CN109444276B - Gas chromatography packed column and preparation method and application thereof - Google Patents
Gas chromatography packed column and preparation method and application thereof Download PDFInfo
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- CN109444276B CN109444276B CN201811222353.0A CN201811222353A CN109444276B CN 109444276 B CN109444276 B CN 109444276B CN 201811222353 A CN201811222353 A CN 201811222353A CN 109444276 B CN109444276 B CN 109444276B
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- G01N30/02—Column chromatography
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention provides a gas chromatography packed column and a preparation method and application thereof, wherein the gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, the packed column stationary phase comprises packed column filler, and the raw material of the packed column filler comprises attapulgite; the preparation method of the packed column filler comprises the steps of crushing attapulgite, and sieving to obtain attapulgite powder with the particle mesh number not less than 200 meshes; adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃; and (3) screening and separating the attapulgite pellets to obtain the uniform packed column packing with the particle mesh number of 40-140 meshes. The invention provides a novel gas chromatography packed column, which expands the types of the gas chromatography packed column; the gas chromatography packed column provided by the invention is applied to analysis of the dissolved gas of the transformer oil, and can realize sensitive, rapid and accurate detection of the dissolved gas of the transformer oil by utilizing the chromatography packed column.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a gas chromatography packed column and a preparation method thereof, and application of the gas chromatography packed column in analysis of dissolved gas in transformer oil.
Background
The chromatography is a separation and analysis method, and is widely applied to detection and analysis in multiple fields of petroleum, chemistry, environment, biology, food and the like. The chromatographic column in the chromatography is directly related to the separation effect and the detection sensitivity, and the preparation of the chromatographic column is an important link for chromatographic analysis. Packing is an important feature of a chromatography column, which determines the basic features of the column, and whether chromatographic peaks can be separated depends on the packing in the first place. The packed column is one of the commonly used chromatographic columns, at present, hundreds of chromatographic packed column packing materials are available, the number of the commonly used chromatographic packed column packing materials is less than ten, and the types of the commonly used packing materials are less. The gas chromatography is one of chromatographs, the types of common gas chromatography packing columns are few, the adsorbent packing in the existing gas chromatography packing column stationary phase packing generally comprises activated carbon, silica gel, molecular sieves, alumina, polymer porous beads and the like, and different packing characteristics are different and are suitable for different component analysis; the filler is a chemically inert porous solid particle which can provide a larger inert surface to ensure that the fixing liquid is uniformly distributed on the surface in a liquid film state, and at present, the filler is commonly passivated diatomite, glass microspheres, polytetrafluoroethylene, high-molecular porous beads and the like.
The attapulgite is a natural mineral which mainly contains water and magnesium-rich silicate, and has a theoretical chemical formula as follows: mg (magnesium)5Si8O20(OH)2(OH2)4.4H2O, chemically inert. The attapulgite has a large specific surface area due to the existence of zeolite channels in the crystal structure of the attapulgite, and single crystals are closely combined to form secondary pores with uneven sizes after drying, so that the specific surface area on the attapulgite is high, and the zeolite channels in the crystals have good adsorption capacity due to the large specific surface area, large surface area, surface physicochemical characteristics and ionic state. The attapulgite adsorption comprises physical adsorption, namely adsorbing adsorbate molecules on the inner and outer surfaces of the attapulgite through Van der Waals force; chemisorption, i.e. based on the presence of adsorption centers on the surface of the attapulgite andadsorbate molecules form chemical bonds, and the adsorption centers comprise Si-OH groups, have strong affinity to organic substances and can adsorb cations and positive polar organic molecules; the rich Si-OH groups on the surface of the attapulgite can react with an organic reactant to form a stable state, so that the attapulgite becomes an ideal catalyst carrier. The adsorption property of attapulgite has enabled the use of attapulgite in a variety of fields, but the use of attapulgite in chromatographic packed columns has not been found.
Transformer oil is the insulating major constituent of oil-filled power equipment, is a fractionation product of petroleum, under normal operating conditions, because oil and solid insulation can age gradually, deteriorate, can decompose out minute quantity of gas, when power equipment is inside to take place overheated nature trouble, discharge nature trouble or when the condition of weing, the output of these gases can increase rapidly. Therefore, the regular measurement of the composition and content of the gas tissue dissolved in the oil during the operation of the equipment is very important for early detection of latent faults inside the oil-filled power equipment. The chromatographic detection of the dissolved gas of the transformer oil requires that more than 7 gases such as hydrogen, methane, ethane, ethylene, acetylene, carbon monoxide, carbon dioxide and the like in the oil are separated, so that the separation time is required to be short. However, the existing gas chromatographic column for analyzing the dissolved gas of the transformer oil generally consists of two chromatographic columns, and adopts a double-column parallel split flow process or a twice sample introduction process; the double-column parallel flow-splitting process greatly reduces the detection sensitivity because the sample is split after entering the instrument and can not enter the detector completely; the two-time sample feeding process is complicated to operate, and the sample analysis time is too long; however, the single chromatographic column analysis prepared by adopting the existing stationary phase filler generally cannot separate various gases clearly, thereby influencing the accuracy.
