SCM-IC-1 molecular sieve composite material, and preparation method and application thereof

Abstract

The application discloses an SCM-IC-1 molecular sieve composite material and a preparation method and application thereof. The SCM-IC-1 molecular sieve composite material comprises a silicon-aluminum porous crystal component, an ammonium phosphomolybdate component and a silicon-based binder component. The SCM-IC-1 molecular sieve composite material provided by the application can be used as an adsorption material for capturing and detecting metal ions in water bodies, especially for cesium ions, and has the technical effects of high capture rate and fast capture rate.

Description

Technical Field

[0001] This invention relates to the field of materials technology, specifically to an SCM-IC-1 molecular sieve composite material and its preparation method, as well as its application as an adsorbent material in the field of metal ion capture and monitoring in water. Background Technology

[0004] Existing research on metal ion capture often focuses more on the capture capacity. CN111871363A discloses an adsorbent material that supports ammonium phosphomolybdate on silica, and preliminarily explores the possibility of dispersing ammonium phosphomolybdate on an inorganic support; however, its effect still cannot meet the requirements for rapid capture of cesium ions. Furthermore, the use of complex compounds such as MOFs (CN107855110A) and layered sulfides (CN101676032A) requires further refinement in terms of adsorption kinetics and material stability.

[0005] In summary, there is a need to develop a new type of material that can rapidly and completely capture metal ions at low metal ion concentration levels, in order to meet the requirements for rapid capture and detection of metal ions, especially radioactive ions, in water bodies. Summary of the Invention

[0006] The technical problem this invention aims to solve is the slow capture rate and excessively long detection cycle of metal ions that cause environmental pollution in water bodies in existing technologies. This invention provides an SCM-IC-1 molecular sieve composite material and its preparation method, as well as its application as an adsorbent material in the capture and detection of metal ions in water bodies. The SCM-IC-1 molecular sieve composite material provided by this invention can be used as an adsorbent material for the capture and detection of metal ions in water bodies, especially for cesium ions, exhibiting high capture rate and fast capture speed.

[0007] The first aspect of the present invention provides an SCM-IC-1 molecular sieve composite material, the material comprising a porous silicon-aluminum crystal component, an ammonium phosphomolybdate component, and a silicon-based binder component.

[0008] Furthermore, in the SCM-IC-1 molecular sieve composite material, the shortest linear distance between Mo and Al elements is <200 nm, preferably 10–150 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, etc., and any value within any range formed by any two of these values. In this invention, in the SCM-IC-1 molecular sieve composite material, the Mo and Al elements at this distance can cause a synergistic effect between the ammonium phosphomolybdate and the two active phases of the molecular sieve, significantly improving the collection efficiency.

[0009] Furthermore, the SCM-IC-1 molecular sieve composite material has a spherical or near-spherical morphology, with an average particle size of 20–150 μm, preferably 30–120 μm, such as 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, etc., and any value within any two of these values, more preferably 50–100 μm.

[0010] Furthermore, the chemical composition of the silicon-aluminum porous crystal component is “xNa2O·ySiO2·xAl2O3”, and satisfies 0.01≤x / y≤0.30, preferably 0.015≤x / y≤0.250, in molar terms.

[0011] Furthermore, the porous silicon-aluminum crystal component has one or more of the topological structures of molecular sieves such as MWW, FAU, BEA, MOR, ATS, CHA, and MFI, preferably one or more of the topological structures of MWW, FAU, CHA, and MFI, and more preferably the topological structure of MWW.

[0012] Furthermore, the porous silicon-aluminum crystal has a spherical, plate-like, or rod-like crystal structure.

[0013] Furthermore, in the SCM-IC-1 molecular sieve composite material, the silicon-based binder component is derived from silicon-based compounds, preferably from at least one of silica sol, tetraethyl silicate, and tetrabutyl silicate.

