CN111841507B - Preparation method of modified collagen fiber material for efficiently capturing iodine vapor - Google Patents

Preparation method of modified collagen fiber material for efficiently capturing iodine vapor Download PDF

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CN111841507B
CN111841507B CN202010723466.XA CN202010723466A CN111841507B CN 111841507 B CN111841507 B CN 111841507B CN 202010723466 A CN202010723466 A CN 202010723466A CN 111841507 B CN111841507 B CN 111841507B
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collagen fiber
collagen fibers
iodine vapor
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fiber material
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CN111841507A (en
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周建
朱辉
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Southwest University of Science and Technology
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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    • 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
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract

The invention discloses a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor, which comprises the following steps: adding collagen fibers into deionized water, ultrasonically cleaning for 5 hours in an ultrasonic cleaning machine, cleaning to be neutral, filtering, and drying in an oven; crushing the cleaned collagen fibers in a crusher, uniformly mixing the collagen fibers and an alkali modifier in proportion, calcining the mixture in a tubular furnace at a certain temperature for a period of time, and cooling the calcined mixture to room temperature; and step three, washing the calcined material to be neutral by using deionized water, filtering and drying in an oven to obtain the modified collagen fiber material. The modified collagen fiber is not easy to absorb water and agglomerate, has large specific surface area, higher adsorption capacity to iodine vapor and higher adsorption material weight ratio and utilization rate than other types of biomass materials. The preparation method is simple in preparation process, green and environment-friendly, and avoids secondary pollution to the environment in the preparation process.

Description

Preparation method of modified collagen fiber material for efficiently capturing iodine vapor
Technical Field
The invention belongs to the environmental protection field of biomass waste resources used for radioactive iodine vapor adsorption in the environment, and particularly relates to a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor.
Background
The leather-making industry of the present society is increasingly popular, but the utilization rate of the raw material animal skin only reaches about 60%, a large amount of leather waste is generated every year, particularly, the waste with small particle size is difficult to reuse, the waste of raw material resources is caused, and meanwhile, the environment is seriously polluted. How to reuse the leather waste resources is always a hot issue of attention of researchers. Research shows that leather waste can be converted into collagen fibers with strong hydrophilicity after being washed, subjected to alkali treatment, dehydrated and the like by a conventional method. As a natural high molecular substance, the collagen fiber has a helical structure consisting of three polypeptide chains,has unique molecular structure and excellent physical performance, and contains various functional groups including-OH, -COOH and-NH2and-CONH2And the like. Although the collagen fiber has strong hydrophilic performance and is insoluble in water, the collagen fiber is in a dispersed state after swelling in water and has good biocompatibility, and is easy to carry out biodegradation treatment in the later period without causing pollution to the environment.
With the rapid development of the nuclear energy industry, the safe treatment of radioactive wastes has become a focus of increasing attention, especially the leakage of the japanese fukushima nuclear power station causes a large amount of radioactive gas iodine and inorganic iodine in the environment of the peripheral region, wherein 129-iodine has a long half-life (1.6 x 107 years) and can cause radiation damage such as thyroid lesion, and the radioactive iodine existing in nature can be finally enriched in a human body through a food chain route. Therefore, the removal of radioactive gaseous iodine from ambient gases is a very important task. At present, the adsorption material for radioactive gaseous iodine mainly comprises zeolite, activated carbon, COFS, MOFS and the like, has a large specific surface area and a microporous structure, has a strong adsorption effect on gaseous iodine, but is limited by factors such as a complex preparation process, low stability, low cyclic utilization rate, difficulty in post-treatment, high practical application cost and the like, so that an alternative adsorption material is urgently needed to be found.
Disclosure of Invention
Aiming at the technical defects, the invention provides the biomass modified iodine vapor adsorbing material which has low cost, simple preparation process, no secondary pollution to the environment, high iodine vapor adsorbing capacity, natural biodegradation and no toxicity or harm. The invention combines the characteristics of collagen fiber, and after the used biomass raw material is subjected to an alkali modifier, intramolecular hydrogen bonds are broken to release more functional groups such as hydroxyl, amino and the like, and researches show that the two functional groups have strong affinity to iodine vapor, and after treatment, the two functional groups are changed from a compact type into a more loose structure, so that the contact area with the iodine vapor is increased, the double effects of chemical adsorption and physical adsorption are simultaneously realized on the iodine vapor, the adsorption capacity of the material on the iodine vapor is greatly enhanced, and the adsorption effect is mainly characterized by physical adsorption and chemical adsorption as side effects.
