Separation column based on support-MIL-100 (Fe) composite material as well as preparation method and application of separation column

Abstract

The invention discloses a separation column based on a support-MIL-100 (Fe) composite material as well as a preparation method and application of the separation column, and relates to the technical field of separation and enrichment materials. The separation column based on the support-MIL-100 (Fe) composite material comprises a column body, the support-MIL-100 (Fe) composite material and partition plates, wherein the support-MIL-100 (Fe) composite material is filled in the column body, and the partition plates are arranged at the two ends of the column body. The MIL-100 (Fe) and the carrier are prepared into the composite material and applied to the separation column, the application range of the MIL-100 (Fe) material is widened, the prepared separation column based on the support-MIL-100 (Fe) composite material can be used for separating and enriching various types of to-be-detected liquid, various application requirements are met, and the separation column has the advantages of being high in adsorption rate and recovery rate and has a good application prospect. The problem that an existing separation and enrichment small column is high in cost can be solved.

Description

Technical Field

[0001] The present invention relates to the technical field of separation and enrichment materials, and in particular to a separation column based on a carrier-MIL-100 (Fe) composite material, and a preparation method and application thereof. Background Art

[0002] With the current emphasis on environmental protection and food safety and the rapid development of biomedical technology, accurate analysis and detection as well as efficient separation and purification pretreatment have become essential routine tasks in the environmental monitoring, food safety and pharmaceutical industries. On the one hand, new pollutants, pesticide residues and environmental hormones are characterized by low concentrations and high toxicity, which poses severe challenges to environmental monitoring and food safety testing. In order to effectively monitor low-concentration components, it is necessary to concentrate and enrich the ultra-low concentration components in the above samples before pretreatment. On the other hand, in the pharmaceutical field, the presence of isomers is a difficulty in drug purification, and the analysis and detection of biomarkers is key to medical research and disease diagnosis, all of which require the separation and analysis of complex components. Therefore, the enrichment of ultra-low concentration components and the separation of complex components have become key technologies in the fields of environmental pollutant detection, food safety, drug purification, component separation, etc., and it is urgent to develop new separation and enrichment materials to meet the above application needs.

[0003] Currently, the separation materials used for analytical testing, separation, and purification in food and drug testing and environmental monitoring primarily rely on commercially available separation-enrichment columns from brands like Agilent and Waters. While these columns can meet a variety of application needs, they are expensive, costing as much as 200 to 300 yuan per column, and are disposable. Therefore, there is an urgent need to independently develop new separation-enrichment materials. Summary of the Invention

[0004] The main purpose of the present invention is to propose a separation column based on a carrier-MIL-100 (Fe) composite material, a preparation method and an application thereof, in order to propose a new separation and enrichment material to solve the problem of high cost of existing separation-enrichment columns.

[0005] To achieve the above objectives, the present invention proposes a separation column based on a carrier-MIL-100(Fe) composite material, which is used for separation and enrichment pretreatment of a liquid to be treated. The separation column based on the carrier-MIL-100(Fe) composite material comprises a column body, a carrier-MIL-100(Fe) composite material filled in the column body, and partitions arranged at both ends of the column body; wherein:

[0006] The separator is provided with a pore structure, and the pore size of the pore structure of the separator is smaller than the particle size of the carrier-MIL-100 (Fe) composite material;

[0007] The preparation method of the carrier-MIL-100 (Fe) composite material comprises the following steps:

[0008] activating the carrier to obtain an activated carrier;

[0009] The activated carrier, the solution containing iron ions and the solution containing trimesic acid are mixed and stirred at room temperature to obtain a suspension containing a carrier-MIL-100 (Fe) composite material. The suspension containing the carrier-MIL-100 (Fe) composite material is subjected to solid-liquid separation to obtain a solid. The solid is washed and dried to obtain a carrier-MIL-100 (Fe) composite material.

[0010] In one embodiment, the carrier-MIL-100(Fe) composite material has a particle size of 0.5 to 50 μm.

[0011] In one embodiment, the amounts of the iron ion-containing solution and the trimesic acid-containing solution are calculated based on a molar ratio of iron ions in the iron ion-containing solution to trimesic acid in the trimesic acid-containing solution of (1-10):(1-10).

[0012] In one embodiment, the step of mixing and stirring the activated carrier, the solution containing iron ions, and the solution containing trimesic acid at room temperature to obtain a suspension containing the carrier-MIL-100 (Fe) composite material comprises:

[0013] soaking the activated support in a solution containing iron ions at room temperature for 0 to 60 minutes to obtain a mixture;

[0014] The mixture and the solution containing trimesic acid are mixed and stirred at room temperature for 1 to 48 hours to obtain a suspension containing the carrier-MIL-100 (Fe) composite material.