[0014] Furthermore, based on the mass of the SCM-IC-1 molecular sieve composite material, the mass content of the silicon-aluminum porous crystal component is 8-30%, preferably 12-25%, for example 12%, 15%, 20%, 21%, 22%, 23%, 25%, 30%, etc., and any value within any range formed by any two of these values.

[0015] Furthermore, based on the mass of the SCM-IC-1 molecular sieve composite material, the mass content of the ammonium phosphomolybdate component is 20-65%, preferably 30-60%, for example 30%, 35%, 37%, 40%, 45%, 48%, 50%, 55%, 60%, etc., and any value within the range formed by any two of these values.

[0016] Furthermore, based on the mass of the SCM-IC-1 molecular sieve composite material, the mass content of the silicon-based binder component is 25-50%, preferably 35-45%, for example 25%, 28%, 31%, 35%, 40%, 42%, 45%, etc., and any value within the range formed by any two of these values.

[0017] A second aspect of this invention provides a method for preparing the above-mentioned SCM-IC-1 molecular sieve composite material, comprising the following steps:

[0018] (1) Mix porous silicon-aluminum crystals with water and heat them to activate them to obtain a solid precursor;

[0019] (2) The solid precursor is mixed with ammonium phosphomolybdate, a silicone binder and water to obtain a mixture;

[0020] (3) The mixture was spray-molded to obtain SCM-IC-1 molecular sieve composite material.

[0021] Further, in step (1), the chemical composition of the silicon-aluminum porous crystal is "xNa2O·ySiO2·xAl2O3", and satisfies 0.01≤x / y≤0.30, preferably 0.015≤x / y≤0.250. The structure of the silicon-aluminum porous crystal has one or more of the topological structures of MWW, FAU, BEA, MOR, ATS, CHA, and MFI molecular sieves, preferably one or more of the topological structures of MWW, FAU, CHA, and MFI, and more preferably the topological structure of MWW.

[0022] Furthermore, in step (1), the porous silicon-aluminum crystal has a spherical, plate-like, or rod-like crystal structure.

[0023] Further, in step (1), the mass ratio of the porous silicon-aluminum crystal to water is 1:(5-50), preferably 1:(10-40).

[0024] Further, in step (1), the operating conditions for the heating activation include: a temperature of 40 to 80°C and a processing time of 0.5 to 4 hours, preferably a temperature of 50 to 70°C and a processing time of 0.5 to 2 hours.

[0025] Furthermore, in step (1), the present invention further includes a solid-liquid separation process after heating and activation. There are no particular limitations on the solid-liquid separation process, and it can be carried out with reference to commonly used methods in the art.

[0026] Further, in step (2), the silicon-based binder is a silicon-based compound, preferably selected from at least one of silica sol with a silica concentration of 30-40 wt%, tetraethyl silicate, and tetrabutyl silicate.

[0027] Further, in step (2), the silicon-based binder is based on silicon dioxide, the solid precursor is based on porous silicon-aluminum crystals, and the mass ratio of the solid precursor to ammonium phosphomolybdate and silicon-based binder is 1:(1-6):(0.75-5), preferably 1:(2-5):(1.7-4), and more preferably 1:(2-5):(2-4).

[0028] Further, in step (2), the solid-liquid ratio in the mixture is 0.1 to 0.5 by mass, preferably 0.2 to 0.5.

[0029] Furthermore, in step (3), the operating conditions for spray molding include: the equipment spray temperature is 150-250°C, preferably 180-240°C.

[0030] The third aspect of the present invention provides the application of the SCM-IC-1 molecular sieve composite material provided in the first aspect or the SCM-IC-1 molecular sieve composite material obtained by the preparation method of the second aspect as an adsorbent material for the capture and detection of metal ions in water.

[0031] Furthermore, the method for metal ion capture and detection includes: immersing the SCM-IC-1 molecular sieve composite material in a test solution containing metal for adsorption capture and detection.