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 purpose of the invention, there is provided a method for preparing a modified collagen fiber iodine vapor capturing material with high efficiency, comprising the steps of:
adding collagen fibers into deionized water, ultrasonically cleaning for 5 hours in an ultrasonic cleaning machine, cleaning to be neutral, filtering, and drying in an oven;
crushing the cleaned collagen fibers in a crusher, uniformly mixing the collagen fibers and an alkali modifier in proportion, calcining the mixture in a tubular furnace at a certain temperature for a period of time, and cooling the calcined mixture to room temperature;
and step three, washing the calcined material to be neutral by using deionized water, filtering and drying in an oven to obtain the modified collagen fiber material.
Preferably, the collagen fiber in the first step is animal skin without tanning treatment, and is subjected to washing, alkali treatment, dehydration and other treatment by a conventional method, and then is crushed by a crusher to obtain granular substances with the grain diameter of 10-80 meshes;
preferably, the ultrasonic cleaning temperature and the oven temperature in the first step are in the range of room temperature to 70 ℃.
Preferably, the particle size of the collagen fiber crushed in the second step is controlled to be 30-100 meshes.
Preferably, in the second step, the alkali modifier is one or a mixture of two of potassium hydroxide and sodium hydroxide.
Preferably, the alkali modifier comprises the following components in parts by weight: 10-15 parts of sodium hydroxide, 3-5 parts of potassium hydroxide, 1-3 parts of urea, 1-2 parts of sodium silicate, 0.5-1.5 parts of triisopropanolamine, 0.1-0.3 part of nonylphenol polyoxyethylene ether, 0.1-0.3 part of polyoxyethylene alkanolamide and 20-30 parts of deionized water.
Preferably, in the second step, the mixing manner of the collagen fibers and the alkali modifier is as follows: mechanically stirring and mixing the collagen fiber and the alkali modifier, and then putting the mixture into a vacuum packaging bag for vacuum packaging, wherein the vacuum degree is controlled to be 0.1 MPa; putting the vacuum packaging bag into a high-pressure treatment kettle, and carrying out high static pressure treatment; placing the mixture subjected to high static pressure treatment in an oven, and evaporating water at 50-60 ℃ to obtain a material subjected to water evaporation; pulverizing, and controlling the particle size of pulverized material to 30-100 meshes; the weight ratio of the collagen fibers to the alkali modifier is 1-3: 1.
Preferably, the pressure of the high static pressure treatment is 260-480 MPa, the treatment time is 30-90 min, the treatment temperature is 25-55 ℃, and the boosting speed is 5-10 MPa/s.
Preferably, the ambient gas of the tubular furnace in the second step is one or a mixture of nitrogen and argon, the calcination time is 1-12h, and the calcination temperature is 120-300 ℃; the oven temperature in step three ranges from room temperature to 70 ℃.
Preferably, the weight ratio of the collagen fibers to the alkali modifier is 1.5 to 3: 1.
The invention at least comprises the following beneficial effects:
(1) the modified collagen fiber is not easy to absorb water and agglomerate, has large specific surface area, higher adsorption capacity to iodine vapor and higher adsorption material weight ratio and utilization rate than other types of biomass materials.
(2) The raw materials used in the invention are waste materials generated by processing the leather scraps, are secondarily and effectively utilized, avoid the problem of environmental pollution, and have wide sources and low price, and the later natural organisms are more easily degraded.
