CN109444276A - A kind of gas-chromatography packed column and its preparation method and application - Google Patents
A kind of gas-chromatography packed column and its preparation method and application Download PDFInfo
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- CN109444276A CN109444276A CN201811222353.0A CN201811222353A CN109444276A CN 109444276 A CN109444276 A CN 109444276A CN 201811222353 A CN201811222353 A CN 201811222353A CN 109444276 A CN109444276 A CN 109444276A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The present invention provides a kind of gas-chromatography packed column and its preparation method and application, and gas-chromatography packed column includes packed column column tube and the packed column stationary phase that is filled in it, and packed column stationary phase includes filling column packing, and the raw material for filling column packing includes attapulgite；Filling column packing preparation step includes that attapulgite crushes, and sieving obtains the concave convex rod powder that particle mesh number is not less than 200 mesh；Binder is added in concave convex rod powder, is uniformly mixed, concave convex rod bead, 250~350 DEG C of dryings is made；Concave convex rod bead sieving separating obtains the filling column packing that uniform, particle mesh number is 40~140 mesh.The present invention provides a kind of new gas-chromatography packed columns, extend the type of gas-chromatography packed column；Gas-chromatography packed column provided by the invention applied to Dissolved Gases in Transformer Oil analyze, can be realized using a kind of chromatography packed column realize it is sensitive, quick, accurately detect Dissolved Gases in Transformer Oil.
Description
Technical field
The present invention relates to analytical chemistry field, in particular to a kind of gas-chromatography packed column and preparation method thereof, Yi Jiqi
Application of the phase chromatography packed column in Dissolved Gases in Transformer Oil analysis.
Background technique
Chromatography is that one kind separates, analyzes method, is widely used in multiple necks such as petroleum, chemistry, environment, biology, food
Detection, the analysis in domain.Chromatographic column is directly related to separating effect and detection sensitivity in chromatography, and preparation chromatographic column is to carry out color
The important link of spectrum analysis.Filler is the important feature of chromatographic column, determines the essential characteristic of chromatographic column, and can chromatographic peak divide
From being dependent firstly on filler.Packed column is one kind more common in chromatographic column, has hundreds of chromatography packed column fillers at present,
Commonly only ten several, customary filler type is fewer.Gas-chromatography is one of chromatography, commonly uses gas-chromatography packed column
Type is also less, and adsorbent class filler generally comprises active carbon, silica gel, divides in existing gas-chromatography packed column fixed phase stuffing
Sub- sieve, aluminium oxide, porous polymer beads etc., different packing properties are different, are suitable for heterogeneity and analyze；There are also a kind of gas phase colors
Fixed phase stuffing is composed, is coated on it for fixer, referred to as carrier, carrier is a kind of chemically inert, porous solid
Particle can provide biggish inactive surfaces, fixer is made to be evenly distributed in its surface with liquid film state, at present at common passivation
Diatomite, glass microsphere, polytetrafluoroethylene (PTFE), porous polymer beads after reason etc..
Attapulgite is the natural minerals based on a kind of aqueous rich magnesium silicate, theoretical chemistry formula are as follows: Mg5Si8O20(OH)2
(OH2)4.4H2O has chemical inertness.There are zeolite channels inside attapulgite crystal structure, thus attapulgite have it is biggish
Specific surface area, after dry, single crystal is closely located together to form the non-uniform secondary pore of size, this feature makes attapulgite
On specific surface area it is very high, biggish specific surface area and Surface Physical Chemistry characteristic and ionic condition, therefore there is preferable inhale
Attached ability, in addition, crystals zeolite cavity size unanimously makes it have the effect of molecular sieve.Attapulgite suction-operated
Pass through the surfaces externally and internally that adsorption molecule is adsorbed on attapulgite by Van der Waals force including physical absorption；Chemisorption is based on
Adsorption site existing for attapulgite's surface and adsorption molecule form chemical bond, these adsorption sites include Si-OH group, right
Organic substance has very strong affinity, being capable of Liquidity limit and positive polar organic molecule；Attapulgite's surface is abundant
Si-OH group can act on forming stable state with organic reaction agent, become a kind of ideal catalyst carrier.Concave convex rod
The adsorptivity of soil can be such that attapulgite applies in multiple fields, but not find also attapulgite being applied to chromatography packed column.
Transformer oil is the insulation chief component of oil-filled power equipment, is that one kind of petroleum divides gold-plating product, just
Under normal operating status, due to oil and solid insulation can gradually aging, rotten, minimal amount of gas can be decomposited, work as power equipment
When Superheated steam drier, discharging fault or dampness situation occur for inside, the yield of these gases can increase sharply.Therefore in equipment
In operational process, the gas structural constituent and content that periodic measurement is dissolved in oil for finding inside oil-filled power equipment early
Existing Hidden fault has very important meaning.Since Dissolved Gases in Transformer Oil chromatography testing requirements are by hydrogen, first in oil
More than the 7 kinds gases such as alkane, ethane, ethylene, acetylene, carbon monoxide, carbon dioxide are separated, it is desirable that disengaging time is short.But mesh
The preceding gas chromatographic column for analyzing Dissolved Gases in Transformer Oil is generally made of two kinds of chromatographic columns, using twin columns parallel shunt stream
Journey or twice sample introduction process；Twin columns parallel shunt process will shunt after entering instrument due to sample, cannot fully enter detection
Device, so greatly reducing the sensitivity of detection；Sample introduction flow operations are cumbersome twice, and sample analysis time is too long；And use one
Single chromatogram column analysis of the existing fixed phase stuffing preparation of kind, does not accomplish generally to understand multiple gases separation, to influence accurately
Degree.