[0032] Furthermore, the method for metal ion capture and detection includes the following steps:

[0033] S1. Take a water sample containing metal ions as the test solution;

[0034] S2. The SCM-IC-1 molecular sieve composite material is loaded into the chromatography column as an adsorption layer, and the test solution in step S1 is subjected to adsorption operation through the chromatography column.

[0035] S3. Detect the adsorbed metal ions and calculate the capture rate.

[0036] Further, in step S1, the metal ions contained in the test solution include non-radioactive metal ions and / or radioactive metal ions; the non-radioactive metal ions are preferably Cs; the radioactive metal ions are preferably radioactive Cs. The radioactive Cs ions can be at least one of Cs-133, Cs-134, and Cs-137, preferably Cs-137.

[0037] Further, in step S1, the concentration of non-radioactive metal ions in the test solution is 0.01–50 mg / L, preferably 0.05–30 mg / L.

[0038] Further, in step S1, the volume activity of the radioactive metal ions in the test solution is 0.1 to 1 Bq / L.

[0039] Further, in step S1, an acidic adjuster is preferably added to the test solution to adjust the pH to 2-4. The pH adjustment can be performed using an acidic adjusting solution conventionally used in the art, such as hydrochloric acid.

[0040] Further, in step S1, when the metal ion is a radioactive metal ion, a corresponding non-radioactive metal source can preferably be added. For example, when the captured metal ion is a radioactive cesium ion, non-radioactive cesium chloride can preferably be added. The purpose of adding it is to increase the overall concentration of metal ions in the solution, thereby better capturing radioactive ions. The mass ratio of the non-radioactive metal source to the test solution is 0.01–50 mg / L, preferably 0.05–30 mg / L, wherein the metal source is by mass and the test solution is by volume.

[0041] Furthermore, in step S1, the water body can be industrial water, domestic water, seawater, fresh water, etc.; seawater is preferred.

[0042] Further, in step S2, the solid-liquid ratio of the adsorbent material and the test liquid is 0.02 to 1 g / L, preferably 0.05 to 0.5 g / L.

[0043] Furthermore, in step S2, the test solution is adsorbed through the adsorption layer of the chromatography column. The injection method can be achieved by using a pump to inject the test solution before or after the chromatography column, and the injection flow rate of the test solution, i.e., the mass hourly space velocity, can be controlled.

[0044] Further, in step S2, the test solution is adsorbed through a chromatography column, and the operating parameters include: the operating temperature is 5-40℃, preferably 10-35℃; the mass hourly space velocity (MAV) of the test solution is 10-180 g / (g·min), preferably 30-150 g / (g·min); wherein, the MAV is the mass of the test solution injected per minute relative to the adsorbent material.

[0045] Furthermore, in step S3, when the metal ions to be captured are non-radioactive metal ions, the test solution after adsorption in S2 needs to be detected and the capture rate calculated.

[0046] Furthermore, in step S3, when the metal ions to be captured are radioactive metal ions, it is necessary to use γ-rays to determine the amount of radioactive particles in the adsorption layer and calculate the capture rate of radioactive metal ions.

[0047] Further, in step S3, the operation steps for the γ-ray measurement are as follows: the adsorption layer is placed in the cavity of the γ-ray tester, tested for 5 to 20 hours, the number of decaying particles is recorded, the relative decay constant is calculated to determine the total number of radioactive particles, and thus the collection efficiency of the adsorption material provided by the present invention for radioactive ions is calculated.

[0048] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0049] 1. The SCM-IC-1 molecular sieve composite material provided by this invention has a special chemical composition and physicochemical properties, and can be applied in a variety of fields.

[0050] 2. When the SCM-IC-1 molecular sieve composite material provided by this invention is used as an adsorbent, compared with standard reagents, it powerfully removes polluting metal ion components, especially radioactive components, from water bodies, particularly in the capture of metal ions, especially radioactive cesium ions. The effect remains outstanding in seawater, where the water system is more complex, exhibiting an excellent capture rate, and achieving complete capture of radioactive cesium ions in a shorter time. Compared with standard reagents, the amount of ammonium phosphomolybdate used is significantly reduced, offering greater environmental advantages in practical applications. Attached Figure Description

[0051] Figure 1 The image shows the XRD pattern of the SCM-IC-1 molecular sieve composite material prepared in Example 1.