(3) The preparation method is simple in preparation process, green and environment-friendly, and avoids secondary pollution to the environment in the preparation process.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an SEM photograph of the modified collagen fiber material prepared in example 1 of the present invention after adsorbing iodine vapor;
FIG. 2 is a schematic representation of a modified collagen fiber prepared in example 1 of the present invention;
FIG. 3 is a diagram of a modified collagen fiber material prepared in example 1 of the present invention after adsorbing iodine vapor;
FIG. 4 is a graph showing EDS results of modified collagen fiber materials prepared in example 1 of the present invention;
FIG. 5 is a graph showing XPS results of modified collagen fiber material prepared in example 1 of the present invention adsorbing iodine vapor;
FIG. 6 is a graph showing XPS results of modified collagen fiber material prepared in example 1 of the present invention adsorbing iodine vapor;
FIG. 7 is a graph of FTIR results for unmodified collagen fibers, modified collagen fiber materials, and modified collagen fiber materials after adsorption of iodine vapor according to example 1 of the present invention;
FIG. 8 is a graph showing the results of adsorption of iodine vapor on the modified collagen fiber materials prepared in examples 1 to 5 of the present invention at different time intervals;
FIG. 9 is a graph showing the results of adsorption of iodine vapor at different intervals for modified collagen fiber materials prepared in examples 3 and 6 of the present invention;
FIG. 10 is a graph showing the results of adsorption of iodine vapor at different intervals for modified collagen fiber materials prepared in examples 4 and 7 of the present invention;
FIG. 11 is a graph showing the results of adsorption of iodine vapor at different intervals for modified collagen fiber materials prepared in examples 5 and 8 of the present invention;
FIG. 12 is a graph showing the results of iodine vapor adsorption by the modified collagen fiber materials prepared in examples 1 to 5 of the present invention;
FIG. 13 is a graph showing the results of iodine vapor adsorption cycle of modified collagen fiber materials prepared in examples 3 and 6 of the present invention;
FIG. 14 is a graph showing the results of iodine vapor adsorption cycle of modified collagen fiber materials prepared in examples 4 and 7 of the present invention;
FIG. 15 is a graph showing the results of iodine vapor adsorption cycle of modified collagen fiber materials prepared in examples 5 and 8 of the present invention;
FIG. 16 is a BET test result chart of the modified collagen fiber material prepared in example 1 of 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 modified collagen fiber material for efficiently capturing iodine vapor comprises the following steps:
step one, washing animal skins which are not tanned, carrying out alkali treatment, dehydration and other treatments according to a conventional method, crushing the animal skins by a crusher to obtain granular collagen fibers with the grain diameter of 50 meshes, adding the granular collagen fibers into deionized water, carrying out ultrasonic washing for 5 hours in an ultrasonic washing machine, washing the collagen fibers to be neutral, filtering the collagen fibers, and drying the collagen fibers in an oven; wherein the ultrasonic cleaning temperature and the oven temperature are controlled to be 40 ℃;
step two, crushing the cleaned collagen fibers in a crusher to obtain collagen fibers with the particle size of 40 meshes; grinding and uniformly mixing 10g of collagen fiber and 5g of sodium hydroxide solid alkali modifier, calcining for 2h at 150 ℃ in a tubular furnace with nitrogen as ambient gas, and cooling to room temperature;
step three, washing the calcined material to be neutral by using deionized water, filtering and drying in a drying oven at 40 ℃ to obtain the modified collagen fiber material; the modified collagen fiber material is subjected to a specific surface area performance test, and the BET specific surface area is 54.8m2(ii)/g, wherein the BET specific surface area of the untreated collagen fibers in the first step is 18.57m2/g。
Example 2:
a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor comprises the following steps:
step one, washing animal skins which are not tanned, carrying out alkali treatment, dehydration and other treatments according to a conventional method, crushing the animal skins by a crusher to obtain granular collagen fibers with the grain diameter of 50 meshes, adding the granular collagen fibers into deionized water, carrying out ultrasonic washing for 5 hours in an ultrasonic washing machine, washing the collagen fibers to be neutral, filtering the collagen fibers, and drying the collagen fibers in an oven; wherein the ultrasonic cleaning temperature and the oven temperature are controlled to be 45 ℃;