Disclosure of Invention
The invention aims to solve the problems that the conventional gas chromatography packing column has fewer common types of stationary phase fillers and fewer corresponding common gas chromatography packing columns, and considers that the chromatographic packing column has the advantages of high temperature use, large adsorption capacity and good thermal stability when the chromatographic packing column is required to be used for adsorbent stationary phase fillers; the inventor finds that the attapulgite has chemical inertness, larger specific surface area, good adsorbability and the function of a molecular sieve after being treated, and the characteristics make the attapulgite suitable for the adsorbent packing of a chromatographic packed column; the attapulgite has the characteristic of being used as a catalyst carrier, and can be used as a carrier for a gas chromatography packed column after surface treatment; based on the discovery, the invention provides a novel gas chromatography packed column and a preparation method thereof, wherein a stationary phase comprises packed column filler prepared by taking attapulgite as a raw material.
The invention provides a gas chromatography packed column.
The invention also provides a preparation method of the gas chromatography packed column.
The invention also provides application of the gas chromatography packed column in analysis of dissolved gas in transformer oil.
The gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column filler, and raw materials of the packed column filler comprise attapulgite; the packed column packing is prepared by a method comprising the following steps:
crushing and sieving the attapulgite to obtain attapulgite powder with the particle mesh number not less than 200 meshes;
b, adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃;
and C, sieving and separating the attapulgite pellets to obtain the uniform packed column packing with 40-140 meshes of particle mesh.
Further, the binder comprises poly (diethylaminoethyl methacrylate) acetate with the mass of 0.1-1% of the attapulgite.
Further, the packed column packing is also subjected to surface treatment.
Further, the surface treatment includes one of silanization, acid washing, and alkali washing.
Furthermore, the fixed phase of the packed column also comprises a stationary liquid, and the stationary liquid is coated on the surface of the packing of the packed column.
Further, the filler of the packed column is activated for 1-3 hours at 250-350 ℃.
The invention also provides a preparation method of the gas chromatography packed column, the gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, and the packed column stationary phase comprises packed column filler; the packed column packing is prepared by a method comprising the following steps: pulverizing attapulgite, and sieving to obtain attapulgite powder with particle mesh number not less than 200 meshes; adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃; screening and separating the attapulgite pellets to obtain the uniform packed column packing with 40-140 meshes of particle mesh;
further, the preparation method of the gas chromatography packed column comprises the following steps: cleaning and drying the packed column pipe; plugging a plug into one end of the packed column tube, tapping the packed column tube, and adding the packed column stationary phase; after the column tube is filled with the stationary phase, the other end of the column tube is plugged with a plug, and the gas chromatography packed column is obtained after aging treatment.
The invention also provides an application of the gas chromatography packed column in analysis of the dissolved gas in the transformer oil, wherein the gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube; the packed column stationary phase comprises packed column packing; the raw material of the packed column packing comprises attapulgite; the packed column packing is prepared by a method comprising the following steps: crushing attapulgite, and sieving to obtain attapulgite powder with particle mesh number not less than 200 meshes; adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃; and (3) sieving and separating the attapulgite pellets to obtain the uniform packed column filler with the particle mesh number of 40-140 meshes.
Further, the filler of the packed column is activated for 1-3 hours at 250-350 ℃.
Further, the analysis and detection conditions are as follows: a flame ionization detector is adopted, the temperature of a column box is 75-85 ℃, the temperature of a vaporization chamber is 95-110 ℃, the temperature of a detection chamber is 110-130 ℃, carrier gas is nitrogen, and the flow rate of the carrier gas is 30-35 mL/min.
Advantageous effects of the invention
The invention provides a gas chromatography packed column and a preparation method thereof, wherein the gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, the packed column stationary phase comprises packed column filler, and the raw material of the packed column filler comprises attapulgite. The attapulgite is a natural non-metallic ore and has good adsorption property; can be used as adsorbent packing in a gas chromatography packed column and can also be used as carrier coating stationary liquid; the invention adopts the filling column filler prepared by taking the attapulgite as the raw material to prepare the gas chromatography filling column, provides a novel gas chromatography filling column, and expands the category of the gas chromatography filling column; the method is applied to gas chromatography and is suitable for analyzing and separating mixed gas.
In the gas chromatography packed column provided by the invention, the packing of the packed column is prepared by the method comprising the following steps: crushing and sieving the attapulgite to obtain attapulgite powder with the particle mesh number not less than 200 meshes; b, adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃; and C, sieving the attapulgite pellets to obtain the uniform packed column packing with the particle mesh number of 40-140 meshes. The granularity of the gas chromatography packed column filler influences the column efficiency and the back pressure of the packed column, and generally, the smaller the granularity is, the higher the column efficiency of the gas chromatography packed column is; however, the smaller the particle size, the greater the column pressure; the attapulgite powder has insufficient uniformity, the granularity is not suitable for most of packed columns, and therefore granulation is required to be carried out to prepare uniform packed column filler with a certain size, and the packed column filler is dried at high temperature to be free of moisture and is suitable for gas chromatography packed columns.