[0015] In one embodiment, the support comprises at least one of silica, alumina, diatomaceous earth, kaolin, illite, and activated carbon.

[0016] The present invention proposes a method for preparing a separation column based on a carrier-MIL-100 (Fe) composite material as described in the above technical solution, comprising the following steps:

[0017] A column arranged in an up-down direction is provided, wherein a pore structure is provided inside the column for filling the carrier-MIL-100 (Fe) composite material and for allowing the liquid to be treated to pass through;

[0018] A partition is placed at the lower end of the column, and then the carrier-MIL-100 (Fe) composite material is loaded into the column, and a partition is placed at the upper end of the column to obtain a separation column based on the carrier-MIL-100 (Fe) composite material.

[0019] In one embodiment, the steps of placing a partition at the lower end of the column, then loading the support-MIL-100(Fe) composite material into the column, and placing a partition at the upper end of the column to obtain a separation column based on the support-MIL-100(Fe) composite material include:

[0020] The carrier-MIL-100(Fe) composite material is mixed with a second solvent to obtain a suspension of the carrier-MIL-100(Fe) composite material:

[0021] A partition is placed at the lower end of the column, and a suspension of the carrier-MIL-100 (Fe) composite material is injected into the column. The second solvent is removed by filtration. A partition is placed at the upper end of the column, and the column is dried to obtain a separation column based on the carrier-MIL-100 (Fe) composite material.

[0022] In one embodiment, the mass concentration of the suspension of the carrier-MIL-100(Fe) composite material is 0.1-100 g / L.

[0023] The present invention proposes an application of a separation column based on a carrier-MIL-100 (Fe) composite material as described in the aforementioned technical solution in separating and enriching a liquid to be treated, wherein the steps of separating and enriching the liquid to be treated include:

[0024] injecting the liquid to be treated into a separation column to obtain a separation column that enriches the liquid to be treated; the separation column is a separation column based on a carrier-MIL-100(Fe) composite material;

[0025] Then, the separation column enriched with the liquid to be treated is eluted with an eluent, and the eluent is collected to obtain a sample to be tested.

[0026] In one embodiment, the liquid to be treated includes any one of antibiotics, amino acids and polypeptides.

[0027] In the technical solution of the present invention, a separation column based on a carrier-MIL-100(Fe) composite material is provided, which comprises a column body, a carrier-MIL-100(Fe) composite material loaded in the column body, and partitions provided at both ends of the column body. The column body is used to load the carrier-MIL-100(Fe) composite material, which serves as a filler and can selectively retain target analytes or impurities through physical adsorption, chemical adsorption, and the like. The partitions facilitate liquid distribution and prevent the loss of the carrier-MIL-100(Fe) composite material. The present invention prepares MIL-100(Fe) and a carrier into a composite material and applies it to a separation column, broadening the application range of the MIL-100(Fe) material. The separation column based on the carrier-MIL-100(Fe) composite material can handle the separation and enrichment of various types of test liquids, meet various application requirements, and has the advantages of high adsorption rate and high recovery rate, which can be used to solve the problem of high cost of existing separation and enrichment columns. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0029] Figure 1 This is a physical picture of the carrier-MIL-100 (Fe) composite material of Example 1 of the present invention;

[0030] Figure 2 Schematic diagram of the structure of a separation column based on a carrier-MIL-100 (Fe) composite material according to Example 2 of the present invention;

[0031] Figure 3 Graph showing the adsorption recovery rate of alanine at different concentrations by the separation column in Example 3 of the present invention;

[0032] Figure 4 Graph showing the effect of column packing amount on alanine adsorption recovery rate of the separation column in Example 4 of the present invention;

[0033] Figure 5 This is a bar graph of the recovery rates of alanine after adsorption on the separation column in Example 5 of the present invention under different eluents.

[0034] Description of reference numerals:

[0035] 100. Separation column based on carrier-MIL-100(Fe) composite material; 1. Column; 2. Partition.

[0036] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION

[0037] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0038] It should be noted that if the embodiments of the present invention involve directional indications (such as up, down, left, right, front, back, etc.), the directional indications are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture. If the specific posture changes, the directional indications will also change accordingly.