step two, crushing the cleaned collagen fibers in a crusher to obtain 60-mesh particles; grinding and uniformly mixing 10g of collagen fiber and 5g of potassium hydroxide solid alkali modifier, calcining for 5h at 180 ℃ in a tubular furnace with nitrogen as ambient gas, and cooling to room temperature;
step three, washing the calcined material to be neutral by using deionized water, filtering and drying in a drying oven at 45 ℃ to obtain the modified collagen fiber material; the specific surface area performance test of the modified collagen fiber material is carried out, and the BET specific surface area is 55.85m2/g。
Example 3:
a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor comprises the following steps:
step one, washing animal skins which are not tanned, carrying out alkali treatment, dehydration and other treatments according to a conventional method, crushing the animal skins by a crusher to obtain granular collagen fibers with the grain diameter of 60 meshes, adding the granular collagen fibers into deionized water, carrying out ultrasonic washing for 5 hours in an ultrasonic washing machine, washing the collagen fibers to be neutral, filtering the collagen fibers, and drying the collagen fibers in an oven; wherein the ultrasonic cleaning temperature and the oven temperature are controlled to be 50 ℃;
step two, crushing the cleaned collagen fibers in a crusher to obtain 80-mesh particles; mixing 10g of collagen fiber with 10g of potassium hydroxide and sodium hydroxide (weight ratio is 1:1), grinding and uniformly mixing the solid alkali modifier, calcining the mixture for 5 hours in a tubular furnace at 220 ℃ in which the ambient gas is nitrogen, and cooling the calcined mixture to room temperature;
step three, washing the calcined material to be neutral by using deionized water, filtering and drying in a drying oven at 50 ℃ to obtain the modified collagen fiber material; the modified collagen fiber material is subjected to a specific surface area performance test, and the BET specific surface area is 59.65m2/g。
Example 4:
a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor comprises the following steps:
step one, washing animal skins which are not tanned, carrying out alkali treatment, dehydration and other treatments according to a conventional method, crushing the animal skins by a crusher to obtain granular collagen fibers with the grain diameter of 40 meshes, adding the granular collagen fibers into deionized water, carrying out ultrasonic washing for 5 hours in an ultrasonic washing machine, washing the collagen fibers to be neutral, filtering the collagen fibers, and drying the collagen fibers in an oven; wherein the ultrasonic cleaning temperature and the oven temperature are controlled to be 50 ℃;
step two, crushing the cleaned collagen fibers in a crusher to obtain 60-mesh particles; mixing 10g of collagen fiber with 5g of potassium hydroxide and sodium hydroxide (weight ratio is 1:1), grinding and uniformly mixing the solid alkali modifier, calcining the mixture for 8 hours at 220 ℃ in a tubular furnace with nitrogen as ambient gas, and cooling the calcined mixture to room temperature;
and step three, washing the calcined material to be neutral by using deionized water, filtering, and drying in a drying oven at 50 ℃ to obtain the modified collagen fiber material. The modified collagen fiber material is subjected to a specific surface area performance test, and the BET specific surface area is 56.38m2/g。
Example 5:
a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor comprises the following steps:
step one, washing animal skins which are not tanned, carrying out alkali treatment, dehydration and other treatments according to a conventional method, crushing the animal skins by a crusher to obtain granular collagen fibers with the grain diameter of 60 meshes, adding the granular collagen fibers into deionized water, carrying out ultrasonic washing for 5 hours in an ultrasonic washing machine, washing the collagen fibers to be neutral, filtering the collagen fibers, and drying the collagen fibers in an oven; wherein the ultrasonic cleaning temperature and the oven temperature are controlled to be 50 ℃;
step two, crushing the cleaned collagen fibers in a crusher to obtain 80-mesh particles; mixing 10g of collagen fiber with 15g of potassium hydroxide and sodium hydroxide (weight ratio is 1:1), grinding and uniformly mixing the solid alkali modifier, calcining the mixture for 10 hours at 220 ℃ in a tubular furnace with nitrogen as ambient gas, and cooling the calcined mixture to room temperature;