The invention also provides an application of the gas chromatography packed column in analysis of the dissolved gas in the transformer oil, wherein the gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, and the packed column stationary phase comprises a packed column filler; the raw material of the packed column packing comprises attapulgite; the packed column packing is prepared by a method comprising the following steps: pulverizing attapulgite, and sieving to obtain granules with mesh numberAttapulgite powder of not less than 200 meshes; adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃; and (3) sieving and separating the attapulgite pellets to obtain the uniform packed column filler with the particle mesh number of 40-140 meshes. In the analysis of the dissolved gas of the transformer oil, the separated gas has more types, wherein the gas can not be clearly separated by adopting a single chromatographic column, and particularly CO and H are difficult to be separated2Two gases are accurately separated and clear analysis peaks are obtained, so that two columns are generally adopted in the prior art; the gas chromatography packed column provided by the invention can realize the clear separation of CO and H by a single packed column2The method can realize the sensitive, rapid and accurate detection of the dissolved gas of the transformer oil by utilizing a chromatographic packed column.
Additional features and corresponding advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an analysis spectrum obtained by analyzing a transformer oil dissolved gas with a gas chromatography packed column provided in example 12 of the present invention;
FIG. 2 is an analysis spectrum obtained by analyzing a transformer oil dissolved gas with a gas chromatography packed column provided in example 13 of the present invention;
FIG. 3 is an analysis spectrum obtained by analyzing a transformer oil dissolved gas with a gas chromatography packed column provided in example 14 of the present invention;
FIG. 4 is an analysis spectrum obtained by analyzing a transformer oil dissolved gas by a comparative example gas chromatography packed column.
Detailed Description
The present invention is described in further detail with reference to the following embodiments, which are not intended to limit the invention, and those skilled in the art can make various modifications and improvements based on the basic idea of the invention, but within the scope of the invention, unless departing from the basic idea of the invention.
In the description of the present invention, unless otherwise specified, terms in the present specification have the same meaning as those generally understood by those skilled in the art, but if different, the definitions in the present specification shall control; unless otherwise specified, the test methods are all conventional methods; unless otherwise specified, the raw materials and test materials used in the present specification are all available commercially in a conventional manner; unless otherwise specified, the percentages (%) in this specification are mass percentages (% by mass).
The invention provides a gas chromatography packed column, which comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column filler, and the raw material of the packed column filler comprises attapulgite; the packed column packing is prepared by a method comprising the following steps:
crushing and sieving the attapulgite to obtain attapulgite powder with the particle mesh number not less than 200 meshes;
b, adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃;
and C, sieving and separating the attapulgite pellets to obtain the uniform packed column packing with 40-140 meshes of particle mesh.
The packed column tube is a packed column tube which can be generally used for gas chromatographic analysis, and has the inner diameter of 2-10 mm and the column length of 0.5-10 m; the column tube is made of stainless steel tube, copper tube, aluminum tube, copper nickel-plated tube, glass tube, polytetrafluoroethylene tube, etc.; the attapulgite in the invention refers to the attapulgite with the purity of more than 85 percent after the natural attapulgite clay is purified; the binder is organic or inorganic binder capable of binding attapulgite powder, such as organic polymer with viscosity, cellulose, starch organic binder, silicate, and phosphate inorganic binder; the attapulgite pellets are sieved to obtain filler particles of the packed column within a proper range, so that the packed column is convenient to pack, the mesh number of the filler particles of the common packed column is controlled to be 40-140 meshes, the filler particles of the packed column are uniform, and the mesh number of the filler particles required by one-time column packing is generally 40-60, 60-80, 80-100, 100-120 or 120-140.
The attapulgite is a natural non-metallic ore and has good adsorption property; can be used as adsorbent stationary phase in a gas-liquid chromatography packed column, and can also be used for gas-liquid chromatography as carrier coating stationary liquid; the invention provides a novel gas chromatography packed column, and the types of packing of the gas chromatography packed column are expanded. The granularity of the gas chromatography packed column filler influences the column efficiency and the back pressure of the packed column, and generally, the smaller the granularity is, the higher the column efficiency of the gas chromatography packed column is; however, the smaller the particle size, the greater the column pressure; the attapulgite powder has insufficient uniformity, the granularity is not suitable for most of packed columns, and therefore granulation is required to be carried out to prepare uniform packed column filler with a certain size, and the packed column filler is dried at high temperature to be free of moisture and is suitable for gas chromatography packed columns.
