CN110694301A - Liquid chromatographic column and preparation method thereof and preparation method of filler thereof - Google Patents
Liquid chromatographic column and preparation method thereof and preparation method of filler thereof Download PDFInfo
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- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
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Abstract
The invention provides a liquid chromatographic column, which comprises a column tube, a clamping sleeve, a sieve plate and a filler arranged in the column tube, wherein the filler comprises a metal-organic framework material liquid chromatographic column filler; the metal-organic framework material liquid chromatographic column packing comprises a matrix and a metal-organic framework compound growing on the matrix, wherein the matrix is attapulgite clay; and the metal-organic framework compound is obtained by in-situ growth of an organic ligand and a metal ion donor on a substrate. The invention also provides a preparation method of the liquid chromatographic column packing and a preparation method of the liquid chromatographic column. The metal-organic framework material is used for the liquid chromatographic column suitable for low-temperature detection, and the metal-organic framework material and the attapulgite are combined to be used as the filler, so that the service life of the liquid chromatographic column containing the metal-organic framework composite material is prolonged.
Description
Technical Field
The invention relates to the field of liquid chromatography, in particular to a liquid chromatographic column, a preparation method thereof and a preparation method of a filler thereof.
Background
Metal-organic frameworks (MOFs) are a new material with porous network structure assembled by metal ions and organic ligands forming ligand bonds. MOFs are of great interest because of their high specific surface area, abundant pore structure, large number of unsaturated metal sites, and structural ordering. Such as the adsorption separation performance and the selectivity, shows attractive application prospect in the development of the chromatographic field.
However, in the practical application process, although MOFs has better adsorbability and abundant chemical properties, and has excellent separation effect on some compounds which are not easy to separate, the types of separable media are widened, but the use of the adsorbability of MOFs for chromatographic analysis is rarely reported. The first reason is that the separation mechanism of the technology is still unclear at the starting stage, so that the technology cannot be accurately applied according to the guidance of the chemical mechanism; secondly, the single MOFs has poor durability, and the chromatographic column after being filled with the MOFs has short service life and poor reproducibility, so the MOFs is difficult to be used in the chromatographic field.
Disclosure of Invention
The invention aims to solve the problems of poor durability and short service life of a metal-organic framework composite material used for chromatographic detection in the prior art. The metal-organic framework material is used for the liquid chromatographic column suitable for low-temperature detection, and the metal-organic framework material and attapulgite are combined in a reaction mode to serve as a filler, so that the service life of the liquid chromatographic column containing the metal-organic framework composite material is prolonged.
In order to solve the technical problem, an embodiment of the invention provides a liquid chromatography column, which comprises a column tube, a clamping sleeve, a sieve plate and a filler arranged in the column tube, wherein the filler comprises a metal-organic framework material liquid chromatography column filler; the metal-organic framework material liquid chromatographic column packing comprises a matrix and a metal-organic framework compound growing on the matrix, wherein the matrix is attapulgite clay; and the metal-organic framework compound is obtained by in-situ growth of an organic ligand and a metal ion donor on a substrate.
By adopting the scheme, the liquid chromatogram is generally used for normal temperature detection, and the liquid chromatogram and the gas chromatogram are always in a detection temperature ratio of more than 100 ℃, and the durability of the metal-organic framework compound can be ensured at the temperature. The attapulgite is clay mineral soil which has a layer chain transition structure and takes water-containing magnesium-rich aluminosilicate as a main component, has low price and high use efficiency, and the metal-organic framework compound takes attapulgite clay as a matrix and grows on the attapulgite clay, and utilizes aluminum ions in the attapulgite clay to generate a complex to grow on the attapulgite clay to form a mutually wrapped structure, thereby bringing unexpected technical effects. The difference between this method and the addition of attapulgite to the organic ligand is that the method is more stable with the attapulgite as a radical, growing directly on it. The technical scheme combines the characteristics of high specific surface area, abundant pore structure, a large amount of unsaturated metal sites of the metal-organic framework compound and the durability of the attapulgite clay, and fully considers the use environment of the combination of the metal-organic framework compound and the attapulgite clay in liquid chromatography, so that the difficult problem of the metal-organic framework compound in chromatographic analysis is realized, and the durability of a chromatographic column is effectively improved.
