CN108261801B - Stationary phase containing eutectic solvent and preparation method and application thereof - Google Patents
Stationary phase containing eutectic solvent and preparation method and application thereof Download PDFInfo
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- CN108261801B CN108261801B CN201810133063.2A CN201810133063A CN108261801B CN 108261801 B CN108261801 B CN 108261801B CN 201810133063 A CN201810133063 A CN 201810133063A CN 108261801 B CN108261801 B CN 108261801B
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Abstract
The invention provides a stationary phase containing a eutectic solvent and a preparation method and application thereof, wherein the stationary phase comprises diatomite and the eutectic solvent with the mass ratio of 10: 0.1-10: 1, the molar ratio of a hydrogen bond acceptor of the eutectic solvent to a hydrogen bond donor is 1: 1-1: 3, a DES stationary phase is filled into a chromatographic column by adopting a decompression method, the separation performance of the chromatographic column on alcohol mixtures such as butanol, pentanol, hexanol and octanol is researched, and the result shows that a filling column using DES as a stationary liquid has good separation efficiency on the alcohol mixtures.
Description
Technical Field
The invention relates to a stationary phase containing a eutectic solvent, and a preparation method and application thereof, and belongs to the technical field of detection and analysis.
Background
Chromatography is a widely used analytical method, and the principle of separation is that components in a mixture are distributed between a mobile phase and a stationary phase, and when the components flow through the stationary phase (or stationary liquid), the effects of different components and the stationary phase differ, i.e., the residence time differs. Thereby realizing the effect of separating the mixture. Under the gas-liquid chromatography mode, the stationary liquid firstly has proper dissolving capacity, and the distribution ratio of the separated components in the stationary liquid is different according to the similar compatibility principle, so that the separation purpose is achieved. Of course, a good fixative must also have certain viscosity, low vapor pressure, and the like. The eutectic solvent (DES) is considered as a novel green solvent, is a eutectic mixture formed by combining a hydrogen bond donor and a hydrogen bond acceptor with a certain stoichiometric ratio, has the advantages of difficult volatilization, low toxicity, degradability, low price, good solubility and thermal stability, easy obtainment, easy preparation and the like, can be adjusted by selecting proper components and proportions, has wide application prospects in many fields, and ensures that the DES is very suitable to be used as a stationary liquid in chromatographic analysis.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a stationary phase containing a eutectic solvent, a preparation method thereof, a chromatographic column containing the stationary phase and application in separating alcohol mixtures.
In order to solve the technical problem, the invention discloses a stationary phase containing a eutectic solvent, which comprises diatomite and the eutectic solvent in a mass ratio of 10: 0.1-10: 1.
Wherein, the hydrogen bond acceptor of the eutectic solvent is selected from one of tetrabutylammonium chloride, tetrabutylammonium bromide, methyl trioctyl ammonium chloride, octadecyl trimethyl ammonium chloride, choline chloride and beet salt, and the hydrogen bond donor of the eutectic solvent is hexanol, octanol, dodecanol, glycerol or glycol; the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor of the eutectic solvent is 1: 1-1: 3, and preferably 1: 2.
The preparation method of the stationary phase containing the eutectic solvent comprises the following steps: mixing a hydrogen bond acceptor and a hydrogen bond donor, heating and stirring in a water bath until clear transparent liquid is formed to obtain a eutectic solvent; sieving diatomite, cleaning and drying for later use; mixing the eutectic solvent and diatomite in volatile organic solvent such as methanol or acetonitrile, mixing, and evaporating to dryness with rotary evaporator.
Wherein the granularity of the diatomite is controlled within the range of 80-100 meshes.
The mass volume ratio of the eutectic solvent to the volatile organic solvent is 0.05: 10-0.1: 10, preferably 0.07:10, and in this case, the diatomite can form a uniform suspension in the eutectic solvent.