Further, the binder comprises poly (diethylaminoethyl methacrylate) acetate with the mass of 0.1-1% of the attapulgite. The diethylaminoethyl methacrylate acetate is prepared by polymerizing diethylaminoethyl methacrylate as a monomer to form the diethylaminoethyl methacrylate acetate; diethylaminoethyl methacrylate contains a reactive amino group and a polymerizable vinyl group, and can increase the adhesiveness, thermosetting property, and the like of a polymer using the diethylaminoethyl methacrylate as a monomer; the method uses poly (diethylaminoethyl methacrylate) acetate as a binder, uniformly bonds the attapulgite together by means of the electrostatic action of the binder, and decomposes the binder into CO through a heating process2、NH2And H2O is removed, so that the property of the attapulgite is not influenced, and the mechanical strength of the filling column filler is enhanced.
Further, the packed column packing is also subjected to surface treatment. Specifically, the surface treatment aims to improve the void structure of the packing column filler, shield the active center of the surface, and any method of removing the active action point by chemical reaction or achieving the surface property purification of the carrier by physical covering can be used. The surface of the gas chromatography packed column is chemically inert to the carrier, but the surface of the attapulgite has rich adsorption centers and can cause the tailing of chromatographic peaks and the reduction of column efficiency when being directly used as the carrier, so that the surface passivation treatment on the packing of the packed column before use is beneficial to the separation and analysis of detected components.
Further, the surface treatment includes one of silanization, acid washing, and alkali washing. Silanization is to react with silanol and silyl ether groups on the surface of the filler of the packed column by using a silanization reagent to remove the hydrogen bonding capacity on the surface of the filler of the packed column, wherein the silanization reagent can be a trimethyl silanization reagent, and specifically can be trimethyl chlorosilane, hexamethyl-disilane, dimethyl-disilane and the like; the pickling is to adopt concentrated inorganic acid, preferably concentrated hydrochloric acid to heat for a period of time, preferably 20-30 min, filter, wash with water to neutrality, drip wash with methanol, dehydrate and dry, the pickling can remove inorganic salt and metal oxide on the surface of the packing of the packed column; the alkaline washing is to soak or reflux the filler in concentrated NaOH or KOH methanol solution, wash the filler to neutrality with water, rinse the filler with methanol, dry the filler with methanol, and remove the acidic carriers on the surface of the filler of the packed column.
Furthermore, the fixed phase of the packed column also comprises a stationary liquid, and the stationary liquid is coated on the surface of the packing of the packed column. Specifically, the fixing solution is dissolved in a suitable solvent such as organic solvents of acetone, ether, chloroform, toluene, etc., and then poured into a packed column filler to be mixed uniformly, and at a suitable temperature, the solvent is evaporated off to obtain the fixing solution, wherein the amount of the solvent is such that the fixing solution is dissolved and the carrier is completely soaked in the solution. The filler of the packed column can be used as a carrier of a liquid stationary phase in a gas-liquid chromatographic packed column, and a stationary liquid is coated on the surface of the filler, wherein the stationary liquid can be a common stationary liquid such as hydrocarbons, polysiloxanes, polyglycols, polyalkyl oxides, lipids and the like. The mass ratio of the fixing liquid to the filler of the packed column as the carrier is 5-30%, preferably 15-25%.
Further, the filler of the packed column is activated for 1-3 hours at 250-350 ℃. Specifically, the purpose of the activation treatment is to improve the adsorption capacity of the packing of the packed column, and the activation treatment can be carried out under normal pressure or reduced pressure; because the packing of the packed column has large adsorption capacity and is easy to permanently adsorb certain components, the packed column is activated before being used as the adsorbent packing of the packed column, which is beneficial to column efficiency and enables the analysis and separation peak shapes to be symmetrical, and the activity of the adsorbent has a certain relation with the water content and needs to be removed to enhance the activity.
The invention also provides a preparation method of the gas chromatography packed column, the gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, and the packed column stationary phase comprises packed column filler; the packed column packing is prepared by a method comprising the following steps: crushing attapulgite, and sieving to obtain attapulgite powder with particle mesh number not less than 200 meshes; adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃; screening and separating the attapulgite pellets to obtain the uniform packed column packing with 40-140 meshes of particle mesh; further, the preparation method of the gas chromatography packed column comprises the following steps: cleaning and drying the packed column pipe; plugging a plug into one end of the packed column tube, tapping the packed column tube, and adding the packed column stationary phase; after the column tube is filled with the stationary phase, the other end of the column tube is plugged with a plug, and the gas chromatography packed column is obtained after aging treatment.