According to another embodiment of the present invention, there is disclosed a liquid chromatography column wherein the metal ion donor comprises iron ions and aluminum ions.
According to another embodiment of the present invention, there is disclosed a liquid chromatography column wherein the organic ligands comprise 4, 4' -bipyridine and 2, 5-dihydroxybenzoic acid.
By adopting the scheme, 4' -bipyridyl and 2, 5-dihydroxybenzoic acid are taken as organic ligands through experiments, and the durability of the chromatographic column is better.
According to another embodiment of the present invention, there is disclosed a liquid chromatography column wherein the metal-organic framework compound is MIL-53(Fe, Al).
With the above scheme, the metal-organic framework compound capable of stably playing a main separation role for a long time in the various metal-organic framework compound products generated is MIL-53(Fe, Al), and MIL-53(Fe, Al) is helpful for stably separating benzene series.
The embodiment of the invention provides a preparation method of a liquid chromatography column filler, which is characterized by comprising the following steps:
s1: taking attapulgite clay crushed to 625-2500 meshes as a matrix, adding ethanol, and activating for 1-3 h;
s2: weighing 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate, and respectively dissolving the 4, 4' -bipyridine, the 2, 5-dihydroxybenzoic acid and the ferric nitrate in ethanol, wherein the 4, 4' -bipyridine and the 2, 5-dihydroxybenzoic acid are used as organic ligands, and the ferric nitrate is used as a metal ion donor;
s3: adding the ethanol solution dissolved with 4, 4' -bipyridyl, the ethanol solution dissolved with 2, 5-dihydroxybenzoic acid and the ethanol solution dissolved with ferric nitrate into the activated attapulgite clay, and mixing and stirring under high-pressure heating for 12-14h to obtain raw slurry;
s4: heating and stirring the raw slurry, refluxing for 1-3h, and filtering out the solvent to obtain a primary material while the primary material is hot;
s5: washing the primary material with distilled water and ethanol at room temperature, standing, and drying the primary material to complete the preparation.
By adopting the scheme, the stable liquid chromatographic column packing made of the metal-organic framework material can be produced and used for a liquid chromatographic column, and the column efficiency is high, and the yield and the success rate are high.
According to another embodiment of the present invention, there is disclosed a method for preparing a packing for a liquid chromatography column, wherein the ratio of the amounts of 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate is 1: 2: 0.1-1.
According to another embodiment of the present invention, a method for preparing a packing material for a liquid chromatography column, wherein the temperature of the high-pressure heating in step S3 is 60 to 80 ℃, and the pressure is 80 to 100kPa, is disclosed.
According to another embodiment of the present invention, in the method for preparing a liquid chromatography column packing according to the embodiment of the present invention, the activating step in S1 includes adding the attapulgite into ethanol, mechanically stirring, ultrasonically stirring, and finally heating with microwave for 5-10 minutes.
The embodiment of the invention provides a preparation method of a liquid chromatographic column, which is characterized by comprising the following steps:
a: cleaning the inner wall of the column tube with ethanol and distilled water, and drying for later use;
b: preparing a liquid chromatographic column packing of the metal-organic framework material;
c: dispersing the liquid chromatographic column filler into an ethanol solution, and performing ultrasonic treatment for 0.5-1h to form homogenate;
d: and (3) taking ethanol as a displacement liquid, and pressing the homogenate liquid into a standby column tube by using a pressure medium, wherein the pressure of the pressure medium is 30-50 MPa.
By adopting the scheme, the column packing method is simple and the column packing success rate is high.
According to another embodiment of the present invention, a method for preparing a liquid chromatography column is disclosed, wherein a liquid chromatography column packing of a metal-organic framework material is prepared by the above method.
