth
- immobilized
- collagen fiber
- plant tannin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/02—Treating gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4856—Proteins, DNA
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method and application of a bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material, which comprises the following steps: crosslinking and curing the activated collagen fibers and the plant tannin aldehyde solution, and drying; adding the prepared material and bismuth nitrate pentahydrate into ethylene glycol, performing ultrasonic reaction, adding a Vc-absolute ethyl alcohol solution, placing the mixture into a hydrothermal reaction kettle for reaction, cooling to room temperature, and filtering; and adding the filtered material into a sodium borohydride-absolute ethyl alcohol solution, standing, reducing, filtering and drying to obtain the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material. The effective immobilization of the plant tannin promotes the bismuth ions to be effectively bonded on the collagen fibers,presents a layer of granular material covering the collagen fiber, has stable property, better iodine vapor immobilization performance and higher stable chemical iodine immobilization amount, and the iodine is mainly captured by BiI3The compound exists in a form, is not easy to volatilize, and is beneficial to the stable storage and treatment of radioactive gaseous iodine.
Description
Technical Field
The invention belongs to the environmental protection field of biomass leather waste materials used for absorbing and immobilizing radioactive gaseous iodine in the environment, and particularly relates to a preparation method and application of a bismuth-based plant tannin and collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material.
Background
The collagen fiber is a renewable natural polymer material with the most abundant content in the nature, and is widely applied to the leather industry. In the process of processing animal skin raw materials, about 140 million tons of leather waste is generated in China every year, most of the waste is difficult to reuse, the waste of raw material resources is caused, and meanwhile, the environment is seriously polluted. Carboxyl, amino and hydroxyl in the collagen fiber have strong induced adsorption effect on iodine molecules, and a large number of active sites are provided for effective adsorption of iodine. However, due to the supercoiled structure between collagen fiber molecules, inter-chain hydrogen bond structures exist between active groups, resulting in shielding of active binding sites, thereby reducing iodine adsorption capacity. How to reuse the leather waste resources is always a hot concern of researchers. Research shows that leather waste can be converted into collagen fiber with strong hydrophilicity after being washed, alkali treated, dewatered and other treated by a conventional method, but the collagen fiber is insoluble in water, is in a dispersed state after being swelled in water, has good biocompatibility, is easy to carry out biodegradation treatment in the later period, and does not pollute the environment.
With the increasing global energy demand, nuclear power has attracted global attention due to its safety, high efficiency, cleanliness, low cost, low-temperature room gas emissions, and the like. At present, more than 400 nuclear power stations are built in 31 countries and regions around the world, the power generation accounts for nearly 11.5% of the global power generation, and the increase of 23% to 100% is expected by 2030. However, the most prominent problem in the operation of nuclear power plants is the generation of a large amount of radioactive wastes in the spent fuel treatment stage, 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 the spent fuel, most substances are further oxidized into volatile I2Wherein 94-99% of I2(129I and131I) is released from the solution in gaseous form.131The half-life of I is short (8.02 days), and no long-term harm is caused to the environment, but129The half-life of I is relatively long (1.57X 10)7Year), is more toxic in the environment and persistsThe time duration is longer. Radioactive iodine is easy to accumulate and diffuse in the atmosphere due to its high fluidity and volatility, and can be concentrated in the body via inhaled gas or food chain, resulting in thyroid diseases and even cancer. During the occurrence of the Kernel Nuobeli and Fudao nuclear leakage accidents, a large amount of radioactive iodine is generated in the air, and cannot be effectively removed in time, so that the air poses serious threats to the health of human bodies. Therefore, efficient capture and immobilization of radioactive iodine vapor has become one of the hot issues of global concern.
In recent years, many researches show that the bismuth-based supported material can rapidly capture iodine simple substances, and compared with other materials (silver-doped zeolite materials, MOFs materials and the like), the bismuth-based supported material has the characteristics of low cost, easiness in synthesis of the material, low toxicity, high adsorption capacity and the like for capturing iodine vapor. The bismuth-based material absorbs iodine vapor and then is converted into BiI3And BiOI, having good thermodynamic stability, even BiI3And the BiOI is more stable in the strongly reductive groundwater environment than the AgI which is reported to be most effective in adsorbing iodine at present, and is a novel high-efficiency iodine curing adsorbent. Bismuth-containing adsorbent material pair I2、I-And IO3 -Showing superior adsorption performance to the current commercial silver-supported zeolites. Compared with silver-based materials, the bismuth-based material has wide sources, low price, stable property and no pollution to the environment, and is a better candidate precursor material.