[0039] In addition, if there are descriptions involving "first", "second", etc. in the embodiments of the present invention, the descriptions of "first", "second", etc. are only for descriptive purposes and cannot be understood as indicating or suggesting their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features limited to "first" and "second" may explicitly or implicitly include at least one of such features. In addition, if "and / or" or "and / or" appears in the full text, its meaning includes three parallel solutions. Taking "A and / or B" as an example, it includes solution A, solution B, or solutions that satisfy both A and B. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in this field to implement. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0040] With the current emphasis on environmental protection and food safety and the rapid development of biomedical technology, accurate analysis and detection as well as efficient separation and purification pretreatment have become essential routine tasks in the environmental monitoring, food safety and pharmaceutical industries. On the one hand, new pollutants, pesticide residues and environmental hormones are characterized by low concentrations and high toxicity, which poses severe challenges to environmental monitoring and food safety testing. In order to effectively monitor low-concentration components, it is necessary to concentrate and enrich the ultra-low concentration components in the above samples before pretreatment. On the other hand, in the pharmaceutical field, the presence of isomers is a difficulty in drug purification, and the analysis and detection of biomarkers is key to medical research and disease diagnosis, all of which require the separation and analysis of complex components. Therefore, the enrichment of ultra-low concentration components and the separation of complex components have become key technologies in the fields of environmental pollutant detection, food safety, drug purification, component separation, etc., and it is urgent to develop new separation and enrichment materials to meet the above application needs.

[0041] Currently, the separation materials used for analytical testing, separation, and purification in food and drug testing and environmental monitoring primarily rely on commercially available separation-enrichment columns from brands like Agilent and Waters. While these columns can meet a variety of application needs, they are expensive, costing as much as 200 to 300 yuan per column, and are disposable. Therefore, there is an urgent need to independently develop new separation-enrichment materials.

[0042] MIL-100(Fe) is a metal-organic framework (MOF) composed of iron (Fe) ions and trimesic acid ligands. MIL-100(Fe) has a very high surface area, providing numerous active sites for processes such as adsorption and catalysis, demonstrating broad application potential in a variety of fields.

[0043] The conventional method for preparing MIL-100(Fe) is to perform a solvothermal reaction between a solution containing iron ions and a solution containing trimesic acid at 120-150°C. This method is not suitable for large-scale continuous production and the reaction conditions are relatively stringent. If MIL-100(Fe) is to be produced at room temperature, an additional promoter is required. These promoters are materials such as quinones, peroxides, or piperidine nitrogen oxide radicals. Currently, there is no published research on the use of MIL-100(Fe) in separation and enrichment columns. This is because MIL-100(Fe) produced by hydrothermal methods is typically a nanopowder material. In practical applications, the particles of MIL-100(Fe) do not meet the requirements for column packing. Furthermore, there is no published research on separation and enrichment columns prepared from composite materials of MIL-100(Fe) and support materials at room temperature.

[0044] Based on the above background, the present invention proposes a separation column 100 based on a carrier-MIL-100 (Fe) composite material, which is used for separation and enrichment pretreatment of a fluid to be treated.

[0045] See also Figure 2 The separation column 100 based on the carrier-MIL-100(Fe) composite material comprises a column 1, a carrier-MIL-100(Fe) composite material (not shown) filled in the column 1, and partitions 2 provided at both ends of the column; wherein:

[0046] The separator 2 is provided with a pore structure, and the pore size of the pore structure of the separator 2 is smaller than the particle size of the carrier-MIL-100 (Fe) composite material;

[0047] The preparation method of the carrier-MIL-100 (Fe) composite material comprises the following steps:

[0048] activating the carrier to obtain an activated carrier;

[0049] The activated carrier, the solution containing iron ions and the solution containing trimesic acid are mixed and stirred at room temperature to obtain a suspension containing a carrier-MIL-100 (Fe) composite material. The suspension containing the carrier-MIL-100 (Fe) composite material is subjected to solid-liquid separation to obtain a solid. The solid is washed and dried to obtain a carrier-MIL-100 (Fe) composite material.

[0050] In the technical solution of the present invention, a separation column 100 based on a carrier-MIL-100 (Fe) composite material is provided, which comprises a column body 1, a carrier-MIL-100 (Fe) composite material loaded in the column body, and partitions 2 provided at both ends of the column body 1. The column body 1 is used to load the carrier-MIL-100 (Fe) composite material, which acts as a filler and can selectively retain target analytes or impurities through physical adsorption, chemical adsorption, and the like. The function of the partitions 2 is to facilitate liquid distribution and prevent the loss of the carrier-MIL-100 (Fe) composite material. The present invention prepares MIL-100 (Fe) and a carrier into a composite material and applies it to a separation column, broadening the application range of the MIL-100 (Fe) material. The separation column based on the carrier-MIL-100 (Fe) composite material can handle the separation and enrichment of various types of test liquids, meeting various application requirements, and has the advantages of high adsorption rate and high recovery rate, which can be used to solve the problem of high cost of existing separation and enrichment columns.

