CN112933660A - Regeneration method of ion chromatography protective column - Google Patents
Regeneration method of ion chromatography protective column Download PDFInfo
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- CN112933660A CN112933660A CN202011488819.9A CN202011488819A CN112933660A CN 112933660 A CN112933660 A CN 112933660A CN 202011488819 A CN202011488819 A CN 202011488819A CN 112933660 A CN112933660 A CN 112933660A
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- 238000004255 ion exchange chromatography Methods 0.000 title claims abstract description 65
- 238000011069 regeneration method Methods 0.000 title claims abstract description 36
- 238000004140 cleaning Methods 0.000 claims abstract description 75
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 49
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- 239000000243 solution Substances 0.000 claims description 89
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 27
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 17
- 239000012498 ultrapure water Substances 0.000 claims description 17
- 238000004587 chromatography analysis Methods 0.000 claims description 13
- 230000001172 regenerating effect Effects 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 6
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- 239000002920 hazardous waste Substances 0.000 description 5
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- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/203—Equilibration or regeneration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/363—Anion-exchange
Abstract
The invention belongs to the technical field of cleaning of ion chromatographic protective columns, and discloses a regeneration method of an ion chromatographic protective column, which comprises the following steps: cleaning the outer surface of the ion chromatography protective column; cleaning the auxiliary component of the ion chromatography protective column; and (3) cleaning and cleaning the chromatographic protective column tube and the stationary phase filled in the chromatographic protective column by adopting a regenerant and ultrasonic wave alternately in sequence, standing, filtering, adding a filler, shaking uniformly, and refilling the chromatographic protective column to finish the performance recovery of the chromatographic protective column. The method is used for removing pollutants through alternate cleaning after the ion chromatography protective column is polluted, then the regeneration is completed after standing, precipitating, removing the pollutants and re-filling, and the performance of the ion chromatography protective column is recovered. The filler is taken out for cleaning, so that the contact time and the contact area of the pollutants and the cleaning liquid are ensured, and the cleaning effect is obviously enhanced. The method can prolong the service life of the ion chromatographic protective column and the chromatographic column, and remarkably reduce the analysis cost.
Description
Technical Field
The invention belongs to the technical field of cleaning of ion chromatographic protective columns, and particularly relates to a regeneration method of an ion chromatographic protective column.
Background
At present, the method for detecting various sulfate, chloride, fluoride and the like by using an ion chromatograph instead of a chemical method becomes a national standard method, and the result is accurate, quick and convenient.
However, because various hazardous waste samples for detection are from various industries and enterprises, and the content of the hazardous waste samples is very complex, metal, organic matters and the like in the hazardous waste samples pollute the protective column of the ion chromatography in the process of anion analysis, the chromatogram separation effect is poor, and if the hazardous waste samples are not replaced in time, the chromatographic column is further polluted, so that the performance of the protective column and even the performance of the chromatographic column cannot meet the analysis requirements. Once contaminated, there is no obvious effect following a typical cleaning protocol, and only a new chromatographic column or guard column can be replaced. At present, the market price of the protective column is about 2000 yuan/prop, the price of the chromatographic column is about 20000 yuan/prop, the replacement period of the protective column is about 1 month, and the replacement period of the chromatographic column is about 3 months (the specific replacement period depends on the components of the sample), so that the analysis cost is high.
In the related technology, the purpose of continuously using the protective column is achieved only by connecting the pipeline after the filter element sheet in the ion chromatographic protective column is placed in the protective column again after the filter element sheet in the ion chromatographic protective column is subjected to ultrasonic treatment by using ultrapure water. In the method, the filling material in the protection column is not cleaned.
In addition, the general cleaning method only allows a certain amount of cleaning solution to pass through the protective column at a certain flow rate, and the effect of the general cleaning method is limited because the contact time of the cleaning solution and the dirt is short and most of the polluted chromatographic columns are blocked by micropores.