Specifically, a packed column tube is selected, cleaned, dried and dried; plugging a plug such as a sieve plate, glass wool, quartz wool and the like into one end of the column tube to prevent the filler from leaking out, and adding the stationary phase containing the filler of the filling column provided by the invention into the column tube while tapping the column tube to ensure that the stationary phase is uniformly and tightly filled; or under the condition of pressurization, namely the outlet at the other end of the filling pool for placing the stationary phase is connected with a pressure reducing valve of a nitrogen or air steel cylinder, the inner diameter of the column tube is different, the air flow velocity is different, and meanwhile, the stationary phase containing the filling column filler provided by the invention is pressed into the column tube while the column tube is tapped; or under the condition of vacuum pumping, namely, the outlet at one end of the column tube plugged with the plug is connected with a buffer safety bottle of a vacuum pump, and under the condition of vacuum pumping (-0.4-0.7 MPa), the stationary phase containing the filling column filler provided by the invention is pressed into the column tube while the column tube is tapped; filling the column tube with the stationary phase until the column tube is filled with the stationary phase, and then plugging the column tube with a plug to obtain a packed column filled with the packing of the packed column; and (3) installing the packed column on a chromatograph for aging treatment, namely introducing carrier gas at normal temperature or higher temperature, and washing residual solvent and volatile impurities in the stationary phase in the packed column to obtain the gas chromatography packed column.
The invention also provides application of the gas chromatography packed column in analysis of the dissolved gas in the transformer oil, wherein the gas chromatography packed column comprises a packed column tube and a filler filled in the packed column tubeThe packed column stationary phase comprises packed column packing; the raw material of the packed column packing comprises attapulgite; the packed column packing is prepared by a method comprising the following steps: crushing attapulgite, and sieving to obtain attapulgite powder with particle mesh number not less than 200 meshes; adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃; screening and separating the attapulgite pellets to obtain the uniform packed column packing with 40-140 meshes of particle mesh; specifically, the inner diameter range of a column tube of the gas chromatography packed column applied to analysis of dissolved gas in transformer oil is 2-5 mm; in the analysis of the dissolved gas of the transformer oil, the separated gas is more in types, wherein H2The retention time of the catalyst is close to that of CO, the gas can not be clearly separated by adopting a traditional single packed column, and H is particularly difficult to be separated2And CO, so that two gases are accurately separated and a clear analysis peak is obtained, and two columns are generally adopted in the prior art; the gas chromatography packed column provided by the invention can realize the clear separation of CO and H by a single packed column2The method can realize the sensitive, rapid and accurate detection of the dissolved gas of the transformer oil by utilizing a chromatographic packed column.
Further, the filler of the packed column is activated for 1-3 hours at 250-350 ℃. Specifically, the purpose of the activation treatment is to improve the adsorption capacity of the packed column packing, and the activation treatment may be performed under normal pressure or reduced pressure.
Further, the analysis and detection conditions are that a flame ionization detector is adopted, the temperature of a column box is as follows: 75-85 ℃, vaporization chamber temperature: 95-110 ℃; detection chamber temperature: 110-130 ℃; the carrier gas is nitrogen, and the flow rate of the carrier gas is as follows: 30-35 mL/min.
Hereinafter, the gas chromatography packed column provided by the present invention and its application in analysis of dissolved gas in transformer oil will be described in detail by way of examples and comparative examples.
Example 1
A gas chromatographic packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column filler,
(1) the filler of the packed column is prepared by attapulgite with the purity of more than 85 percent, and the preparation steps are as follows:
crushing and sieving the attapulgite to obtain attapulgite powder with the particle mesh number larger than 200 meshes;
b, adding poly (diethylaminoethyl methacrylate) acetate accounting for 0.5 percent of the mass of the attapulgite and a small amount of water into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 300 ℃;
c, after drying, sieving and separating the attapulgite clay pellets to obtain the uniform packed column filler with the particle mesh number of 40-60 meshes;
(2) the preparation method of the gas chromatography packed column comprises the following steps:
selecting a stainless steel packed column tube with the inner diameter of 8mm and the length of 8m, cleaning and drying;
while tapping the column tube, the stationary phase containing the packing provided by the embodiment is pressed into the column tube under the condition of vacuum-0.4 MPa;
filling the stationary phase into the column tube, and plugging the column tube with a plug glass wool to obtain a filled column filled with the filler of the filled column;
and (3) mounting the packed column on a chromatograph for aging treatment, introducing carrier gas at a higher temperature, and washing residual solvent and volatile impurities in the stationary phase in the packed column to obtain the gas chromatography packed column.
The binder poly (diethylaminoethyl methacrylate) acetate of this embodiment may be replaced by other organic or inorganic binders capable of binding attapulgite powder, such as viscous organic polymers, celluloses, and starches, specifically, polyacrylamide, carboxymethyl cellulose, carboxymethyl starch, and hydroxypropyl cellulose; organic binders such as silicates, phosphates, and the like.