[0052] Figure 2 SEM image of the SCM-IC-1 molecular sieve composite material prepared in Example 1;

[0053] Figure 3 The image shows the XRD pattern of the SCM-IC-1 molecular sieve composite material prepared in Example 3. Detailed Implementation

[0054] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited to the following description.

[0055] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0056] In the context of this specification, the structure of the sample is determined by X-ray diffraction (XRD), which is measured by an X-ray powder diffractometer using a Cu-Kα ray source and a nickel filter.

[0057] In the context of this specification, including in the following examples and comparative examples, the X-ray powder diffractometer used for the samples is a Panalytical X-PERPRO type X-ray powder diffractometer, and the CuKα-ray source is used to analyze the phase composition of the samples. Nickel filter, 2θ scanning range 2~50°, operating voltage 40kV, current 40mA, scanning rate 10° / min.

[0058] In the context of this specification, including in the following examples and comparative examples, the scanning electron microscope (SEM) used for the samples is an S-4800II field emission scanning electron microscope. The method for measuring the crystal size of the samples was as follows: The molecular sieve was observed using this SEM at a magnification of 10,000x. A field of view was randomly selected, and the average sum of the crystal sizes in that field of view was calculated. This operation was repeated a total of 10 times. The average sum of the 10 averages was taken as the crystal size.

[0059] In the context of this specification, the shortest linear distance between Mo and Al elements in the material was determined by observing the distance between any Mo bright spot and its nearest Al bright spot in a randomly selected field of view using a transmission electron microscope (FEI G2F30 transmission electron microscope, operating voltage 300kV) at a magnification of 100,000x in EDS mode. Thirty different Mo bright spots were measured using the above procedure, and the average distance was taken.

[0060] In the context of this specification, including the following examples and comparative examples, the inductively coupled plasma atomic emission spectrometer (ICP) used is a Varian 725-ES. For solid samples, the elemental content was determined by dissolving the sample in hydrofluoric acid and analyzing the content in moles. For test solutions, the content of each element in the solution was directly measured.

[0061] In the context of this specification, including in the embodiments, the formula for the capture rate of the non-radioactive cesium metal ions is:

[0062] The capture rate of cesium metal ions % = (c0-c1) / c0×100%; c0 is the initial mass concentration of cesium metal ions in the test solution, and c1 is the mass concentration of cesium metal ions in the test solution after capture.

[0063] In the context of this specification, including the following examples and comparative examples, the measured radioactive cesium ion capture rate is extrapolated from the captured radioactive Cs-137, and is measured by using a gamma-ray counter to measure the content of gamma decay rays captured by the instrument per unit time. In step S1, a Cs-137 solution is added to a selected water sample (deionized water) to achieve a specific range of radioactive volume activity of radioactive cesium in the water, thus simulating a radioactive water sample from industrial or domestic use.

[0064] The formula for the capture rate of radioactive cesium ions is:

[0065] Radioactive cesium ion capture rate % = γ1*t0 / (γ0*t1)×100%; γ1 is the radiation dose of the adsorbed layer after capture in the gamma-ray test, and t1 is the gamma-ray test time. In contrast, γ0 and t0 are the test radiation dose and test time of the standard, respectively.

[0066] Example 1

[0067] 1. Material preparation:

[0068] 100g of Na-type MCM-22 molecular sieve (0.033Na2O·SiO2·0.033Al2O3) was added to 2L of deionized water, stirred and heated to 50℃, maintained for 1h, and then centrifuged and decanted to obtain a solid precursor. The morphology of the MCM-22 molecular sieve was multilayered and plate-like.