Therefore, the method is a problem worth discussing on the premise that the ion chromatographic column is protected and the detection result is normal in the subsequent detection process after the anion chromatographic column is polluted.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention aims to provide a method for regenerating an ion chromatography guard column.
The technical scheme adopted by the invention is as follows: a regeneration method of an ion chromatography protective column comprises the steps of cleaning a stationary phase filled in the chromatography protective column by adopting a regenerant and ultrasonic waves alternately in sequence, standing and filtering to finish the performance recovery of the chromatography protective column.
Preferably, the regenerant comprises one or more of an organic solvent, an aqueous organic solvent solution, an inorganic acid solution, and an organic acid solution.
Preferably, the organic solvent comprises one or more of methanol, ethanol, acetone and acetonitrile.
Preferably, the organic solvent aqueous solution includes one or more of methanol aqueous solution, ethanol aqueous solution, acetone aqueous solution and acetonitrile aqueous solution.
Preferably, the mass concentration of the methanol aqueous solution comprises 80% -90%;
the mass concentration of the ethanol water solution is 90-95%;
the mass concentration of the acetone aqueous solution is 60-70%;
the mass concentration of the acetonitrile water solution is 80-90%.
Preferably, the inorganic acid solution includes a sulfuric acid solution;
the molar concentration of the sulfuric acid solution comprises 1mol/L-2 mol/L.
Preferably, the organic acid solution includes an oxalic acid solution;
the molar concentration of the oxalic acid solution is 1-2 mol/L.
Preferably, when the fixed phase filled in the chromatographic protection column is washed by sequentially and alternately adopting the regenerant and the ultrasonic wave, the number of times of alternate washing comprises 2-3 times.
Preferably, after the stationary phase filled in the chromatographic protection column is cleaned, the chromatographic protection is refilled by adding a filling agent.
Preferably, the filler comprises one or more of methanol, ethanol, acetonitrile and ultrapure water.
The invention has the beneficial effects that:
the invention provides a regeneration method of an ion chromatographic protective column, which can be used for removing pollutants after the ion chromatographic protective column is polluted by alternately cleaning with cleaning agents, regeneration liquid and ultrasonic waves, then completing the regeneration of the ion chromatographic protective column after standing, precipitating, filtering to remove the pollutants and refilling fillers, and recovering the performance of the ion chromatographic protective column.
According to the regeneration method, the filler is taken out, and different cleaning solutions are used for soaking, ultrasonic cleaning and the like, so that sufficient contact time and sufficient contact area of pollutants and the cleaning solution are ensured, and the cleaning effect is obviously enhanced. However, it should be noted that improper packing of the washed packing results in reduced column efficiency and even splitting.
The regeneration method can greatly prolong the service life of the ion chromatographic protective column and the chromatographic column, and remarkably reduce the analysis cost.
Drawings
FIG. 1 is a flow chart of an embodiment of the method for regenerating the ion chromatography guard column;
FIG. 2 is a parameter map of a standard curve of the ion chromatography column of example 1 after regeneration;
FIG. 2 is a graph of data processing of standard curve parameters after regeneration of the ion chromatography guard column of example 1;
FIG. 3 is a graph of the standard curve parameters of the ion chromatography column of example 2 after regeneration;
FIG. 3 is a graph of data processing of standard curve parameters after regeneration of the ion chromatography guard column of example 2;
FIG. 4 is a chromatogram obtained by detecting the regenerated ion chromatography column of example 1;
FIG. 5 is a chromatogram obtained after regeneration of example 2 of the ion chromatography column control group;
FIG. 6 is a schematic diagram of the symmetry test of the ion chromatography protective column.
Detailed Description
The present invention is further illustrated below with reference to specific examples. It will be appreciated by those skilled in the art that the following examples, which are set forth to illustrate the present invention, are intended to be part of the present invention, but not to be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples were carried out under the conventional conditions, unless otherwise specified. The reagents used are all conventional products which are commercially available.
