CN114749157A - Cesium adsorption material with prussian blue compounds loaded on collagen fibers, and preparation method and application thereof - Google Patents

Cesium adsorption material with prussian blue compounds loaded on collagen fibers, and preparation method and application thereof Download PDF

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CN114749157A
CN114749157A CN202210514295.9A CN202210514295A CN114749157A CN 114749157 A CN114749157 A CN 114749157A CN 202210514295 A CN202210514295 A CN 202210514295A CN 114749157 A CN114749157 A CN 114749157A
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cesium
collagen fibers
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hexacyanoferrate
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彭良琼
张文华
石碧
李佶衡
廖学品
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Sichuan University
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Abstract

The invention relates to the technical field of preparation of adsorption materials, and discloses a cesium adsorption material with prussian blue compounds loaded on collagen fibers, and a preparation method and application thereof. The preparation method of cesium adsorption material with collagen fiber as carrier comprises crosslinking reaction of first metal ion and collagen fiber to obtain intermediate material; the intermediate material is fully reacted with the second metal ions and the hexacyanoferrate; the first metal ions are ions which can perform a cross-linking reaction with amino groups and/or carboxyl groups on collagen fibers and can be coordinated with cyanide in hexacyanoferrate, and the second metal ions are ions which can be coordinated with cyanide ions in hexacyanoferrate and can regulate and control the size of a formed cavity with a crystal structure of the polymetallic Prussian blue analogue so that the cavity with the crystal structure can contain cesium ions. A cesium adsorption material is prepared by the preparation method. The cesium adsorption material provided by the application has good selective adsorption capacity on cesium, and can be applied to cesium separation.

Description

Cesium adsorbing material with prussian blue compounds loaded on collagen fibers as well as preparation method and application of cesium adsorbing material
Technical Field
The invention relates to the technical field of adsorption material preparation, in particular to a cesium adsorption material with prussian blue compounds loaded on collagen fibers, and a preparation method and application thereof.
Background
The metal hexacyanoferrate, also called prussian blue and the like, shows better adsorption selectivity and higher adsorption capacity for cesium ions, and is the most promising cesium ion adsorbent at present, however, the prussian blue and the like are usually very fine particles, are not easy to settle and filter, and are difficult to be practically applied. At present, prussian blue analogue is fixed by magnetic carriers, carbon-based carriers, high-molecular carriers, ion exchange resin carriers, colloid carriers, silicon oxide carriers and membrane material carriers and is used for treating cesium-containing wastewater, but the carriers have certain limitation on column separation, need to be dispersed and separated in practical application, are complex to operate and are not economical and practical enough.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a cesium adsorption material with a prussian blue compound loaded on collagen fibers, a preparation method of the cesium adsorption material with the prussian blue compound loaded on the collagen fibers and application of the cesium adsorption material with the prussian blue compound loaded on the collagen fibers in cesium separation.
The invention is realized by the following steps:
in a first aspect, the invention provides a preparation method of a cesium adsorption material with prussian blue compounds loaded on collagen fibers, which comprises the following steps:
carrying out cross-linking reaction on the first metal ions and the collagen fibers to obtain an intermediate material;
enabling the second metal ions, the hexacyanoferrate and the first metal ions on the intermediate material to form polymetallic Prussian blue compounds to prepare the adsorbing material;
the first metal ions are ions which can perform cross-linking reaction with amino and/or carboxyl on collagen fibers and can coordinate with cyanide in hexacyanoferrate; the second metal ions can coordinate with cyanide ions in hexacyanoferrate and can regulate and control the size of the formed crystal structure cavity of the polymetallic Prussian blue analogue so that the crystal structure cavity can contain cesium ions.