[0069] Add 200g of ammonium phosphomolybdate, 500g of 40wt% silica sol solution, and deionized water to the solid precursor (100g Na-type MCM-22 molecular sieve) and stir until homogeneous to prepare a 1.5L mixture (solid-liquid mass ratio of 0.5).

[0070] The above mixture was injected at 50 mL / min and spray-molded at 200 °C to obtain the SCM-IC-1 molecular sieve composite material.

[0071] The obtained material XRD pattern is as follows Figure 1 As shown in the figure, XRD analysis reveals that the material retains the MWW molecular sieve and ammonium phosphomolybdate structure overall. The SEM image of the material is shown below. Figure 2 As shown, it is spherical. The composition and physicochemical properties of the material are shown in Table 1.

[0072] Example 2

[0073] 1. Material preparation:

[0074] 100g of Na-type MCM-22 molecular sieve (0.025Na2O·SiO2·0.025Al2O3) was added to 2L of deionized water, stirred and heated to 50℃, maintained for 1h, and then centrifuged and decanted to obtain a solid precursor. The morphology of the MCM-22 molecular sieve was multilayered and plate-like.

[0075] Add 200g of ammonium phosphomolybdate, 500g of 40wt% silica sol solution, and deionized water to the solid precursor (100g Na-type MCM-22 molecular sieve) and stir until homogeneous to prepare a 1.5L mixture (solid-liquid mass ratio of 0.5).

[0076] The above mixture was injected at 50 mL / min and spray-molded at 200 °C to obtain the SCM-IC-1 molecular sieve composite material.

[0077] The obtained material XRD patterns, SEM images and Figure 1 , Figure 2 Similar. The composition and physicochemical properties of the materials are shown in Table 1.

[0078] Example 3

[0079] 1. Material preparation:

[0080] 100g of Na-type ZSM-5 molecular sieve (0.025Na2O·SiO2·0.025Al2O3) was added to 2L of deionized water, stirred and heated to 50℃, maintained for 1h, and then centrifuged and decanted to obtain a solid precursor. The morphology of ZSM-5 was nearly spherical.

[0081] Add 200g of ammonium phosphomolybdate, 500g of 40wt% silica sol solution, and deionized water to the solid precursor (100g Na-type ZSM-5 molecular sieve) and stir until homogeneous to prepare a 1.5L mixture (solid-liquid mass ratio of 0.5).

[0082] The above mixture was injected at 50 mL / min and spray-molded at 200 °C to obtain the SCM-IC-1 molecular sieve composite material.

[0083] The obtained catalyst XRD pattern is as follows Figure 3 As shown in the XRD pattern, the catalyst retains the MFI molecular sieve and ammonium phosphomolybdate structure overall. SEM images and... Figure 2 Similar. The composition and physicochemical properties of the materials are shown in Table 1.

[0084] Example 4

[0085] 1. Material preparation:

[0086] 50g of Na-type MCM-22 molecular sieve (0.033Na2O·SiO2·0.033Al2O3) was added to 2L of deionized water, stirred and heated to 50℃, maintained for 1h, and then centrifuged and decanted to obtain a solid precursor. The morphology of the MCM-22 molecular sieve was multilayered and plate-like.

[0087] Add 250g of ammonium phosphomolybdate, 500g of 40wt% silica sol solution, and deionized water to the solid precursor (50g Na-type MCM-22 molecular sieve) and stir until homogeneous to prepare a 1.5L mixture (solid-liquid mass ratio of 0.5).

[0088] The above mixture was injected at 50 mL / min and spray-molded at 200 °C to obtain the SCM-IC-1 molecular sieve composite material.

[0089] The obtained material XRD patterns, SEM images and Figure 1 , Figure 2 Similar. The composition and physicochemical properties of the materials are shown in Table 1.

[0090] Example 5

[0091] 1. Material preparation:

[0092] 100g of Na-type MCM-22 molecular sieve (0.033Na2O·SiO2·0.033Al2O3) was added to 2L of deionized water, stirred and heated to 50℃, maintained for 1h, and then centrifuged and decanted to obtain a solid precursor. The morphology of the MCM-22 molecular sieve was multilayered and plate-like.

