CN115138836B - High performance liquid chromatographic column sieve plate and preparation method thereof - Google Patents

High performance liquid chromatographic column sieve plate and preparation method thereof Download PDF

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Publication number
CN115138836B
CN115138836B CN202210791845.1A CN202210791845A CN115138836B CN 115138836 B CN115138836 B CN 115138836B CN 202210791845 A CN202210791845 A CN 202210791845A CN 115138836 B CN115138836 B CN 115138836B
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Prior art keywords
sieve plate
metal powder
spherical metal
gradient
pore diameter
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CN115138836A (en
Inventor
张静
王昱
刘静
羿昌波
刘高建
李来平
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Western Baode Technologies Co ltd
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Western Baode Technologies Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/052Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08Selective adsorption, e.g. chromatography
    • B01D15/10Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/22Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06Metallic powder characterised by the shape of the particles
    • B22F1/065Spherical particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1103Making porous workpieces or articles with particular physical characteristics
    • B22F3/1109Inhomogenous pore distribution
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Abstract

The invention provides a high performance liquid chromatography column sieve plate and a preparation method thereof, and relates to the technical field of chromatographic equipment application; the preparation method comprises the following steps: placing the spherical metal powder into a mould, and vibrating for 5-30 min at a vibrating table with the vibration frequency of 40-160 Hz and the amplitude of 0.2-3 mm to obtain the spherical metal powder which is arranged in a gradient manner from the thick to the thin along the axial direction from bottom to top; and (3) placing a die provided with spherical metal powder in gradient arrangement in a sintering furnace, and sintering at high temperature to obtain the sieve plate. The sieve plate is not easy to be blocked, the service pressure of the chromatographic column can be reduced by the sieve plate, the service life of equipment is prolonged, and the testing speed is accelerated.

Description

High performance liquid chromatographic column sieve plate and preparation method thereof
Technical Field
The invention relates to the technical field of chromatographic equipment application, in particular to a high performance liquid chromatographic column sieve plate and a preparation method thereof.
Background
The high performance liquid chromatography is an important analysis and separation technology, and the method has the advantages of high analysis speed, good repeatability, high quantitative accuracy and wide application range, and plays an important role in the fields of chemistry, molecular biology, medicine, agriculture, environmental protection and the like.
The chromatographic column plays an important role in a chromatographic system, a sieve plate is an essential accessory of the chromatographic column, and the aperture and flux of the sieve plate are closely related to the working pressure and the service life of the chromatographic column. The common metal powder sintering sieve plate has irregular pore morphology, uneven pore distribution and wide pore size distribution, is easy to block in the use process to cause column pressure rise, and is easy to remain impurities to influence the detection accuracy.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a high-performance liquid chromatographic column sieve plate.
In order to achieve the above object, the present invention provides the following technical solutions:
a high performance liquid chromatography column sieve plate is prepared from spherical metal powder.
Preferably, the spherical metal powder has a particle size gradient, with a particle size range of 2-50 microns.
Preferably, the spherical metal powder is made of any one of stainless steel, titanium, nickel, hastelloy or monel.
The invention further aims at providing a preparation method of the high performance liquid chromatography column sieve plate, which comprises the following steps:
placing the spherical metal powder into a mould, and vibrating for 5-30 min at a vibrating table with the vibration frequency of 40-160 Hz and the amplitude of 0.2-3 mm to obtain the spherical metal powder which is arranged in a gradient manner from the thick to the thin along the axial direction from bottom to top;
and (3) placing a die provided with spherical metal powder in gradient arrangement in a sintering furnace, and sintering at a high temperature of 700-1250 ℃ to obtain the sieve plate.
Preferably, the apertures of the holes in the sieve plate are spherical or spheroid, and the aperture sizes are arranged in a gradient from top to bottom (here, the sizes of the holes are gradient from top to bottom), and the bottom aperture of the sieve plate is larger than the top aperture; when in use, the top of the sieve plate faces to the packing end of the chromatographic column, and the bottom faces to the outer end of the chromatographic column.