Compared with the prior art, the invention has the following beneficial effects:
the liquid chromatographic column packing provided by the invention grows a metal-organic framework compound by taking attapulgite as a group, and can obviously improve the durability and the column manufacturing success rate of the liquid chromatographic column.
Drawings
FIG. 1 is a chromatogram obtained by detecting xylene with a liquid chromatography column in example 1 of the present invention.
Detailed Description
For purposes of the following detailed description, it is to be understood that the application may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present application. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The terminology used in the present application is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The expression "at least one" of an expression, for example, modifies an entire list of elements when preceding or following the list of elements, without modifying individual elements of the list.
Further, the terms "comprises" or "comprising," when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
As used herein, "about" or "approximately" includes the recited value and means, for example, within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art in view of the measurement in question and the error associated with measurement of the particular quantity (i.e., limitations of the measurement system). All ratios of components refer to weight percent (wt.%), unless otherwise specified; unless otherwise indicated, all parameter ranges disclosed include the endpoints and all values therebetween.
The embodiment of the invention discloses a liquid chromatographic column, which comprises a column tube, a clamping sleeve, a sieve plate and a filler arranged in the column tube, and is characterized in that the filler comprises a liquid chromatographic column filler; the metal-organic framework material liquid chromatographic column packing comprises a matrix and a metal-organic framework compound growing on the matrix, wherein the matrix is attapulgite clay; and the metal-organic framework compound is obtained by in-situ growth of an organic ligand and a metal ion donor on a substrate.
Specifically, the metal-organic framework compound may be a metal-organic framework material such as HKUST-1, MOF-5, MIL-53, MIL-88, MIL-100, MIL-101, ZIF-7 or ZIF-8. The metal-organic framework compound grows on the attapulgite clay, and the attapulgite clay is used as a matrix to be filled in the chromatographic column. The attapulgite clay is used as a matrix and also provides aluminum ions as metal ion donors, and the main component of the attapulgite clay is the contained water-rich magnesium-rich aluminosilicate, and the octahedron of the attapulgite clay contains cations, namely the aluminum ions.
The metal ion donor includes at least one of iron ion, aluminum ion, copper ion, zinc ion and chromium ion.
The organic ligand includes a heterocyclic compound containing two atoms substituted and/or a cyclic organic compound containing at least one carboxyl group. Among them, the heterocyclic compound includes pyridine or imidazole, such as 4, 4 '-bipyridine derivatives such as 4, 4' -bipyridine and 4, 4 '-diamino-2, 2' -bipyridine, or 2-methylimidazole, benzimidazole, etc.; the cyclic organic compound having at least one carboxyl group includes derivatives of benzoic acid such as terephthalic acid, dihydroxybenzoic acid, trimesic acid, and the like.
As a preferred embodiment of the present invention, the metal ion donor includes iron ion and aluminum ion.
Specifically, the iron ions may be iron nitrate solution, iron sulfate solution, etc. which are compounds containing iron ions commonly used by those skilled in the art. In the present embodiment, aluminum ions are mainly supplied by attapulgite, and a solution containing aluminum ions, such as aluminum nitrate, may be additionally added.
It is understood that even the same metal ion donor produces metal-organic framework compounds that differ according to the organic ligand, e.g., MIL-100(Fe, Al), MIL-53(Fe, Al), ZIF-8(Fe, Al), etc.
As a preferred embodiment of the present invention, the organic ligands include 4, 4' -bipyridine and 2, 5-dihydroxybenzoic acid.
Specifically, the metal ions are in double coordination with N atoms in 4, 4 '-bipyridyl and carboxylic acid oxygen atoms in 2, 5-dihydroxybenzoic acid, and the 4, 4' -bipyridyl and 2, 5-dihydroxybenzoic acid are used as organic ligands through experiments, so that the durability of the chromatographic column is better.
As a preferred embodiment of the present invention, the metal-organic framework compound is MIL-53(Fe, Al).
The embodiment of the invention also discloses a preparation method of the liquid chromatographic column packing, which comprises the following steps:
s1: taking attapulgite clay crushed to 625-2500 meshes as a matrix, adding ethanol, and activating for 1-3 h.