The chromatographic column contains the stationary phase containing the eutectic solvent, and the filling amount of the stationary phase containing the eutectic solvent in the chromatographic column is 0.12-0.16 g/cm3。
The invention also provides application of the stationary phase containing the eutectic solvent in separation of alcohol mixtures.
The alcohol mixture comprises at least two of butanol, pentanol, hexanol and octanol.
The application of the chromatographic column containing the eutectic solvent stationary phase in separating alcohol mixtures at least comprising two of butanol, pentanol, hexanol and octanol is also in the protection scope of the invention.
Has the advantages that:
1. according to the invention, the eutectic solvent is introduced as the stationary phase for the first time, and the chromatographic column containing the eutectic solvent stationary phase is prepared, and has good separation performance on alcohol mixtures such as butanol, pentanol, hexanol, octanol and the like.
The eutectic solvent has the characteristic of no volatility, and can be applied to the premise of chromatographic analysis, and the eutectic solvent has various types, so that sufficient selection is provided for potential analysis objects, and the eutectic solvent has a very wide application prospect in the field of chromatographic column separation.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a graph of the separation effectiveness of a hexanol-tetrabutylammonium chloride DES stationary phase gas chromatography column prepared in example 1;
FIG. 2 is a graph of the separation effect of the ethylene glycol-choline chloride DES stationary phase gas chromatography column prepared in example 2;
FIG. 3 is a graph of the separation effect of a urea-tetrabutylammonium chloride DES stationary phase gas chromatography column prepared in comparative example 1;
FIG. 4 is a graph of the separation effectiveness of the hexanoic acid-tetrabutylammonium chloride DES stationary phase gas chromatography column prepared in comparative example 2;
Detailed Description
The invention will be better understood from the following examples.
Example 1
Mixing hexanol and tetrabutylammonium chloride according to a molar ratio of 2:1, heating and stirring in a water bath until clear and transparent liquid is formed, and preparing hexanol-tetrabutylammonium chloride DES (eutectic solvent);
sieving diatomite to control the granularity of the diatomite within the range of 80-100 meshes, and cleaning and drying the diatomite for later use;
weighing 0.5g of DES, dissolving in 70mL of methanol, weighing 5g of cleaned dry diatomite, pouring into the DES methanol solution, shaking up, and evaporating the mixture at 50 ℃ by using a rotary evaporator to obtain the DES stationary phase.
Selecting a stainless steel column with the length of 50cm, the outer diameter of 6mm and the inner diameter of 4mm as a chromatographic column body, and filling the prepared 4g DES stationary phase into the chromatographic column by adopting a decompression method, wherein the specific process is as follows:
connecting one end of the stainless steel column with silanized glass wool and then connecting the stainless steel column with a buffer safety bottle of a vacuum pump;
pouring the stationary phase into a filler pond, wherein a calcium chloride-silica gel drying tower is additionally arranged at an air inlet of the filler pond, and an air outlet of the filler pond is connected with a stainless steel column;
and opening a vacuum pump, filling the stationary phase into the stainless steel column, tapping the stainless steel column in the filling process to ensure that the stationary phase is uniformly filled until all the stationary phases are filled into the stainless steel column, and thus finishing the preparation of the chromatographic column. The effective column length was measured to be 45 cm.
Example 2
Mixing ethylene glycol and choline chloride according to a molar ratio of 2:1, heating and stirring in a water bath until clear and transparent liquid is formed, and thus preparing the ethylene glycol-choline chloride DES (eutectic solvent).
Sieving diatomite to control the granularity of the diatomite within the range of 80-100 meshes, and cleaning and drying the diatomite for later use;
weighing 0.5g of DES, dissolving in 70mL of methanol, weighing 5g of cleaned diatomite, pouring into the DES methanol solution, shaking up, and evaporating the mixture at 50 ℃ by using a rotary evaporator to obtain the DES stationary phase.
The column preparation was the same as in example 1, and 3.8g of the DES stationary phase prepared above was packed into the column by reduced pressure method, and the column prepared had an effective column length of 43 cm.