The plant polyphenol is a renewable plant resource commonly existing in nature, contains rich phenolic hydroxyl structures, has a strong chelating effect on metal ions, and also has a certain induced adsorption effect on iodine. Many researchers fix plant tannin on water-insoluble matrixes such as cellulose, filter membranes and the like, can realize effective adsorption of heavy metal ions in a 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 low cost, does not cause secondary pollution to the environment, has stable property, is not easy to volatilize after iodine is captured, can be naturally biodegraded, and is non-toxic and harmless. The invention combines the characteristics of collagen fiber and biomass raw materialAfter alkali treatment, more hydroxyl and amino groups are exposed in the collagen fibers, and more polyphenol structures can be introduced by the solid-carrying of the plant tannin, so that the bismuth ion loading and iodine capture are facilitated; the addition of Vc can effectively prevent the oxidation of bismuth ions in the process of preparing the hydrothermal carbon, and simultaneously, the added sodium borohydride solution further reduces the bismuth in the oxidation state into zero-valent bismuth. The solid adsorption of iodine vapor is mainly that zero-valent bismuth and iodine react to generate stable BiI3And a part of the BiOI product, and a lower physical adsorption amount.
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 vegetable tannin @ collagen fiber hydrothermal charcoal high-efficiency iodine vapor-entrapping material, comprising the steps of:
firstly, crosslinking and curing activated collagen fibers and plant tannin in an aldehyde solution with a certain concentration, and then drying;
step two, adding the material prepared in the step one and bismuth nitrate pentahydrate into ethylene glycol, carrying out ultrasonic reaction, then adding a Vc-absolute ethyl alcohol solution, placing the mixture into a hydrothermal reaction kettle for reaction, cooling to room temperature, and filtering;
and step three, adding the material filtered in the step two into a sodium borohydride-absolute ethyl alcohol solution, standing, reducing, 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 into 30-100 meshes by using a crusher, dissolving the crushed collagen fibers in deionized water, adding alkali to adjust the pH value of the solution, carrying out ultrasonic treatment for 1-3 hours, cleaning the solution with deionized water, filtering the solution, and drying the filtered solution in a vacuum drying oven for later use.
Preferably, the temperature of ultrasonic cleaning is room temperature to 70 ℃, and the temperature of drying in a vacuum drying oven is room temperature to 70 ℃; the collagen fiber is animal skin without tanning treatment, and is cleaned, subjected to alkali treatment and dehydration treatment by a conventional method, and crushed by a crusher to obtain granular substances with the particle size of 10-80 meshes; the frequency of ultrasonic cleaning 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; adjusting the pH value of the solution to 8-14.
Preferably, the vegetable tannin is any one of gallotannin, myricetin, ellagitannin and condensed tannin; the time of the crosslinking curing is 1-24 hours, the temperature is 0-80 ℃, the crosslinking curing is 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 fibers to the plant tannin is 0.1-10: 1; the aldehyde solution is 0.1-20 wt% of formaldehyde solution or glutaraldehyde solution; the mass-volume ratio of the total mass of the activated collagen fibers and the vegetable tannin to the aldehyde solution is 5g:50 mL.
Preferably, the crosslinking and curing are carried out in a microwave and ultrasonic integrated reactor for cooperative treatment at 65-85 ℃ for 30-45 min; the microwave power of the synergistic 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 the bismuth nitrate pentahydrate is 0.1-35: 1; the mass volume ratio of the material prepared in the first step to glycol is 3g: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 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.
Preferably, in the second step, before the hydrothermal reaction kettle is placed for reaction, the mixed material is subjected to three-frequency ultrasound 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 for 30-60 s at the 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.
Preferably, in the third step, the concentration of the sodium borohydride-absolute ethyl alcohol solution is 0.01-20 mol/L; the mass-volume ratio of the material prepared in the step one to the sodium borohydride-absolute ethyl alcohol solution is 3g:30 mL; and standing and reducing for 2-12 h.
The invention also provides application of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared by the preparation method in radioactive iodine removal.
The invention at least comprises the following beneficial effects:
(1) through effective immobilization of the plant tannin, bismuth ions are promoted to be effectively combined on collagen fibers, a layer of granular substance is coated on the collagen fibers, the collagen fibers have stable property, good iodine vapor immobilization performance and high stable chemical iodine immobilization amount which is far higher than that of a currently reported biomass material, and the captured iodine is mainly BiI3The compound exists in a form, is not easy to volatilize, and is beneficial to the stable storage and treatment of radioactive gaseous iodine.