Preferably, the average pore diameter of the sieve plate is 0.2-5 μm, the maximum pore diameter is 2-10 μm, and the air permeability is 5-50 m 3 /(h·m 2 ·kPa)。
Preferably, the bottom powder particle size of the sieve plate is 10-50 μm, and the top powder particle size is 2-20 μm.
Preferably, the mold is any one of alumina, zirconia, molybdenum or graphite.
The high performance liquid chromatography column sieve plate and the preparation method thereof have the following beneficial effects:
the invention obtains spherical metal powder which is arranged in a gradient way from the bottom to the top along the axial direction by placing the spherical metal powder in a mould for vibration, and then placing the mould filled with the spherical metal powder which is arranged in a gradient way in a sintering furnace for high-temperature sintering to obtain a sieve plate; the sieve plate is not easy to be blocked, the service pressure of the chromatographic column can be reduced by the sieve plate, the service life of equipment is prolonged, and the testing speed is accelerated.
Drawings
In order to more clearly illustrate the embodiments of the present invention and the design thereof, the drawings required for the embodiments will be briefly described below. The drawings in the following description are only some of the embodiments of the present invention and other drawings may be made by those skilled in the art without the exercise of inventive faculty.
Fig. 1 is a side view of a high performance liquid chromatography column screen plate according to embodiment 1 of the invention.
Reference numerals illustrate:
the top of the 1-screen plate, the bottom of the 2-screen plate, and the holes in the 3-screen plate.
Detailed Description
The present invention will be described in detail below with reference to the drawings and the embodiments, so that those skilled in the art can better understand the technical scheme of the present invention and can implement the same. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
The invention provides a high performance liquid chromatography column sieve plate which is prepared from spherical metal powder.
Further, the spherical metal powder in this example has a particle size gradient in the range of 2 to 50 microns.
Further, the spherical metal powder in the present embodiment is made of any one of stainless steel, titanium, nickel, hastelloy or monel.
The invention further aims at providing a preparation method of the high performance liquid chromatography column sieve plate, which comprises the following steps:
step 1, placing spherical metal powder into a die, and vibrating for 5-30 min at a vibrating table with the vibration frequency of 40-160 Hz and the amplitude of 0.2-3 mm to obtain spherical metal powder which is arranged in a gradient manner from the bottom to the top along the axial direction; in this embodiment, the spherical metal powder may be any one of stainless steel, titanium, nickel, hastelloy or monel; the mold in this embodiment is any one of alumina, zirconia, molybdenum, or graphite.
And step 2, placing a die provided with spherical metal powder in gradient arrangement in a sintering furnace, and sintering at high temperature to obtain a sieve plate.
Specifically, as shown in fig. 1, the pore morphology of the pores 3 in the sieve plate is spherical or spheroidic, the pores 3 are arranged in a gradient manner along the axial direction, and the pore diameter of the bottom 2 of the sieve plate is larger than that of the top 1; when in use, the top 1 of the sieve plate faces to the packing end of the chromatographic column, and the bottom faces to the outer end of the chromatographic column.
The average pore diameter of the sieve plate is 0.2-5 mu m, the maximum pore diameter is 2-10 mu m, and the air permeability is 5-50 m by adopting a bubble pressure method test 3 /(h·m 2 ·kPa)。
Further, in this example, the bottom powder particle size of the screen plate is 10 to 50 μm, the top powder particle size is 2 to 20 μm, and the diameter of the screen plate is 2 to 5mm. The diameter of the sieve plate prepared in the embodiment is 2.1mm, 3mm, 4.6mm and 4.9mm; the height is 1mm and 1.5mm; matching with the standard size of common chromatographic column.
Example 1
This example provides a sieve plate suitable for a 2 μm packed chromatography column prepared from stainless steel 316L spherical powder having a particle size gradient in the range of 5-20 μm.