[0051] When preparing a carrier-MIL-100(Fe) composite material, a conventional activation method is first used to activate the carrier material. Then, the activated carrier, a solution containing iron ions, and a solution containing trimesic acid are stirred and reacted at room temperature, so that the coordination between the iron ions and terephthalic acid forms MIL-100(Fe) with a three-dimensional framework structure. At the same time, MIL-100(Fe) interacts with the carrier material to obtain the carrier-MIL-100(Fe) composite material. Compared with conventional preparation methods, the carrier-MIL-100(Fe) composite material provided by the present invention can be prepared by reaction at room temperature, does not rely on specific equipment, has mild reaction conditions and is easy to control, and does not require the addition of additional materials such as promoters. Therefore, it has the advantages of simple preparation, low cost, and continuous reaction, and is convenient for large-scale application.

[0052] In an embodiment of the present invention, the average particle size of the carrier-MIL-100(Fe) composite material is 0.5 to 50 μm. The technical solution of the present invention does not require strict control of the particle size range and can be adjusted according to the actual requirements of the sample to be processed. When the particle size of the carrier-MIL-100(Fe) composite material is set within this range, the adsorption efficiency is high.

[0053] In an embodiment of the present invention, the amounts of the iron ion-containing solution and the trimesic acid-containing solution are calculated based on a molar ratio of iron ions in the iron ion-containing solution to trimesic acid in the trimesic acid-containing solution of (1-10):(1-10).

[0054] In an embodiment of the present invention, the carrier comprises at least one of silicon oxide, aluminum oxide, diatomaceous earth, kaolin, illite, and activated carbon. The technical solution of the present invention uses conventional carrier materials in the art as the carrier, including but not limited to metal oxides with silicon oxide, aluminum oxide, etc. as the main components, natural minerals such as diatomaceous earth, kaolin, illite, and activated carbon materials, and there is no strict requirement for particle size.

[0055] In an embodiment of the present invention, the solution containing iron ions can be obtained by dissolving metallic iron, inorganic iron salts or organic iron-containing compounds in a solvent, and the solvent includes at least one of water, methanol, ethanol and DMF.

[0056] In an embodiment of the present invention, the trimesic acid-containing solution is obtained by dissolving trimesic acid in a solvent, and the solvent includes water.

[0057] In an embodiment of the present invention, the step of activating the carrier to obtain the activated carrier comprises:

[0058] The carrier is soaked in a first solvent for 30 to 60 minutes to obtain a soaked carrier, and then the soaked carrier is sequentially cleaned and dried to obtain an activated carrier; wherein the first solvent includes at least one of water, acid, alkali and alcohol.

[0059] During activation, the support is pretreated with an appropriate solvent (typically an organic solvent or buffer solution) to ensure adequate wetting of the support. This activation treatment creates sites on the support surface that are favorable for the physical or chemical attachment of MIL-100(Fe). It should be noted that the surface cleaning and activation steps for the support material vary depending on the support material used, and may include, but are not limited to, water washing, acid washing, alkaline washing, and soaking in organic solvents such as alcohols.

[0060] In an embodiment of the present invention, the step of mixing and stirring the activated carrier, the solution containing iron ions, and the solution containing trimesic acid at room temperature to obtain a suspension containing the carrier-MIL-100 (Fe) composite material comprises:

[0061] soaking the activated support in a solution containing iron ions at room temperature for 0 to 60 minutes to obtain a mixture;

[0062] The mixture and the solution containing trimesic acid are mixed and stirred at room temperature for 1 to 48 hours to obtain a suspension containing the carrier-MIL-100 (Fe) composite material.

[0063] Adopting the above technical scheme, the carrier after activation can be first mixed with the solution containing iron ions and then mixed with the solution containing trimesic acid to react, or the carrier after activation, the solution containing iron ions and the solution containing trimesic acid can be selected to be mixed together and react. The inventors have found that the separation and enrichment effect when the carrier after activation is first mixed with the solution containing iron ions and then mixed with the solution containing trimesic acid to react is better. Therefore, in some embodiments of the present invention, the carrier after activation is selected to be mixed with the solution containing iron ions to obtain a mixture, and then the mixture is mixed with the solution containing trimesic acid to react.

[0064] The present invention provides a method for preparing the separation column 100 based on the carrier-MIL-100(Fe) composite material, comprising the following steps:

[0065] A column 1 is provided in an up-down direction, wherein a pore structure is provided inside the column 1 for filling the carrier-MIL-100 (Fe) composite material and for allowing the liquid to be treated to pass through;

[0066] A partition 2 is placed at the lower end of the column 1, and then the carrier-MIL-100 (Fe) composite material is loaded into the column 1, and a partition 2 is placed at the upper end of the column 1 to obtain a separation column 100 based on the carrier-MIL-100 (Fe) composite material.

