Post-treatment method of porous filler
By using aqueous alcohol compound solutions and ultrasonic cleaning technology, the cleaning process of porous fillers is optimized, and the problem of reducing cleaning effect in the existing technology is solved, efficient and low-cost impurity removal is achieved, and high removal rate and safety of fillers are ensured. .
Patent Information
- Application Number
- CN202411616592.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-13
- Publication Date
- 2024-12-27
AI Technical Summary
In the prior art, the cleaning effect of porous filler decreases with the increase in the number of cleaning times, and the polymerization reaction by-products cannot be effectively removed, which is costly and inefficient.
Use an aqueous solution of alcohol compounds as detergent and perform two cleanings through ultrasonic cleaning. The volume fractions of alcohol compounds of the first detergent and the second detergent are different. The alcohol compounds are a mixture of methanol and ethanol, and the alcohol solvent combination is optimized. Compared with ultrasonic cleaning time, ensure that the impurity removal rate is not less than 80%.
It significantly improves the efficiency of decomposition removal, reduces the number of cleaning times, reduces the cost, and reaches more than 90%, avoids cleaning agent residues, and is simple and safe to operate.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to a chromatography filler cleaning method, in particular to a porous filler post-treatment method. Background Art
[0002] Liquid chromatography fillers usually refer to stationary phase materials used in liquid chromatography technology. They usually have a porous structure. This structure gives the fillers a larger specific surface area and can provide more effective adsorption sites. Their main function is to separate different components in the mixture during the chromatography process. During the synthesis of the fillers, polymerization byproducts often remain, such as polypropylene and ethyl acrylate analogs. These impurities not only affect the appearance quality of the fillers, but may also reduce their performance. Therefore, effective cleaning is crucial.
[0003] In the prior art, the prepared filler is simply washed alternately with pure ethanol and purified water, such as the cleaning method described in the preparation method of poly(glycidyl methacrylate) microspheres disclosed in the invention patent application with publication number CN 115010851 A. In this cleaning method, the cleaning effect decreases with the increase of the number of cleaning times. After multiple cleanings, the detergent loses its cleaning effect and cannot effectively clean the residual byproducts in the filler, which is costly and inefficient. The invention patent application with publication number CN115043984A discloses a preparation method of ultra-large-porous organic polymer microspheres. In this scheme, the product is washed several times with hot deionized water and methanol to obtain ultra-large-porous poly(glycidyl methacrylate) microspheres, but methanol has a low boiling point and a low safety factor. Summary of the invention
[0004] Purpose of the invention: The purpose of the present invention is to provide a method for cleaning porous fillers to improve the impurity removal efficiency of porous fillers.
[0005] Technical solution: The post-processing method of a porous filler of the present invention comprises the following steps:
[0006] (1) mixing the porous filler with a first detergent and performing a first ultrasonic cleaning;
[0007] (2) mixing the porous filler obtained in step (1) with a second detergent and performing a second ultrasonic cleaning;
[0008] In step (1) and step (2), the first detergent and the second detergent are both aqueous solutions of alcohol compounds, and the volume fractions of the alcohol compounds in the first detergent and the second detergent are different.
[0009] Preferably, the volume fraction of the alcohol compound in the first detergent and the second detergent is 15-55%.
[0010] Preferably, the alcohol compound is at least one of methanol and ethanol.
[0011] Preferably, the volume fraction of alcohol compounds in the first detergent is greater than that in the second detergent.
[0012] Preferably, in order to make the impurity removal rate not less than 80%, the first detergent and the second detergent are mixed aqueous solutions of ethanol and methanol, and the volume fraction of ethanol in the first detergent and the second detergent is not less than that of methanol.
[0013] Preferably, in the first detergent, the amount of methanol added is 1 / 20 to 1 / 2 of that of ethanol.
[0014] Preferably, in the second detergent, the amount of methanol added is 1 / 10 to 1 of that of ethanol.
[0015] Preferably, the first cleaning and the second cleaning last no less than 2 hours.
[0016] Preferably, the added amount of the first detergent and the second detergent is 2.0 to 3.5 times the wet weight of the porous filler.
[0017] Preferably, stirring is performed during the first ultrasonic cleaning and the second ultrasonic cleaning.