Example 1:
after completely removing the labels and other accessories on the outer surface of the polluted ion chromatography protective column, cleaning the surface of the protective column for 2-4 times by using ultrapure water, opening and taking down the fixing nut and the filter disc, placing the fixing nut and the filter disc in a 50mL beaker filled with a nitric acid solution (with the mass concentration of 5 percent), and ultrasonically cleaning the filter disc until no visible dirt exists on the filter disc.
Putting an ion chromatography protective column tube and a stationary phase (filler) in a protective column into a 50mL measuring cylinder, soaking the ion chromatography protective column tube and the stationary phase (filler) in the protective column by using a methanol aqueous solution (with the mass concentration of 5%), then carrying out ultrasonic cleaning, and filtering after standing and precipitating; soaking by using acetonitrile water solution (the mass concentration is 80 percent), then carrying out ultrasonic cleaning, standing for precipitation, and then filtering; the solution was immersed in about 50mL of a sulfuric acid solution (2 mol/L), then ultrasonically cleaned, and after standing and precipitating, filtered. The cleaning process of the methanol aqueous solution (5%) -the ultrasonic-acetonitrile aqueous solution (80%) -the ultrasonic-sulfuric acid solution (with the concentration of 2mol/L) -ultrasonic can be repeated for 2-3 times.
Adding a stationary phase (filler) in the ion chromatography protective column into methanol to prepare a methanol solution of the stationary phase with the volume ratio of 5% (m/v), shaking up, and refilling by using a disposable plastic syringe to finish the performance recovery of the chromatography protective column.
The above-mentioned 5% (m/v) stationary phase methanol solution was prepared by adding 100mL of methanol to 5g of stationary phase.
The flow of the cleaning method in this embodiment is shown in FIG. 1.
Example 2:
after completely removing the labels and other accessories on the outer surface of the polluted ion chromatography protective column, cleaning the surface of the protective column for 3-5 times by using ultrapure water, opening and taking down the fixing nut and the filter disc, placing the fixing nut and the filter disc in a 50mL beaker filled with nitric acid solution (with the mass concentration of 3 percent), and ultrasonically cleaning until the filter disc has no visible dirt.
Putting an ion chromatography protective column tube and a stationary phase (filler) in a protective column into a 50mL measuring cylinder, soaking the ion chromatography protective column tube and the stationary phase (filler) in the protective column by using a methanol aqueous solution (with the mass concentration of 5%), then carrying out ultrasonic cleaning, and filtering after standing and precipitating; soaking the mixture by using a methanol aqueous solution (the mass concentration is 90 percent), then carrying out ultrasonic cleaning, standing and precipitating, and then filtering; the solution was immersed in about 50mL of a sulfuric acid solution (1 mol/L) and then ultrasonically cleaned, and after standing and precipitating, the solution was filtered. The cleaning process of the methanol aqueous solution (5%) -ultrasonic wave-methanol aqueous solution (90%) -ultrasonic wave-sulfuric acid solution (concentration of 1mol/L) -ultrasonic wave can be repeated for 2-3 times.
Adding a stationary phase (filler) in the ion chromatography protective column into methanol to prepare a methanol solution of the stationary phase with the volume ratio of 5% (m/v), shaking up, and refilling by using a disposable plastic syringe to finish the performance recovery of the chromatography protective column.
The above-mentioned 5% (m/v) stationary phase methanol solution was prepared by adding 100mL of methanol to 5g of stationary phase.
The flow of the cleaning method in this embodiment is shown in FIG. 1.
Example 3:
after completely removing the labels and other accessories on the outer surface of the polluted ion chromatography protective column, cleaning the surface of the protective column for 3-5 times by using ultrapure water, opening and taking down the fixing nut and the filter disc, placing the fixing nut and the filter disc in a 50mL beaker filled with nitric acid solution (with the mass concentration of 3 percent), and ultrasonically cleaning until the filter disc has no visible dirt.