Summary of the invention
The present invention is to solve existing gas-chromatography packed column fixed phase stuffing often to use type less, accordingly common gas phase color
Compose packed column type also less problem, it is contemplated that chromatography packed column requires adsorbent class fixed phase stuffing can be in high temperature
Lower use, adsorption capacity is big, the good advantage of thermal stability；Inventor find attapulgite processing after have chemical inertness, have compared with
Big specific surface area, good adsorptivity, there is molecular sieve, these features make that it is suitable for chromatography packed column adsorbent classes
Filler；And attapulgite has the characteristic that can be used as catalyst carrier, can be used for gas-chromatography packed column after being surface-treated
As carrier；Based on the above discovery, the present invention provides a kind of new gas-chromatography packed column and preparation method thereof, wherein stationary phase
Including the filling column packing prepared using attapulgite as raw material, gas-chromatography packed column provided by the invention is for gas-chromatography point
Analysis is particularly suitable for analysis Dissolved Gases in Transformer Oil, is able to solve the prior art and is become using a kind of analysis of chromatographic column list packed column
The not high problem of depressor dissolved gas in oil accuracy.
The present invention provides a kind of gas-chromatography packed column.
The present invention also provides a kind of preparation methods of gas-chromatography packed column.
The present invention also provides a kind of application of gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis.
Specifically, the present invention provides a kind of gas-chromatography packed column, including packed column column tube and the filling being filled in it
Column stationary phase, packed column stationary phase include filling column packing, and the raw material for filling column packing includes attapulgite；It is logical to fill column packing
Method comprising the following steps are crossed to be made:
A attapulgite crushes, sieving, obtains the attapulgite powder that particle mesh number is not less than 200 mesh；
Binder is added in B attapulgite powder, is uniformly mixed, attapulgite bead, 250~350 DEG C of dryings is made；
C attapulgite bead sieving separating obtains the filling column packing that uniform, particle mesh number is 40~140 mesh.
Further, binder includes the polymethylacrylic acid lignocaine ethyl ester acetic acid of attapulgite quality 0.1~1%
Salt.
Further, filling column packing is also by surface treatment.
Further, surface treatment includes one of silanization treatment, pickling, alkali cleaning.
Further, packed column stationary phase further includes fixer, and fixer is coated on packed column filler surface.
Further, for filling column packing also by being activated, activation processing is 250~350 DEG C of 1~3h of activation.
The present invention also provides a kind of preparation method of gas-chromatography packed column, gas-chromatography packed column includes packed column column tube
With the packed column stationary phase being filled in it, packed column stationary phase includes filling column packing；Column packing is filled by including following
The method of step is made: attapulgite crushes, sieving, obtains the concave convex rod powder that particle mesh number is not less than 200 mesh；Attapulgite powder
Binder is added in end, is uniformly mixed, attapulgite bead, 250~350 DEG C of dryings is made；Attapulgite bead sieving separating,
Obtain the filling column packing that uniform, particle mesh number is 40~140 mesh；
Further, gas-chromatography packed column the preparation method comprises the following steps: packed column column tube is cleaned, is dried；In packed column column
Tamper is filled in pipe one end, touches packed column column tube, while packed column stationary phase is added；After stationary phase fills column tube, then with stifled
Plug thing clogs the packed column column tube other end, obtains gas-chromatography packed column through aging process.
The present invention also provides a kind of application of gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis, gas-chromatographies
Packed column includes packed column column tube and the packed column stationary phase that is filled in it；Packed column stationary phase includes filling column packing；It fills out
The raw material for filling column packing includes attapulgite；Fill column packing to be made by method comprising the following steps: attapulgite crushes,
Sieving obtains the attapulgite powder that particle mesh number is not less than 200 mesh；Binder is added in attapulgite powder, is uniformly mixed, system
At attapulgite bead, 250~350 DEG C of dryings；Attapulgite bead sieving separating, obtaining uniform, particle mesh number is 40~140
Purpose fills column packing.
Further, for filling column packing also by being activated, activation processing is 250~350 DEG C of 1~3h of activation.
Further, analysis detection condition are as follows: use flame ionization detector, post case temperature is 75~85 DEG C, vaporization
Room temperature is 95~110 DEG C, and detection room temperature is 110~130 DEG C, and carrier gas is nitrogen, and flow rate of carrier gas is 30~35mL/min.
Advantageous effect of the invention
The present invention provides a kind of gas-chromatography packed column and preparation method thereof, and gas-chromatography packed column includes packed column column tube
With the packed column stationary phase being filled in it, the stationary phase of packed column includes filling column packing, and the raw material for filling column packing includes
Attapulgite.Attapulgite is a kind of natural non-metallic mine, has good characterization of adsorption；It can be used as in gas-chromatography packed column
Adsorbent class filler, it is also possible to make carrier coating fixer；The present invention uses the packed column prepared using attapulgite as raw material
Filler preparative gas chromatography packed column provides a kind of new gas-chromatography packed column, extends the kind of gas-chromatography packed column
Class；Applied to gas chromatographic analysis, it is suitable for analysis, separation mixed gas.
In gas-chromatography packed column provided by the invention, filling column packing is made by method comprising the following steps: A is recessed
Convex stick soil crushes, sieving, obtains the attapulgite powder that particle mesh number is not less than 200 mesh；Bonding is added in B attapulgite powder
Agent is uniformly mixed, attapulgite bead, 250~350 DEG C of dryings is made；The sieving of C attapulgite bead, obtains uniform, particle mesh
Number is the filling column packing of 40~140 mesh.Gas-chromatography packed column filler particle size influences the column effect and back pressure of packed column, general next
It says, granularity is smaller, and the column effect of gas-chromatography packed column is higher；However granularity is smaller, column pressure is bigger；The attapulgite powder uniformity
Not enough, granule size is not suitable for most packed column, it is therefore desirable to pelletize, be prepared into uniform, a certain size packed column
Filler, high temperature drying make its moisture-free, are suitable for gas-chromatography packed column.
The present invention also provides a kind of application of gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis, gas-chromatographies
Packed column includes packed column column tube and the packed column stationary phase that is filled in it, and packed column stationary phase includes filling column packing；It fills out
The raw material for filling column packing includes attapulgite；Fill column packing to be made by method comprising the following steps: attapulgite crushes,
Sieving obtains the attapulgite powder that particle mesh number is not less than 200 mesh；Binder is added in attapulgite powder, is uniformly mixed, system
At attapulgite bead, 250~350 DEG C of dryings；Attapulgite bead sieving separating, obtaining uniform, particle mesh number is 40~140
Purpose fills column packing.In Dissolved Gases in Transformer Oil analysis, separation gaseous species are more, wherein not using single chromatographic column
Gas can be made to understand separation, especially difficulty makes CO and H2Two kinds of gases are precisely separating and obtain clearly analyzing peak, therefore the prior art
Generally use two pillars；Using gas-chromatography packed column provided by the invention may be implemented single packed column understand separation CO and
H2, can be realized using a kind of chromatography packed column realize it is sensitive, quick, accurately detect Dissolved Gases in Transformer Oil.
Other features of the invention and corresponding beneficial effect are described in the aft section of specification, and should be managed
Solution, at least partly beneficial effect becomes apparent from the record in description of the invention.
Detailed description of the invention
Fig. 1 is that the gas-chromatography packed column that the embodiment of the present invention 12 provides analyzes the analysis that Dissolved Gases in Transformer Oil obtains
Spectrogram；
Fig. 2 is that the gas-chromatography packed column that the embodiment of the present invention 13 provides analyzes the analysis that Dissolved Gases in Transformer Oil obtains
Spectrogram；
Fig. 3 is that the gas-chromatography packed column that the embodiment of the present invention 14 provides analyzes the analysis that Dissolved Gases in Transformer Oil obtains
Spectrogram；
Fig. 4 is the analysis of spectra that comparative example gas-chromatography packed column analyzes that Dissolved Gases in Transformer Oil obtains.
Specific embodiment
The present invention is described in further details below by specific embodiment, but it is to limit of the invention that this, which is not,
System, those skilled in the art's basic thought according to the present invention, various modifications may be made and improves, but without departing from this
The basic thought of invention, within the scope of the present invention.
In the description of the present invention, unless otherwise specified, the meaning of the term in this specification and those skilled in the art
The meaning of general understanding is identical, but if any difference, the definition in this specification shall prevail；Unless otherwise specified, test method is equal
For conventional method；Unless otherwise specified, raw material used in this specification and test material are routinely to be commercially available；Such as
Without specified otherwise, the percentage (%) in this specification is mass percent (quality %).
The present invention provides a kind of gas-chromatography packed column, fixes including packed column column tube and the packed column being filled in it
Phase, packed column stationary phase include filling column packing, and the raw material for filling column packing includes attapulgite；Filling column packing is by including
The method of following steps is made:
A attapulgite crushes, sieving, obtains the attapulgite powder that particle mesh number is not less than 200 mesh；
Binder is added in B attapulgite powder, is uniformly mixed, attapulgite bead, 250~350 DEG C of dryings is made；
C attapulgite bead sieving separating obtains the filling column packing that uniform, particle mesh number is 40~140 mesh.
Packed column column tube, which is selected, in the present invention is typically used for the packed column column tube of gas chromatographic analysis, 2~10mm of internal diameter,
0.5~10m of column length；The material of column tube usually has stainless steel tube, copper pipe, aluminum pipe, copper plating nickel tube, glass tube and polytetrafluoroethylene (PTFE)
Pipe etc.；After attapulgite refers to that natural attapulgite clay is purified in the present invention, purity reaches 85% or more attapulgite；
Binder is the organic or inorganic binder that attapulgite powder can be made to bond, and such as has sticking organic polymer, cellulose
Class, starch organic bond, silicates, phosphoric acid salt inorganic binder；The sieving of attapulgite bead makes to obtain packed column
Filler particles are in suitable range, and convenient for dress column, general packed column filler particles mesh number, control is filled in 40~140 mesh
Column packing particle needs uniformly, and filler particles mesh number needed for general primary dress column is 40~60,60~80,80~100,100~120
Or 120~140 range.
Attapulgite is a kind of natural non-metallic mine, has good characterization of adsorption；It can be used as in gas-liquid chromatography packed column
Adsorbent class stationary phase, it can also be used to gas-liquid chromatography as carrier coat fixer；The present invention provides a kind of new gas phases
Chromatography packed column extends the type of gas-chromatography packed column filler.Gas-chromatography packed column filler particle size influences packed column
Column effect and back pressure, in general, granularity is smaller, and the column effect of gas-chromatography packed column is higher；However granularity is smaller, column pressure is bigger；
The attapulgite powder uniformity is inadequate, and granule size is not suitable for most packed column, it is therefore desirable to pelletize, be prepared into uniformly
, a certain size filling column packing, high temperature drying makes its moisture-free, is suitable for gas-chromatography packed column.
Further, binder includes the polymethylacrylic acid lignocaine ethyl ester acetic acid of attapulgite quality 0.1~1%
Salt.Polymethylacrylic acid lignocaine ethyl ester acetate is using diethylaminoethyl methacrylate as monomer, and polymerization forms poly-
The acetate form of diethylaminoethyl methacrylate；Diethylaminoethyl methacrylate contains reactive amino and polymerization
Sex ethylene base can increase using it as the adhesiveness of the polymer of monomer, thermosetting property etc.；Use polymethylacrylic acid lignocaine second
Ester acetate makes attapulgite uniformly be bonded together as binder, by the electrostatic interaction of binder, then heated mistake
Journey makes binder be decomposed into CO2、NH2And H2O is removed, and does not influence the property of attapulgite, while being conducive to reinforce filling
The mechanical strength of column packing.
Further, filling column packing is also by surface treatment.Specifically, the purpose of surface treatment is to improve packed column to fill out
Expect gap structure, the activated centre of shielded surfaces is all to remove active function point with chemical reaction or covered with physics to reach
Method to cmy vector surface nature can use.Requirement surface of the gas-chromatography packed column to carrier is chemical inertness
, but attapulgite's surface has adsorption site abundant, is directly used as carrier, will cause chromatographic peak hangover and column effect decline,
Therefore filling column packing progress surface passivating treatment is conducive to separate, analyze detection ingredient using preceding.
Further, surface treatment includes one of silanization, pickling, alkali cleaning.Silanization is to use silylating reagent, with
Silanol, the silicon ether group of packed column filler surface react, and remove the H-bonding capability of packed column filler surface, silanization examination
Agent can be able to be specifically trim,ethylchlorosilane, hexamethyl dioxy silane, dimethyl dioxy for trimethyl silicone hydride reagent
Silane etc.；Pickling is using dense inorganic acid, and preferably concentrated hydrochloric acid heat treatment a period of time, preferably 20~30min is filtered, washing
To neutrality, methanol elution, dewatered drying, pickling can remove the inorganic salts and metal oxide of packed column filler surface；Alkali cleaning is
It impregnates or flows back using the methanol solution of dense NaOH or KOH, be washed to neutrality, methanol rinse is dried, and alkali cleaning can remove packed column
The acid position carrier of filler surface.
Further, packed column stationary phase further includes fixer, and fixer is coated on packed column filler surface.Specifically,
Fixer is dissolved in appropriate solvent such as acetone, ether, chloroform, in toluene organic solvent, filling column packing is subsequently poured into and mixes,
At moderate temperatures, it evaporates solvent and is made, the amount of solvent should be such that fixer dissolves and be immersed in carrier all in solution.
Filling column packing can be used as the carrier of stationary liquid phase in gas-liquid chromatography packed column, coat fixer on surface, fixer can
Think the common fixers such as hydro carbons, polysiloxane-based, polyethylene glycols and poly- trialkylphosphine oxide, lipid.Fixer with as carrier
Packed column packing quality ratio be 5%~30%, preferably 15~25%.
Further, for filling column packing also by being activated, activation processing is 250~350 DEG C of 1~3h of activation.Specifically
Ground, the purpose of activation processing are to improve the adsorption capacity of filling column packing, and activation processing can also can depressurize under normal pressure
Under the conditions of carry out；Since packed column filling adsorption capacity is big, permanent absorption is easy to happen to certain components, therefore as filling out
It is activated before filling the use of column adsorbent class filler, is conducive to column effect, and keep analysis, separation peak shape symmetrical, and inhale
Attached dose of activity has certain relationship with water content, needs to remove moisture to enhance activity.
The present invention also provides a kind of preparation method of gas-chromatography packed column, gas-chromatography packed column includes packed column column tube
With the packed column stationary phase being filled in it, packed column stationary phase includes filling column packing；Column packing is filled by including following
The method of step is made: attapulgite crushes, sieving, obtains the attapulgite powder that particle mesh number is not less than 200 mesh；Attapulgite
Binder is added in powder, is uniformly mixed, attapulgite bead, 250~350 DEG C of dryings is made；Attapulgite bead crosses screening
From the filling column packing that acquisition is uniformly, particle mesh number is 40~140 mesh；Further, the preparation method of gas-chromatography packed column
Are as follows: packed column column tube is cleaned, is dried；Tamper is filled in packed column column tube one end, packed column column tube is touched, is added simultaneously
Packed column stationary phase；After stationary phase fills column tube, then with tamper the packed column column tube other end is clogged, obtains gas through aging process
Phase chromatography packed column.
Specifically, packed column column tube is selected, cleaned, dry up drying；Tamper such as sieve plate, glass are filled in column tube one end
Glass cotton, silica wool etc., to prevent filler from leaking out, being added when touching column tube toward column tube includes that packed column provided by the invention is filled out
The stationary phase of material makes stationary phase fill uniform close；Or under an increased pressure, i.e., in the other end in the filler pond for placing stationary phase
Outlet links with the pressure reducing valve of nitrogen or air steel cylinder, and column tube internal diameter difference is passed through air velocity difference, while column tube is touched on side
While will include that the stationary phase provided by the invention for filling column packing is pressed into column tube；Or under vacuum-pumping conditions, i.e., in column tube plug
The baffle safety bottle of one end outlet and vacuum pump that enter tamper links, under the conditions of vacuumizing (- 0.4~0.7MPa), while side
Tapping column tube side will include that the stationary phase provided by the invention for filling column packing is pressed into column tube；Until stationary phase fills column tube,
Column tube is clogged with tamper again, obtains the packed column for having been filled with filling column packing；Packed column is mounted on chromatograph always
Change processing is passed through carrier gas that is, under room temperature or higher temperature, and the residual solvent and volatility in flushing packed column in stationary phase are miscellaneous
Matter obtains gas-chromatography packed column.
The present invention also provides a kind of application of gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis, gas-chromatographies
Packed column includes packed column column tube and the packed column stationary phase that is filled in it, and packed column stationary phase includes filling column packing；It fills out
The raw material for filling column packing includes attapulgite；Fill column packing to be made by method comprising the following steps: attapulgite crushes,
Sieving obtains the attapulgite powder that particle mesh number is not less than 200 mesh；Binder is added in attapulgite powder, is uniformly mixed, system
At attapulgite bead, 250~350 DEG C of dryings；Attapulgite bead sieving separating, obtaining uniform, particle mesh number is 40~140
Purpose fills column packing；Specifically, it applies in gas-chromatography packed column of the present invention and is filled in Dissolved Gases in Transformer Oil analysis
Column column tube inside diameter ranges should be in 2~5mm；In Dissolved Gases in Transformer Oil analysis, separation gaseous species are more, wherein H2And CO
Retention time is close, and two cannot make gas understand separation using traditional single packed column, and especially difficulty makes H2With two kinds of gases of CO
It is precisely separating and obtains clearly analyzing peak, therefore the prior art generally uses two pillars；Using gas phase color provided by the invention
Spectrum packed column may be implemented single packed column and understand separation CO and H2, can be realized using a kind of chromatography packed column realize it is sensitive,
Quickly, Dissolved Gases in Transformer Oil is accurately detected.
Further, for filling column packing by being activated, activation processing is 250~350 DEG C of 1~3h of activation.Specifically,
The purpose of activation processing is to improve the adsorption capacity of filling column packing, and activation processing can under normal pressure, can also be in decompression item
It is carried out under part.
Further, analysis detection condition is, using flame ionization detector, post case temperature: and 75~85 DEG C, vaporizing chamber
Temperature: 95~110 DEG C；Detection room temperature: 110~130 DEG C；Carrier gas is nitrogen, flow rate of carrier gas: 30~35mL/min.
It hereinafter will be by embodiment and comparative example to gas-chromatography packed column provided by the invention and its in transformer
Application in dissolved gas in oil analysis is described in detail.
Embodiment 1
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing,
(1) filling column packing reaches 85% or more attapulgite preparation, preparation step using purity are as follows:
A attapulgite crushes, sieving, obtains the attapulgite powder that particle mesh number is greater than 200 mesh；
The polymethylacrylic acid lignocaine ethyl ester acetate of attapulgite quality 0.5% is added in B attapulgite powder
And a small amount of water, it is uniformly mixed, attapulgite bead, 300 DEG C of dryings is made；
Attapulgite bead sieving separating after C is dry obtains the filling column packing that uniform, particle mesh number is 40~60 mesh；
(2) gas-chromatography packed column the preparation method comprises the following steps:
Internal diameter 8mm is selected, the packed column column tube of the stainless steel material of length 8m is cleaned, dried；
It will include that packed column provided in this embodiment is filled out under the conditions of vacuumizing -0.4MPa, while when touching column tube
The stationary phase of material is pressed into column tube；
Until stationary phase fills column tube, then with tamper mineral wool clog column tube, acquisition has been filled with filling column packing
Packed column；
Packed column is mounted on aging process on chromatograph, at relatively high temperatures, is passed through carrier gas, is rinsed fixed in packed column
Residual solvent and volatile impurity in phase obtain gas-chromatography packed column.
The binder polymethylacrylic acid lignocaine ethyl ester acetate of the present embodiment, also can be used can make concave convex rod
Other organic or inorganic binders substitution of native powder bonding, organic binder such as have sticking organic polymer, cellulose family,
Starch, specific such as polyacrylamide, carboxymethyl cellulose, carboxymethyl starch, hydroxypropyl cellulose；Organic binder such as silicon
Barbiturates, phosphoric acid salt etc..
Embodiment 2
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
(1) filling column packing reaches 85% or more attapulgite preparation, preparation step using purity are as follows:
A attapulgite crushes, sieving, obtains the attapulgite powder that particle mesh number is greater than 200 mesh；
The polymethylacrylic acid lignocaine ethyl ester acetate of attapulgite quality 1% is added in B attapulgite powder, mixes
It closes uniformly, attapulgite bead, 350 DEG C of dryings is made；
Attapulgite bead sieving separating after C is dry obtains the filling column packing that uniform, particle mesh number is 60~80 mesh；
(2) gas-chromatography packed column the preparation method comprises the following steps:
Internal diameter 4mm is selected, the packed column column tube of the stainless steel material of length 6m is cleaned, dried；
Link in the other end outlet for placing the filler pond of stationary phase with the pressure reducing valve of nitrogen or air steel cylinder, air velocity
It is adjusted to 30mL/min, under an increased pressure, while will include filling column packing provided in this embodiment when touching column tube
Stationary phase be pressed into column tube；
Until stationary phase fills column tube, then with tamper mineral wool clog column tube, acquisition has been filled with filling column packing
Packed column；
Packed column is mounted on aging process on chromatograph, at relatively high temperatures, is passed through carrier gas, is rinsed fixed in packed column
Residual solvent and volatile impurity in phase obtain gas-chromatography packed column.
Embodiment 3
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
(1) filling column packing reaches 85% or more attapulgite preparation, preparation step using purity are as follows:
A attapulgite crushes, sieving, obtains the attapulgite powder that particle mesh number is greater than 250 mesh；
The polymethylacrylic acid lignocaine ethyl ester acetate of attapulgite quality 0.1% is added in B attapulgite powder,
It is uniformly mixed, attapulgite bead, 250 DEG C of dryings is made；
Attapulgite bead sieving separating after C is dry obtains the packed column that uniform, particle mesh number is 100~120 mesh and fills out
Material；
2) gas-chromatography packed column the preparation method comprises the following steps:
Internal diameter 5mm is selected, the packed column column tube of the stainless steel material of length 10m is cleaned, dried；
Tamper silica wool is filled in column tube one end, under the conditions of vacuumizing -0.4MPa, while will be upper when touching column tube
The stationary phase indentation column tube for the filling column packing stated；
Until stationary phase fills column tube, then with tamper glass quartz clog column tube, acquisition has been filled with filling column packing
Packed column；
Packed column is mounted on aging process on chromatograph, at relatively high temperatures, is passed through carrier gas, is rinsed fixed in packed column
Residual solvent and volatile impurity in phase obtain gas-chromatography packed column.
Embodiment 4
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
(1) filling column packing reaches 85% or more attapulgite preparation, preparation step using purity are as follows:
A attapulgite crushes, sieving, obtains the attapulgite powder that particle mesh number is greater than 300 mesh；
The polymethylacrylic acid lignocaine ethyl ester acetate of attapulgite quality 0.6% is added in B attapulgite powder,
It is uniformly mixed, attapulgite bead, 250 DEG C of dryings is made；
Attapulgite bead sieving separating after C is dry obtains the filling column packing that uniform, particle mesh number is 80~100 mesh；
2) gas-chromatography packed column the preparation method comprises the following steps:
Internal diameter 3mm is selected, the packed column column tube of the stainless steel material of length 8m is cleaned, dried；
Tamper sieve plate is filled in column tube one end, being added when touching column tube toward column tube includes provided in this embodiment fill out
The stationary phase for filling column packing makes stationary phase fill uniform close；
It until stationary phase fills column tube, then with tamper sieve plate clogs column tube, obtains and have been filled with filling column packing
Packed column；
Packed column is mounted on aging process on chromatograph, at normal temperature, is passed through carrier gas, is rinsed in packed column in stationary phase
Residual solvent and volatile impurity, obtain gas-chromatography packed column.
Embodiment 5
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
Filling column packing reaches 85% or more attapulgite preparation using purity, and preparation step is referring to embodiment 4, difference
It is attapulgite bead sieving separating after drying for step C, obtains the packed column that uniform, particle mesh number is 120~140 mesh and fill out
Material；
The preparation method of gas-chromatography packed column is distinguished as selection internal diameter 2mm, the glass material of length 4m referring to embodiment 4
The packed column column tube of matter.
Embodiment 6
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
Filling column packing reaches 85% or more attapulgite preparation using purity, and preparation step is referring to embodiment 2, difference
For the filling column packing of acquisition is also surface-treated, and the packed column filler surface after surface treatment coats fixer, step
Are as follows: D filling column packing is surface-treated with 25% silylating reagent trimethyl silicone hydride reagent；E by with as carrier
Packed column packing quality pours into filling column packing than being dissolved in acetone for 15% fixer dimethyl polysiloxane, mix it is even,
Stirring is placed on infrared lamp and dries until acetone volatilizees；
The preparation method of gas-chromatography packed column is distinguished as selection internal diameter 6mm, the stainless steel of length 10m referring to embodiment 2
The packed column column tube of material, vacuumized conditions are -0.7MPa.
Embodiment 7
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
Filling column packing reaches 85% or more attapulgite preparation using purity, and preparation step is referring to embodiment 3, difference
For the filling column packing of acquisition is also surface-treated, and the packed column filler surface after surface treatment coats fixer, step
Are as follows:
D fills column packing and heats 20~30min of digestion with concentrated hydrochloric acid, and filtering is washed to neutrality, methanol elution, and dehydration is dried
It is dry；
E, than being dissolved in ethyl alcohol for 10% fixer polyethylene glycol, will be poured into the packed column packing quality as carrier
Column packing is filled, even, stirring is mixed, until ethyl alcohol volatilizees when quick-drying, is placed in heating water bath drying；
The preparation method of gas-chromatography packed column is referring to embodiment 3.
Embodiment 8
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
Filling column packing reaches 85% or more attapulgite preparation using purity, and preparation step is referring to embodiment 4, difference
For the filling column packing of acquisition is also surface-treated, and the packed column filler surface after surface treatment coats fixer, step
Are as follows:
D fills column packing and is impregnated or flowed back with the methanol solution of dense NaOH or KOH, is washed to neutrality；
E by with the packed column packing quality as carrier than being dissolved in chloroform for 20% fixer binaryglycol ester succinic acid
In, filling column packing is poured into, even, stirring is mixed, until chloroform volatilizees when quick-drying, is placed on infrared lamp and dries；
The preparation method of gas-chromatography packed column is referring to embodiment 4.
Embodiment 9
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
Filling column packing reaches 85% or more attapulgite preparation using purity, and preparation step is referring to embodiment 2, difference
For the filling column packing of acquisition is also activated, step are as follows:
D fills column packing in atmospheric conditions, 300 DEG C of activation 3h；
The preparation method of gas-chromatography packed column is referring to embodiment 2.
Embodiment 10
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
Filling column packing reaches 85% or more attapulgite preparation using purity, and preparation step is referring to embodiment 3, difference
For the filling column packing of acquisition is also activated, step are as follows:
D fills column packing at reduced pressure conditions, 250 DEG C of activation 3h；
The preparation method of gas-chromatography packed column is referring to embodiment 3.
Embodiment 11
A kind of gas-chromatography packed column, including packed column column tube and the packed column stationary phase being filled in it, packed column is solid
Fixed mutually includes filling column packing；
Filling column packing reaches 85% or more attapulgite preparation using purity, and preparation step is referring to embodiment 4, difference
For the filling column packing of acquisition is also activated, step are as follows:
D fills column packing in atmospheric conditions, 350 DEG C of activation 1h；
The preparation method of gas-chromatography packed column is referring to embodiment 4.
Embodiment 12
Embodiment 9 obtains application of the gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis；Analysis detection condition
For using flame ionization detector, post case temperature is 80 DEG C, and temperature of vaporization chamber is 95 DEG C, and detection room temperature is 120 DEG C, is carried
Gas is nitrogen, and flow rate of carrier gas: 35mL/min, bridge electric current are 90mA；Obtain transformer oil standard specimen dissolved gas standard sample analytical spectra
Figure such as Fig. 1, evaluates data such as table 1.
Table 1
From Fig. 1 and table 1 as can be seen that the gas-chromatography packed column of the present embodiment can separate seven dissolved in transformer oil
Kind gas, and all gas completes separation analysis in 7 minutes, it is high-efficient；Wherein, H2With the separation of having arrived of CO, but due to protect
It stays the time to be closer to, is not properly separated.
Embodiment 13
Embodiment 10 obtains application of the gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis；Analysis detection condition
For using flame ionization detector, post case temperature is 85 DEG C, and temperature of vaporization chamber is 110 DEG C, and detection room temperature is 130 DEG C, is carried
Gas is nitrogen, and flow rate of carrier gas: 35mL/min, bridge electric current are 90mA；Obtain transformer oil standard specimen dissolved gas standard sample analytical spectra
Figure such as Fig. 2, evaluates data such as table 2.
Table 2
| Retention time | Title | 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 |
From Fig. 2 and table 2 as can be seen that the gas-chromatography packed column of the present embodiment can separate seven dissolved in transformer oil
Kind gas, separating degree is good, and all gas completes separation analysis in 8 minutes, high-efficient；Wherein, H2It has been obtained completely with CO
Separation, high sensitivity.
Embodiment 14
Embodiment 11 obtains application of the gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis；Analysis detection condition
For using flame ionization detector, post case temperature is 75 DEG C, and temperature of vaporization chamber is 100 DEG C, and detection room temperature is 120 DEG C, is carried
Gas is nitrogen, and flow rate of carrier gas: 30mL/min, bridge electric current are 90mA；Obtain transformer oil standard specimen dissolved gas standard sample analytical spectra
Figure such as Fig. 3, evaluates data such as table 3.
Table 3
| Retention time | Title | 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 |
From Fig. 3 and table 3 as can be seen that the gas-chromatography packed column of the present embodiment can separate seven dissolved in transformer oil
Kind gas, separating degree is good, and all gas completes separation analysis in 8 minutes, high-efficient；Wherein, H2It has been obtained completely with CO
Separation, high sensitivity.
Comparative example
Gas-chromatography packed column is selected, stainless steel tube, internal diameter 3mm, length 8m, and filling column packing is 80~100
Purpose carbon molecular sieve filler；Analysis detection condition obtains the analysis of transformer oil standard specimen dissolved gas standard sample referring to embodiment 14
Spectrogram is as schemed, and 4, evaluate data such as table 4.
Table 4
| Retention time | Title | 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 |
From Fig. 4 and table 4 as can be seen that the gas-chromatography packed column of comparative example is not completely separated in transformer oil dissolution
Seven kinds of gases, although CH4、CO2、C2H4、C2H6、C2H2It is separated, but wherein H2With not separated for CO, Wu Fafen
Two kinds of gas contents are analysed, is not carried out and is kept completely separate and all gas, sensitivity is not high, and the time for completing separation analysis is compared
The time of the embodiment of the present invention is longer, low efficiency.
The present invention provides a kind of new gas-chromatography packed columns, extend the type of gas-chromatography packed column；It is applied to
Gas chromatographic analysis is suitable for analysis, separation mixed gas.
The present invention also provides a kind of application of gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis, may be implemented
Single packed column understands separation CO and H2, can be realized using a kind of chromatography packed column realize it is sensitive, quick, accurately detect transformation
Device dissolved gas in oil.
The above content is specific embodiment is combined, further detailed description of the invention, and it cannot be said that this hair
Bright specific implementation is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, it is not taking off
Under the premise of from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to protection of the invention
Range.
Claims (10)
1. a kind of gas-chromatography packed column, which is characterized in that including packed column column tube and the packed column stationary phase that is filled in it,
The packed column stationary phase includes filling column packing, and the raw material of the filling column packing includes attapulgite；The packed column is filled out
Material is made by method comprising the following steps:
Attapulgite described in A crushes, sieving, obtains the attapulgite powder that particle mesh number is not less than 200 mesh；
Binder is added in attapulgite powder described in B, is uniformly mixed, attapulgite bead, 250~350 DEG C of dryings is made；
Attapulgite bead sieving separating described in C, obtaining uniform, particle mesh number is to fill column packing described in 40~140 purposes.
2. gas-chromatography packed column according to claim 1, which is characterized in that the binder includes the attapulgite
The polymethylacrylic acid diethylaminoethyl acetate of quality 0.1~1%.
3. gas-chromatography packed column according to claim 1 or 2, which is characterized in that the filling column packing also passes through table
Surface treatment.
4. gas-chromatography packed column according to claim 3, which is characterized in that the surface treatment includes at silanization
One of reason, pickling, alkali cleaning.
5. gas-chromatography packed column according to claim 3, which is characterized in that the packed column stationary phase further includes fixing
Liquid, the fixer are coated on the packed column filler surface.
6. gas-chromatography packed column according to claim 1 or 2, which is characterized in that the filling column packing is also through making a living
Change processing, the activation processing is 250~350 DEG C of 1~3h of activation.
7. a kind of preparation method of gas-chromatography packed column, which is characterized in that the gas-chromatography packed column includes packed column column
The packed column stationary phase in it is managed and is filled in, the packed column stationary phase includes filling column packing；The filling column packing is logical
Cross method comprising the following steps to be made: the attapulgite crushes, sieving, obtains the concave convex rod that particle mesh number is not less than 200 mesh
Native powder；Binder is added in the attapulgite powder, is uniformly mixed, attapulgite bead, 250~350 DEG C of dryings is made；
The attapulgite bead sieving separating, obtaining uniform, particle mesh number is to fill column packing described in 40~140 purposes；
Further, the gas-chromatography packed column the preparation method comprises the following steps: the packed column column tube is cleaned, is dried up；Described
Tamper is filled in packed column column tube one end, and the packed column stationary phase is added when touching the packed column column tube；The fixation
After mutually filling column tube, then with tamper the packed column column tube other end is clogged, obtains the gas-chromatography through aging process and fill out
Fill column.
8. a kind of application of gas-chromatography packed column in Dissolved Gases in Transformer Oil analysis, which is characterized in that the gas phase color
Compose the packed column stationary phase that packed column includes packed column column tube and is filled in it；The packed column stationary phase includes that packed column is filled out
Material；The raw material of the filling column packing includes attapulgite；The filling column packing is made by method comprising the following steps:
The attapulgite crushes, sieving, obtains the attapulgite powder that particle mesh number is not less than 200 mesh；In the attapulgite powder
Binder is added, is uniformly mixed, attapulgite bead, 250~350 DEG C of dryings is made；The attapulgite bead sieving separating,
Obtaining uniform, particle mesh number is to fill column packing described in 40~140 purposes.
9. application of the gas-chromatography packed column according to claim 8 in Dissolved Gases in Transformer Oil analysis, feature
It is, for the filling column packing also by being activated, the activation processing is 250~350 DEG C of 1~3h of activation.
10. application of the gas-chromatography packed column according to claim 8 or claim 9 in Dissolved Gases in Transformer Oil analysis,
It is characterized in that, analysis detection condition are as follows: use flame ionization detector, post case temperature is 75~85 DEG C, and temperature of vaporization chamber is
95~110 DEG C, detection room temperature is 110~130 DEG C, and carrier gas is nitrogen, and flow rate of carrier gas is 30~35mL/min.
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