[0093] Add 100g of Na-type MCM-22 molecular sieve to 250g of ammonium phosphomolybdate, 500g of 30wt% silica sol solution, and appropriate amount of deionized water, and stir well to prepare 2L of mixture (solid-liquid mass ratio of 0.33).

[0094] The above mixture was injected at 50 mL / min and spray-molded at 200 °C to obtain the SCM-IC-1 molecular sieve composite material.

[0095] The obtained material XRD patterns, SEM images and Figure 1 , Figure 2 Similar. The composition and physicochemical properties of the materials are shown in Table 1.

[0096] Example 6

[0097] 1. Material preparation:

[0098] 100g of Na-type MCM-22 molecular sieve (0.033Na2O·SiO2·0.033Al2O3) was added to 2L of deionized water, stirred and heated to 50℃, maintained for 1h, and then centrifuged and decanted to obtain a solid precursor. The morphology of the MCM-22 molecular sieve was multilayered and plate-like.

[0099] Add 100g of solid precursor (Na-type MCM-22 molecular sieve) to 200g of ammonium phosphomolybdate, 500g of 40wt% silica sol solution, and add appropriate amount of deionized water and stir well to prepare 2L of mixture (solid-liquid mass ratio 0.33).

[0100] The above mixture was injected at 80 mL / min and spray-molded at 230 °C to obtain the SCM-IC-1 molecular sieve composite material.

[0101] The obtained material XRD patterns, SEM images and Figure 1 , Figure 2 Similar. The composition and physicochemical properties of the materials are shown in Table 1.

[0102] Example 7

[0103] 1. Material preparation:

[0104] 100g of Na-type USY molecular sieve (0.1Na2O·SiO2·0.1Al2O3) was added to 2L of deionized water, stirred and heated to 50℃, maintained for 1h, and then centrifuged to obtain a solid precursor. The morphology of USY was nearly spherical.

[0105] Add 200g of ammonium phosphomolybdate, 500g of 40wt% silica sol solution, and deionized water to the solid precursor (100g Na-type USY molecular sieve) and stir until homogeneous to prepare a 1.5L mixture (solid-liquid mass ratio of 0.5).

[0106] The above mixture was injected at 50 mL / min and spray-molded at 200 °C to obtain the SCM-IC-1 molecular sieve composite material.

[0107] XRD analysis of the obtained material shows that the material as a whole retains the FAU molecular sieve and ammonium phosphomolybdate structure. SEM images and... Figure 2 Similar. The composition and physicochemical properties of the materials are shown in Table 1.

[0108] Example 8

[0109] 1. Material preparation:

[0110] 100g of Na-type SSZ-13 molecular sieve (0.017Na2O·SiO2·0.017Al2O3) was added to 2L of deionized water, stirred and heated to 50℃, and kept for 1h before centrifugation and decantation to obtain a solid precursor. The morphology of SSZ-13 was nearly spherical.

[0111] Add 200g of ammonium phosphomolybdate, 500g of 40wt% silica sol solution, and deionized water to the solid precursor (100g Na SSZ-13 molecular sieve) and stir until homogeneous to prepare a 1.5L mixture (solid-liquid mass ratio of 0.5).

[0112] The above mixture was injected at 50 mL / min and spray-molded at 200 °C to obtain the SCM-IC-1 molecular sieve composite material.

[0113] XRD analysis of the obtained material shows that the material as a whole retains the CHA molecular sieve and ammonium phosphomolybdate structure. SEM images and... Figure 2 Similar. The composition and physicochemical properties of the materials are shown in Table 1.