Specifically, the activation step can be adding attapulgite clay into ethanol and stirring to form a suspension, then adding hydrochloric acid, hydrofluoric acid, nitric acid and other acids for activation, and mechanically stirring during activation; the activation can also be carried out by heating and stirring, ultrasonic stirring and the like. The activated attapulgite has enhanced reactivity and adsorptivity, higher reaction efficiency with organic ligands and metal ions, and higher separation effect as chromatographic packing.
S2: weighing 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate, and respectively dissolving 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate in ethanol, wherein 4, 4' -bipyridine and 2, 5-dihydroxybenzoic acid are used as organic ligands, and ferric nitrate is used as a metal ion donor.
Specifically, when 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate are dissolved in ethanol, an acid such as nitric acid, hydrochloric acid and the like may be added to establish an acidic system, so that the dissolution reaction is better performed. Further, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate were mixed, and then stirred and mixed under an inert gas atmosphere such as nitrogen or helium.
S3: adding the ethanol solution dissolved with 4, 4' -bipyridyl, the ethanol solution dissolved with 2, 5-dihydroxybenzoic acid and the ethanol solution dissolved with ferric nitrate into the activated attapulgite clay, and mixing and stirring under high-pressure heating for 12-14h to obtain the original slurry.
Specifically, the mass ratio of 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate was 1: 2: 0.1-2, preferably 1: 2: 0.1-1. Adding the activated attapulgite clay suspension into the ethanol solution of the mixed solution, heating and refluxing in a high-pressure environment, and stirring in an inert gas environment such as nitrogen or helium. Wherein the high-pressure heating temperature is 50-100 deg.C, preferably 60-80 deg.C, and the pressure is 60-100kPa, preferably 80-100 kPa.
S4: heating and stirring the raw slurry, refluxing for 1-3h, and filtering out the solvent to obtain a primary material while the primary material is hot;
specifically, the raw slurry is heated and stirred in an inert gas atmosphere such as nitrogen or helium.
S5: washing the primary material with distilled water and ethanol at room temperature, standing, and drying the primary material to complete the preparation.
Specifically, the number of washing may be three or more, the time of standing may be 12 hours, and the drying may be drying with a dryer.
In a preferred embodiment of the present invention, in the method for preparing a packing for a liquid chromatography column, the ratio of the amounts of 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate is 1: 2: 0.1-1.
In a preferred embodiment of the present invention, in the method for preparing a packing for a liquid chromatography column, the temperature of the high-pressure heating in step S3 is 60 to 80 ℃ and the pressure is 80 to 100 kPa.
In a preferred embodiment of the present invention, in the method for preparing the liquid chromatography column packing, the activation step in S1 comprises adding attapulgite into ethanol, mechanically stirring, ultrasonically stirring, and heating with microwave for 5-10 min.
It is to be understood that the time of the mechanical agitation and the ultrasonic agitation is not particularly specified in the present embodiment.
The embodiment of the invention discloses a preparation method of a liquid chromatographic column, which is characterized by comprising the following steps:
a: cleaning the inner wall of the column tube with ethanol and distilled water, and drying for later use;
b: preparing a liquid chromatographic column packing of the metal-organic framework material;
c: dispersing the liquid chromatographic column filler into an ethanol solution, and performing ultrasonic treatment for 0.5-1h to form homogenate;
d: and (3) taking ethanol as a displacement liquid, and pressing the homogenate liquid into a standby column tube by using a pressure medium, wherein the pressure of the pressure medium is 30-50 MPa.
In a preferred embodiment of the present invention, the liquid chromatography column packing of metal-organic framework material in the method for preparing a liquid chromatography column may be prepared by the above-mentioned method for preparing a liquid chromatography column packing.