[0067] In the technical solution of the present invention, a conventional column and separator can be used to prepare the separation column. By loading the carrier-MIL-100(Fe) composite material into the column 1, the separation column 100 based on the carrier-MIL-100(Fe) composite material can be obtained. It should be noted that the present invention does not limit the method of loading the carrier-MIL-100(Fe) composite material into the column 1. For example, the carrier-MIL-100(Fe) composite material can be loaded into the column 1 in the form of powder or slurry.

[0068] In an embodiment of the present invention, the steps of placing a partition 2 at the lower end of the column 1, then loading the carrier-MIL-100(Fe) composite material into the column 1, and placing the partition 2 at the upper end of the column 1 to obtain a separation column 100 based on the carrier-MIL-100(Fe) composite material include:

[0069] The carrier-MIL-100(Fe) composite material is mixed with a second solvent to obtain a suspension of the carrier-MIL-100(Fe) composite material:

[0070] A partition 2 is placed at the lower end of the column 1, and a suspension of the carrier-MIL-100 (Fe) composite material is injected into the column 1. The second solvent is removed by filtration. A partition 2 is placed at the upper end of the column 1, and the column is dried to obtain a separation column 100 based on the carrier-MIL-100 (Fe) composite material.

[0071] When the carrier-MIL-100(Fe) composite material is loaded into the column 1 in the form of a slurry, the carrier-MIL-100(Fe) composite material is first mixed with a second solvent to obtain a suspension of the carrier-MIL-100(Fe) composite material, and then the suspension of the carrier-MIL-100(Fe) composite material is loaded into the column 1. Figure 2 For ease of operation, a sleeve can be used to assist. First, the column 1 and the lower end partition 2 are placed in a sleeve of matching size. Then, a suspension of the carrier-MIL-100(Fe) composite material is injected into the column. After removing the second solvent by suction filtration, the partition 2 is placed on the upper end of the column 1 and dried to obtain a separation column 100 based on the carrier-MIL-100(Fe) composite material. The preparation method provided by the present invention does not require reliance on specific equipment, has low production and application costs, is simple in preparation, and offers reliable application efficiency.

[0072] In an embodiment of the present invention, the mass concentration of the suspension of the carrier-MIL-100(Fe) composite material is 0.1 to 100 g / L. The suspension of the carrier-MIL-100(Fe) composite material affects the loading amount of the carrier-MIL-100(Fe) composite material in the column. The higher the loading amount, the greater the adsorption rate of the separation column to the treated liquid, thereby improving the final recovery rate. Setting the mass concentration of the suspension of the carrier-MIL-100(Fe) composite material to 0.1 to 100 g / L is beneficial to actual operation.

[0073] The present invention proposes an application of a separation column based on a carrier-MIL-100 (Fe) composite material as described in the aforementioned technical solution in separating and enriching a liquid to be treated, wherein the steps of separating and enriching the liquid to be treated include:

[0074] injecting the liquid to be treated into a separation column to obtain a separation column that enriches the liquid to be treated; the separation column is a separation column based on a carrier-MIL-100(Fe) composite material;

[0075] Then, the separation column enriched with the liquid to be treated is eluted with an eluent, and the eluent is collected to obtain a sample to be tested.

[0076] When separating and enriching the liquid to be treated, the separation column based on the carrier-MIL-100(Fe) composite material provided by the present invention can be carried out according to conventional processes without any special processing. The technical solution of the present invention does not limit the eluent, and the eluent can be ultrapure water (UP water), HCl solution, sodium dihydrogen phosphate solution, acetonitrile-water solvent, etc., and can be reasonably selected according to the characteristics of the liquid to be treated.

[0077] In an embodiment of the present invention, the liquid to be treated includes any one of antibiotics, amino acids, and polypeptides. The antibiotics include but are not limited to chloramphenicol and its analogs, sulfonamides, tetracycline and its analogs, enrofloxacin and its analogs, metronidazole and its analogs, and the amino acids include but are not limited to alanine and methionine.

[0078] The separation column based on the carrier-MIL-100(Fe) composite material provided by the present invention can realize efficient component separation and enrichment applications, can be directly put into practical application, and has a wide range of application fields. It can be used for separation and enrichment pretreatment in the fields of environmental pollutant detection, food safety, drug purification, component separation, etc.

