CN1049735C - Capillary chromatographic column filled with aluminum trioxide and its preparation method - Google Patents
Capillary chromatographic column filled with aluminum trioxide and its preparation method Download PDFInfo
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- CN1049735C CN1049735C CN 94105028 CN94105028A CN1049735C CN 1049735 C CN1049735 C CN 1049735C CN 94105028 CN94105028 CN 94105028 CN 94105028 A CN94105028 A CN 94105028A CN 1049735 C CN1049735 C CN 1049735C
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Abstract
The present invention provides an aluminium trioxide filling capillary chromatographic column. A thick-wall glass tube can be filled by the fine particle of aluminium trioxide; can be pulled to a molding by adding glass softening point. Because the processing method of the filler aluminium trioxide adopts sylvite infiltration and section heating activation, the short chromatographic column can be used for achieving high separating power to the low carbon hydrocarbon. The present invention has the advantages of good stability and long service life; in addition, the both ends of the capillary column of filling glass are connected with a flexible quartz capillary respectively, which enhances the operability of the glass capillary column.
Description
The present invention relates to a kind of capillary chromatographic column filled with aluminum trioxide and preparation method thereof, belong to the chromatographic resolution field in the analytical chemistry field.
Gas chromatograph is the key instrument during lighter hydrocarbons are analyzed, and chromatographic column is to play the critical component of centrifugation in this instrument.The technology of preparing of chromatographic column is related to the quality of column performance and separating power thereof.The column type of the general chromatographic column of using has 1. packed column in the analysis of lower carbon number hydrocarbons, 2. 3. porous layer open tubular column of packed capillary column (comprising little post of filling out), and the material of use has tubing such as metal, quartz, glass, nylon.
Packed column: in early days to the analysis of lower carbon number hydrocarbons what is called " distribution type " packed column [the P.K.Kuchal.et al that is coated with the stain stationary phase commonly used, Chromatographia 8641 (1975) blue fossil oil rubber petroleum gas workshop " petrochemical technology " 3.4.6 (1973)], the advantage of these posts is that column capacity is big, to chromatographic sampling system, detection system and operating personnel require lower, are Industry Control analysis column types commonly used.The shortcoming of this class post is a poor permeability, and the column length of use is restricted, and generally is no more than 10m, and the separating power of post is lower, can not analyze complicated material composition, and needs to press before the higher post and lower column temperature (room temperature or 0 ℃ ice-water bath).If room temperature changes, the degree of separation of each component of sample can change, and it is relatively poor to analyze data repeatability.
Al
2O
3Wall is coated with open tubular column: its advantage is the good penetrability of post, can make very longly (tens meters to rice up to a hundred).Total number of effective plate of post is very high, and separating power is also stronger.But this class post is attached to the Al on the tube wall
2O
3Coating comes off easily, the poor repeatability (cost raising) of system post.And the column capacity of open tubular column is low, and the dead volume of instrument air-channel system is had relatively high expectations, and operation easier is also big.
Packed capillary column: performance Jie gives packed column and wall is coated with between the post, imitates height than the post of packed column, and the capacity that is coated with post than wall is big, and the system column method is simple, good reproducibility, and the post cost is low.The domestic people of having develops a kind of packed capillary column (Yang Haiying " chromatogram " 3 (1987) 71) that inner core arranged has higher permeability and gratifying post to imitate, but this post is still longer analysis time, in addition owing to contain inner core in the middle of the pillar, therefore, this post and instrument to be connected versatility poor.
The objective of the invention is to overcome the shortcoming that wall is coated with post and conventional filled capillary pipe, propose a kind of short but can analyze C quickly and efficiently
1-C
7The novel packed capillary column of lower carbon number hydrocarbons.
Al of the present invention
2O
3The preparation process of filling glass capillary column is as follows:
1. choose about long 1m, external diameter 6-7mm, the heavy wall glass tube of internal diameter 2-3mm, clean inwall successively with washing lotion, distilled water, drying:
2. take by weighing 30gAl
2O
3(chromatography usefulness, 180-200 order) soaks half an hour with the KCl solution of 30ml 1.5mol, after the filtration, activates 4h down at 380-420 ℃; 490-520 ℃ activates 5h down, relays in exsiccator;
3. after cooling, in the 1. described glass tube of packing into, on the kapillary drawing machine with 1: 100 drawing than being drawn into the filling glass capillary column that internal diameter is 0.45-0.5mm;
4. get its Len req (1-6m is long), 5mmAl is removed at the post two ends
2O
3Particle, the glass fiber a little (accounting for the 2mm pipe range) that the silanization of packing into is handled respectively inserts one section then greater than the long flexible quartz capillary of 50mm, with resistant to elevated temperatures silicone rubber seal junction.
The Al of moulding
2O
3Capillary chromatographic column filled structure as shown in Figure 1, among the figure: the 1st, glass is capillary chromatographic column filled; The 2nd, Al
2O
3Particle; The 3rd, glass fiber; The 4th, silicon rubber; The 5th, flexible quartz capillary.