and step three, washing the calcined material to be neutral by using deionized water, filtering, and drying in a drying oven at 50 ℃ to obtain the modified collagen fiber material. The modified collagen fiber material is subjected to specific surface area performance test, and the BET ratio of the modified collagen fiber materialSurface area 63.25m2/g。
Example 6:
a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor comprises the following steps:
step one, washing animal skins which are not tanned, carrying out alkali treatment, dehydration and other treatments according to a conventional method, crushing the animal skins by a crusher to obtain granular collagen fibers with the grain diameter of 60 meshes, adding the granular collagen fibers into deionized water, carrying out ultrasonic washing for 5 hours in an ultrasonic washing machine, washing the collagen fibers to be neutral, filtering the collagen fibers, and drying the collagen fibers in an oven; wherein the ultrasonic cleaning temperature and the oven temperature are controlled to be 50 ℃;
step two, crushing the cleaned collagen fibers in a crusher to obtain 80-mesh particles; taking 10g of collagen fiber and 10g of alkali modifier, mechanically stirring and mixing, then putting into a vacuum packaging bag for vacuum packaging, and controlling the vacuum degree to be 0.1 MPa; putting the vacuum packaging bag into a high-pressure treatment kettle, and carrying out high static pressure treatment; placing the mixture subjected to high static pressure treatment in an oven, and evaporating water at 50 ℃ to obtain a material subjected to water evaporation; crushing, and controlling the particle size after crushing to be 80 meshes; calcining the crushed material in a tubular furnace with nitrogen as ambient gas at 220 ℃ for 5h, and cooling to room temperature; the pressure of the high static pressure treatment is 380MPa, the treatment time is 45min, the treatment temperature is 35 ℃, and the pressure increasing speed is 5 MPa/s; the alkali modifier comprises the following components: 14g of sodium hydroxide, 4g of potassium hydroxide, 2g of urea, 1g of sodium silicate, 0.5g of triisopropanolamine, 0.3g of nonylphenol polyoxyethylene ether, 0.1g of polyoxyethylene alkanolamide and 30g of deionized water; the alkali modifier can more effectively realize that the collagen fiber breaks the hydrogen bonds in the molecule, releases more functional groups such as hydroxyl, amino and the like, is more favorable for the reaction of the alkali modifier and the collagen fiber through high static pressure treatment, and can directly modify the collagen fiber through the high static pressure treatment, thereby improving the specific surface area and further improving the adsorption performance;
and step three, washing the calcined material to be neutral by using deionized water, filtering, and drying in a drying oven at 50 ℃ to obtain the modified collagen fiber material. Subjecting the modified collagen fiber material to specific surface area propertyIt can be measured and has a BET specific surface area of 62.55m2/g。
Example 7:
a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor comprises the following steps:
step one, washing animal skins which are not tanned, carrying out alkali treatment, dehydration and other treatments according to a conventional method, crushing the animal skins by a crusher to obtain granular collagen fibers with the grain diameter of 40 meshes, adding the granular collagen fibers into deionized water, carrying out ultrasonic washing for 5 hours in an ultrasonic washing machine, washing the collagen fibers to be neutral, filtering the collagen fibers, and drying the collagen fibers in an oven; wherein the ultrasonic cleaning temperature and the oven temperature are controlled to be 50 ℃;
step two, crushing the cleaned collagen fibers in a crusher to obtain 60-mesh particles; taking 10g of collagen fiber and 5g of alkali modifier, mechanically stirring and mixing, then putting into a vacuum packaging bag for vacuum packaging, and controlling the vacuum degree to be 0.1 MPa; putting the vacuum packaging bag into a high-pressure treatment kettle, and carrying out high static pressure treatment; placing the mixture subjected to high static pressure treatment in an oven, and evaporating water at 50 ℃ to obtain a material subjected to water evaporation; crushing, and controlling the particle size after crushing to be 60 meshes; calcining the crushed material in a tubular furnace with nitrogen as ambient gas at 220 ℃ for 8h, and cooling to room temperature; the pressure of the high static pressure treatment is 400MPa, the treatment time is 40min, the treatment temperature is 35 ℃, and the boosting speed is 5 MPa/s; the alkali modifier comprises the following components: 15g of sodium hydroxide, 3g of potassium hydroxide, 1g of urea, 1g of sodium silicate, 0.5g of triisopropanolamine, 0.1g of nonylphenol polyoxyethylene ether, 0.2g of polyoxyethylene alkanolamide and 25g of deionized water.