[0079] The technical solutions of the present invention are further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0080] Example 1

[0081] A method for preparing a carrier-MIL-100 (Fe) composite material, wherein the carrier is silicon micropowder (SiO2), and the method for preparing the carrier-MIL-100 (Fe) composite material comprises the following steps:

[0082] (1) immersing the silicon micropowder in a 0.1% dilute NaOH solution for 30 minutes, then centrifuging and washing with ultrapure water until neutral, and then drying the washed silicon micropowder to obtain activated silicon micropowder;

[0083] (2) Take 0.54g of ferric nitrate hexahydrate and dissolve it in 7.5mL of water to obtain the iron ion (Fe 3+ ) solution, and immersing the activated silicon micropowder in the solution containing iron ions for 30 minutes at room temperature to obtain a mixture;

[0084] (3) 0.31 g of trimesic acid was dissolved in 7.5 mL of water, and the solution containing trimesic acid was then mixed with the mixture of step (2), and the mixture was stirred for 24 h to obtain a suspension containing the carrier-MIL-100 (Fe) composite material. The suspension containing the carrier-MIL-100 (Fe) composite material was subjected to solid-liquid separation to obtain a solid. The solid was washed and dried to obtain an orange powder sample, as shown in FIG. Figure 1 , which is the carrier-MIL-100 (Fe) composite material.

[0085] Example 2

[0086] A separation column based on a carrier-MIL-100(Fe) composite material, comprising a sleeve, a column, a carrier-MIL-100(Fe) composite material loaded within the column, and partitions disposed at both ends of the column; wherein the carrier-MIL-100(Fe) composite material is the carrier-MIL-100(Fe) composite material prepared in Example 1; the partitions are provided with a porous structure, and the pore size of the porous structure of the partitions is smaller than the particle size of the carrier-MIL-100(Fe) composite material;

[0087] The method for preparing the separation column based on the carrier-MIL-100 (Fe) composite material comprises the following steps:

[0088] (1) providing two partitions, a sleeve, a column, and the carrier-MIL-100(Fe) composite material prepared in Example 1; dissolving the carrier-MIL-100(Fe) composite material in anhydrous ethanol to obtain a suspension of the carrier-MIL-100(Fe) composite material with a mass concentration of 100 g / L; the particle size of the carrier-MIL-100(Fe) composite material is 5 μm;

[0089] (2) A partition and a column are placed in the sleeve in sequence, and a predetermined volume of 1 mL of a suspension of the carrier-MIL-100(Fe) composite material is injected into the column. The second solvent is removed by filtration, and then a partition is placed on the upper end of the column, and the column is dried at 60°C to obtain a separation column based on the carrier-MIL-100(Fe) composite material.

[0090] Example 3

[0091] A separation column based on a carrier-MIL-100 (Fe) composite material is used to separate and enrich a liquid to be treated, comprising the following steps:

[0092] (1) Preparation of the liquid to be treated: dissolving alanine in different volumes of water to prepare alanine solutions with concentrations of 1.0 to 10.0 ppm;

[0093] (2) Using the separation column based on the carrier-MIL-100(Fe) composite material prepared in Example 2 as a separation column, 1 mL of a 1.0-10.0 ppm alanine solution was injected into the separation column, and the filtrate was filtered under reduced pressure to obtain a separation column enriched with alanine solution; then, the concentration of alanine in the filtrate was detected on a microplate reader using OPA (o-phthalaldehyde) fluorescence spectrophotometry;

[0094] (3) Add 1 mL of 5 ppm sodium dihydrogen phosphate solution to the separation column of the alanine-enriched solution obtained in step (2), obtain an eluate by vacuum filtration, and detect the concentration of alanine in the eluate on a microplate reader using OPA fluorescence spectrophotometry.

[0095] Test results: The separation and enrichment performance of alanine was tested based on the separation column of the carrier-MIL-100(Fe) composite material. Figure 3 A bar graph shows the adsorption rate and recovery rate of different initial alanine concentrations using the separation column based on the carrier-MIL-100(Fe) composite material of Example 2. The results show that the adsorption rate of alanine by the separation column based on the carrier-MIL-100(Fe) composite material can reach 81%. Using sodium dihydrogen phosphate as the eluent, the effective recovery rate of alanine adsorbed in the separation column based on the carrier-MIL-100(Fe) composite material is as high as 89%.