In an alternative embodiment, the first metal ion comprises Zr4+、Fe3+、Ti4+、Cr3+And Zn2+At least one of; preferably Zr4+。
In an alternative embodiment, the second metal ion comprises Zn2+、Co2+、Ni2+、Cu2+And Fe3+At least one of (1); preferably Zn2+。
In an alternative embodiment, the crosslinking reaction of the first metal ions with the collagen fibers to produce the intermediate material is:
mixing enough first metal ions and collagen fibers in a solution system, adjusting the pH of the reaction system to 2.0-3.0, reacting at 20-30 ℃ for 2-5 h, adjusting the pH of the reaction system to 3.2-4.0 by using a pH regulator, controlling the temperature of the reaction system to 35-45 ℃, and reacting for 2-5 h; standing for 2-14 h after the reaction is finished;
in an alternative embodiment, the pH adjusting agent is sodium bicarbonate solution; more preferably, the mass concentration of the sodium bicarbonate solution is 5-15%;
in an optional embodiment, after the standing is finished, the prepared material is cleaned by distilled water to obtain an intermediate material;
in an alternative embodiment, the mixing of the first metal ion with the collagen fibril in the solution system is: mixing and stirring a salt solution of a first metal ion and collagen fibers; more preferably, the salt solution of the first metal ion is a sulfate salt solution or a nitrate salt solution.
In an alternative embodiment, before the cross-linking reaction of the first metal ions and the collagen fibers, the method further comprises: and soaking the collagen fibers in deionized water for 4-20 h.
In an alternative embodiment, reacting the intermediate material with the second metal ion and the hexacyanoferrate is sufficient to:
soaking the intermediate material in a salt solution of a second metal ion, and stirring for 20-40 min;
then dropwise adding hexacyanoferrate into the reaction system under the stirring condition, and stirring for reaction for 20-40 min;
standing for at least 12h after the reaction is finished; preferably, the standing time after the reaction is finished is 20-28 h;
preferably, the salt solution of the second metal ions is a sulfate salt solution or a nitrate salt solution;
preferably, the concentration of the salt solution of the second metal ion is 0.1-0.4 mol/L in terms of the second metal ion;
preferably, the concentration of hexacyanoferrate is 0.1-0.4 mol/L.
In alternative embodiments, the hexacyanoferrate is at least one of potassium ferrocyanide, sodium ferrocyanide, and ammonium ferrocyanide; potassium ferrocyanide is preferred.
In an alternative embodiment, the intermediate material, after reacting with the second metal ion and the hexacyanoferrate sufficiently, further comprises:
cleaning and drying a reaction product;
preferably, the cleaning mode is washing by deionized water; more preferably, the number of washing times is 2-4;
preferably, the drying mode is that the washed product is dried for 10-14 hours at the temperature of 40-55 ℃.
In a second aspect, the present application provides a cesium adsorption material with prussian blue compounds supported by collagen fibers, and the cesium adsorption material is prepared by the preparation method provided in any one of the above embodiments.
In a third aspect, the present application provides an application of the cesium adsorption material loading prussian blue compounds with collagen fibers in cesium separation.
The invention has the following beneficial effects:
according to the scheme provided by the application, collagen fibers are selected as a carrier, and the mass transfer resistance of the collagen fibers in flowing liquid is low, so that the collagen fibers serving as the adsorption material of the carrier have good adsorption performance on cesium in chromatographic column adsorption; according to the preparation method, the collagen fiber is used as a carrier to load the Prussian blue analogue to prepare the cesium adsorption material, so that the problems that the Prussian blue analogue is easy to agglomerate in an aqueous solution, the mass transfer resistance is high and the like can be well solved, and the preparation method has a high application value; the collagen fiber-loaded prussian blue compound cesium adsorption material prepared by the preparation method has a good adsorption effect on cesium, is used as a filler to be arranged in a chromatographic column, is used for separating cesium ions in low-radioactivity wastewater containing potassium, sodium, calcium, magnesium, strontium and cesium, and has a good separation effect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a diagram showing the column adsorption effect of the zirconium crosslinked fiber-loaded zinc hexacyanoferrate adsorbent prepared in example 1;
FIG. 2 is a diagram showing the column adsorption effect of the chromium crosslinked fiber-loaded copper hexacyanoferrate adsorbent prepared in example 6;