Putting an ion chromatography protective column tube and a stationary phase (filler) in a protective column into a 50mL measuring cylinder, soaking the ion chromatography protective column tube and the stationary phase (filler) in the protective column by using an ethanol aqueous solution (the mass concentration is 5 percent), then carrying out ultrasonic cleaning, and filtering after standing and precipitating; soaking the mixture by using an ethanol water solution (the mass concentration is 90 percent), then carrying out ultrasonic cleaning, standing and precipitating, and then filtering; about 50mL of oxalic acid solution (with the concentration of 1mol/L) is used for soaking, then ultrasonic cleaning is carried out, and filtration is carried out after standing and precipitating. The cleaning process of the ethanol aqueous solution (5%) -ultrasonic wave-ethanol aqueous solution (90%) -ultrasonic wave-oxalic acid solution (concentration is 1mol/L) -ultrasonic wave can be repeated for 2-3 times.
Adding a stationary phase (filler) in the ion chromatography protective column into methanol to prepare a methanol solution of the stationary phase with the volume ratio of 5% (m/v), shaking up, and refilling by using a disposable plastic syringe to finish the performance recovery of the chromatography protective column.
The above-mentioned 5% (m/v) stationary phase methanol solution was prepared by adding 100mL of methanol to 5g of stationary phase.
The flow of the cleaning method in this embodiment is shown in FIG. 1.
Example 4:
after completely removing the labels and other accessories on the outer surface of the polluted ion chromatography protective column, cleaning the surface of the protective column for 3-5 times by using ultrapure water, opening and taking down the fixing nut and the filter disc, placing the fixing nut and the filter disc in a 50mL beaker filled with a nitric acid solution (with the mass concentration of 5 percent), and ultrasonically cleaning the filter disc until no visible dirt exists on the filter disc.
Putting an ion chromatography protective column tube and a stationary phase (filler) in a protective column into a 50mL measuring cylinder, soaking the ion chromatography protective column tube and the stationary phase (filler) in the protective column by using an ethanol aqueous solution (the mass concentration is 5 percent), then carrying out ultrasonic cleaning, and filtering after standing and precipitating; soaking the raw materials in an ethanol aqueous solution (the mass concentration is 95 percent), then carrying out ultrasonic cleaning, standing and precipitating, and then filtering; about 50mL of oxalic acid solution (with the concentration of 2mol/L) is used for soaking, then ultrasonic cleaning is carried out, and filtration is carried out after standing and precipitating. The cleaning process of the ethanol aqueous solution (5%) -ultrasonic wave-ethanol aqueous solution (95%) -ultrasonic wave-oxalic acid solution (concentration is 2mol/L) -ultrasonic wave can be repeated for 2-3 times.
Adding a stationary phase (filler) in the ion chromatography protective column into methanol to prepare a methanol solution of the stationary phase with the volume ratio of 5% (m/v), shaking up, and refilling by using a disposable plastic syringe to finish the performance recovery of the chromatography protective column.
The above-mentioned 5% (m/v) stationary phase methanol solution was prepared by adding 100mL of methanol to 5g of stationary phase.
The flow of the cleaning method in this embodiment is shown in FIG. 1.
Example 5:
after completely removing the labels and other accessories on the outer surface of the polluted ion chromatography protective column, cleaning the surface of the protective column for 3-5 times by using ultrapure water, opening and taking down the fixing nut and the filter disc, placing the fixing nut and the filter disc in a 50mL beaker filled with a nitric acid solution (with the mass concentration of 5 percent), and ultrasonically cleaning the filter disc until no visible dirt exists on the filter disc.
Putting an ion chromatography protective column tube and a stationary phase (filler) in a protective column into a 50mL measuring cylinder, soaking the ion chromatography protective column tube and the stationary phase (filler) in the protective column by using an acetone aqueous solution (with the mass concentration of 5%), then carrying out ultrasonic cleaning, and filtering after standing and precipitating; soaking the raw materials in an acetone aqueous solution (the mass concentration is 60 percent), then carrying out ultrasonic cleaning, standing and precipitating, and then filtering; the solution was immersed in about 50mL of a sulfuric acid solution (1 mol/L) and then ultrasonically cleaned, and after standing and precipitating, the solution was filtered. The cleaning process of the acetone aqueous solution (5%) -ultrasonic wave-acetone aqueous solution (60%) -ultrasonic wave-sulfuric acid solution (concentration is 1mol/L) -ultrasonic wave can be repeated for 2-3 times.