The embodiment also provides a preparation method of the high performance liquid chromatography column sieve plate, which comprises the following specific steps:
step 1, placing 316L stainless steel spherical powder with granularity of 5-20 mu m into a mould, wherein the mould is made of alumina.
And 2, vibrating the die filled with the 316L stainless steel spherical powder on a vibrating table for 20min, wherein the vibration frequency is 70Hz, the amplitude is 1.0 mm, and the 316L stainless steel spherical powder which is arranged in a gradient manner from the thick to the thin along the axial direction is obtained.
The 316L stainless steel spherical powder which is arranged in a gradient way from the thick to the thin along the axial direction is the bottom powder with a thicker particle size of 10-20 mu m, and the top particle with a thinner particle size of 5-10 mu m.
And 3, placing a die provided with 316L stainless steel spherical powder which is arranged in a gradient manner along the axial direction in an atmosphere sintering furnace, and sintering for 2 hours at 1050 ℃ in a hydrogen atmosphere, wherein the heating system is 5 ℃/min, so that a sieve plate suitable for a 2 mu m packing chromatographic column can be obtained.
The sieve plate for 2 μm packed chromatographic column provided in this example has spherical pore diameter, gradient arrangement along the axial direction, larger bottom pore diameter, smaller top pore diameter, average pore diameter of 2.58 μm, maximum pore diameter of 3.58 μm, and air permeability of 20.36m under 200kPa pressure 3 /(h·m 2 ·kPa)。
The diameter of the sieve plate is 4.9mm, and the thickness is 1mm; is suitable for common chromatographic columns with the diameter of 4.9 mm.
When the sieve plate is used, the top with smaller pore diameter of the sieve plate faces the packing end of the chromatographic column, and the bottom with larger pore diameter faces the outer end of the chromatographic column, so that the 2 mu m packing can be prevented from leakage by using the sieve plate.
Example 2
The present example also provides another screen suitable for a 2 μm packing chromatography column prepared from stainless steel 316L spherical powder having a particle size gradient in the range of 5-10 μm.
The embodiment also provides a preparation method of the high performance liquid chromatography column sieve plate, which comprises the following specific steps:
step 1, placing 316L stainless steel spherical powder with granularity of 5-10 mu m into a mould, wherein the mould is made of alumina.
And 2, placing the die filled with 316L stainless steel spherical powder in an atmosphere sintering furnace, and sintering for 2 hours at 1000 ℃ in a hydrogen atmosphere, wherein the temperature rise degree is 5 ℃/min, so that the sieve plate suitable for the 2 mu m filler chromatographic column can be obtained.
The sieve plate aperture suitable for the 2 mu m packing chromatographic column is spherical, the average aperture is 1.50 mu m, the maximum aperture is 3.01 mu m, and the air permeability under 340kPa pressure is 10.78m by adopting a bubble pressure method 3 /(h·m 2 ·kPa)。
The diameter of the sieve plate is 4.9mm, and the thickness is 1mm; is suitable for common chromatographic columns with the diameter of 4.9 mm.
When in use, the sieve plate has no positive and negative differences, two sides can be randomly installed, and the use of the sieve plate can ensure that the filler with the size of 2 mu m is not leaked.
In this example, no vibration step was performed, the pore size in the screen plate was uniform, the overall pore size was close to that of the top of example 1 in order to achieve the blocking effect, and since the overall pore size was small, the air permeability was smaller than that of example 1, the flow rate was smaller in use, and the analysis efficiency was lower than that of the screen plate of example 1.
Example 3
The embodiment also provides a sieve plate suitable for a 2 μm packing chromatographic column, wherein the chromatographic column sieve plate is prepared from stainless steel 316L non-spherical powder, and the granularity of the stainless steel 316L non-spherical powder ranges from 5 μm to 15 μm.