And step three, washing the calcined material to be neutral by using deionized water, filtering, and drying in a drying oven at 50 ℃ to obtain the modified collagen fiber material. The modified collagen fiber material is subjected to a specific surface area performance test, and the BET specific surface area is 58.75m2/g。
Example 8:
a preparation method of a modified collagen fiber material for efficiently capturing iodine vapor comprises the following steps:
step one, washing animal skins which are not tanned, carrying out alkali treatment, dehydration and other treatments according to a conventional method, crushing the animal skins by a crusher to obtain granular collagen fibers with the grain diameter of 40 meshes, adding the granular collagen fibers into deionized water, carrying out ultrasonic washing for 5 hours in an ultrasonic washing machine, washing the collagen fibers to be neutral, filtering the collagen fibers, and drying the collagen fibers in an oven; wherein the ultrasonic cleaning temperature and the oven temperature are controlled to be 50 ℃;
step two, crushing the cleaned collagen fibers in a crusher to obtain 60-mesh particles; taking 10g of collagen fiber and 15g of alkali modifier, mechanically stirring and mixing, then putting into a vacuum packaging bag for vacuum packaging, and controlling the vacuum degree to be 0.1 MPa; putting the vacuum packaging bag into a high-pressure treatment kettle, and carrying out high static pressure treatment; placing the mixture subjected to high static pressure treatment in an oven, and evaporating water at 50 ℃ to obtain a material subjected to water evaporation; crushing, and controlling the particle size after crushing to be 60 meshes; calcining the crushed material in a tubular furnace with nitrogen as ambient gas at 220 ℃ for 10h, and cooling to room temperature; the pressure of the high static pressure treatment is 450MPa, the treatment time is 45min, the treatment temperature is 35 ℃, and the boosting speed is 5 MPa/s; the alkali modifier comprises the following components: 12g of sodium hydroxide, 4g of potassium hydroxide, 1g of urea, 1g of sodium silicate, 0.5g of triisopropanolamine, 0.1g of nonylphenol polyoxyethylene ether, 0.1g of polyoxyethylene alkanolamide and 20g of deionized water.
And step three, washing the calcined material to be neutral by using deionized water, filtering, and drying in a drying oven at 50 ℃ to obtain the modified collagen fiber material. The modified collagen fiber material is subjected to a specific surface area performance test, and the BET specific surface area is 65.87m2/g。
FIG. 1 is an SEM image of the modified collagen fiber material prepared in example 1 of the present invention after adsorbing iodine vapor, and it can be seen from the SEM image that the modified collagen fiber material has rough and uneven surface and is composed of many capillary fibers.
FIG. 2 is a pictorial representation of a modified collagen fiber prepared in accordance with example 1 of the present invention, which is in loose dark gray color; fig. 3 is a diagram of a modified collagen fiber material prepared in example 1 of the present invention after absorbing iodine vapor, wherein the color of the material turns to reddish brown and has a loose structure after absorbing iodine vapor.
Fig. 4 is an EDS result chart of the modified collagen fiber material prepared in example 1 of the present invention, from which it can be seen that iodine element is present and contained in a high amount, which proves successful adsorption of iodine and a large adsorption amount.
FIGS. 5 and 6 are XPS results of modified collagen fiber material prepared in example 1 of the present invention adsorbing iodine vapor; after adsorption of the iodine vapor, new peaks of I3d5 and I3d3 appeared near 618 and 629, respectively, demonstrating that the material successfully adsorbed iodine. The peak-splitting fitting is carried out on the new iodine adsorption peak, and the material shows double functions of physical adsorption and chemical adsorption on the iodine.
FIG. 7 is a graph of FTIR results for unmodified collagen fibers, modified collagen fiber materials, and modified collagen fiber materials after adsorption of iodine vapor according to example 1 of the present invention; 755.09cm-1Out-of-plane bending vibrations attributed to amide bonds C ═ O. After alkali treatment of collagen fibers, the modified collagen fibers and the modified iodine adsorbed samples can be found to be absorbed, and the functional groups at the positions disappear by vibration, which proves that the amide bond structures in the collagen fiber molecules are damaged by the alkali. 697.52cm-1And belongs to O-H out-of-plane bending vibration. The intermolecular hydrogen bond is formed and weakened after the alkali treatment, which indicates that the intermolecular hydrogen bond is broken.