(2) The raw materials used in the invention are waste materials and natural plant resources generated by processing the leather scraps, simultaneously solve the problem of environmental pollution, and have rich sources and low price, and the later natural organisms are more easily degraded.
(3) The preparation process is green and 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 plant 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 Bi-based vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency iodine vapor-immobilized material Bi-BT @ ACF HC prepared in example 2; FIG. 1c shows the Bi-based vegetable tannin @ collagen fiber prepared in example 2Bi-BT @ ACF HC-I after iodine is adsorbed by vitamin hydrothermal carbon high-efficiency iodine-immobilized vapor material2SEM picture of (1);
FIG. 2a is a PXRD diagram of the plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material BT @ ACF HC prepared in the comparative example 1 before and after iodine adsorption; FIG. 2b is a PXRD diagram of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in example 2 before and after iodine adsorption;
FIG. 3 shows Bi-BT @ ACF HC and Bi-BT @ ACF HC-I2XPS total spectrum of (a);
FIG. 4 shows Bi-BT @ ACF HC and Bi-BT @ ACF HC-I2XPS chart (Bi4 f);
FIG. 5 shows Bi-BT @ ACF HC and Bi-BT @ ACF HC-I2XPS chart (I3 d);
FIG. 6 is a graph showing the effect of chemical iodine fixation and physical iodine fixation of materials prepared according to the present invention;
FIG. 7 is a graph showing the effect of chemical iodine fixation and physical iodine fixation of the material prepared by the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
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 plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material comprises the following steps:
step one, crosslinking and curing 4g of activated collagen fibers and 1g of myricetin in 50mL of glutaraldehyde solution with the concentration of 10 wt%, and drying; the time of the crosslinking curing is 4 hours, the temperature is 45 ℃, the crosslinking curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125 rpm;
step two, adding 3g of the material prepared in the step one and 0.1g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, carrying out ultrasonic reaction for 3h (the power of the ultrasonic reaction is 800W, the frequency is 45KHz), 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;
step three, adding 30mL of 0.3mol/L sodium borohydride-absolute ethyl alcohol solution into the material filtered in the step two, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin @ collagen fiber hydrothermal carbon efficient immobilized iodine vapor material;
the preparation method of the activated collagen fiber comprises the following steps: cleaning, alkali treatment and dehydration treatment are carried out on animal skins which are not tanned according to a conventional method, and then the animal skins are crushed by a crusher to obtain granular collagen fibers with the grain diameter of 30 meshes; adding collagen fibers into deionized water, ultrasonically cleaning for 5 hours to be neutral, filtering, and drying in a vacuum drying oven; crushing 5g of dried collagen fibers into 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, washing the solution by using the deionized water, filtering the solution, and drying the filtered solution in a vacuum drying oven for later use; controlling the ultrasonic cleaning temperature and the vacuum drying temperature to be 35 ℃; the ultrasonic cleaning frequency is 45kHz, and the power is 800W;
example 2:
a preparation method of a bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material comprises the following steps:
step one, crosslinking and curing 4g of activated collagen fibers and 1g of myricetin in 50mL of glutaraldehyde solution with the concentration of 10 wt%, and then drying; the time of the crosslinking curing is 4 hours, the temperature is 45 ℃, the crosslinking curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125 rpm;
step two, adding 3g of the material prepared in the step one and 0.5g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, carrying out ultrasonic reaction for 3h (the power of the ultrasonic reaction is 800W, the frequency is 45KHz), 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;
step three, adding 30mL of 0.3mol/L sodium borohydride-absolute ethyl alcohol solution into the material filtered in the step two, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin @ collagen fiber hydrothermal carbon efficient immobilized iodine vapor material (Bi-BT @ ACF HC);
the preparation method of the activated collagen fiber is described in example 1;
example 3:
a preparation method of a bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material comprises the following steps:
step one, crosslinking and curing 4g of activated collagen fibers and 1g of myricetin in 50mL of glutaraldehyde solution with the concentration of 10 wt%, and drying; the time of the crosslinking curing is 4 hours, the temperature is 45 ℃, the crosslinking curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125 rpm;
step two, adding 3g of the material prepared in the step one and 1g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, carrying out ultrasonic reaction for 3h (the power of the ultrasonic reaction is 800W, the frequency is 45KHz), 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;
step three, adding 30mL of 0.3mol/L sodium borohydride-absolute ethyl alcohol solution into the filtered material obtained in the step two, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material;
the preparation method of the activated collagen fiber is described in example 1;
example 4:
a preparation method of a bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material comprises the following steps:
step one, crosslinking and curing 4g of activated collagen fibers and 1g of myricetin in 50mL of glutaraldehyde solution with the concentration of 10 wt%, and drying; the time of the crosslinking curing is 4 hours, the temperature is 45 ℃, the crosslinking curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125 rpm;
step two, adding 3g of the material prepared in the step one and 5g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, carrying out ultrasonic reaction for 3h (the power of the ultrasonic reaction is 800W, the frequency is 45KHz), 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;