[0096] Example 4

[0097] The effect of different column loading amounts on the separation and enrichment performance of a separation column based on a carrier-MIL-100(Fe) composite material comprises the following steps:

[0098] (1) Using the separation column based on the carrier-MIL-100(Fe) composite material prepared in Example 2 as a separation column, 0.5 mL, 1 mL, 1.5 mL, 2 mL, and 2.5 mL of a 5 ppm alanine solution were injected into each separation column, and the filtrate was filtered under reduced pressure to obtain a separation column enriched with alanine solution; then, the concentration of alanine in the filtrate was detected on a microplate reader using OPA fluorescence spectrophotometry;

[0099] (2) Add 1 mL of 5 ppm sodium dihydrogen phosphate solution to the separation column of the alanine-enriched solution obtained in step (1), obtain an eluate by vacuum filtration, and detect the concentration of alanine in the eluate on a microplate reader using OPA fluorescence spectrophotometry.

[0100] Test results: Figure 4A bar graph shows the adsorption and recovery rates of alanine using a separation column based on a support-MIL-100(Fe) composite at different column loadings. The results show a linear positive correlation between the adsorption rates of alanine using the support-MIL-100(Fe) composite column at different column loadings. However, the average recovery rate of alanine adsorbed on the support-MIL-100(Fe) composite column using sodium dihydrogen phosphate as the eluent reached 96%, and was minimally affected by column loading.

[0101] Example 5

[0102] The effects of different eluents on the separation and enrichment performance of a separation column based on a carrier-MIL-100(Fe) composite material include the following steps:

[0103] (1) Using the separation column based on the carrier-MIL-100(Fe) composite material prepared in Example 2 as a separation column, 1 mL of a 5 ppm alanine solution was injected into the separation column, and the filtrate was filtered under reduced pressure to obtain a separation column enriched with alanine solution; then, the concentration of alanine in the filtrate was detected on a microplate reader using OPA fluorescence spectrophotometry;

[0104] (2) 1 mL of ultrapure water (UP water), 0.01 to 0.1 mmol / L HCl solution, 0.5 to 10 ppm sodium dihydrogen phosphate solution, and 10% to 80% by volume acetonitrile-water solvent were added to the separation columns of the enriched alanine solutions obtained in the steps (1), respectively. Different eluates were obtained by vacuum filtration, and the concentration of alanine in the eluates was detected on a microplate reader using OPA fluorescence spectrophotometry.

[0105] Test results: Figure 5 The following table summarizes the recovery rates of alanine after adsorption onto a separation column based on a support-MIL-100(Fe) composite material and elution with different eluents. The results show that both acetonitrile and sodium dihydrogen phosphate can effectively elute alanine adsorbed onto the separation column, achieving recoveries of up to 94%.

[0106] Example 6

[0107] Compared with Example 1, the difference is that the amount of ferric nitrate hexahydrate used is 0.54 g, and the amount of trimesic acid used is 5.4 g.

[0108] Test results: The carrier-MIL-100 (Fe) composite material prepared in Example 6 was made into a separation column based on the carrier-MIL-100 (Fe) composite material according to the method of Example 2, and then the adsorption rate and recovery rate at 5 ppm were tested according to the method of Example 3. The results were 60% and 89%, respectively.

[0109] Example 7

[0110] Compared with Example 1, the difference is that the amount of ferric nitrate hexahydrate used is 3.1 g, and the amount of trimesic acid used is 0.31 g.

[0111] The carrier-MIL-100(Fe) composite material prepared in Example 7 was made into a separation column based on the carrier-MIL-100(Fe) composite material according to the method of Example 2, and then the adsorption rate and recovery rate at 5 ppm were tested according to the method of Example 3. The results were 71% and 98%, respectively.

[0112] Example 8

[0113] Compared with Example 1, the difference is that the particle size of the carrier-MIL-100(Fe) composite material is 20 μm.

[0114] Test results: The carrier-MIL-100(Fe) composite material prepared in Example 8 was made into a separation column based on the carrier-MIL-100(Fe) composite material according to the method of Example 2, and then the adsorption rate and recovery rate at 5 ppm were tested according to the method of Example 3. The results were 53% and 92%, respectively.

[0115] Example 9

[0116] Compared with Example 1, the difference is that the particle size of the carrier-MIL-100(Fe) composite material is 50 μm.

[0117] Test results: The carrier-MIL-100(Fe) composite material prepared in Example 9 was made into a separation column based on the carrier-MIL-100(Fe) composite material according to the method of Example 2, and then the adsorption rate and recovery rate at 5 ppm were tested according to the method of Example 3. The results were 49% and 87%, respectively.

[0118] Example 10

[0119] Compared with Example 3, the difference is that tetracycline is used instead of alanine.

[0120] Test results: The adsorption rate and recovery rate at 5 ppm were tested according to the method of Example 3, and the results were 76% and 82% respectively.

[0121] The above description is merely an exemplary embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformation made by utilizing the contents of the present invention's description and drawings under the technical concept of the present invention, or directly / indirectly applied in other related technical fields, is included in the patent protection scope of the present invention.