Adding a stationary phase (filler) in the ion chromatography protective column into methanol to prepare a methanol solution of the stationary phase with the volume ratio of 5% (m/v), shaking up, and refilling by using a disposable plastic syringe to finish the performance recovery of the chromatography protective column.
The above-mentioned 5% (m/v) stationary phase methanol solution was prepared by adding 100mL of methanol to 5g of stationary phase.
The flow of the cleaning method in this embodiment is shown in FIG. 1.
Example 6:
after completely removing the labels and other accessories on the outer surface of the polluted ion chromatography protective column, cleaning the surface of the protective column for 3-5 times by using ultrapure water, opening and taking down the fixing nut and the filter disc, placing the fixing nut and the filter disc in a 50mL beaker filled with nitric acid solution (with the mass concentration of 3 percent), and ultrasonically cleaning until the filter disc has no visible dirt.
Putting an ion chromatography protective column tube and a stationary phase (filler) in a protective column into a 50mL measuring cylinder, soaking the ion chromatography protective column tube and the stationary phase (filler) in the protective column by using an acetone aqueous solution (with the mass concentration of 5%), then carrying out ultrasonic cleaning, and filtering after standing and precipitating; soaking the raw materials in an acetone aqueous solution (the mass concentration is 70 percent), then carrying out ultrasonic cleaning, standing and precipitating, and then filtering; about 50mL of oxalic acid solution (with the concentration of 2mol/L) is used for soaking, then ultrasonic cleaning is carried out, and filtration is carried out after standing and precipitating. The cleaning process of the acetone aqueous solution (5%) -the ultrasonic wave-acetone aqueous solution (70%) -the ultrasonic wave-oxalic acid solution (with the concentration of 2mol/L) -ultrasonic wave can be repeated for 2-3 times.
Adding a stationary phase (filler) in the ion chromatography protective column into methanol to prepare a methanol solution of the stationary phase with the volume ratio of 5% (m/v), shaking up, and refilling by using a disposable plastic syringe to finish the performance recovery of the chromatography protective column.
The above-mentioned 5% (m/v) stationary phase methanol solution was prepared by adding 100mL of methanol to 5g of stationary phase.
In the above embodiment, the number of times of the ultrapure water cleaning of the surface of the ion chromatography protective column is provided, and the number of times of the cleaning is applicable to the embodiment of the embodiment. The number of times of the ultrapure water cleaning of the surface of the ion chromatography protective column is not limited to the data provided above, and the data provided above does not limit the method for regenerating the ion chromatography protective column.
In the above embodiment, the beaker and the measuring cylinder are selected as the cleaning tool during cleaning, and the volume of the cleaning tool is provided, the selection of the cleaning tool is not limited to the above selection, and all the cleaning tools can be used for soaking the cleaning agent applicable to the ion chromatography protective column tube, the protective column packing and the like, and the invention belongs to the protection scope of the invention.
In the above embodiment, the cleaning tool is required to be used for cleaning tools and the like.
In the above embodiment, a disposable plastic syringe is selected for filling, and the selection of the filling tool selected for filling is not limited to the above, and all that is required is to complete the filling of the ion chromatography protective column filler, and at the same time, it is ensured that the filling result and effect are consistent with those achieved by the present application, and the present invention is within the protection scope of the present invention.
The ultrasonic cleaning device selected for use in the above embodiment is: KQ-250E model ultrasonic cleaner, volume 10L, ultrasonic frequency 40 KHZ. The selection of the ultrasonic cleaning device is not limited to the above, and all devices capable of realizing the ultrasonic cleaning function belong to the protection scope of the invention.
The flow of the cleaning method in this embodiment is shown in FIG. 1.