Example 1
A preparation method of a liquid chromatography column packing comprises the following steps:
s1: taking the attapulgite clay ground to 625 meshes as a matrix, adding ethanol, stirring, and mechanically stirring and activating for 3 hours;
s2: weighing the materials in a weight ratio of 1: 2: 0.1 of 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate, and respectively dissolving 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate in ethanol, wherein 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid are used as organic ligands, and ferric nitrate is used as a metal ion donor;
s3: adding the ethanol solution dissolved with 4, 4' -bipyridyl, the ethanol solution dissolved with 2, 5-dihydroxybenzoic acid and the ethanol solution dissolved with ferric nitrate to the activated attapulgite clay, and mixing and stirring for 12h under the conditions of 100kPa and 80 ℃ to obtain raw slurry;
s4: heating and stirring the raw slurry, refluxing for 3h, and filtering out the solvent to obtain a primary material while the primary material is hot;
s5: washing the primary material with distilled water and ethanol at room temperature, standing, and drying the primary material to complete the preparation.
This example, S1-S5, was conducted to obtain a metal-organic framework material packing for a liquid chromatography column, which comprises an attapulgite clay as a matrix and MIL-53(Fe, Al) grown thereon.
A liquid chromatographic column comprises a column tube, a clamping sleeve, a sieve plate and a filler arranged in the column tube, wherein the filler is prepared by the preparation method of the liquid chromatographic column filler.
A preparation method of a liquid chromatographic column comprises the following steps:
a: cleaning the inner wall of the column tube with ethanol and distilled water, and drying for later use;
b: preparing the liquid chromatographic column packing of the metal-organic framework material by the same method as the method of S1-S5;
c: dispersing the liquid chromatographic column filler into an ethanol solution, and performing ultrasonic treatment for 0.5-1h to form homogenate;
d: and (3) taking ethanol as a displacement liquid, and pressing the homogenate liquid into a standby column tube by using a pressure medium, wherein the pressure of the pressure medium is 30-50 MPa.
Example 2
A preparation method of a liquid chromatography column packing comprises the following steps:
s1: taking the attapulgite clay ground to 2500 meshes as a matrix, adding ethanol, stirring, adding acid, heating, stirring and activating for 1 h;
s2: weighing the materials in a weight ratio of 1: 2: 1 of 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate, wherein 4, 4' -bipyridine and 2, 5-dihydroxybenzoic acid are used as organic ligands, ferric nitrate is used as a metal ion donor, and 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate are respectively dissolved in ethanol;
s3: adding the ethanol solution dissolved with 4, 4' -bipyridyl, the ethanol solution dissolved with 2, 5-dihydroxybenzoic acid and the ethanol solution dissolved with ferric nitrate to the activated attapulgite clay, and mixing and stirring for 14h under the conditions of 80kPa and 60 ℃ to obtain raw slurry;
s4: heating and stirring the raw slurry, refluxing for 1, and filtering out the solvent to obtain a primary material;
s5: washing the primary material with distilled water and ethanol at room temperature, standing, and drying the primary material to complete the preparation.
After the liquid chromatographic column packing of the metal-organic framework material is prepared, the liquid chromatographic column packing is packed in the same manner as in example 1, and finally the liquid chromatographic column with the metal-organic framework material as the stationary phase is obtained.
This example, S1-S5, was conducted to obtain a liquid chromatography column packing material, which comprises attapulgite clay as a matrix and MIL-53(Fe, Al) grown thereon.
A liquid chromatographic column comprises a column tube, a clamping sleeve, a sieve plate and a filler arranged in the column tube, wherein the filler is prepared by the method, namely the liquid chromatographic column filler.
A liquid chromatography column was prepared in the same manner as in example 1.
Example 3
A preparation method of a liquid chromatography column packing comprises the following steps:
s1: taking attapulgite clay which is crushed to 1500 meshes as a matrix, adding ethanol, stirring, heating, stirring and activating for 2 hours;
s2: weighing the materials in a weight ratio of 1: 2: 0.6 of 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate, wherein 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid are used as organic ligands, ferric nitrate is used as a metal ion donor, and 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate are dissolved in ethanol, respectively;
s3: adding the ethanol solution dissolved with 4, 4' -bipyridyl, the ethanol solution dissolved with 2, 5-dihydroxybenzoic acid and the ethanol solution dissolved with ferric nitrate to the activated attapulgite clay, and mixing and stirring at 70 ℃ and 90kPa for 13h to obtain raw slurry;
s4: heating and stirring the raw slurry, refluxing for 2h, and filtering out the solvent to obtain a primary material while the primary material is hot;
s5: washing the primary material with distilled water and ethanol at room temperature, standing, and drying the primary material to complete the preparation.