Example 2
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
(1) the filler of the packed column is prepared by attapulgite with the purity of more than 85 percent, and the preparation steps are as follows:
crushing and sieving the attapulgite to obtain attapulgite powder with the particle mesh number larger than 200 meshes;
b, adding poly (diethylaminoethyl methacrylate) acetate accounting for 1% of the mass of the attapulgite into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 350 ℃;
c, after drying, sieving and separating the attapulgite clay pellets to obtain the uniform packed column filler with the particle mesh number of 60-80 meshes;
(2) the preparation method of the gas chromatography packed column comprises the following steps:
selecting a stainless steel packed column tube with the inner diameter of 4mm and the length of 6m, cleaning and drying;
connecting the outlet of the other end of the filler pool for placing the stationary phase with a pressure reducing valve of a nitrogen or air steel cylinder, adjusting the air flow rate to be 30mL/min, and simultaneously tapping the column tube under the pressurizing condition to press the stationary phase containing the filler of the packed column provided by the embodiment into the column tube;
filling the stationary phase into the column tube, and plugging the column tube with a plug glass wool to obtain a filled column filled with the filler of the filled column;
and (3) mounting the packed column on a chromatograph for aging treatment, introducing carrier gas at a higher temperature, and washing residual solvent and volatile impurities in the stationary phase in the packed column to obtain the gas chromatography packed column.
Example 3
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
(1) the filler of the packed column is prepared by attapulgite with the purity of more than 85 percent, and the preparation steps are as follows:
crushing and sieving attapulgite to obtain attapulgite powder with the particle mesh number larger than 250 meshes;
b, adding poly diethylaminoethyl methacrylate acetate accounting for 0.1 percent of the mass of the attapulgite into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250 ℃;
c, after drying, sieving and separating the attapulgite clay pellets to obtain the uniform packed column filler with the particle mesh number of 100-120 meshes;
2) the preparation method of the gas chromatography packed column comprises the following steps:
selecting a stainless steel packed column tube with the inner diameter of 5mm and the length of 10m, cleaning and drying;
plugging quartz wool into one end of the column tube, and tapping the column tube while pressing the stationary phase of the packed column filler into the column tube under the condition of vacuum-0.4 MPa;
filling the stationary phase into the column tube, and then plugging the column tube with a plug of vitreous silica to obtain a packed column filled with the packing of the packed column;
and (3) mounting the packed column on a chromatograph for aging treatment, introducing carrier gas at a higher temperature, and washing residual solvent and volatile impurities in the stationary phase in the packed column to obtain the gas chromatography packed column.
Example 4
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
(1) the filler of the packed column is prepared by attapulgite with the purity of more than 85 percent, and the preparation steps are as follows:
crushing attapulgite, and sieving to obtain attapulgite powder with particle mesh number larger than 300 mesh;
b, adding poly diethylaminoethyl methacrylate acetate accounting for 0.6 percent of the mass of the attapulgite into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250 ℃;
c, after drying, sieving and separating the attapulgite clay pellets to obtain the uniform packed column filler with the particle mesh number of 80-100 meshes;
2) the preparation method of the gas chromatography packed column comprises the following steps:
selecting a stainless steel packed column tube with the inner diameter of 3mm and the length of 8m, cleaning and drying;
one end of the column tube is plugged into a plug sieve plate, and the stationary phase containing the filling column filler provided by the embodiment is added into the column tube while the column tube is tapped, so that the stationary phase is uniformly and tightly filled;
filling the stationary phase into the column tube, and plugging the column tube by using a plugging material sieve plate to obtain a packed column filled with the packing of the packed column;
and (3) mounting the packed column on a chromatograph for aging treatment, introducing carrier gas at normal temperature, and washing residual solvent and volatile impurities in the stationary phase in the packed column to obtain the gas chromatography packed column.
Example 5
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
the packing column filler is prepared from attapulgite with the purity of more than 85%, the preparation steps refer to example 4, and the difference is that in the step C, the attapulgite balls are sieved and separated after being dried, so that the uniform packing column filler with the particle mesh number of 120-140 meshes is obtained;
a packed column for gas chromatography was prepared by referring to example 4 except that a glass packed column tube having an inner diameter of 2mm and a length of 4m was selected.
Example 6
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
the packed column packing is prepared by using attapulgite with the purity of more than 85%, the preparation steps refer to example 2, the difference is that the obtained packed column packing is further subjected to surface treatment, the surface of the packed column packing after the surface treatment is coated with a fixing solution, and the steps are as follows: d, performing surface treatment on the packed column filler by using 25% of a silylation reagent, namely a trimethyl silylation reagent; e, dissolving the fixed liquid dimethyl polysiloxane which is 15 percent of the filler of the filling column as a carrier in acetone, pouring the filler of the filling column into the acetone, mixing the mixture evenly, stirring the mixture until the acetone is volatilized, and placing the mixture on an infrared lamp for drying;
a packed column for gas chromatography was prepared in accordance with example 2 except that a packed column tube of stainless steel having an inner diameter of 6mm and a length of 10m was selected and evacuated to a vacuum of-0.7 MPa.