Example 3
Hexanol and methyltrioctylammonium chloride were mixed in a molar ratio of 1:1, and the rest of the preparation procedure was the same as in example 1 to obtain a DES stationary phase.
The column preparation was the same as in example 1, and 3g of DES stationary phase was packed into the column by depressurization to prepare a column having an effective column length of 35 cm.
Example 4
And mixing dodecanol and tetrabutylammonium chloride according to a molar ratio of 3:1, and performing the same preparation process as the example 1 to obtain the DES stationary phase.
The column preparation was the same as in example 1, and 3.5g of DES stationary phase was packed into the column by depressurization to prepare a column having an effective column length of 39 cm.
Example 5
Mixing ethylene glycol and choline chloride according to a molar ratio of 2:1, and carrying out the other preparation processes in the same manner as in example 2, wherein the volatile organic solvent is acetonitrile, the mass-to-volume ratio of the eutectic solvent, the diatomite and the acetonitrile is 0.1:10:20, namely DES 0.5g and the diatomite 50g are dissolved in 100ml of acetonitrile, so as to obtain the DES stationary phase.
The column preparation was the same as in example 2, and 4g of DES stationary phase was packed into the column by depressurization to prepare a column having an effective column length of 45 cm.
Comparative example 1
And mixing urea and tetrabutylammonium chloride according to a molar ratio of 2:1, and obtaining the DES stationary phase by the same preparation process as the example 1.
The column preparation was the same as in example 1, and 4g of DES stationary phase was packed into the column by depressurization to prepare a column having an effective column length of 45 cm.
Comparative example 2
And mixing caproic acid and tetrabutylammonium chloride according to the molar ratio of 2:1, and performing the same preparation process as the example 1 to obtain the DES stationary phase.
The column preparation was the same as in example 1, and 4g of DES stationary phase was packed into the column by depressurization to prepare a column having an effective column length of 45 cm.
Example 6
The columns prepared in examples 1 to 5 and comparative examples 1 and 2 were separately loaded into a chromatograph to measure the effect of separating alcohol mixtures.
Gas chromatography conditions:
chromatograph: tianmei GC7900 gas chromatograph;
carrier gas: high-purity nitrogen (purity is more than or equal to 99.999 percent) and flow rate is 24mL/min
A detector: FID detector
Sample inlet temperature: 200 deg.C
Detector temperature: 200 deg.C
Sample introduction amount: 1 mu L, split-flow sample injection, and the split-flow ratio is 10: 1.
Temperature rising procedure: the initial temperature is 60 deg.C, and the temperature is maintained for 1min, and the temperature is increased to 180 deg.C at the rate of 10 deg.C/min, and maintained for 10 min.
Sample preparation: respectively taking 20 mu L of butanol, pentanol, hexanol and octanol, mixing, and then using methanol to fix the volume to 1mL to obtain the sample.
And (3) analysis results: the effects of example 1 and example 2 are most pronounced.
FIG. 1 is a graph showing the separation effect of the hexyl alcohol-tetrabutylammonium chloride DES stationary phase gas chromatography column prepared in example 1, wherein components 1, 2, 3 and 4 are respectively butyl alcohol, amyl alcohol, hexyl alcohol and octyl alcohol, and the number of the tower plates is n1＝641，n2＝1265，n3＝2560，n43463. The separation of butanol from pentanol was 2.03, the separation of pentanol from hexanol was 2.47, and the separation of hexanol from octanol was 3.69.
FIG. 2 is a graph showing the separation effect of the ethylene glycol-choline chloride DES stationary phase gas chromatography column prepared in example 2, in which components 1, 2, 3, and 4 are respectively butanol, pentanol, hexanol, and octanol, and the number of plates thereof is n1＝84，n2＝230，n3＝676，n41129. The separation of butanol from pentanol was 1.45, the separation of pentanol from hexanol was 1.42, and the separation of hexanol from octanol was 2.40.