After the liquid chromatographic column packing of the metal-organic framework material is prepared, the liquid chromatographic column packing is packed in the same manner as in example 1, and finally, a liquid chromatographic column is obtained.
This example, S1-S5, was conducted to obtain a metal-organic framework material packing for a liquid chromatography column, which comprises an attapulgite clay as a matrix and MIL-53(Fe, Al) grown thereon.
The liquid chromatographic column includes column tube, clamping sleeve, sieve plate and stuffing inside the column tube, and the stuffing is prepared through the said process.
A liquid chromatography column was prepared in the same manner as in example 1.
Example 4
A preparation method of a liquid chromatography column packing comprises the following steps:
s1: taking attapulgite clay which is crushed to 1500 meshes as a matrix, adding ethanol, stirring, heating, stirring and activating for 2.5 hours;
s2: weighing the materials in a weight ratio of 1: 2: 0.6 of 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate, wherein 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid are used as organic ligands, ferric nitrate is used as a metal ion donor, and 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate are dissolved in ethanol, respectively;
s3: adding the ethanol solution dissolved with 4, 4' -bipyridyl, the ethanol solution dissolved with 2, 5-dihydroxybenzoic acid and the ethanol solution dissolved with ferric nitrate to the activated attapulgite clay, refluxing, heating, mixing and stirring for 13h at 100 ℃ and 120kPa to obtain raw slurry;
s4: heating and stirring the raw slurry, refluxing for 2h, and filtering out the solvent to obtain a primary material while the primary material is hot;
s5: washing the primary material with distilled water and ethanol at room temperature, standing, and drying the primary material to complete the preparation.
After the liquid chromatographic column packing of the metal-organic framework material is prepared, the liquid chromatographic column packing is packed in the same manner as in example 1, and finally, a liquid chromatographic column is obtained.
This example, S1-S5, was conducted to obtain a liquid chromatography column packing material, which comprises attapulgite clay as a matrix and MIL-53(Fe, Al) grown thereon.
The liquid chromatographic column includes column tube, clamping sleeve, sieve plate and stuffing inside the column tube, and the stuffing is prepared through the said process.
A liquid chromatography column was prepared in the same manner as in example 1.
Example 5
A preparation method of a liquid chromatography column filler is the same as that of example 1, and is different from the preparation method of the liquid chromatography column filler in that firstly attapulgite is added into ethanol, then mechanical stirring and ultrasonic stirring are carried out, finally microwave heating is carried out for 5-10 minutes, and the total activation time is 3 hours.
It is to be understood that the time of the mechanical stirring and the ultrasonic stirring is not specifically defined in the present embodiment, for example, the time of the mechanical stirring may be 100min, and the time of the ultrasonic stirring may be 70 min.
This example, S1-S5, was conducted to obtain a liquid chromatography column packing material, which comprises attapulgite clay as a matrix and MIL-53(Fe, Al) grown thereon.
The liquid chromatographic column includes column tube, clamping sleeve, sieve plate and stuffing inside the column tube, and the stuffing is prepared through the said process.
A method for preparing a liquid chromatographic column comprises preparing a liquid chromatographic column filler, packing the liquid chromatographic column filler into a column in the same manner as in example 1, and finally obtaining the liquid chromatographic column.
Example 6
A liquid chromatographic column comprises a column tube, a cutting sleeve, a sieve plate and a filler arranged in the column tube, wherein the filler is a liquid chromatographic column filler made of a metal-organic framework material, and more specifically MOF-5(Fe, Al).