[0018] Preferably, the pore size of the porous filler is More preferably, the pore size of the porous filler is
[0019]
[0020] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: 1. Improve impurity removal efficiency: reduce the original cleaning and impurity removal times from 5 times or more to 2 times, and after washing according to the method of the present invention, the removal efficiency can reach more than 70%; 2. Reduce costs: replace the commonly used organic solvents with organic solvent aqueous solutions, reduce the use of organic solvents, reduce costs, and are safer; 3. High removal rate: after 2 cleanings, the optimal removal rate is not less than 90%, and impurities in the filler are effectively removed; 4. Eliminate the risk of introducing new impurities: use common alcohol solvents with lower boiling points, and after cleaning, no cleaning agent remains in the filler; 5. Simple operation: alcohol solvents and ultrasonic cleaning are both common cleaning methods. Reasonable adjustment of the alcohol solvent ratio and the use of alcohol solvents and ultrasonic cleaning in combination can effectively remove impurities, and the cleaning agent is simple to prepare and the cleaning process is simple. DETAILED DESCRIPTION
[0021] The technical scheme of the present invention is further described below in conjunction with the examples. The Monomix Mab60-Q anion exchange chromatography filler used in the following examples was purchased from Saifen Technology Yangzhou Co., Ltd., with a particle size of 60 μm and a pore size of
[0022] Example 1: Different mixing methods
[0023] Cleaning method: put 2.5 times the volume fraction of 20% ethanol and 1.0 times the wet weight of porous Monomix Mab60-Q filler into the reactor, stir and disperse for 5 minutes, then heat to 40°C, maintain normal stirring or ultrasonic stirring for 2 hours; after the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter until dry, and cool to ensure safe operation.
[0024] Detection method: The Monomix Mab60-Q filler that has been filtered to dryness is loaded into a chromatography column and rinsed with purified water, 1 cv each time, for a total of 5 times. The filtrate after the 5th rinse is collected and injected into a TOC total organic carbon analyzer to test the organic carbon content. The test results are shown in Table 1 below, in mg / L.
[0025] Repeat the above steps for 5 times.
[0026] Table 1: Test data of Example 1
[0027]
[0028] In the above table: Removal rate = (initial TOC-test TOC) / initial TOC×100%
[0029] Ultrasonic cleaning helps impurities or stains in the pores to diffuse into the cleaning medium. As the number of cleaning times increases, the effect of introducing ultrasonic vibrations does not increase significantly, and the cleaning effect of Monomix Mab60-Q is limited.
[0030] Example 2: Using detergents with different concentrations
[0031] Experiment 2.1: First, 20% ethanol by volume and then 40% ethanol by volume
[0032] First cleaning: put 20% ethanol in an amount of 2.5 times, and porous Monomix Mab60-Q filler in an amount of 1.0 times by wet weight into the reactor, stir and disperse for 5 minutes, then raise the temperature to 40°C, maintain the temperature and stir ultrasonically for 2 hours, and after the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter until dry; the detection method is the same as in Example 1.
[0033] Second cleaning: add 2.5 times the amount of 40% ethanol into the reactor, and add 1.0 times the wet weight of the porous MonomixMab60-Q filler after the first cleaning. After stirring and dispersing for 5 minutes, raise the temperature to 40°C, maintain the temperature and ultrasonically stir for 2 hours. After the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter it until dry. The detection method is the same as in Example 1.
[0034] Table 2-1: Test data of Experiment 2.1 of Example 2:
[0035] Initial TOC first Second time Removal rate / % 47 32 12 74.47
[0036] Experiment 2.2: 40% ethanol followed by 20% ethanol
[0037] First cleaning: put 2.5 times the amount of 40% ethanol and 1.0 times the wet weight of porous Monomix Mab60-Q filler into the reactor, stir and disperse for 5 minutes, then raise the temperature to 40°C, maintain the temperature and stir ultrasonically for 2 hours. After the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter until dry; the detection method is the same as in Example 1.
[0038] Second cleaning: add 2.5 times the amount of 20% ethanol into the reactor, and add 1.0 times the wet weight of the porous MonomixMab60-Q filler after the first cleaning. After stirring and dispersing for 5 minutes, raise the temperature to 40°C, maintain the temperature with ultrasonic stirring for 2 hours, and when the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter it until dry. The detection method is the same as in Example 1.
[0039] Table 2-2: Test data of Experiment 2.2 of Example 2:
[0040] Initial TOC first Second time Removal rate / % 47 34 10 78.72
[0041] The solubility of excess ethyl acrylate in ethanol solutions of different concentrations is slightly different. Excess ethyl acrylate analogs in the filler can be fully removed by washing with ethanol of different concentrations.
[0042] Example 3: Detergents with different components
[0043] Experiment 3.1: Introducing methanol based on Experiment 2.2 of Example 2
[0044] First cleaning: put 2.084 times the amount of 40% ethanol, 0.42 times the amount of anhydrous methanol, and 1.0 times the wet weight of porous MonomixMab60-Q filler into the reactor, stir and disperse for 5 minutes, then raise the temperature to 40°C, maintain the temperature and ultrasonically stir for 2 hours. After the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter until dry; the detection method is the same as in Example 1.
[0045] Second cleaning: add 20% ethanol (2.084 times the amount), anhydrous methanol (0.42 times the amount), and the wet weight of the porous Monomix Mab60-Q filler after the first cleaning: 1.0 times the amount into the reactor. After stirring and dispersing for 5 minutes, raise the temperature to 40°C, maintain the temperature with ultrasonic stirring for 2 hours, and after the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter it to dryness. The detection method is the same as in Example 1.