The above results show that the chromatographic column prepared by using the eutectic solvent as the stationary phase has good separation performance on alcohol mixtures such as butanol, pentanol, hexanol and octanol.
The present invention provides a stationary phase containing eutectic solvent, and a preparation method and application thereof, and a plurality of methods and approaches for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and embellishments can be made without departing from the principle of the present invention, and these modifications and embellishments should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (4)
1. The application of the chromatographic column containing the eutectic solvent stationary phase in separating alcohol mixtures is characterized in that:
the filling amount of the stationary phase containing the eutectic solvent in a chromatographic column is 0.12-0.16 g/cm3；
The eutectic solvent stationary phase comprises diatomite and a eutectic solvent in a mass ratio of 10: 0.1-10: 1;
the hydrogen bond acceptor of the eutectic solvent is selected from one of tetrabutylammonium chloride, tetrabutylammonium bromide and choline chloride, and the hydrogen bond donor of the eutectic solvent is hexanol or ethylene glycol; the molar ratio of a hydrogen bond acceptor to a hydrogen bond donor of the eutectic solvent is 1: 1-1: 3;
the alcohol mixture comprises at least two of butanol, pentanol, hexanol and octanol.
2. Use of a chromatographic column comprising a eutectic solvent stationary phase according to claim 1 for separating a mixture of alcohols, wherein said eutectic solvent stationary phase is prepared by: mixing a hydrogen bond acceptor and a hydrogen bond donor, heating and stirring in a water bath until clear transparent liquid is formed to obtain a eutectic solvent; sieving diatomite, cleaning and drying for later use; and mixing the eutectic solvent and the diatomite in a volatile organic solvent, uniformly mixing, and evaporating by using a rotary evaporator to dryness to obtain the product.
3. The application of the chromatographic column containing the eutectic solvent stationary phase in separating the alcohol mixture according to claim 2, wherein the particle size of the diatomite is controlled within a range of 80-100 meshes.
4. The application of the chromatographic column containing the eutectic solvent stationary phase in separating the alcohol mixture according to claim 2, wherein the mass volume ratio of the eutectic solvent to the volatile organic solvent is 0.05: 10-0.1: 10.
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| CN109261231B (en) * | 2018-10-15 | 2021-02-02 | 天津医科大学 | Application of graphene oxide-doped monolithic column microfluidic chip with eutectic solvent in polycyclic aromatic hydrocarbon enrichment |
| CN109694723B (en) * | 2018-12-27 | 2021-08-27 | 青岛科技大学 | Eutectic solvent and method for extracting non-alkaline nitrogen from simulated gasoline |
| CN110270131B (en) * | 2019-07-21 | 2021-06-29 | 河南师范大学 | Extraction application of hydrophobic eutectic solvent based on paraben compounds |
| CN111675640B (en) * | 2020-07-27 | 2021-06-22 | 中国科学院兰州化学物理研究所 | Method for separating and preparing high-purity zeaxanthin |
| CN112705131B (en) * | 2020-12-29 | 2023-01-24 | 广西中烟工业有限责任公司 | Preparation method of eutectic solvent/hydroxypropyl-beta-cyclodextrin menthol microcapsule |
| CN114832799B (en) * | 2022-06-01 | 2023-02-28 | 中国科学院兰州化学物理研究所 | Preparation and application of carbon-point bonded silica gel chromatographic stationary phase based on eutectic solvent |
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| CN104926605A (en) * | 2015-05-21 | 2015-09-23 | 济南大学 | Benzene-propanol azeotrope rectification separation method based on choline chloride further-co-melting solvent |
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Application publication date: 20180710 Assignee: Jincheng Changrun Changtong Agricultural Development Technology Co.,Ltd. Assignor: CHANGZHI University Contract record no.: X2023980035792 Denomination of invention: A stationary phase containing low eutectic solvent and its preparation method and application Granted publication date: 20201127 License type: Common License Record date: 20230522 |
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