Example 7
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
the packed column packing is prepared by using attapulgite with the purity of more than 85%, the preparation steps refer to example 3, the difference is that the obtained packed column packing is further subjected to surface treatment, the surface of the packed column packing after the surface treatment is coated with a fixing solution, and the steps are as follows:
d, heating and soaking the filler of the packed column for 20-30 min by using concentrated hydrochloric acid, filtering, washing with water to be neutral, leaching with methanol, dehydrating and drying;
e, dissolving the fixed liquid polyethylene glycol which is 10 percent of the mass ratio of the fixed liquid polyethylene glycol to the filling material of the filling column as the carrier into the ethanol, pouring the fixed liquid polyethylene glycol into the filling material of the filling column, mixing uniformly, stirring, and placing in a water bath for heating and drying when the ethanol is volatilized and dried quickly;
the preparation method of the gas chromatography packed column refers to example 3.
Example 8
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
the packed column packing is prepared by using attapulgite with the purity of more than 85%, the preparation steps refer to example 4, the difference is that the obtained packed column packing is further subjected to surface treatment, the surface of the packed column packing after the surface treatment is coated with a fixing solution, and the steps are as follows:
d, soaking or refluxing the filling material of the packed column by using a methanol solution of concentrated NaOH or KOH, and washing the filling material of the packed column to be neutral;
e, dissolving the fixed liquid diethylene glycol succinate serving as the carrier and 20% of the filler of the packed column by mass in the chloroform, pouring the filler of the packed column into the chloroform, mixing uniformly, stirring, and placing the mixture on an infrared lamp for drying when the chloroform is volatilized and dried quickly;
the preparation method of the gas chromatography packed column refers to example 4.
Example 9
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
the filler of the packed column is prepared by attapulgite with the purity of more than 85 percent, the preparation steps refer to example 2, and the difference is that the obtained filler of the packed column is also subjected to activation treatment, and the steps are as follows:
d, activating the packed column packing for 3 hours at 300 ℃ under the normal pressure condition;
the preparation method of the gas chromatography packed column refers to example 2.
Example 10
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
the packed column packing is prepared by using attapulgite with the purity of more than 85%, the preparation steps refer to example 3, and the difference is that the obtained packed column packing is also subjected to activation treatment, and the steps are as follows:
d, activating the packed column packing for 3 hours at 250 ℃ under a reduced pressure condition;
the preparation method of the gas chromatography packed column refers to example 3.
Example 11
A gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube, wherein the packed column stationary phase comprises packed column packing;
the filler of the packed column is prepared by attapulgite with the purity of more than 85 percent, the preparation steps refer to example 4, the difference is that the obtained filler of the packed column is also subjected to activation treatment, and the steps are as follows:
d, activating the packed column packing for 1h at 350 ℃ under the normal pressure condition;
the preparation method of the gas chromatography packed column refers to example 4.
Example 12
Example 9 application of the obtained gas chromatography packed column to analysis of dissolved gas in transformer oil; the analysis and detection conditions are that a flame ionization detector is adopted, the temperature of a column box is 80 ℃, the temperature of a vaporization chamber is 95 ℃, the temperature of a detection chamber is 120 ℃, carrier gas is nitrogen, and the flow rate of the carrier gas is as follows: 35mL/min, and the bridge current is 90 mA; an analysis spectrogram of a standard sample of the dissolved gas of the standard sample of the transformer oil is shown in figure 1, and evaluation data is shown in table 1.
TABLE 1
As can be seen from fig. 1 and table 1, the gas chromatography packed column of the present embodiment can separate seven gases dissolved in transformer oil, and all the gases are separated and analyzed within 7 minutes, which is highly efficient; wherein H2And CO, but not completely due to the closer retention times.
Example 13
Example 10 application of a gas chromatography packed column to analysis of dissolved gas in transformer oil; the analysis and detection conditions are that a flame ionization detector is adopted, the temperature of a column box is 85 ℃, the temperature of a vaporization chamber is 110 ℃, the temperature of a detection chamber is 130 ℃, carrier gas is nitrogen, and the flow rate of the carrier gas is as follows: 35mL/min, and the bridge current is 90 mA; and obtaining an analysis spectrogram of a standard sample of the dissolved gas of the standard sample of the transformer oil as shown in figure 2, and evaluation data as shown in table 2.
TABLE 2
| Retention time | Name (R) | Peak area | Peak height |
| 1.537 | H2 | 6063 | 1375 |
| 1.876 | CO | 8911 | 2286 |
| 2.211 | CH4 | 3193 | 596 |
| 4.124 | CO2 | 2887 | 331 |
| 5.179 | C2H4 | 4439 | 395 |
| 6.163 | C2H6 | 5610 | 453 |
| 7.583 | C2H2 | 3510 | 203 |
As can be seen from FIG. 2 and Table 2, the gas chromatography packed column of this example was able to separate seven gases dissolved in transformer oil, had good separation, and all the gases were separated within 8 minutesThe separation analysis is high in efficiency; wherein H2And CO is completely separated, and the sensitivity is high.