Example 7:
after completely removing the labels and other accessories on the outer surface of the polluted ion chromatography protective column, cleaning the surface of the protective column for 3-5 times by using ultrapure water, opening and taking down the fixing nut and the filter disc, placing the fixing nut and the filter disc in a 50mL beaker filled with a nitric acid solution (with the mass concentration of 5 percent), and ultrasonically cleaning the filter disc until no visible dirt exists on the filter disc.
Putting an ion chromatography protective column tube and a stationary phase (filler) in a protective column into a 50mL measuring cylinder, soaking the ion chromatography protective column tube and the stationary phase (filler) in the protective column by using an acetonitrile aqueous solution (the mass concentration is 5 percent), then carrying out ultrasonic cleaning, and filtering after standing and precipitating; soaking by using acetonitrile water solution (the mass concentration is 90 percent), then carrying out ultrasonic cleaning, standing for precipitation, and then filtering; the solution was immersed in about 50mL of a sulfuric acid solution (1 mol/L) and then ultrasonically cleaned, and after standing and precipitating, the solution was filtered. The cleaning process of the acetonitrile aqueous solution (5%) -the ultrasonic wave-acetonitrile aqueous solution (90%) -the ultrasonic wave-sulfuric acid solution (with the concentration of 1mol/L) -ultrasonic wave can be repeated for 2-3 times.
Adding a stationary phase (filler) in the ion chromatography protective column into methanol to prepare a methanol solution of the stationary phase with the volume ratio of 5% (m/v), shaking up, and refilling by using a disposable plastic syringe to finish the performance recovery of the chromatography protective column.
The above-mentioned 5% (m/v) stationary phase methanol solution was prepared by adding 100mL of methanol to 5g of stationary phase.
The flow of the cleaning method in this embodiment is shown in FIG. 1.
Examples of the experiments
The experimental conditions are as follows:
1. the instrument comprises the following steps: the chromatographic instrument is specified in chromatographic test conditions; an ultrasonic cleaner; ultra pure water system MING-CHE 24 UV;
2. reagents and materials: concentrated sulfuric acid, superior grade pure;
anhydrous sodium carbonate: purity not less than 99.99%, Aladdin reagent (Shanghai) Co., Ltd;
sodium bicarbonate: chromatographic grade is more than or equal to 99.8%, Aladdin reagent (Shanghai) Co., Ltd;
3. and (3) regeneration of the guard column:
after the contaminated accessory such as the label of the protection column is completely removed, the surface of the column is cleaned for a plurality of times by ultrapure water;
the fixture nut and filter were opened with a cleaning tool and removed in a clean 50mL beaker containing 3% -5% nitric acid solution and the filter was ultrasonically cleaned until no visible contamination was observed.
The protective column tube and the stationary phase (filler) therein are vertically placed in a clean 50mL measuring cylinder, and are alternately soaked (about 60 minutes each time) and ultrasonically cleaned (about 15 minutes each time) by using 5% acetonitrile, 90% acetonitrile solution, 1mol/L sulfuric acid solution and ultrapure water, and are kept standing for precipitation, and then filtration operation is performed, and the operation of the step is generally required to be repeated for 2-3 times.
Methanol was added at a mass to volume ratio of about 5% (m/v) and shaken and refilled with a clean disposable plastic syringe.
And (4) installing the filter disc, tightening the fixing nut by using a cleaning tool, installing the filter disc into the ion chromatography flow path system for leakage test, and testing the performance parameters according to the chromatography conditions in the step (4) after the filter disc is confirmed to be normal.