[0114] Example 9

[0115] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0116] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 1 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0117] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0118] Example 10

[0119] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0120] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 2 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0121] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0122] Example 11

[0123] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0124] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 3 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0125] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0126] Example 12

[0127] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0128] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 4 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0129] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0130] Example 13

[0131] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0132] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 5 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0133] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0134] Example 14

[0135] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0136] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 6 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0137] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0138] Example 15

[0139] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0140] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 7 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0141] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0142] Example 16

[0143] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0144] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 8 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0145] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0146] Example 17

[0147] Add 1 Bq Cs-137 to 3 L of filtered seawater, adjust the pH to 2.5 with concentrated hydrochloric acid, and add 30 mg of cesium chloride to prepare the target test solution.

[0148] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 1 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 100g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0149] The chromatography column was removed and placed entirely into a gamma-ray counter to measure the cesium capture rate. The results are recorded in Table 2.

[0150] Example 18

[0151] 30 mg of cesium chloride was added to 3 L of filtered seawater to prepare the target test solution.

[0152] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 1 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0153] Take 20 mL of the adsorbed test solution and determine the Cs content in the sample using ICP. Record the calculated Cs capture rate in Table 2.

[0154] Example 19

[0155] Add 1 Bq Cs-137 to 3 L of filtered seawater to prepare the target test solution.

[0156] Take 1g of the SCM-IC-1 molecular sieve composite material synthesized in Example 1 and load it into a chromatography column. Under the condition of 20°C, the sample of the test liquid is injected at a mass space velocity of 50g / (g·min) for adsorption until all the test liquid passes through the chromatography column.

[0157] The chromatography column was removed and placed in a gamma-ray counter for 10 hours to measure the total number of radioactive particles with energies between 661.5 and 662 keV. The calculated Cs-137 capture rate was recorded in Table 2.

[0158] Comparative Example 1

[0159] The trapping effect was compared under the same conditions as in Example 9, except that the adsorbent material was conventional ammonium phosphomolybdate.

[0160] For ease of comparison, the composition of the materials and the evaluation results are listed in Tables 1 and 2.

[0161] Comparative Example 2

[0162] The trapping effect was compared under the same conditions as in Example 9, except that a 15:1 composite material of MCM-22 and silica sol was selected as the adsorbent. In other words, the only difference from Example 1 was the absence of ammonium phosphomolybdate in the adsorbent. The specific preparation process is as follows:

[0163] Take 167g of Na-type MCM-22 molecular sieve (same as in Example 1) and 833g of 40wt% silica sol solution, add deionized water and stir evenly to prepare 1.5L of mixture (solid-liquid mass ratio of 0.5).

[0164] The above mixture was injected at a rate of 50 mL / min and spray-molded at an operating temperature of 200 °C to obtain a molecular sieve composite material.

[0165] For ease of comparison, the composition and evaluation results of the adsorption materials are listed in Tables 1 and 2.

[0166] Comparative Example 3

[0167] The trapping effect was compared under the same conditions as in Example 9. The difference was that the adsorbent material was different from that in Example 1. 10g of MCM-22 in a 15:1 ratio and 20g of ammonium phosphomolybdate were mechanically mixed, then pressed into tablets and ground to obtain mixed particle samples as adsorbent material.

[0168] For ease of comparison, the composition and evaluation results of the adsorption materials are listed in Tables 1 and 2.

[0169] Comparative Example 4

[0170] The trapping was performed under the same conditions as in Example 9, except that the mass hourly space velocity was 200 g / (g·min).

[0171] For ease of comparison, the evaluation results of the adsorption materials are listed in Table 2.

[0172] Table 1. Material composition and physicochemical properties obtained from each embodiment and comparative example.

[0173]

[0174] To facilitate comparison of the trapping performance of the materials prepared in the examples and comparative examples, the specific results are listed in Table 2.

[0175] Table 2. Capture performance data for each embodiment and comparative example.

[0176]

[0177]

[0178] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. An SCM-IC-1 molecular sieve composite material, characterized in that, The material comprises a porous silicon-aluminum crystal component, an ammonium phosphomolybdate component, and a silicon-based binder component.