In which MOF-5 was prepared by the method of preparing the liquid chromatography column packing of example 1, wherein the difference from example 1 is that iron sulfate was used to provide iron ions and terephthalic acid was used as an organic ligand in steps S2 and S3.
The method for preparing the liquid chromatography column in this example is the same as that of example 1.
Example 7
A liquid chromatographic column comprises a column tube, a clamping sleeve, a sieve plate and a filler arranged in the column tube, wherein the filler is a liquid chromatographic column filler made of a metal-organic framework material, and is more specifically ZIF-8(Fe, Al).
Among them, ZIF-8 was prepared by the method for preparing the packing for a liquid chromatography column of example 1, which is different from example 1 in that 2-methylimidazole was used as an organic ligand in steps S2 and S3.
The method for preparing the liquid chromatography column in this example is the same as that of example 1.
Example 8
A liquid chromatographic column comprises a column tube, a clamping sleeve, a sieve plate and a filler arranged in the column tube, wherein the filler is a liquid chromatographic column filler made of a metal-organic framework material, and more specifically MIL-100 Fe.
In which MIL-100Fe was prepared by the method for preparing a packing for a chromatography column of example 1, wherein the difference from example 1 is that trimesic acid was used as an organic ligand, iron powder was used as a metal ion donor, solvent ethanol was replaced with 40 wt% hydrofluoric acid in steps S2 and S3, and a washing step was added after step S3 and before step S4, in which the raw slurry was washed 3-5 times with deionized water and then with ethanol 3-5 times.
The method of preparing the liquid chromatography column in this example was the same as that of example 1.
Example 9
A liquid chromatographic column comprises a column tube, a cutting sleeve, a sieve plate and a filler arranged in the column tube, wherein the filler is a liquid chromatographic column filler made of a metal-organic framework material, and is more specifically MIL-53(Gr, Al).
In which MIL-53(Gr, Al) was prepared by the method for preparing a packing for a chromatography column of example 1, wherein the difference from example 1 is that chromium nitrate hexahydrate was used as a metal ion donor in steps S2 and S3.
The method of preparing the liquid chromatography column in this example was the same as that of example 1.
Comparative example 1:
the method comprises the steps of purchasing the existing metal-organic framework compound MIL-53Fe, directly filling the MIL-53Fe without attapulgite into a liquid phase chromatographic column tube by a homogenate filling method, namely adding a solvent into the MIL-53Fe to disperse into homogenate, filling a chromatographic column and an extension tube thereof with a mobile phase, then pouring the homogenate into a homogenate filler, and quickly injecting the homogenate into the chromatographic column under high pressure.
And (3) effect analysis:
the liquid chromatography column in example 1 was used for the detection of xylene separation, and a chromatogram as shown in fig. 1 was obtained under the analysis conditions as shown in table 1 and the analysis results as shown in table 2:
TABLE 1
TABLE 2
As can be seen from fig. 1 and table 2, the liquid chromatography column provided by the present invention can completely separate paraxylene and isomers thereof, i.e., the liquid chromatography column provided by the present invention can be used for chromatographic detection of substances difficult to separate, which widens the variety of detectable media, and solves the problem of detection of substances difficult to separate in the prior art.