4. Chromatographic experimental conditions:
the ion chromatograph instrument model: wantong ECO-IC;
autosampler model: 863compact autosampler;
a chromatographic column: wantong A17 anion chromatographic column, 4mm × 150 mm;
protection of the column: wantong A17 anion-protected column or Dionex IonPac AG22 anion-protected column;
a suppressor: msiii chemical inhibitor;
a detector: a conductance detector;
leachates (leachates refer to the mobile phase of ion chromatography. ion chromatography is a type of liquid chromatography. leachates are mentioned in the detection conditions): 5.0mmol/L Na2CO3-0.2mmol/L NaHCO3A solution;
regeneration liquid: 5 per mill (V/V) sulfuric acid solution;
sample introduction volume: 10 mu l of the mixture;
flow rate: 0.6 mL/min;
temperature of the column box: 25 ℃;
standard solution: sulfate standard solution with concentration of 50 mg/L.
The cleaning method comprises the following steps:
control group washing method: adding 50mL of 1.0mol/L sulfuric acid solution into 450mL of chromatographic acetonitrile, shaking uniformly, performing suction filtration by using a 0.22-micron organic filter membrane (cleaning solution A), sucking 20mL of ultrapure water for several times by using a disposable plastic syringe (5mL) to wash a guard column, sucking not less than 100mL of cleaning solution A for several times to wash the guard column, and sucking 20mL of ultrapure water for several times to wash the guard column;
the cleaning method of the experimental group comprises the following steps: the cleaning method in each of the above embodiments.
The detection principle is as follows: the regeneration effect of the guard column was confirmed with reference to the theoretical plate number of the sulfate ion chromatographic peak and asymmetry data. And a standard curve is drawn again after regeneration and a standard adding recovery test verifies that the regenerated protective column can completely meet the requirement of anion analysis.
The detection method comprises the following steps: the experiment is suitable for detecting anions (such as fluorine, chlorine, bromine, sulfate radical and the like) of the hazardous waste sample by the ion chromatograph.
When the guard column is contaminated, it is difficult to restore the separation effect to the desired detection condition by a general cleaning method.
The detection result shows indexes: under the chromatographic test conditions, before and after the regeneration of the protective column, continuous sample injection is carried out for 6 times by using sulfate radical standard solution with the concentration of 5.0mg/L respectively, the theoretical plate number and asymmetry of a sulfate radical chromatographic peak are calculated, and the arithmetic mean value of parallel measurement is taken as a final result. The sample injection amount of the sulfate radical standard solution with the concentration of 50mg/L is 10 mul, and the number of the tower plates is not lower than 4000 according to the calculation of a sulfate radical ion chromatographic peak.
As shown in fig. 6, asymmetry: the tailing factor (T) was used for evaluation. The tailing factor (T) is calculated as:
W0.05hthe peak width at 5% of the peak height of the chromatographic peak is defined; d1The distance from the projection point of the horizontal coordinate parallel line of the peak top of the chromatogram peak at the position of 5 percent of the peak height to the intersection point of the front edge of the peak and the parallel line.
When the peak area is taken as a quantitative parameter, the judgment of the baseline and the chromatographic peak start and stop and the accuracy of peak area integration can be influenced by serious tailing.
The results are shown in the following table:
TABLE 1 comparison table of performance parameters before and after regeneration of guard posts
Note: the data of the number of the tower plates in the experimental group and the control group are all the same type of anion chromatographic column.
The above data shows that the column efficiency (theoretical plate number) of the protective column regenerated by the method disclosed by the patent is obviously improved. When the asymmetry of the chromatographic peak is poor, the asymmetry is improved significantly after regeneration by the regeneration method described in this patent. The column efficiency (theoretical plate number) and asymmetry of the chromatographic column after the control group is cleaned are not obviously improved.
TABLE 2 Standard Curve parameter Table after regeneration of guard post
FIG. 2 is a parameter diagram of a standard curve drawn after the ion chromatography column was regenerated using example 1. The standard curve drawn by the protective column regenerated by the method has good linearity and meets the standard that the correlation coefficient r is more than or equal to 0.999.
FIG. 3 is a parameter diagram of a standard curve drawn after the ion chromatography column was regenerated using example 2.
TABLE 3 post-regeneration labeling recovery experiment of guard posts
As shown in FIG. 4, the detection chromatogram after the regeneration of the ion chromatography protective column in example 1 is shown. The protective column after regeneration by the method meets the standard requirement of 95-105% of recovery rate in a standard recovery test.