step three, adding 30mL of 0.3mol/L sodium borohydride-absolute ethyl alcohol solution into the filtered material obtained in the step two, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material;
the preparation method of the activated collagen fiber is described in example 1;
comparative example 1:
step one, crosslinking and curing 4g of activated collagen fibers and 1g of myricetin in 50mL of glutaraldehyde solution with the concentration of 10 wt%, and drying; the time of the crosslinking curing is 4 hours, the temperature is 45 ℃, the crosslinking curing is carried out in a constant-temperature shaking table, and the shaking amplitude of the constant-temperature shaking table is 125 rpm;
step two, adding 3g of the material prepared in the step one into 30mL of glycol, carrying out ultrasonic reaction for 3h (the power of the ultrasonic reaction is 800W, the frequency is 45KHz), 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;
step three, adding 30mL of 0.3mol/L sodium borohydride-absolute ethyl alcohol solution into the material filtered in the step two, standing and reducing for 6 hours, filtering and drying to obtain the plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material (BT @ ACF HC);
the preparation method of the activated collagen fiber is described in example 1;
example 5:
a preparation method of a bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material comprises the following steps:
step one, crosslinking and curing 4g of activated collagen fibers and 1g of myricetin in 50mL of glutaraldehyde solution with the concentration of 10 wt%, and drying; the crosslinking and curing are carried out in a microwave ultrasonic integrated reactor for cooperative treatment at the temperature of 70 ℃ for 30 min; the microwave power of the cooperative treatment is 1200W, the ultrasonic power is 800W, and the ultrasonic frequency is 45 KHz;
step two, adding 3g of the material prepared in the step one and 0.5g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, carrying out ultrasonic reaction for 3h (the power of the ultrasonic reaction is 800W, the frequency is 45KHz), 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;
step three, adding 30mL of 0.3mol/L sodium borohydride-absolute ethyl alcohol solution into the material filtered in the step two, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin @ collagen fiber hydrothermal carbon efficient immobilized iodine vapor material;
the preparation method of the activated collagen fiber is described in example 1;
example 6:
a preparation method of a bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material comprises the following steps:
step one, crosslinking and curing 4g of activated collagen fibers and 1g of myricetin in 50mL of glutaraldehyde solution with the concentration of 10 wt%, and drying; performing synergistic treatment in a microwave ultrasonic integrated reactor at 70 deg.C for 30 min; the microwave power of the cooperative treatment is 1200W, the ultrasonic power is 800W, and the ultrasonic frequency is 45 KHz;
step two, adding 3g of the material prepared in the step one and 0.5g of bismuth nitrate pentahydrate into 30mL of ethylene glycol, carrying out ultrasonic reaction for 3h (the power of the ultrasonic reaction is 800W, the frequency is 45KHz), then adding 30mL of Vc-absolute ethanol solution with the concentration of 0.01g/mL, applying three-frequency ultrasonic to the mixed material, stirring for 20min, placing the mixed material into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 160 ℃, cooling to room temperature, and filtering; the three-frequency ultrasound is applied in an alternating mode, and the applying process in the alternating mode comprises the following steps: processing 60s at the frequency of 35KHz, 90s at 145KHz and 60s at 90 KHz; the power of the three-frequency ultrasonic wave is 1200W;
step three, adding 30mL of 0.3mol/L sodium borohydride-absolute ethyl alcohol solution into the filtered material obtained in the step two, standing and reducing for 6 hours, filtering and drying to obtain the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material;
the preparation method of the activated collagen fiber is described in example 1;
FIG. 1a is an SEM image of a plant 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 Bi-based vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency iodine vapor-immobilized material Bi-BT @ ACF HC prepared in example 2; FIG. 1c shows Bi-BT @ ACF HC-I of the Bi-based vegetable tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in example 2 after adsorbing iodine2SEM picture of (1);
FIG. 2a is a PXRD diagram of the plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material BT @ ACF HC prepared in the comparative example 1 before and after iodine adsorption; the result shows that the BT @ ACF HC is amorphous before and after capturing iodine, no characteristic diffraction peak of the crystal iodine appears, no absorption vibration peak of the crystal iodine exists near 731cm < -1 >, and the BT @ ACF HC captures the iodine not by depositing iodine crystals on the surface of the material but by acting with active sites. FIG. 2b is a PXRD diagram of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in example 2 before and after iodine adsorption; the Bi-BT @ ACF HC material has typical diffraction characteristic peaks, which show that crystal structures are generated in the material, and the diffraction peaks are found to be classified into Bi0(PDF No.44-1246) in 22.5, 27.2, 38.0, 39.6, 44.6, 48.7, 56.1, 62.2 and 64.50 through standard card comparison. And Bi-BT @ ACF HC-I2The diffraction peaks of the curve are obviously changed, which indicates that the crystal structure of the Bi-BT @ ACF HC is changed after iodine capture, the diffraction peak originally attributed to Bi0 disappears, and new diffraction characteristic peaks appear, and the comparison shows that the Bi-BT @ ACF HC is attributed to BiI 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 72.803(PDF No.48-1795), which shows that BiI is generated after the elementary bismuth and the iodine react3And (4) phase(s). The reaction mechanism of the bismuth metal for capturing iodine is mainly Bi0 and I2BiI is generated after chemical reaction3Phase-fixed iodine.