2. The SCM-IC-1 molecular sieve composite material according to claim 1, characterized in that... In the SCM-IC-1 molecular sieve composite material, the shortest linear distance between Mo and Al elements is <200nm, preferably 10-150nm. And / or, the SCM-IC-1 molecular sieve composite material has a spherical or near-spherical morphology, with an average particle size of 20-150 μm, preferably 30-120 μm, and more preferably 50-100 μm.

3. The SCM-IC-1 molecular sieve composite material according to claim 1, characterized in that, The chemical composition of the porous silicon-aluminum crystal component is "xNa2O·ySiO2·xAl2O3", and satisfies 0.01≤x / y≤0.30, preferably 0.015≤x / y≤0.250, in molar terms; And / or, the structure of the silicon-aluminum porous crystal component has one or more of the topological structures of molecular sieves such as MWW, FAU, BEA, MOR, ATS, CHA, and MFI, preferably one or more of the topological structures of molecular sieves such as MWW, FAU, CHA, and MFI.

4. The SCM-IC-1 molecular sieve composite material according to claim 1, characterized in that, Based on the mass of the SCM-IC-1 molecular sieve composite material, the mass content of the silica-alumina porous crystal component is 8-30%, preferably 12-25%. And / or, based on the mass of the SCM-IC-1 molecular sieve composite material, the mass content of the ammonium phosphomolybdate component is 20-65%, preferably 30-60%; And / or, based on the mass of the SCM-IC-1 molecular sieve composite material, the mass content of the silicon-based binder component is 25-50%, preferably 35-45%.

5. A method for preparing the SCM-IC-1 molecular sieve composite material according to any one of claims 1-4, comprising the following steps: (1) Mix porous silicon-aluminum crystals with water and heat them to activate them to obtain a solid precursor; (2) The solid precursor is mixed with ammonium phosphomolybdate, a silicone binder and water to obtain a mixture; (3) The mixture was spray-molded to obtain SCM-IC-1 molecular sieve composite material.

6. The preparation method according to claim 5, characterized in that, In step (1), the chemical composition of the porous silicon-aluminum crystal is "xNa2O·ySiO2·xAl2O3", and satisfies 0.01≤x / y≤0.30, preferably 0.015≤x / y≤0.250, in molar terms; And / or, in step (1), the structure of the silicon-aluminum porous crystal has one or more of the topological structures of molecular sieves such as MWW, FAU, BEA, MOR, ATS, CHA, and MFI, preferably one or more of the topological structures of molecular sieves such as MWW, FAU, CHA, and MFI. And / or, in step (1), the mass ratio of the porous silicon-aluminum crystal to water is 1:(5-50), preferably 1:(10-40).

7. The preparation method according to claim 5, characterized in that, In step (1), the operating conditions for the heating activation include: a temperature of 40 to 80°C and a processing time of 0.5 to 4 hours, preferably a temperature of 50 to 70°C and a processing time of 0.5 to 2 hours.

8. The preparation method according to claim 5, characterized in that, In step (2), the silicon-based binder is a silicon-based compound, preferably selected from at least one of silica sol with a silica concentration of 30-40 wt%, tetraethyl silicate, and tetrabutyl silicate; And / or, in step (2), the silicon-based binder is based on silicon dioxide, the solid precursor is based on porous silicon-aluminum crystals, and the mass ratio of the solid precursor to ammonium phosphomolybdate and silicon-based binder is 1:(1-6):(0.75-5); And / or, in step (2), the solid-liquid ratio in the mixture is 0.1 to 0.5 by mass, preferably 0.2 to 0.

5.

9. The preparation method according to claim 5, characterized in that, In step (3), the operating temperature of the spray molding is 150-250°C, preferably 180-240°C.

10. The SCM-IC-1 molecular sieve composite material according to any one of claims 1-4 or the SCM-IC-1 molecular sieve composite material obtained by the preparation method according to any one of claims 5-9 is used as an adsorbent material for the capture and detection of metal ions in water.

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