Example 14
Example 11 application of a gas chromatography packed column to analysis of dissolved gas in transformer oil; the analysis and detection conditions are that a flame ionization detector is adopted, the temperature of a column box is 75 ℃, the temperature of a vaporization chamber is 100 ℃, the temperature of a detection chamber is 120 ℃, carrier gas is nitrogen, and the flow rate of the carrier gas is as follows: 30mL/min, and the bridge current is 90 mA; an analysis spectrogram of the standard sample of the dissolved gas of the standard sample of the transformer oil is shown in figure 3, and evaluation data is shown in table 3.
TABLE 3
| Retention time | Name (R) | Peak area | Peak height |
| 1.263 | H2 | 6057 | 1366 |
| 1.498 | CO | 8821 | 2204 |
| 1.969 | CH4 | 3263 | 603 |
| 3.888 | CO2 | 2883 | 329 |
| 4.935 | C2H4 | 4442 | 402 |
| 5.784 | C2H6 | 5578 | 439 |
| 7.327 | C2H2 | 3414 | 197 |
As can be seen from fig. 3 and table 3, the gas chromatography packed column of the present embodiment can separate seven gases dissolved in transformer oil, has good separation degree, and has high efficiency because all the gases are separated and analyzed within 8 minutes; wherein H2And CO is completely separated, and the sensitivity is high.
Comparative example
Selecting a gas chromatography packed column, namely selecting a stainless steel column tube, wherein the inner diameter is 3mm, the length is 8m, and the packing of the packed column is 80-100 meshes of carbon molecular sieve packing; analysis and detection conditions referring to example 14, an analysis spectrum of a standard sample of the dissolved gas of the transformer oil standard sample is shown in the figure, 4, and evaluation data are shown in table 4.
TABLE 4
| Retention time | Name (R) | Peak area | Peak height |
| 1.652 | H2 | - | - |
| 1.652 | CO | - | - |
| 1.321 | CH4 | 3250 | 596 |
| 4.695 | CO2 | 3012 | 322 |
| 6.289 | C2H4 | 4356 | 405 |
| 7.472 | C2H6 | 5630 | 451 |
| 8.875 | C2H2 | 3510 | 186 |
As can be seen from FIG. 4 and Table 4, the gas chromatography packed column of the comparative example could not completely separate seven gases dissolved in the transformer oil, although CH4、CO2、C2H4、C2H6、C2H2Is separated but in which H2And CO is not separated, the contents of two gases cannot be analyzed, complete separation is not realized, all gases are not separated, the sensitivity is not high, and compared with the time for completing separation analysis, the method has the advantages of longer time and low efficiency.
The invention provides a novel gas chromatography packed column, which expands the types of the gas chromatography packed column; the method is applied to gas chromatography and is suitable for analyzing and separating mixed gas.
The invention also provides application of the gas chromatography packed column in analysis of dissolved gas in transformer oil, which can realize clear separation of CO and H by using a single packed column2The method can realize the sensitive, rapid and accurate detection of the dissolved gas of the transformer oil by utilizing a chromatographic packed column.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (2)
1. The application of the gas chromatography packed column in the analysis of the dissolved gas in the transformer oil is characterized in that the gas chromatography packed column comprises a packed column tube and a packed column stationary phase filled in the packed column tube; the packed column stationary phase comprises packed column packing; the raw material of the packed column packing comprises attapulgite; the packed column packing is prepared by a method comprising the following steps: crushing and sieving the attapulgite to obtain attapulgite powder with the particle mesh number not less than 200 meshes; adding a binder into the attapulgite powder, uniformly mixing to prepare attapulgite pellets, and drying at 250-350 ℃; sieving and separating the attapulgite pellets to obtain the packed column packing which is uniform and has 40-140 meshes of particle size;
wherein the attapulgite is purified to have a purity of more than 85%; the binder comprises 0.1-1% of poly (diethylaminoethyl methacrylate) acetate by mass of the attapulgite; wherein the content of the first and second substances,
the analysis and detection conditions for separating 7 gases of hydrogen, methane, ethane, ethylene, acetylene, carbon monoxide and carbon dioxide in the transformer oil are as follows: a flame ionization detector is adopted, the temperature of a column box is 75-85 ℃, the temperature of a vaporization chamber is 95-110 ℃, the temperature of a detection chamber is 110-130 ℃, carrier gas is nitrogen, and the flow rate of the carrier gas is 30-35 mL/min.
2. The application of the gas chromatography packed column in analysis of dissolved gas in transformer oil according to claim 1, wherein the packed column packing is further subjected to activation treatment, and the activation treatment is 250-350 ℃ for 1-3 h.
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| CN112763635B (en) * | 2019-10-21 | 2022-03-22 | 中昊晨光化工研究院有限公司 | Gas chromatographic column, application and low-boiling-point fluorine-containing compound separation method |
| CN110836940B (en) * | 2019-11-13 | 2022-05-13 | 国网福建省电力有限公司 | Micro-filling column for portable insulating oil chromatographic analyzer and preparation method and application thereof |
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