[0046] Table 3-1: Test data of Experiment 3.1 of Example 3:
[0047] Initial TOC first Second time Removal rate / % 47 16 4 91.49
[0048] Experiment 3.2: Based on the experiment 3.1 of this example, the amount of methanol was reduced. The detergent ratio used for the first cleaning was 2.46 times the amount of 40% ethanol and 0.04 times the amount of methanol. The second cleaning was 2.46 times the amount of 20% ethanol and 0.04 times the amount of methanol. The rest of the operations were the same as those of the experiment 3.1 of this example. The test data are shown in the following table.
[0049] Table 3-2: Test data of Experiment 3.2 of Example 3:
[0050] Initial TOC first Second time Removal rate / % 46 21 5 89.13
[0051] Comparative Example 1: Cleaning with detergents of different volume fractions
[0052] Experiment 1.1: Cleaning method: put 2.5 times the volume fraction of 98% / 50% / 20% ethanol and 1.0 times the wet weight of porous Monomix Mab60-Q filler into the reactor, stir and disperse for 5 minutes, then heat to 40°C, maintain the temperature and stir for 2 hours; after the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter until dry, and the detection method is the same as Example 1. Repeat the above steps for cleaning 5 times.
[0053] Table 4-1: Comparative Example 1 Experiment 1.1 Test data
[0054]
[0055] Ethanol as a washing solvent can effectively dissolve the organic reagents remaining after the synthesis. Ethanol solutions of different concentrations have a greater impact on the washing effect. 20% ethanol solution can more effectively remove the unreacted ethyl acrylate analogs.
[0056] Experiment 1.2: Cleaning method: put 2.5 times the volume fraction of 99% / 20% methanol and 1.0 times the wet weight of porous Monomix Mab60-Q filler into the reactor, stir and disperse for 5 minutes, then heat to 40°C, maintain the temperature and stir for 2 hours; after the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter until dry, and the detection method is the same as in Example 1. Repeat the above steps for cleaning 5 times.
[0057] Table 4-2: Test data of experiment 1.2 of comparative example 1
[0058]
[0059] The cleaning effect of methanol-water solution as a detergent is better than that of single-component methanol. Compared with ethanol-water solution, methanol-water solution is less effective.
[0060] Comparative Example 2: Multiple Cleaning with Pure Water
[0061] Cleaning method: put 2.5 times the amount of purified water and 1.0 times the wet weight of porous Monomix Mab60-Q filler into the reactor, stir and disperse for 5 minutes, then raise the temperature to 80 / 60 / 40°C, maintain the temperature and stir for 2 hours; after the reaction is completed, cool to room temperature, transfer the material to a Buchner funnel and filter until dry, and the detection method is the same as Example 1.
[0062] Repeat the above steps for 5 times.
[0063] Table 5: Comparative Example 2 Test Data
[0064]
[0065] The temperature of the cleaning process has little effect on the cleaning effect. In order to optimize the use of energy, the cleaning temperature can be set at 40±2℃.
[0066] Comparative Example 3: This comparative example is similar to Experiment 2.2 of Example 2, except that ultrasonic cleaning was not used. The test data are shown in the following table:
[0067] Initial TOC first Second time Removal rate / % 47 35 22 53.19
[0068] When ultrasonic cleaning is not used, changing the cleaning agent ratio used in the second cleaning can help promote impurity removal, but the effect is limited.
Claims
1. A post-processing method for a porous filler, characterized in that: The following steps are involved: (1) mixing the porous filler with a first detergent and performing a first ultrasonic cleaning; (2) mixing the porous filler obtained in step (1) with a second detergent and performing a second ultrasonic cleaning; In step (1) and step (2), the first detergent and the second detergent are both aqueous solutions of alcohol compounds, and the volume fractions of the alcohol compounds in the first detergent and the second detergent are different.
2. The post-processing method of porous filler according to claim 1, characterized in that: The volume fraction of the alcohol compound in the first detergent and the second detergent is 15% to 55%.
3. The post-processing method of porous filler according to claim 1, characterized in that: The alcohol compound is at least one of methanol and ethanol.
4. The post-processing method of porous filler according to claim 1 or 2, characterized in that: The volume fraction of alcohol compounds in the first detergent is greater than that in the second detergent.
5. The post-processing method of porous filler according to claim 1 or 2, characterized in that: The first detergent and the second detergent are mixed aqueous solutions of ethanol and methanol. In the first detergent and the second detergent, the volume fraction of ethanol is not lower than that of methanol.
6. The post-processing method of porous filler according to claim 5, characterized in that: In the first detergent, the amount of methanol added is 1 / 20 to 1 / 2 of that of ethanol.
7. The post-processing method of porous filler according to claim 5, characterized in that: In the second detergent, the amount of methanol added is 1 / 10 to 1 of that of ethanol.
8. The post-processing method of porous filler according to claim 1, characterized in that: The first cleaning and the second cleaning should last no less than 2 hours.
9. The post-processing method of porous filler according to claim 1, characterized in that: The added amount of the first detergent and the second detergent is 2.0 to 3.5 times the wet weight of the porous filler.
10. The post-processing method of porous filler according to claim 1, characterized in that: Stirring is performed during the first ultrasonic cleaning and the second ultrasonic cleaning.