XPS characterization was used to study the valence state change of the element, further revealing the interaction between Bi-BT @ acfhc and iodine.FIG. 3 shows Bi-BT @ ACF HC and Bi-BT @ ACF HC-I2XPS total spectrum of (a); FIG. 4 shows Bi-BT @ ACF HC and Bi-BT @ ACF HC-I2XPS chart (Bi4 f); FIG. 5 shows Bi-BT @ ACF HC and Bi-BT @ ACF HC-I2XPS chart (I3 d); Bi-BT @ ACF HC and Bi-BT @ ACF HC-I2Peaks at 159.2eV and 164.5eV correspond to the characteristic peaks of Bi4f7/2 and Bi4f5/2, respectively, indicating that the material successfully supports bismuth. When the Bi-BT @ ACF HC captures iodine, new peaks at 619.4eV and 630.9eV correspond to characteristic peaks I3d5/2 and I3d3/2, respectively, indicating that iodine is adsorbed on the Bi-BT @ ACF HC. The Bi4f spectrum of Bi-BT @ ACF HC decomposed into two sets of overlapping peaks, Bi3+ (164.2eV and 158.8eV) and Bi0(163.5eV and 158.2eV), indicating that the fraction of Bi3+ immobilized in the material was reduced to Bi 0. When the Bi-BT @ ACF HC captures iodine, the Bi4f spectrum only has a group of overlapping peaks which are characteristic peaks of Bi3+ (164.5eV and 159.1eV), and Bi3+ substances are generated after the Bi0 and the iodine react. Further analysis of the peak information in combination with iodine revealed that the I3d spectrum of Bi-BT @ ACF HC-I2 decomposed primarily into two sets of overlapping peaks, I2(631.4eV and 619.7eV) and I-or I3- (630.8eV and 619.3eV), indicating that the chemical action of iodine vapor upon contact with Bi-BT @ ACF HC produced I-and I3-species. The combination of Bi4f spectral information supposes that BiI3 is possibly generated by the reaction of Bi0 and I2, and the characterization analysis result of PXRD is further verified; from the above results, it is presumed that the capture of iodine by Bi-BT @ acfc is mainly achieved by chemical reaction of Bi0 and I2 to form Bi3 phase, and meanwhile, partial iodine is bonded with active groups in the material to cause the iodine molecules to be captured after polarization, so that the capture of iodine by Bi-BT @ acfc is mainly achieved by chemical adsorption and accompanied by physical adsorption.