Claims

1. A separation column based on a carrier-MIL-100 (Fe) composite material, characterized in that: For separation and enrichment pretreatment of a liquid to be treated, the separation column based on the carrier-MIL-100(Fe) composite material comprises a column body, a carrier-MIL-100(Fe) composite material filled in the column body, and partitions arranged at both ends of the column body; wherein: The separator is provided with a pore structure, and the pore size of the pore structure of the separator is smaller than the particle size of the carrier-MIL-100 (Fe) composite material; The preparation method of the carrier-MIL-100 (Fe) composite material comprises the following steps: activating the carrier to obtain an activated carrier; The activated carrier, the solution containing iron ions and the solution containing trimesic acid are mixed and stirred at room temperature to obtain a suspension containing a carrier-MIL-100 (Fe) composite material. The suspension containing the carrier-MIL-100 (Fe) composite material is subjected to solid-liquid separation to obtain a solid. The solid is washed and dried to obtain a carrier-MIL-100 (Fe) composite material.

2. The separation column based on the carrier-MIL-100(Fe) composite material according to claim 1, characterized in that: The particle size of the carrier-MIL-100 (Fe) composite material is 0.5 to 50 μm.

3. The separation column based on the carrier-MIL-100(Fe) composite material according to claim 1, characterized in that: The amounts of the solution containing iron ions and the solution containing trimesic acid are calculated based on a molar ratio of iron ions in the solution containing iron ions to trimesic acid in the solution containing trimesic acid of (1-10):(1-10).

4. The separation column based on the carrier-MIL-100(Fe) composite material according to claim 1, characterized in that The step of mixing and stirring the activated carrier, the solution containing iron ions and the solution containing trimesic acid at room temperature to obtain a suspension containing the carrier-MIL-100 (Fe) composite material comprises: soaking the activated support in a solution containing iron ions at room temperature for 0 to 60 minutes to obtain a mixture; The mixture and the solution containing trimesic acid are mixed and stirred at room temperature for 1 to 48 hours to obtain a suspension containing the carrier-MIL-100 (Fe) composite material.

5. The separation column based on the carrier-MIL-100(Fe) composite material according to claim 1, characterized in that: The carrier includes at least one of silicon oxide, aluminum oxide, diatomaceous earth, kaolin, illite and activated carbon.

6. A method for preparing a separation column based on a carrier-MIL-100(Fe) composite material according to any one of claims 1 to 5, characterized in that: The following steps are involved: A column arranged in an up-down direction is provided, wherein a pore structure is provided inside the column for filling the carrier-MIL-100 (Fe) composite material and for allowing the liquid to be treated to pass through; A partition is placed at the lower end of the column, and then the carrier-MIL-100 (Fe) composite material is loaded into the column, and a partition is placed at the upper end of the column to obtain a separation column based on the carrier-MIL-100 (Fe) composite material.

7. The method for preparing a separation column based on a carrier-MIL-100(Fe) composite material according to claim 6, wherein: The steps of placing a partition at the lower end of the column, then loading the carrier-MIL-100(Fe) composite material into the column, and placing a partition at the upper end of the column to obtain a separation column based on the carrier-MIL-100(Fe) composite material include: The carrier-MIL-100(Fe) composite material is mixed with a second solvent to obtain a suspension of the carrier-MIL-100(Fe) composite material: A partition is placed at the lower end of the column, and a suspension of the carrier-MIL-100 (Fe) composite material is injected into the column. The second solvent is removed by filtration. A partition is placed at the upper end of the column, and the column is dried to obtain a separation column based on the carrier-MIL-100 (Fe) composite material.

8. The method for preparing a separation column based on a carrier-MIL-100(Fe) composite material according to claim 7, wherein: The mass concentration of the suspension of the carrier-MIL-100 (Fe) composite material is 0.1-100 g / L.

9. Use of a separation column based on a carrier-MIL-100(Fe) composite material according to any one of claims 1 to 5 in separating and enriching a liquid to be treated, characterized in that: The step of separating and enriching the liquid to be treated comprises: injecting the liquid to be treated into a separation column to obtain a separation column that enriches the liquid to be treated; the separation column is a separation column based on a carrier-MIL-100(Fe) composite material; Then, the separation column enriched with the liquid to be treated is eluted with an eluent, and the eluent is collected to obtain a sample to be tested.

10. Use of the separation column based on the carrier-MIL-100(Fe) composite material according to claim 9 in separating and enriching a liquid to be treated, characterized in that: The liquid to be treated includes any one of antibiotics, amino acids and polypeptides.

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