FIGS. 3 to 7 are experimental examples 3 for the verification of Na+、K+、Ca2+、Mg2+、Sr2+The effect of the adsorbent prepared in example 1 on the adsorption capacity of cesium ions is shown in the figure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
The preparation method of the cesium adsorption material using collagen fibers to load prussian blue compounds provided by the embodiment of the application comprises the following steps:
performing a cross-linking reaction on the first metal ions and the collagen fibers to prepare an intermediate material;
enabling the second metal ions, the hexacyanoferrate and the first metal ions on the intermediate material to form polymetallic Prussian blue compounds to prepare the adsorbing material;
the first metal ions are ions which can perform cross-linking reaction with amino and/or carboxyl on collagen fibers and can coordinate with cyanide in hexacyanoferrate; the second metal ions can coordinate with cyanide ions in hexacyanoferrate and can regulate and control the size of the formed crystal structure cavity of the polymetallic Prussian blue analogue so that the crystal structure cavity can contain cesium ions. Performing a cross-linking reaction between the first metal ions and the collagen fibers, wherein the process enables the collagen fibers to be fully dispersed, and enables the first metal ions to become metal sites for fixing the Prussian blue analogue; the intermediate material, the second metal ion and the hexacyanoferrate react fully under the stirring condition, so that the hexacyanoferrate is coprecipitated with the first metal ion and the second metal ion to form crystals. According to the method, the collagen fiber is selected as the carrier, the mass transfer resistance of the collagen fiber in flowing liquid is low, so that the cesium adsorption material which uses the collagen fiber to load the Prussian blue compound has a good separation effect on cesium in chromatographic column adsorption, and the method is simple to operate, economical and convenient. The method utilizes collagen fibers as a carrier to regulate and control loaded metal ions to form a polymetallic Prussian blue analogue crystal, and the size of a structural cavity of the polymetallic Prussian blue analogue crystal can just accommodate cesium ions (the size of the structural cavity of the crystal is about the same)
Figure BDA0003638964560000051
) Preparing cesium adsorbing materialThe problems that the prussian blue analogue is easy to agglomerate in an aqueous solution, the mass transfer resistance is high and the like are solved, and the application value is high; the collagen fiber-loaded prussian blue compound cesium adsorption material prepared by the preparation method has a good separation effect on cesium, is placed in a chromatographic column as a filler, is used for separating cesium ions in low-radioactivity wastewater containing potassium, sodium, calcium, magnesium, strontium and cesium, and has a good separation effect.
The preparation method of the cesium adsorption material loaded with prussian blue compounds by collagen fibers provided in the examples of the present application is described in more detail below:
and S1, performing a cross-linking reaction on the first metal ions and the collagen fibers to obtain the intermediate material.
Soaking collagen fibers in deionized water for 4-20 h (such as 4h, 8h, 12h, 15h, 18h or 20h), and filtering to remove water; the collagen fibers soaked for a long time can be better immersed in water, and the step is carried out for avoiding that the collagen fibers which are not soaked can not be completely immersed in a solution system in the subsequent reaction, so that the crosslinking is insufficient.
Adding distilled water into the soaked collagen fibers to immerse the collagen fibers; weighing sufficient first metal ion salt, dissolving the first metal ion salt in distilled water, and adding the dissolved first metal salt solution into a system in which collagen fibers are positioned; adjusting the pH of the reaction system to 2.0-3.0 (such as 2.0, 2.3, 2.6 and 3.0), and reacting at 20-30 deg.C (such as 20 deg.C, 25 deg.C or 30 deg.C) for 2-5 h (such as 2h, 3h or 5h) to allow the first metal ions to diffuse on the collagen fibers;
then, adjusting the pH of the reaction system to 3.2-4.0 (such as 3.2, 3.5, 3.8 and 4.0) by using a pH regulator, and then controlling the temperature of the reaction system to 35-45 ℃ for reaction for 2-5 h; the first metal ions and the amino and/or carboxyl of the collagen fibers are subjected to a crosslinking reaction, so that the collagen fibers are fully dispersed and become metal sites for fixing the Prussian blue analogue;
and standing for at least 8h, preferably 10-14 h (for example 10h, 12h or 14h) after the reaction is finished so as to enable the metal ions to react with the collagen fibers more fully.