The invention adopts non-radioactive iodine simple substance to replace radioactive iodine simple substance to carry out iodine fixation experiment. Firstly, placing excessive iodine simple substance at the bottom of a 250mL serum bottle, placing 100mg of bismuth-based plant tannin @ collagen fiber hydrothermal carbon material (respectively, the material 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)) in a filter paper folded into a funnel shape, placing the filter paper at the mouth of the serum bottle, screwing the bottle cap, sealing the bottle cap with a sealing film, placing the serum bottle in an oven at 200 ℃, adsorbing for 6h, taking out the serum bottle from the oven, cooling to room temperature, and removing the iodine simple substanceThe content of iodine vapor adsorbed by the bismuth-based plant tannin @ collagen fiber hydrothermal carbon is determined by a gravimetric method, each adsorbing material is subjected to three adsorption experiments in parallel, and an average value is obtained. After the material after capturing iodine is treated in an oven at 119 ℃ for 6h, weighing again, and calculating the stable chemical iodine fixation amount according to the mass loss before and after the material is weighed; wherein the Bi-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in the embodiment 2 is expressed as Bi-BT @ ACF HC-I after adsorbing iodine2(ii) a The plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared in the comparative example 1 is expressed as (BT @ ACF HC-I) after adsorbing iodine2)；
FIG. 6 shows the iodine adsorption effects of examples 1-4, comparative example 1 and pure bismuth powder, and it can be seen from the figure that the material prepared by the invention has good iodine vapor immobilization performance and high stable chemical iodine immobilization amount; fig. 7 shows the iodine adsorption effect of the embodiment 2 and the embodiment 5 to 6, and it can be seen from the figure that the chemical iodine fixation amount of the material prepared in the embodiments 5 to 6 is significantly increased, because the reaction is performed in the microwave and ultrasonic wave integrated reactor, the cross-linking and curing effect is improved by utilizing the cavitation of the ultrasonic wave and the high-speed oscillation principle of the microwave, the chemical iodine fixation amount of the material is further increased, and meanwhile, the mixing uniformity of each material is further increased by adopting the multi-frequency ultrasonic, 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 increased.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of a bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material is characterized by comprising the following steps:
firstly, crosslinking and curing activated collagen fibers and plant tannin in an aldehyde solution with a certain concentration, and then drying;
step two, adding the material prepared in the step one and bismuth nitrate pentahydrate into ethylene glycol, carrying out ultrasonic reaction, then adding a Vc-absolute ethyl alcohol solution, placing the mixture into a hydrothermal reaction kettle for reaction, cooling to room temperature, and filtering;
and step three, adding the material filtered in the step two into a sodium borohydride-absolute ethyl alcohol solution, standing, reducing, filtering and drying to obtain the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material.
2. The preparation method of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material as claimed in claim 1, wherein 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 into 30-100 meshes by using a crusher, dissolving the crushed collagen fibers in deionized water, adding alkali to adjust the pH value of the solution, carrying out ultrasonic treatment for 1-3 hours, cleaning the solution with deionized water, filtering the solution, and drying the filtered solution in a vacuum drying oven for later use.
3. The preparation method of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material as claimed in claim 2, wherein the temperature of ultrasonic cleaning is room temperature to 70 ℃, and the temperature of drying in a vacuum drying oven is room temperature to 70 ℃; the collagen fiber is animal skin without tanning treatment, and is cleaned, subjected to alkali treatment and dehydration treatment by a conventional method, and crushed by a crusher to obtain granular substances with the particle size of 10-80 meshes; the frequency of ultrasonic cleaning 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; adjusting the pH value of the solution to 8-14.
4. The preparation method of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material as claimed in claim 1, wherein the plant tannin is any one of gallotannin, myricetin, ellagitannin and condensed tannin; the time of the crosslinking curing is 1-24 hours, the temperature is 0-80 ℃, the crosslinking curing is 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 fibers to the plant tannin is 0.1-10: 1; the aldehyde solution is 0.1-20 wt% of formaldehyde solution or glutaraldehyde solution; the mass-volume ratio of the total mass of the activated collagen fibers and the vegetable tannin to the aldehyde solution is 5g:50 mL.
5. The preparation method of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material as claimed in claim 1, wherein the cross-linking curing is performed by performing synergistic treatment in a microwave and ultrasonic integrated reactor, wherein the temperature of the synergistic treatment is 65-85 ℃ and the time is 30-45 min; the microwave power of the synergistic treatment is 800-1200W, the ultrasonic power is 800-1200W, and the ultrasonic frequency is 35-45 KHz.
6. The preparation method of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material as claimed in claim 1, wherein 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 glycol is 3g: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.
7. The preparation method of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material as claimed in claim 1, wherein in the second step, the mass-to-volume ratio of the material prepared in the first step to the Vc-absolute ethanol solution is 3 g/30 mL, 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.
8. The preparation method of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material as claimed in claim 1, wherein in the second step, before the mixture is placed in a hydrothermal reaction kettle for reaction, the mixture is subjected to three-frequency ultrasound and stirred for 15-30 min, the three-frequency ultrasound is applied in an alternating manner, and the application process in the alternating manner is as follows: treating for 30-60 s at the 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.