Further, the liquid chromatography columns of examples 1 to 5, and the liquid chromatography column of comparative example 1 were used for the analysis of xylene, continued to be used after the first test, and tested at the time points of 20 hours, 40 hours, 80 hours, 160 hours, and 500 hours of the operation of the flow chromatography column, the retention values of the columns were checked by repeated experiments, and the life of the columns was evaluated using the retention values. The analysis conditions are shown in Table 3, and the specific results are shown in Table 4:
TABLE 3
| A chromatographic column: | 5*250mm，5μm |
| mobile phase: | acetonitrile: water (60: 40) |
| Detection wavelength: | 250nm |
| column temperature: | 30℃ |
| flow rate: | 1ml/min |
| sample introduction amount: | 5μl |
TABLE 4
As can be seen from Table 4, the retention values in examples 1 to 5 do not change much with the increase of the service time, and still can ensure better column efficiency and separation degree after long-term use, i.e. the liquid chromatography column provided by the invention has good durability and longer service life, meanwhile, the retention value of comparative example 1 is continuously deteriorated with the increase of the service time, wherein the retention value can not be used in the detection of continuous use for 500 hours. Therefore, the liquid chromatographic column provided by the invention has the advantages of higher durability and long service life, can still keep better separation effect after being used for multiple times, and solves the technical problem that the metal-organic framework compound is difficult to be used for chromatographic detection in the prior art.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more detailed description of the invention, taken in conjunction with the specific embodiments thereof, and that no limitation of the invention is intended thereby. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A liquid chromatographic column comprises a column tube, a cutting sleeve, a sieve plate and a filler arranged in the column tube, and is characterized in that the filler comprises a metal-organic framework material liquid chromatographic column filler; and the number of the first and second electrodes,
the metal-organic framework material liquid chromatography column filler comprises a matrix and a metal-organic framework compound growing on the matrix, wherein the matrix is attapulgite clay; and the number of the first and second electrodes,
the metal-organic framework compound is obtained by in-situ growth of an organic ligand and a metal ion donor on the substrate.
2. The liquid chromatography column of claim 1, wherein the metal ion donor comprises iron ions and aluminum ions.
3. The liquid chromatography column of claim 2, wherein the organic ligands comprise 4, 4' -bipyridine and 2, 5-dihydroxybenzoic acid.
4. The liquid chromatography column of claim 3, wherein the metal-organic framework compound is MIL-53(Fe, Al).
5. The preparation method of the liquid chromatography column packing is characterized by comprising the following steps:
s1: taking attapulgite clay crushed to 625-2500 meshes as a matrix, adding ethanol, and activating for 1-3 h;
s2: weighing 4, 4' -bipyridine, 2, 5-dihydroxybenzoic acid and ferric nitrate, and dissolving the 4, 4' -bipyridine, the 2, 5-dihydroxybenzoic acid and the ferric nitrate in ethanol, wherein the 4, 4' -bipyridine and the 2, 5-dihydroxybenzoic acid are used as organic ligands, and the ferric nitrate is used as a metal ion donor;
s3: adding the ethanol solution dissolved with the 4, 4' -bipyridyl, the ethanol solution dissolved with the 2, 5-dihydroxybenzoic acid and the ethanol solution dissolved with the ferric nitrate into the activated attapulgite clay, and mixing and stirring under high-pressure heating for 12-14h to obtain a raw slurry;
s4: heating and stirring the raw slurry, refluxing for 1-3h, and filtering out the solvent to obtain a primary material;
s5: and washing the primary material with distilled water and ethanol at room temperature, standing, and drying the primary material to finish the preparation.
6. The method of preparing a packing material for a liquid chromatography column according to claim 5, wherein the amount of the 4, 4' -bipyridine, the 2, 5-dihydroxybenzoic acid and the iron nitrate is 1: 2: 0.1-1.
7. The method for preparing a packing material for a liquid chromatography column according to claim 5, wherein the high-pressure heating in step S3 is performed at a temperature of 60 to 80 ℃ and a pressure of 80 to 100 kPa.
8. The method for preparing a liquid chromatography column packing material of claim 5, wherein the activating step in S1 comprises adding the attapulgite into ethanol, then mechanically stirring, then ultrasonically stirring, and finally heating with microwave for 5-10 minutes.
9. A method of preparing a liquid chromatography column, comprising:
a: cleaning the inner wall of the column tube with ethanol and distilled water, and drying for later use;
b: preparing a liquid chromatographic column packing of the metal-organic framework material;
c: dispersing the liquid chromatographic column filler into an ethanol solution, and performing ultrasonic treatment for 0.5-1h to form homogenate;
d: and (3) taking ethanol as a displacement liquid, pressing the homogenate liquid into the standby column tube by using a pressurizing medium, wherein the pressure of the pressurizing medium is 30-50 MPa.
10. A method of preparing a liquid chromatography column as claimed in claim 9, wherein the liquid chromatography column packing is prepared by the method of claim 7.
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