FIG. 5 shows the chromatogram of the regenerated ion chromatography column control group. The sulfate ion chromatographic peak still seriously trails in the detection spectrogram of the protective column regenerated by using the control group cleaning method. The column effect and the symmetry degree are not obviously improved after cleaning, and the obtained product is an abnormal spectrogram.
The invention provides a regeneration method of an ion chromatographic protective column, which can be used for removing pollutants after the ion chromatographic protective column is polluted by alternately cleaning with cleaning agents, regeneration liquid and ultrasonic waves, then completing the regeneration of the ion chromatographic protective column after standing, precipitating, filtering to remove the pollutants and refilling fillers, and recovering the performance of the ion chromatographic protective column.
According to the regeneration method, the filler is taken out, and different cleaning solutions are used for soaking, ultrasonic cleaning and the like, so that sufficient contact time and sufficient contact area of pollutants and the cleaning solution are ensured, and the cleaning effect is obviously enhanced. However, it should be noted that improper packing of the washed packing results in reduced column efficiency and even splitting.
The regeneration method can greatly prolong the service life of the ion chromatographic protective column and the chromatographic column, and remarkably reduce the analysis cost.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the present invention is not limited to the above-described alternative embodiments, and that various other forms of product may be devised by anyone in light of the present invention. The foregoing detailed description should not be construed as limiting the scope of the invention, and those skilled in the art will understand that various modifications can be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features can be equivalently replaced, without departing from the spirit and scope of the invention, and at the same time, such modifications or replacements do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the invention; the scope of the invention should be determined with reference to the appended claims, and the description should be construed to interpret the claims.
Claims (10)
1. The regeneration method of the ion chromatography protective column is characterized by comprising the steps of cleaning a stationary phase filled in the chromatography protective column by adopting a regenerant and ultrasonic waves alternately in sequence, standing and filtering to finish the performance recovery of the chromatography protective column.
2. The method for regenerating an ion chromatography protective column as claimed in claim 1, wherein the regenerating agent comprises one or more of an organic solvent, an aqueous organic solvent solution, an inorganic acid solution and an organic acid solution.
3. The method for regenerating an ion chromatography protective column as claimed in claim 2, wherein the organic solvent comprises one or more of methanol, ethanol, acetone and acetonitrile.
4. The method for regenerating an ion chromatography protective column as claimed in claim 2, wherein the aqueous organic solvent solution comprises one or more of an aqueous methanol solution, an aqueous ethanol solution, an aqueous acetone solution and an aqueous acetonitrile solution.
5. The method for regenerating the ion chromatographic protective column according to claim 4, wherein the mass concentration of the methanol aqueous solution comprises 80% -90%;
the mass concentration of the ethanol water solution is 90-95%;
the mass concentration of the acetone aqueous solution is 60-70%;
the mass concentration of the acetonitrile water solution is 80-90%.
6. The method for regenerating an ion chromatography protective column as claimed in claim 2, wherein the inorganic acid solution comprises a sulfuric acid solution;
the molar concentration of the sulfuric acid solution comprises 1mol/L-2 mol/L.
7. The method for regenerating an ion chromatography protective column as claimed in claim 2, wherein the organic acid solution comprises an oxalic acid solution;
the molar concentration of the oxalic acid solution is 1-2 mol/L.
8. The regeneration method of the ion chromatographic protective column according to claim 1, wherein when the regenerant and the ultrasonic wave are sequentially and alternately used for cleaning the stationary phase filled in the chromatographic protective column, the number of times of alternate cleaning comprises 2-3 times.
9. The regeneration method of the ion chromatography protective column as claimed in claim 1, wherein after the stationary phase filled in the ion chromatography protective column is cleaned, the re-filling chromatography protection is completed by adding a filling agent.
10. The method of claim 9, wherein the packing material comprises one or more of methanol, ethanol, acetonitrile, and ultrapure water.
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