9. The preparation method of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material as claimed in claim 1, wherein in the third step, the concentration of the sodium borohydride-absolute ethyl alcohol solution is 0.01-20 mol/L; the mass-volume ratio of the material prepared in the step one to the sodium borohydride-absolute ethyl alcohol solution is 3g:30 mL; and standing and reducing for 2-12 h.
10. The application of the bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material prepared by the preparation method of any one of claims 1-9 in radioactive iodine removal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210380147.2A CN114669279B (en) | 2022-04-12 | 2022-04-12 | Preparation and application of bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210380147.2A CN114669279B (en) | 2022-04-12 | 2022-04-12 | Preparation and application of bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114669279A true CN114669279A (en) | 2022-06-28 |
| CN114669279B CN114669279B (en) | 2023-09-15 |
Family
ID=82077822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210380147.2A Active CN114669279B (en) | 2022-04-12 | 2022-04-12 | Preparation and application of bismuth-based vegetable tannin@collagen fiber hydrothermal carbon efficient immobilized iodine vapor material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114669279B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116251566A (en) * | 2023-03-01 | 2023-06-13 | 西华师范大学 | Preparation method and application of bismuth-doped polyvinylpyrrolidone porous carbon material |
| CN116459790A (en) * | 2023-04-24 | 2023-07-21 | 西华师范大学 | Preparation method of flying wadding fiber loaded zero-valent nano silver high-efficiency fixed gaseous iodine material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2110446A1 (en) * | 2008-04-18 | 2009-10-21 | C & J Clark International Limited | Tanning of hides and skins |
| CN110479216A (en) * | 2019-08-26 | 2019-11-22 | 西南科技大学 | The preparation method of collagen fiber supported tannin load nano zero-valence Fe-Ni bimetallic ball absorbing and reducing material |
| WO2020165467A1 (en) * | 2019-02-13 | 2020-08-20 | Oilkontrol Products, S. L. | Method for obtaining a modified collagen absorbent product from leather |
| CN111841505A (en) * | 2020-07-24 | 2020-10-30 | 西南科技大学 | Preparation method of collagen fiber aerogel material for efficiently capturing iodine vapor |
| CN111841506A (en) * | 2020-07-24 | 2020-10-30 | 西南科技大学 | Preparation method of bismuth-based collagen fiber material for efficiently capturing iodine vapor |
| CN112023896A (en) * | 2020-08-26 | 2020-12-04 | 西南科技大学 | Preparation method of nano-silver-based collagen fiber aerogel material for efficiently capturing iodine vapor |
| CN113368809A (en) * | 2021-06-18 | 2021-09-10 | 西南科技大学 | Preparation method of bismuth-based silicon dioxide material and application of bismuth-based silicon dioxide material in radioactive iodine trapping |
| CN113877517A (en) * | 2021-11-23 | 2022-01-04 | 西南科技大学 | Bismuth sulfide aerogel adsorbent for removing radioactive iodine and preparation method and application thereof |
| CN113996267A (en) * | 2021-11-23 | 2022-02-01 | 西南科技大学 | Preparation method of silicon-based fibrofelt-bismuth-based composite material and application of silicon-based fibrofelt-bismuth-based composite material in radioactive iodine adsorption |
-
2022
- 2022-04-12 CN CN202210380147.2A patent/CN114669279B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2110446A1 (en) * | 2008-04-18 | 2009-10-21 | C & J Clark International Limited | Tanning of hides and skins |
| WO2020165467A1 (en) * | 2019-02-13 | 2020-08-20 | Oilkontrol Products, S. L. | Method for obtaining a modified collagen absorbent product from leather |
| CN110479216A (en) * | 2019-08-26 | 2019-11-22 | 西南科技大学 | The preparation method of collagen fiber supported tannin load nano zero-valence Fe-Ni bimetallic ball absorbing and reducing material |
| CN111841505A (en) * | 2020-07-24 | 2020-10-30 | 西南科技大学 | Preparation method of collagen fiber aerogel material for efficiently capturing iodine vapor |
| CN111841506A (en) * | 2020-07-24 | 2020-10-30 | 西南科技大学 | Preparation method of bismuth-based collagen fiber material for efficiently capturing iodine vapor |
| CN112023896A (en) * | 2020-08-26 | 2020-12-04 | 西南科技大学 | Preparation method of nano-silver-based collagen fiber aerogel material for efficiently capturing iodine vapor |
| CN113368809A (en) * | 2021-06-18 | 2021-09-10 | 西南科技大学 | Preparation method of bismuth-based silicon dioxide material and application of bismuth-based silicon dioxide material in radioactive iodine trapping |
| CN113877517A (en) * | 2021-11-23 | 2022-01-04 | 西南科技大学 | Bismuth sulfide aerogel adsorbent for removing radioactive iodine and preparation method and application thereof |