And after the standing is finished, cleaning the prepared material by using distilled water to obtain an intermediate material. Preferably, in order to ensure sufficient cleaning, the cleaning can be performed 2-4 times, and generally 3 times.
In the step, the adding amount of each reaction raw material is not particularly limited, no matter what the proportion of the raw materials is, the finally obtained product can form a binding site for fixing the Prussian blue analogue, and only the number of the fixed sites is different; generally, during preparation, excessive first metal ions are subjected to full crosslinking reaction with amino groups and/or carboxyl groups on collagen fibers, so that more fixing points are ensured, the collagen fibers are fully dispersed, and gaps for growing prussian blue analogues are reserved; the remaining ions in the solution system can be washed away in the washing step.
Preferably, the collagen fibers are selected from conventional animal skin collagen fibers of pig, cattle or sheep.
Preferably, the first metal ion Zr4+、Fe3+、Ti4+、Cr3+And Zn2+At least one of; preferably Zr4+. Selection of Zr4+Cross-linking with collagen fibrils vs. other ions, Zr4+The coordination with cyanide is more stable, and the prepared adsorbing material has better performance of adsorbing cesium.
Preferably, the pH adjusting agent is sodium bicarbonate solution; more preferably, the sodium bicarbonate solution has a mass concentration of 5 to 15%, and a sodium bicarbonate solution having a mass concentration of 10% is generally selected.
Preferably, the first metal ion salt solution is a sulphate or nitrate solution.
S2, fully reacting the intermediate material with the second metal ions and hexacyanoferrate.
Soaking the intermediate material in a salt solution of a second metal ion, stirring and shaking for reaction for 20-40 min (for example, 20min, 25min, 30min, 35min or 40 min); uniformly mixing the second metal ions with the intermediate material;
slowly dripping hexacyanoferrate into the reaction system, and performing oscillation reaction for 25-35 min (for example, 25min, 30min or 35min) to ensure that the first metal ions, the second metal ions and the hexacyanoferrate are coprecipitated to form crystals;
standing for at least 12h, preferably 20-28 h (for example 20h, 24h or 28h) after the reaction is finished.
Preferably, the second metal ion comprises Zn2+、Co2+、Ni2+、Cu2+And Fe3+At least one of (1); preferably Zn2+. Selection of Zn2+The Prussian blue analogue obtained by coordination has a more complete crystal structure and the best adsorption effect on cesium.
Further, the hexacyanoferrate is at least one of potassium ferrocyanide, sodium ferrocyanide or ammonium ferrocyanide; potassium ferrocyanide is preferred.
Preferably, the concentration of the salt solution of the second metal ion is 0.1 to 0.4mol/L (e.g., 0.1mol/L, 0.2mol/L, or 0.4mol/L) based on the second metal ion.
Preferably, the salt solution of the second metal ion is a sulfate salt solution or a nitrate salt solution.
Preferably, the concentration of hexacyanoferrate is 0.1-0.4 mol/L (e.g., 0.1mol/L, 0.2mol/L, or 0.4 mol/L).
And S3, washing and drying the reaction product.
And after the standing in the previous step is finished, filtering the product, washing the product for 2-4 times (generally selecting 3 times) by using deionized water after the filtering, and then drying the product for 10-14 h (for example, 10h, 12h or 14h) at 45-55 ℃ (for example, 45 ℃, 50 ℃ or 55 ℃).
Drying to obtain pure product.
The embodiment of the application also provides a cesium adsorbing material with the prussian blue compounds loaded on the collagen fibers, and the cesium adsorbing material is prepared by the preparation method provided by the embodiment of the application.
The embodiment of the application also provides application of the collagen fiber loaded prussian blue compound cesium adsorption material in cesium separation.
Example 1
The application provides a preparation method of zirconium crosslinked collagen fiber loaded zinc ferrocyanide, which specifically comprises the following steps:
s1, soaking 10.0g of oxhide collagen fiber in distilled water for 12 hours; filtering to remove water, and soaking in collagen fiberAdding 200mL of distilled water; dissolving enough zirconium sulfate with 100mL of distilled water, adding the dissolved zirconium sulfate, and adjusting the pH value to 2.0; the reaction was first carried out at 25 ℃ for 4h and then with 10% (w/w) NaHCO3The pH value of the solution is adjusted to 3.5, the temperature is increased to 40 ℃, and the reaction is carried out for 4 hours; standing for 12h after the reaction is finished; washing with 1000mL of distilled water for three times to obtain an intermediate material;
s2, soaking the intermediate material in 150mL of 0.2mol/L zinc sulfate solution, stirring and oscillating for about 30min, then slowly dropwise adding 150mL of 0.2mol/L potassium ferrocyanide solution, oscillating for about 30min, and standing for 24h to obtain a mixture containing a final product;
s3, washing the mixture containing the final product with 1000mL of distilled water for three times, and drying at 50 ℃ for 12h to obtain the zirconium cross-linked fiber loaded zinc ferrocyanide adsorbing material.
Examples 2 to 17
Examples 2 to 17 are substantially the same as example 1 except that the first metal ion and the second metal ion are selected differently and that the resulting adsorbent is different; see table 1 for details.
Experimental example 1
The specific adsorption capacity of the zirconium crosslinked fiber-supported zinc hexacyanoferrate adsorption material prepared in example 1 and the chromium crosslinked collagen fiber-supported copper hexacyanoferrate prepared in example 6 on cesium was tested in the following specific manner:
weighing 1.000g of prepared adsorbing material, and placing in a packed column with diameter of 1cm, column height of 7.7cm and 9.0cm, and column bed volume of 6.05cm3And 7.07cm3(ii) a The prepared solution contains 114.76mg/L Na+、5mg/L Mg2+、41.38mg/L K+、11.94mg/L Ca2+、8.55mg/L Sr+、50mg/L Cs+The solution of (4) was passed through a packed column at a flow rate of 0.6 mL/min.
The adsorption effect of example 1 is shown in fig. 1, and the breakthrough point of cesium adsorption of the packed column is 500BV, which shows that the adsorption material prepared in example 1 has excellent adsorption effect.
The adsorption effect of example 6 is shown in fig. 2, and the breakthrough point of cesium adsorption of the packed column is 150BV, which shows that the adsorption material prepared in example 6 also has excellent adsorption effect.
Experimental example 2
The examples were tested for cesium adsorption in the following manner:
the CsCl solution having a concentration of 144mg/L was adsorbed by using 1g/L of the adsorbent, and the adsorption effect was shown in Table 1.
TABLE 1 adsorption Capacity of the adsorbents for cesium
Figure BDA0003638964560000091
As can be seen from the above table, the adsorbent provided by the application has better adsorption capacity for cesium.
Experimental example 3
Na is mixed with+、K+、Ca2+、Mg2+、Sr2+The adsorption material prepared in example 1 was examined for its selectivity for cesium ions, using a material amount of 1g/L, and the effect of coexisting ions on the adsorption capacity of cesium ions, as shown in FIGS. 3 to 7.
As can be seen from FIGS. 3 to 7, these ions have little effect on the adsorption capacity of cesium ions, and only potassium ions have a slight effect at a concentration of 10mmol/L because the radius of the hydrated ions of potassium ions is
Figure BDA0003638964560000092
Hydrated ionic radius with cesium ion
Figure BDA0003638964560000093
Close, thereby interfering with the adsorption effect, but the overall effect is not significant. The zirconium cross-linked collagen fiber loaded zinc hexacyanoferrate prepared by the preparation method provided by the application example 1 has good selective adsorption for cesium ions, and the collagen fiber used as a carrier is proved to have no influence on the selectivity of prussian blue analogues for adsorbing cesium ions, so that the adsorption material prepared by the preparation method provided by the application has selectivity for adsorbing cesium.
In conclusion, according to the preparation method of the cesium adsorption material with the prussian blue compounds loaded on the collagen fibers, the collagen fibers are used as carriers, the mass transfer resistance in flowing liquid is low, and the cesium adsorption material has good adsorption performance in chromatographic column adsorption; according to the preparation method, the collagen fiber is used as a carrier to load the Prussian blue analogue to prepare the cesium adsorption material, so that the problems of easy agglomeration, high mass transfer resistance and the like of the Prussian blue analogue in an aqueous solution can be well solved, and the preparation method has high application value; the collagen fiber-loaded prussian blue compound cesium adsorption material prepared by the preparation method has a good adsorption effect on cesium, is used as a filler to be arranged in a chromatographic column, is used for separating cesium ions in low-radioactivity wastewater containing potassium, sodium, calcium, magnesium, strontium and cesium, and has a good separation effect.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a cesium adsorption material with a prussian blue compound loaded on collagen fibers is characterized by comprising the following steps:
performing a cross-linking reaction on the first metal ions and the collagen fibers to prepare an intermediate material;
enabling second metal ions, hexacyanoferrate and the first metal ions on the intermediate material to form a polymetallic Prussian blue compound to prepare an adsorbing material;
the first metal ions are ions which can perform a cross-linking reaction with amino groups and/or carboxyl groups on the collagen fibers and can coordinate with cyanide in hexacyanoferrate; the second metal ions can coordinate with cyanide ions in hexacyanoferrate and can regulate and control the size of a crystal structure cavity of the formed polymetallic Prussian blue analogue, so that the crystal structure cavity can contain ions of cesium ions.
2. The method according to claim 1, wherein the first metal ion comprises Zr4+、Fe3+、Ti4 +、Cr3+And Zn2+At least one of; preferably Zr4+。
3. The method according to claim 1, wherein the second metal ion includes Zn2+、Co2+、Ni2 +、Cu2+And Fe3+At least one of (1); preferably Zn2+。
4. The method according to claim 1, wherein the step of crosslinking the collagen fibers with a first metal ion to obtain the intermediate material comprises:
mixing sufficient first metal ions and the collagen fibers in a solution system, adjusting the pH of the reaction system to 2.0-3.0, reacting at 20-30 ℃ for 2-5 h, adjusting the pH of the reaction system to 3.2-4.0 by using a pH regulator, controlling the temperature of the reaction system to 35-45 ℃, and reacting for 2-5 h; standing for 2-14 h after the reaction is finished;
preferably, the pH adjusting agent is sodium bicarbonate solution; more preferably, the mass concentration of the sodium bicarbonate solution is 5-15%;
preferably, after the standing is finished, the prepared material is washed by distilled water to obtain the intermediate material;
preferably, the mixing of the first metal ion and the collagen fiber in the solution system is: mixing and stirring a salt solution of a first metal ion with the collagen fibers; more preferably, the salt solution of the first metal ion is a sulfate solution or a nitrate solution.
5. The method for preparing collagen fibers according to claim 1, further comprising, prior to the step of crosslinking the collagen fibers with the first metal ions: and soaking the collagen fibers in deionized water for 4-20 hours.
6. The method of any one of claims 1 to 5, wherein reacting the intermediate material with a second metal ion and a hexacyanoferrate is sufficient to:
soaking the intermediate material in a salt solution of a second metal ion, and stirring for 20-40 min;
then dropwise adding the hexacyanoferrate into a reaction system under the stirring condition, and stirring for reaction for 20-40 min;
standing for at least 12h after the reaction is finished; preferably, the standing time is 20-28 h after the reaction is finished;
preferably, the salt solution of the second metal ions is a sulfate salt solution or a nitrate salt solution;
preferably, the concentration of the salt solution of the second metal ion is 0.1-0.4 mol/L based on the second metal ion;
preferably, the concentration of the hexacyanoferrate is 0.1-0.4 mol/L.
7. The method according to any one of claims 1 to 5, wherein the hexacyanoferrate is at least one of potassium ferrocyanide, sodium ferrocyanide and ammonium ferrocyanide; preferably potassium ferrocyanide.
8. The method according to any one of claims 1 to 5, wherein the intermediate material, after being sufficiently reacted with the second metal ion and the hexacyanoferrate, further comprises:
cleaning and drying a reaction product;
preferably, the cleaning mode is washing by using deionized water; more preferably, the number of washing times is 2-4;
preferably, the drying mode is that the washed product is dried for 10-14 hours at the temperature of 40-55 ℃.
9. A cesium adsorbing material with a prussian blue compound loaded on collagen fibers, characterized by being prepared by the preparation method according to any one of claims 1 to 8.
10. Use of a cesium adsorbent material loaded with prussian blue-like compounds with collagen fibers according to claim 9 for cesium separation.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115178296A (en) * 2022-07-25 2022-10-14 佛山市安芯纤维科技有限公司 Functional fiber loaded with prussian-like blue-light catalyst, preparation method and application
CN115232893A (en) * 2022-08-18 2022-10-25 四川大学 Flexible neutron shielding material based on collagen fibers and preparation method
CN115672286A (en) * 2022-11-14 2023-02-03 四川大学 Material for simultaneously adsorbing and separating cesium and strontium, preparation method and adsorption and separation method
CN116510695A (en) * 2023-03-28 2023-08-01 浙江坤泽环境科技有限公司 Collagen fiber/beta-cyclodextrin adsorbent and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1593746A (en) * 2004-07-07 2005-03-16 四川大学 Collagen fiber solid borne metallic ion adsorbing material, preparation method and purpose thereof
CN108163923A (en) * 2018-01-18 2018-06-15 清华大学 One kind is used to adsorb Cs+Load ferrocyanide bacteria cellulose membrane preparation method
CN109797579A (en) * 2019-01-19 2019-05-24 赖沅祺 A kind of preparation method of dyefunctionalized cotton fiber composite material
CN110090618A (en) * 2019-04-30 2019-08-06 北京化工大学 Prussian blue/classifying porous charcoal compound adsorbent of one kind and its preparation method and application
JP2019132650A (en) * 2018-01-30 2019-08-08 日本製紙株式会社 Cesium adsorption material
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1593746A (en) * 2004-07-07 2005-03-16 四川大学 Collagen fiber solid borne metallic ion adsorbing material, preparation method and purpose thereof
CN108163923A (en) * 2018-01-18 2018-06-15 清华大学 One kind is used to adsorb Cs+Load ferrocyanide bacteria cellulose membrane preparation method
JP2019132650A (en) * 2018-01-30 2019-08-08 日本製紙株式会社 Cesium adsorption material
CN109797579A (en) * 2019-01-19 2019-05-24 赖沅祺 A kind of preparation method of dyefunctionalized cotton fiber composite material
CN110090618A (en) * 2019-04-30 2019-08-06 北京化工大学 Prussian blue/classifying porous charcoal compound adsorbent of one kind and its preparation method and application
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JIAYI YANG ET AL.: "Recovery of cesium from saline lake brine with potassium cobalt hexacyanoferrate-modified chrome-tanned leather scrap adsorbent", 《COLLOIDS AND SURFACES A》 *
杨嘉怡: "盐湖中铯、铷选择性吸附剂的制备及应用基础研究", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 *
陈武勇等: "《鞣制化学》", 31 May 2018, 中国轻工业出版社 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115178296A (en) * 2022-07-25 2022-10-14 佛山市安芯纤维科技有限公司 Functional fiber loaded with prussian-like blue-light catalyst, preparation method and application
CN115232893A (en) * 2022-08-18 2022-10-25 四川大学 Flexible neutron shielding material based on collagen fibers and preparation method
CN115672286A (en) * 2022-11-14 2023-02-03 四川大学 Material for simultaneously adsorbing and separating cesium and strontium, preparation method and adsorption and separation method
CN115672286B (en) * 2022-11-14 2024-05-28 四川大学 Material for simultaneously adsorbing and separating cesium and strontium, preparation method and adsorption and separation method
CN116510695A (en) * 2023-03-28 2023-08-01 浙江坤泽环境科技有限公司 Collagen fiber/beta-cyclodextrin adsorbent and preparation method thereof

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