The embodiment also provides a preparation method of the high performance liquid chromatography column sieve plate, which comprises the following specific steps:
step 1, placing 316L stainless steel non-spherical powder with granularity of 5-15 mu m into a mould, wherein the mould is made of alumina.
And 2, placing the die filled with 316L stainless steel spherical powder in an atmosphere sintering furnace, and sintering for 2 hours at 1000 ℃ in a hydrogen atmosphere, wherein the temperature rise degree is 5 ℃/min, so that the sieve plate suitable for the 2 mu m filler chromatographic column can be obtained.
The sieve plate aperture suitable for the 2 mu m filler chromatographic column is irregular, the average aperture is 0.24 mu m, the maximum aperture is 3.85 mu m, and the air permeability under 200kPa pressure is 4.75m by adopting a bubble pressure method 3 /(h·m 2 ·kPa)。
The diameter of the sieve plate is 4.9mm, and the thickness is 1mm; is suitable for common chromatographic columns with the diameter of 4.9 mm.
When in use, the sieve plate has no positive and negative differences, two sides can be randomly installed, and the use of the sieve plate can ensure that the filler with the size of 2 mu m is not leaked.
The example uses non-spherical powder, the pore diameter inside the prepared sieve plate is irregular, the average pore diameter is smaller, the air permeability is smaller than that of the example 1 and the example 2, the flow rate of the mobile phase is lower in use, meanwhile, irregular pores are easier to block, the irregular pores are difficult to recoil, and the column pressure is easy to rise and the analyte is easy to pollute.
The high performance liquid chromatography column sieve plate prepared by the invention is applied to a chromatography system for chromatographic analysis and separation, has high analysis speed, good repeatability, high quantitative precision and wide application range, and plays an important role in the fields of chemistry, molecular biology, medicine, agriculture, environmental protection and the like.
The above embodiments are merely preferred embodiments of the present invention, the protection scope of the present invention is not limited thereto, and any simple changes or equivalent substitutions of technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention disclosed in the present invention belong to the protection scope of the present invention.

Claims (5)

1. The high performance liquid chromatography column sieve plate is characterized by being prepared by high-temperature sintering of spherical metal powder;
the spherical metal powder has a particle size gradient, and the particle size range is 2-50 microns;
the spherical metal powder is made of any one of stainless steel, titanium, nickel, hastelloy or monel;
the sieve plate comprises a plurality of holes, the holes in the sieve plate are spherical or quasi-spherical in pore diameter, and the pore diameter sizes are arranged in a gradient manner from top to bottom, wherein the pore sizes are gradient from top to bottom, and the bottom pore diameter of the sieve plate is larger than the top pore diameter; when in use, the top of the sieve plate faces to the filling end of the chromatographic column, and the bottom of the sieve plate faces to the outer end of the chromatographic column;
the sieve plate is obtained by vibrating spherical metal powder with the granularity range of 2-50 microns to obtain spherical metal powder which is arranged in a gradient way from the thick to the thin along the axial direction, and then sintering the spherical metal powder which is arranged in a gradient way from the thick to the thin.
2. The preparation method of the high performance liquid chromatography column sieve plate is characterized by comprising the following steps of:
placing the spherical metal powder into a die, and vibrating for 5-30 min in a vibrating table, wherein the vibration frequency is 40-160 Hz, and the amplitude is 0.2-3 mm, so as to obtain the spherical metal powder which is arranged in a gradient manner from the thick to the thin along the axial direction from bottom to top;
placing a die provided with spherical metal powder in gradient arrangement in a sintering furnace, and sintering at a high temperature of 700-1250 ℃ to obtain the sieve plate;
the spherical metal powder has a particle size gradient, and the particle size range is 2-50 microns;
the spherical metal powder is made of any one of stainless steel, titanium, nickel, hastelloy or monel;
the sieve plate comprises a plurality of holes, the holes in the sieve plate are spherical or quasi-spherical in pore diameter, and the pore diameter sizes are arranged in a gradient manner from top to bottom, wherein the pore sizes are gradient from top to bottom, and the bottom pore diameter of the sieve plate is larger than the top pore diameter; when in use, the top of the sieve plate faces to the packing end of the chromatographic column, and the bottom faces to the outer end of the chromatographic column.