| CN113996267A (en) * | 2021-11-23 | 2022-02-01 | 西南科技大学 | Preparation method of silicon-based fibrofelt-bismuth-based composite material and application of silicon-based fibrofelt-bismuth-based composite material in radioactive iodine adsorption |
Non-Patent Citations (2)
| Title |
|---|
| HUI ZHU ET AL.: "Interface assembly of specific recognition gripper wrapping on activated collagen fiber for synergistic capture effect of iodine", vol. 210, pages 112216 * |
| ZHENJIANG TIAN ET AL.: "Novel bismuth-based electrospinning materials for highly efficient capture of radioiodine", vol. 412, pages 128687 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116251566A (en) * | 2023-03-01 | 2023-06-13 | 西华师范大学 | Preparation method and application of bismuth-doped polyvinylpyrrolidone porous carbon material |
| CN116251566B (en) * | 2023-03-01 | 2024-04-30 | 西华师范大学 | Preparation method and application of bismuth-doped polyvinylpyrrolidone porous carbon material |
| CN116459790A (en) * | 2023-04-24 | 2023-07-21 | 西华师范大学 | Preparation method of flying wadding fiber loaded zero-valent nano silver high-efficiency fixed gaseous iodine material |
| CN116459790B (en) * | 2023-04-24 | 2024-03-29 | 西华师范大学 | Preparation method of flying wadding fiber loaded zero-valent nano silver high-efficiency fixed gaseous iodine material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114669279B (en) | 2023-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114669279A (en) | Preparation and application of bismuth-based plant tannin @ collagen fiber hydrothermal carbon high-efficiency iodine-immobilized vapor material | |
| WO2021082761A1 (en) | Lanthanum carbonate modified co-pyrolysis sludge biochar and preparation method and application thereof | |
| CN109225132B (en) | Biochar-based silicon-loaded adsorbent and preparation method and application thereof | |
| CN102249228B (en) | Method for preparing activated carbon from pinecone | |
| CN111841506B (en) | Preparation method of bismuth-based collagen fiber material for efficiently capturing iodine vapor | |
| CN107552027B (en) | Method for preparing carbon material from biomass waste and application of prepared carbon material | |
| CN104587956B (en) | A kind of preparation method being coated with the graphene oxide composite granule coated nano zero valence iron as carrier with multilamellar activated carbon | |
| CN113499754B (en) | Composite adsorption material based on gangue and fly ash and preparation process thereof | |
| CN106423086A (en) | Preparation of functional magnetic composite materials modified by biology-based celluloses and application of functional magnetic composite materials | |
| US11369943B2 (en) | Starch-based carbon composite and use thereof in selective and efficient adsorption of mercury ion and methylene blue | |
| CN105502558B (en) | A kind of preparation method of activated sludge and Nanoscale Iron carbon/carbon-copper composite material | |
| CN110694588A (en) | Modified composite biochar and preparation method and application thereof | |
| CN111841505B (en) | Preparation method of collagen fiber aerogel material for efficiently capturing iodine vapor | |
| CN107903408B (en) | Cellulose-feather protein hydrogel nano metal compound and preparation method thereof | |
| CN101601991A (en) | Remove biomass adsorbent and preparation, application and the renovation process of lead ion in the waste water | |
| CN102580698A (en) | Persimmon tannin adsorption material and preparation method thereof | |
| CN114505054A (en) | Preparation method and application of high-content zero-valent ferromagnetic loaded biochar | |
| CN113477226A (en) | Method for removing trivalent antimony in aqueous solution by using chitosan modified charcoal | |
| CN101912767A (en) | Method for preparing modified furfural residue heavy metal adsorbent | |
| Guan et al. | Adsorption of heavy metals by Lycium barbarum branch-based adsorbents: raw, fungal modification, and biochar | |
| CN111085196B (en) | Method for preparing composite photocatalyst containing metal elementary substance particles from carbon-containing solid waste | |
| CN102423695A (en) | Straw cellulose-polyhydroxyaluminium salt phosphorus removal adsorbent capable of complete degradation, and manufacturing method thereof | |
| CN112028071A (en) | Waste mango kernel biochar and preparation method thereof | |
| CN112023896A (en) | Preparation method of nano-silver-based collagen fiber aerogel material for efficiently capturing iodine vapor | |
| CN115155592B (en) | Preparation method and application of iron cobaltate/coal gangue catalyst for efficiently activating persulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |