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

Abstract

The invention relates to the technical field of preparation of adsorbent materials, and discloses a cesium adsorbent material loaded with Prussian blue compounds by collagen fibers, and a preparation method and application thereof. The preparation method of the cesium adsorption material with collagen fiber as carrier, comprising: making the first metal ion and collagen fiber carry out a cross-linking reaction to obtain an intermediate material; Make the intermediate material fully react with the second metal ion and hexacyanoferrate; The first metal ion is an ion that can carry out a cross-linking reaction with the amino group and/or carboxyl group on the collagen fiber, and can also coordinate with the cyanide group in hexacyanoferrate, and the second metal ion is an ion that can interact with the hexacyano group. The cyanide ion in the ferrite is coordinated, and the size of the crystal structure cavity of the formed polymetallic Prussian blue analog can be controlled, so that the crystal structure cavity can accommodate the ions of the cesium ion. A cesium adsorption material is prepared by the above preparation method. The cesium adsorption material provided by the present application has good selective adsorption capacity for cesium, and can be applied to cesium separation.

Description

Cesium adsorption material loaded with Prussian blue compounds by collagen fibers, preparation method and application thereof

technical field

The invention relates to the technical field of adsorption material preparation, in particular to a cesium adsorption material loaded with Prussian blue compounds by collagen fibers, and a preparation method and application thereof.

Background technique

Metal hexacyanoferrate, also known as Prussian blue and its analogs, exhibits good adsorption selectivity and high adsorption capacity for cesium ions, and is currently the most promising adsorbent for cesium ions, however, Prussian The precipitates of blue and its analogs are usually very fine particles, which are not easy to settle and filter, and are difficult to be practically applied. At present, there are studies using magnetic carriers, carbon-based carriers, polymer carriers, ion exchange resin carriers, colloidal carriers, silica carriers, and membrane material carriers to immobilize Prussian blue analogs for the treatment of cesium-containing wastewater, but these carriers are separated in the column. There are certain limitations, and it also needs to be dispersed and separated in practical applications, the operation is complicated, and it is not economical enough.

In view of this, the present invention is proposed.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a cesium adsorbent material loaded with Prussian blue compounds by collagen fibers, a preparation method of a cesium adsorption material loaded by collagen fibers with Prussian blue compounds, and a cesium adsorption material loaded by collagen fibers with Prussian blue compounds in cesium separation applications in .

The present invention is realized in this way:

First aspect, the present invention provides a kind of preparation method of the cesium adsorption material of Prussian blue compound with collagen fiber load, comprising:

Make the first metal ion and the collagen fiber to carry out the cross-linking reaction to obtain the intermediate material;

The second metal ion, hexacyanoferrate and the first metal ion on the intermediate material form a polymetallic Prussian blue compound to prepare an adsorbent material;

The first metal ion is an ion that can react with amino groups and/or carboxyl groups on collagen fibers, and can also coordinate with cyanide in hexacyanoferrate; the second metal ion is an ion that can interact with hexacyanoferrate. The cyanide ion in the acid salt is coordinated, and the size of the crystal structure cavity of the formed polymetallic Prussian blue analog can be controlled, so that the crystal structure cavity can accommodate the ions of the cesium ion.

In an optional embodiment, the first metal ion includes at least one of Zr ⁴⁺ , Fe ³⁺ , Ti ⁴⁺ , Cr ³⁺ and Zn ²⁺ ; preferably Zr ⁴⁺ .

In an optional embodiment, the second metal ion includes at least one of Zn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ and Fe ³⁺ ; preferably Zn ²⁺ .

In an optional embodiment, the intermediate material obtained by the cross-linking reaction between the first metal ion and the collagen fiber is:

Mix a sufficient amount of first metal ions with collagen fibers in a solution system, adjust the pH of the reaction system to 2.0-3.0, react at 20-30 ° C for 2-5 hours, and then adjust the pH of the reaction system to 3.2 by a pH adjuster ～4.0, then control the temperature of the reaction system to be 35～45°C, and react for 2～5h; after the reaction, let stand for 2～14h;

In an optional embodiment, the pH adjusting agent is a sodium bicarbonate solution; more preferably, the mass concentration of the sodium bicarbonate solution is 5-15%;

In an optional embodiment, after the standing is completed, distilled water is used to clean the prepared material to obtain the intermediate material;

In an optional embodiment, mixing the first metal ion and the collagen fibers in the solution system is: mixing and stirring the salt solution of the first metal ion and the collagen fibers; more preferably, the salt solution of the first metal ion is sulfuric acid salt solution or nitrate solution.

In an optional embodiment, before performing the cross-linking reaction between the first metal ion and the collagen fiber, the method further includes: soaking the collagen fiber in deionized water for 4-20 hours.

In an alternative embodiment, reacting the intermediate material with the second metal ion and hexacyanoferrate is sufficient to:

Immerse the intermediate material in the salt solution of the second metal ion, and stir for 20-40 minutes;

Then add hexacyanoferrate dropwise to the reaction system under stirring, and stir for 20-40min;

After the reaction is finished, stand for at least 12h; preferably, the standing time is 20～28h after the reaction is finished;

Preferably, the salt solution of the second metal ion is a sulfate solution or a nitrate 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 an optional embodiment, the hexacyanoferrate is at least one of potassium ferrocyanide, sodium ferrocyanide and ammonium ferrocyanide; preferably potassium ferrocyanide.

In an optional embodiment, after the intermediate material is sufficiently reacted with the second metal ion and hexacyanoferrate, it also includes:

The reaction product is washed and dried;

Preferably, the cleaning method is to use deionized water for washing; more preferably, the number of washings is 2 to 4 times;

Preferably, the drying method is to dry the washed product at 40-55° C. for 10-14 hours.

In the second aspect, the examples of the present application provide a cesium adsorption material loaded with Prussian blue compounds by collagen fibers, which is prepared by using the preparation method provided in any of the above embodiments.

In a third aspect, the embodiments of the present application provide the application of the above-mentioned cesium adsorption material loaded with Prussian blue compounds by collagen fibers in cesium separation.

The present invention has the following beneficial effects:

In the solution provided in this application, collagen fibers are used as carriers, which have low mass transfer resistance in flowing liquid, so that the adsorption materials using collagen fibers as carriers have better adsorption performance for cesium in chromatographic column adsorption; this application uses collagen fibers as carriers. Using fiber as a carrier to load Prussian blue analogs to prepare cesium adsorption materials can well solve the problems of easy agglomeration and high mass transfer resistance of Prussian blue analogs in aqueous solutions, and has high application value; through the preparation method provided in this application The prepared cesium adsorbent material loaded with Prussian blue compounds by collagen fibers has a good adsorption effect on cesium, and is used as a filler device in a chromatographic column to separate low radioactive substances containing potassium, sodium, calcium, magnesium, strontium and cesium. Cesium ions in wastewater have better separation effect.

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore do not It should be regarded as a limitation of the scope, and for those of ordinary skill in the art, other related drawings can also be obtained according to these drawings without any creative effort.

Fig. 1 is the column adsorption effect diagram of the zirconium cross-linked fiber-supported zinc ferrocyanide adsorption material prepared in Example 1;

Fig. 2 is the column adsorption effect diagram of the chromium cross-linked fiber-supported copper ferrocyanide adsorption material obtained in Example 6;

Figures 3-7 are graphs showing the effect of Na ⁺ , K ⁺ , Ca ²⁺ , Mg ²⁺ , Sr ²⁺ on the adsorption capacity of the adsorbent prepared in Example 1 on the adsorption capacity of cesium ions in Experimental Example 3.

Detailed ways

In order to make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

The features and performances of the present invention will be further described in detail below in conjunction with the embodiments.

The preparation method of the cesium adsorption material with collagen fiber-loaded Prussian blue compound provided by the embodiment of the application, including:

Make the first metal ion and the collagen fiber to carry out the cross-linking reaction to obtain the intermediate material;

The second metal ion, hexacyanoferrate and the first metal ion on the intermediate material form a polymetallic Prussian blue compound to prepare an adsorbent material;

)，制备铯吸附材料，可以很好地解决普鲁士蓝类似物在水溶液中易团聚、传质阻力高等问题，具有较高的应用价值；通过本申请提供的制备方法制得的以胶原纤维负载普鲁士蓝类化合物的铯吸附材料对铯具有较好的分离效果，作为填料置于色谱柱中，用于分离含钾、钠、钙、镁、锶、铯的低放射性废水中的铯离子，有较好的分离效果。The first metal ion is an ion that can carry out a cross-linking reaction with the amino group and/or carboxyl group on the collagen fiber, and can also coordinate with the cyanide in hexacyanoferrate; the second metal ion is an ion that can interact with hexacyanoferrate. The cyanide ion in the acid salt is coordinated, and the size of the crystal structure cavity of the formed polymetallic Prussian blue analog can be regulated, so that the crystal structure cavity can accommodate the ions of the cesium ion. The first metal ion and the collagen fiber are subjected to a cross-linking reaction, the process makes the collagen fiber fully dispersed, and the first metal ion becomes the metal site for immobilizing the Prussian blue analog; the intermediate material is combined with the second metal ion and hexacyanoferrate The acid salt reacts sufficiently under stirring conditions, so that the hexacyanoferrate coprecipitates with the first metal ion and the second metal ion to form a crystal. In this application, collagen fibers are used as the carrier, which has low mass transfer resistance in flowing liquid, so that the cesium adsorption material loaded with Prussian blue compounds by collagen fibers has a good separation effect on cesium in the adsorption of chromatographic columns, and the operation is simple and economical. convenient. In this application, collagen fibers are used as carriers to control and load metal ions to form polymetallic Prussian blue analog crystals, and the size of the structural cavity is just enough to accommodate cesium ions (the size of the crystal structure cavity is about

), the preparation of cesium adsorption materials can well solve the problems of easy agglomeration and high mass transfer resistance of Prussian blue analogs in aqueous solutions, and has high application value; The cesium adsorption material of blue compounds has a good separation effect on cesium. It is placed in a chromatographic column as a filler to separate cesium ions in low radioactive wastewater containing potassium, sodium, calcium, magnesium, strontium and cesium. good separation effect.

The following is a more specific description of the preparation method of the cesium adsorption material with collagen fibers loaded with Prussian blue compounds provided in the embodiments of the present application:

S1. The first metal ion is subjected to a cross-linking reaction with collagen fibers to obtain an intermediate material.

Soak the collagen fibers in deionized water for 4-20h (for example, 4h, 8h, 12h, 15h, 18h or 20h), and filter to remove the water; the collagen fibers soaked for a long time can be better immersed in water. The purpose of this step is to To avoid that the unsoaked collagen fibers cannot be completely immersed in the solution system during the subsequent reaction, resulting in insufficient cross-linking.

Add distilled water to the soaked collagen fibers to immerse them; take a sufficient amount of the first metal ion salt, dissolve it in distilled water, and add the first metal salt solution obtained by dissolving into the system where the collagen fibers are located; adjust the pH of the reaction system is 2.0-3.0 (eg 2.0, 2.3, 2.6 and 3.0), first react at 20-30°C (eg 20°C, 25°C or 30°C) for 2-5h (eg 2h, 3h or 5h) to make the first metal The ions are fully diffused on the collagen fibers;

Then, the pH of the reaction system is adjusted to be 3.2-4.0 (for example, 3.2, 3.5, 3.8 and 4.0) by a pH adjuster, and then the temperature of the reaction system is controlled to be 35-45°C, and the reaction is carried out for 2-5 hours; Amino and/or carboxyl cross-linking reactions, which fully disperse collagen fibers and become metal sites for immobilizing Prussian blue analogs;

After the reaction is completed, it is allowed to stand for at least 8 hours, preferably 10 to 14 hours (for example, 10 hours, 12 hours or 14 hours), so as to make the metal ions and collagen fibers react more fully.

After standing, the prepared material is washed with distilled water to obtain an intermediate material. Preferably, in order to ensure sufficient cleaning, the cleaning can be performed 2 to 4 times, generally 3 times.

In this step, there is no specific limit on the amount of each reaction raw material added. No matter what the ratio of raw materials is, the final product will form binding sites for immobilizing Prussian blue analogs, but the number of immobilized sites is different; generally in During preparation, the first metal ion is excessive and fully cross-linked with the amino group and/or carboxyl group on the collagen fiber to ensure that there are more fixation sites, and the collagen fiber is also fully dispersed, leaving a gap for the growth of Prussian blue analogs; The remaining ions in the solution system can be washed away in the cleaning step.

Preferably, the collagen fibers are selected from conventional animal skin collagen fibers such as pigs, cattle or sheep.

Preferably, the first metal ion is at least one of Zr ⁴⁺ , Fe ³⁺ , Ti ⁴⁺ , Cr ³⁺ and Zn ²⁺ ; preferably Zr ⁴⁺ . Compared with other ions, the ^{coordination of Zr 4+ and} cyanide is more stable, and the adsorption material prepared has better adsorption performance of cesium.

Preferably, the pH adjusting agent is a sodium bicarbonate solution; more preferably, the mass concentration of the sodium bicarbonate solution is 5-15%, and a sodium bicarbonate solution with a mass concentration of 10% is generally selected.

Preferably, the first metal ion salt solution is a sulfate or nitrate solution.

S2. Make the intermediate material fully react with the second metal ion and hexacyanoferrate.

The intermediate material is immersed in the salt solution of the second metal ion, and the reaction is stirred and shaken for 20-40 min (for example, 20 min, 25 min, 30 min, 35 min or 40 min); the second metal ion and the intermediate material are mixed uniformly;

Then slowly add hexacyanoferrate dropwise to the reaction system, and shake the reaction for 25-35min (for example, 25min, 30min or 35min), so that the first metal ion, the second metal ion and the hexacyanoferrate are coprecipitated to form a crystal ;

After the reaction is completed, stand for at least 12h, preferably 20-28h (for example, 20h, 24h or 28h).

Preferably, the second metal ion includes at least one of Zn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ and Fe ³⁺ ; preferably Zn ²⁺ . The crystal structure of Prussian blue analogs obtained by Zn ²⁺ coordination is more complete, and the adsorption of cesium is the best.

Further, the hexacyanoferrate is at least one of potassium ferrocyanide, sodium ferrocyanide or ammonium ferrocyanide; preferably potassium ferrocyanide.

Preferably, the concentration of the salt solution of the second metal ion is 0.1-0.4 mol/L (eg, 0.1 mol/L, 0.2 mol/L or 0.4 mol/L) based on the second metal ion.

Preferably, the salt solution of the second metal ion is a sulfate solution or a nitrate solution.

Preferably, the concentration of hexacyanoferrate is 0.1-0.4 mol/L (eg 0.1 mol/L, 0.2 mol/L or 0.4 mol/L).

S3, washing and drying the reaction product.

After the previous step, the product is filtered, washed with deionized water for 2 to 4 times (usually 3 times), and then dried at 45 to 55°C (for example, 45°C, 50°C or 55°C). 10-14h (eg 10h, 12h or 14h).

The pure product was obtained after drying.

The embodiment of the present application also provides a cesium adsorption material loaded with a Prussian blue compound by collagen fibers, which is prepared by using the preparation method provided by the embodiment of the present application.

The embodiments of the present application also provide the application of the above-mentioned cesium adsorbent material loaded with Prussian blue compounds by collagen fibers in cesium separation.

Example 1

The application provides a preparation method for zirconium cross-linked collagen fibers loaded with zinc ferrocyanide, specifically:

S1. Soak 10.0 g of cowhide collagen fibers in distilled water for 12 hours; filter to remove water, and add 200 mL of distilled water to the soaked collagen fibers; dissolve a sufficient amount of zirconium sulfate in 100 mL of distilled water and add it to adjust pH 2.0; The reaction was carried out for 4 h, then the pH was adjusted to 3.5 with 10% (w/w) NaHCO ₃ solution, the temperature was raised to 40 °C, and the reaction was continued for 4 h; after the reaction was completed, it was left to stand for 12 h; washed three times with 1000 mL of distilled water to obtain the intermediate material;

S2. Soak the material intermediate material in 150mL 0.2mol/L zinc sulfate solution, stir and shake for about 30min, then slowly dropwise add 150mL 0.2mol/L potassium ferrocyanide solution and shake for about 30min, and let stand for 24h to obtain the final product containing mixture;

S3. The mixture containing the final product was washed three times with 1000 mL of distilled water, and dried at 50° C. for 12 h to obtain a zirconium cross-linked fiber-supported zinc ferrocyanide adsorption material.

Example 2-17

Examples 2-17 are basically the same as Example 1, the only difference is that the selected first metal ions and second metal ions are different, and thus the obtained adsorbent materials are different; see Table 1 for details.

Experimental example 1

The specific adsorption capacity of the zirconium cross-linked fiber-loaded zinc ferrocyanide adsorption material prepared in Example 1 and the chromium cross-linked collagen fiber-loaded copper ferrocyanide prepared in Example 6 was tested for cesium. The specific methods are:

Weigh 1.000g of the prepared adsorbent material, put it in a packing column with a diameter of 1cm, the column heights are respectively 7.7cm and 9.0cm, and the column bed volume is divided into 6.05cm ³ and 7.07cm ³ ; the preparation contains 114.76mg/L Na ⁺ , 5 mg/L Mg ²⁺ , 41.38 mg/LK ⁺ , 11.94 mg/L Ca ²⁺ , 8.55 mg/L Sr ⁺ , 50 mg/L Cs ⁺ , passed through the packed column at a flow rate of 0.6 mL/min.

The adsorption effect of Example 1 is shown in Figure 1. The penetration point of the packed column for adsorbing cesium is 500 BV, indicating that the adsorption material prepared in Example 1 has excellent adsorption effect.

The adsorption effect of Example 6 is shown in Figure 2, and the penetration point of the packed column for adsorbing cesium is 150 BV, indicating that the adsorption material prepared in Example 6 also has excellent adsorption effect.

Experimental example 2

The adsorption capacity of each embodiment for cesium is tested, and the experimental method is as follows:

The CsCl solution with a concentration of 144 mg/L was adsorbed according to the dosage of 1 g/L of adsorbent material, and the adsorption effect was shown in Table 1.

Table 1 Adsorption capacity of each adsorbent for cesium

It can be seen from the above table that the adsorbent provided by the present application has good adsorption capacity for cesium.

Experimental example 3

Na ⁺ , K ⁺ , Ca ²⁺ , Mg ²⁺ , Sr ²⁺ are respectively matched with cesium ions, and the concentration of cesium ions in the solution is about 180 mg/L, to verify the selection of cesium ions of the adsorbent prepared in Example 1 The effect of coexisting ions on the adsorption capacity of cesium ions was investigated, and the results are shown in Figure 3-7.

与铯离子水合离子半径

相近，从而干扰吸附效果，但整体影响不大。说明了本申请实施例1提供的制备方法制得的锆交联胶原纤维负载亚铁氰化锌对于铯离子具有好的选择吸附性，证明采用胶原纤维作为载体对于普鲁士蓝类似物吸附铯离子的选择性没有影响，从而可以说明本申请提供的制备方法制得的吸附材料对铯的吸附具有选择性。It can be seen from Figure 3-7 that these ions have little effect on the adsorption capacity of cesium ions, and only potassium ions have a slight effect when the concentration is 10 mmol/L, because the hydrated ion radius of potassium ions is

Hydrated ionic radius with cesium ion

It is similar to that, which interferes with the adsorption effect, but the overall effect is not large. It is illustrated that the zirconium cross-linked collagen fibers loaded with zinc ferrocyanide prepared by the preparation method provided in Example 1 of the present application have good selective adsorption for cesium ions, and it is proved that the use of collagen fibers as a carrier is effective for the adsorption of cesium ions by Prussian blue analogs. The selectivity has no effect, so it can be shown that the adsorption material prepared by the preparation method provided in the present application has selectivity for the adsorption of cesium.

To sum up, the preparation method of the cesium adsorption material with collagen fibers loaded with Prussian blue compounds provided by the present application uses collagen fibers as the carrier, which has low mass transfer resistance in flowing liquid, and has better performance in chromatographic column adsorption. Adsorption performance; the application uses collagen fibers as a carrier to load Prussian blue analogs to prepare cesium adsorption materials, which can well solve the problems of easy agglomeration and high mass transfer resistance of Prussian blue analogs in aqueous solutions, and has high application value; The cesium adsorption material prepared by the preparation method provided in the present application with collagen fibers supporting Prussian blue compounds has a good adsorption effect on cesium, and is used as a filler device in a chromatographic column to separate potassium, sodium, calcium and magnesium. , strontium, cesium cesium ions in the low radioactive waste water, have a better separation effect.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within 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⁺、Ti^{4 +}、Cr³⁺And Zn²⁺At least one of; preferably Zr⁴⁺。

3. The method according to claim 1, wherein the second metal ion includes Zn²⁺、Co²⁺、Ni^{2 +}、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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