3. The method for preparing a high performance liquid chromatography column sieve plate according to claim 2, wherein the average pore diameter of the sieve plate is 0.2-5 μm, the maximum pore diameter is 2-10 μm, and the air permeability is 5-50 m 3 /(h·m 2 ·kPa)。
4. The method for preparing a high performance liquid chromatography column sieve plate according to claim 3, wherein the particle size of the bottom powder of the sieve plate is 10-50 μm, and the particle size of the top powder is 2-20 μm.
5. The method for preparing a high performance liquid chromatography column sieve plate according to claim 2, wherein the mold is any one of alumina, zirconia, molybdenum or graphite.
CN202210791845.1A 2022-07-06 2022-07-06 High performance liquid chromatographic column sieve plate and preparation method thereof Active CN115138836B (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2608033A1 (en) * 2001-02-16 2002-08-22 Sumitomo Titanium Corporation Titanium powder sintered compact
JP2003129111A (en) * 2001-10-18 2003-05-08 Sanalloy Industry Co Ltd Porous sintered compact
DE102009001756A1 (en) * 2009-03-23 2009-07-30 Agilent Technologies Inc., Santa Clara Filter screen e.g. dirt filter, for sample separation device e.g. high-performance liquid chromatography system, has filter arranged at inlet and/or outlet of separating column and impermeable for particles with size above threshold value
CN102794053A (en) * 2012-08-21 2012-11-28 韶关市贝瑞过滤科技有限公司 Powder-sintered filter core with gradient multilayer composite structure and production method thereof
CN212111286U (en) * 2020-04-26 2020-12-08 江苏同济分析仪器有限公司 High-pressure liquid chromatographic column sieve plate
CN113145850A (en) * 2021-03-13 2021-07-23 山东省科学院新材料研究所 High-flux preparation method of metal material with gradient structure
CN113275569A (en) * 2021-04-22 2021-08-20 大连理工大学 Composite micro-cavity gradient porous surface for liquid film boiling and preparation method thereof
CN113295811A (en) * 2021-05-20 2021-08-24 西部宝德科技股份有限公司 Chromatographic column sieve plate and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2608033A1 (en) * 2001-02-16 2002-08-22 Sumitomo Titanium Corporation Titanium powder sintered compact
CN1531470A (en) * 2001-02-16 2004-09-22 ס�����������ʽ���� Titanium powder sintered compact
JP2003129111A (en) * 2001-10-18 2003-05-08 Sanalloy Industry Co Ltd Porous sintered compact
DE102009001756A1 (en) * 2009-03-23 2009-07-30 Agilent Technologies Inc., Santa Clara Filter screen e.g. dirt filter, for sample separation device e.g. high-performance liquid chromatography system, has filter arranged at inlet and/or outlet of separating column and impermeable for particles with size above threshold value
CN102794053A (en) * 2012-08-21 2012-11-28 韶关市贝瑞过滤科技有限公司 Powder-sintered filter core with gradient multilayer composite structure and production method thereof
CN212111286U (en) * 2020-04-26 2020-12-08 江苏同济分析仪器有限公司 High-pressure liquid chromatographic column sieve plate
CN113145850A (en) * 2021-03-13 2021-07-23 山东省科学院新材料研究所 High-flux preparation method of metal material with gradient structure
CN113275569A (en) * 2021-04-22 2021-08-20 大连理工大学 Composite micro-cavity gradient porous surface for liquid film boiling and preparation method thereof
CN113295811A (en) * 2021-05-20 2021-08-24 西部宝德科技股份有限公司 Chromatographic column sieve plate and preparation method thereof

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