Carrying out an iodine vapor adsorption experiment on the modified collagen fiber materials prepared in the examples 1-8; the method comprises the following steps: the invention adopts non-radioactive iodine simple substance to replace radioactive iodine simple substance; firstly, putting excessive iodine elementary substance at the bottom of a 250mL serum bottle, putting 100mg of modified collagen fiber material (examples 1-8) in funnel-shaped filter paper folded, putting the filter paper in a serum bottle mouth, screwing a bottle cap, sealing the bottle cap with a sealing film, putting the serum bottle in a 75 ℃ oven, adsorbing for 24 hours at the longest in different time intervals, taking out the serum bottle from the oven, cooling to room temperature, and measuring the content of iodine vapor adsorbed by the modified collagen fiber according to a gravimetric method. The calculation formula is as follows: q ═ m2-m1)/m1X 100 wt%, wherein Q (wt%) is the adsorption amount of iodine, m1(mg) and m2(mg) the weight of the modified collagen fiber material before and after iodine adsorption, each adsorption material was subjected to adsorption experiments in parallel for three times, and the average value was obtained, the results are shown in fig. 8 to 11;
after adsorbing iodine vapor, the modified collagen fiber material is desorbed in absolute ethyl alcohol, and circularly adsorbs the iodine vapor again after drying (the process is consistent as the first adsorption experiment), and the circular adsorption result is shown in figures 12-15, and the result shows that the adsorption quantity is reduced along with the increase of the number of circulation times; the material with high initial adsorption capacity continuously maintains higher adsorption capacity in the same cycle batch after five times of cycles.
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 (5)

1. A preparation method of a modified collagen fiber material for efficiently capturing iodine vapor is characterized by comprising the following steps:
adding collagen fibers into deionized water, ultrasonically cleaning for 5 hours in an ultrasonic cleaning machine, cleaning to be neutral, filtering, and drying in an oven;
crushing the cleaned collagen fibers in a crusher, uniformly mixing the collagen fibers and an alkali modifier in proportion, calcining the mixture in a tubular furnace at a certain temperature for a period of time, and cooling the calcined mixture to room temperature;
step three, washing the calcined material to be neutral by using deionized water, filtering and drying in an oven to obtain a modified collagen fiber material;
the alkali modifier comprises the following components in parts by weight: 10-15 parts of sodium hydroxide, 3-5 parts of potassium hydroxide, 1-3 parts of urea, 1-2 parts of sodium silicate, 0.5-1.5 parts of triisopropanolamine, 0.1-0.3 part of nonylphenol polyoxyethylene ether, 0.1-0.3 part of polyoxyethylene alkanolamide and 20-30 parts of deionized water;
in the second step, the uniform mixing mode of the collagen fibers and the alkali modifier is as follows: mechanically stirring and mixing the collagen fiber and the alkali modifier, and then putting the mixture into a vacuum packaging bag for vacuum packaging, wherein the vacuum degree is controlled to be 0.1 MPa; putting the vacuum packaging bag into a high-pressure treatment kettle, and carrying out high static pressure treatment; placing the mixture subjected to high static pressure treatment in an oven, evaporating water at 50-60 ℃ to obtain a material subjected to water evaporation, and crushing the material, wherein the particle size of the crushed material is controlled to be 30-100 meshes; the weight ratio of the collagen fibers to the alkali modifier is 1-3: 1-3;
in the second step, the ambient gas of the middle-tube furnace is one or a mixture of nitrogen and argon, the calcination time is 1-12h, and the calcination temperature is 120-300 ℃; the oven temperature in step three ranges from room temperature to 70 ℃.
2. The method for preparing a material for efficiently capturing iodine vapor from modified collagen fibers as claimed in claim 1, wherein the collagen fibers in the first step are animal skins which are not tanned, and are washed, alkali-treated, dehydrated and pulverized by a pulverizer to obtain granular substances with a particle size of 10-80 meshes according to a conventional method.
3. The method for preparing a modified collagen fiber material capable of capturing iodine vapor efficiently as claimed in claim 1, wherein the ultrasonic cleaning temperature and the oven temperature in the first step are in the range of room temperature to 70 ℃.
4. The method for preparing a modified collagen fiber material for capturing iodine vapor with high efficiency as claimed in claim 1, wherein the particle size of the collagen fiber pulverized in the second step is controlled to 30-100 mesh.
5. The method for preparing the modified collagen fiber material for efficiently capturing iodine vapor as claimed in claim 1, wherein the pressure of the high static pressure treatment is 260-480 MPa, the treatment time is 30-90 min, the treatment temperature is 25-55 ℃, and the pressure increasing speed is 5-10 MPa/s.
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