The present invention is because to Al
2O
3Adopt soluble potassium salt to soak into and the segmentation methods of heating treatment, make its adsorbability just right, therefore produced following effect lower carbon number hydrocarbons:
1. strengthened separating power, used short post, in the short time, can make C such as oil gas unsaturated hydrocarbon
1-C
7Hydrocarbon is well separated, and uses column temperature higher (exceeding room temperature more than 30 ℃), is convenient to control.
2. on any one gas chromatograph that has a capillary system, all can use, because the two ends of post have flexible quartz ampoule, increase the elasticity of glass capillary column to a certain extent simultaneously, be convenient to install dismounting.
3. column capacity is big, and method for making is simple, good reproducibility, and cost is low.
The concrete structure of capillary column of the present invention is provided by following embodiment and accompanying drawing thereof.
Fig. 1 is Al of the present invention
2O
3Capillary chromatographic column filled structural drawing.
Fig. 2 is the analysis chromatogram of general packed capillary column to pyrolysis gas.
Fig. 3 is for containing the inner core packed capillary column to C
1-C
4The analysis chromatogram of hydrocarbon.
Fig. 4 is that capillary column of the present invention is to C
1-C
4The analysis chromatogram of hydrocarbon.
Fig. 5 is the chromatogram that separate of capillary column of the present invention to n-butene and anti-butylene material.
Fig. 6 is Al of the present invention
2O
3Capillary chromatographic column filled separating power chromatogram to organic fluoride.
Describe the details and the working condition of the concrete device that proposes according to the present invention in detail below in conjunction with accompanying drawing.
Al
2O
3The preparation of filling glass capillary column:
1. choose long 1m, outer path length 6-7mm, the heavy wall glass tube of internal diameter 2-3mm cleans inwall, drying successively with washing lotion, distilled water.
2. take by weighing 30gAl
2O
3(chromatography usefulness, 180-200 order) soaks half an hour with the KCL solution of 30ml 1.5N, after the filtration, activates 4h down at 380-420 ℃; 490-520 ℃ activates 5h down, relays in exsiccator;
3. after cooling, in the 1. described glass tube of packing into, on the day GDM-IB type drawing machine produced of island proper Tianjin company with 1: 100 drawing than being drawn into the filling glass capillary column that internal diameter is 0.45-0.5mm;
4. get its Len req (1-6m is long), 5mmAl is removed at the post two ends
2O
3Particle, the glass fiber a little (accounting for the 2mm pipe range) of packing into and handling through silanization, it is long respectively to insert a segment length 20-30cm then, and the flexible quartz capillary of internal diameter 0.32mm is with resistant to elevated temperatures silicone rubber seal junction.
Present embodiment is the present invention and general packed capillary column and contains the comparison of the packed capillary column of inner core to the oil gas component analysis.Analysis condition and the results are shown in Table 1 is found out by table, because to Al
2O
3Therefore the disposal route difference, column type is out of the ordinary, similar sample is analyzed employed column length and also differ widely analysis time.(seeing Fig. 2 .3.4.) Fig. 2 is the analysis chromatogram [Shanghai Gaoqiao chemical plant " petrochemical complex communication " of general packed capillary column to pyrolysis gas, 2,1-23, (1975)], Fig. 3 and Fig. 4 are respectively and contain inner core packed capillary column [patent No.: CN88 2 02689U] and the present invention to C
1-C
4The analysis chromatogram of hydrocarbon.Comparison diagram 2 and Fig. 4, n-pentane and four C
4The olefin isomer appearance time is about 8min, but among Fig. 2 just, the degree of separation of anti-butylene is less than 30% still, can't satisfy quantitative requirement, positive and negative butylene degree of separation is more than 70% among Fig. 4; And Fig. 2 column length is that 10m Fig. 4 then is 4m; Comparison diagram 3 and Fig. 4, to the analysis of same sample, the former must use the 18m column length, analysis time 17min, the latter only uses 4m, analysis time 8min.Analyze propine and 1.3-butadiene, general packed capillary column needs 10min, and containing inner leg is 32min (the 3rd the capillary chromatography proceedings in the whole nation, the 35th page), and the present invention only needs 8in.General packed capillary column is analyzed benzene and is needed 75min, and [first national capillary chromatography proceedings 1964, P390] do not report the analysis of toluene, and the present invention to analyze the time of benzene be 14min, toluene 17min.In addition, if post is lengthened to 6m, press when being increased to 3.2MPa before the post, n-butene separates almost reaching fully with anti-butylene material.See Fig. 5.
In the chromatogram of present embodiment, the component of chromatographic peak number representative is: 1, and methane; 2, ethane; 3, ethene; 4, propane; 5, trimethylene; 6, isobutane; 7, propylene; 8, normal butane; 9, acetylene; 10, propadiene; 11, isopentane; 12, n-butene; 13, anti-butylene; 14, isobutylene; 15, maleic; 16, propine; 17, the 1.3-butadiene; 18, n-pentane.
The present invention proves further that by the analysis to the freon combination gas this post also has good separating power to organofluorine compound, sees Fig. 6.
Present embodiment further specifies the efficient column performance of separating fast of the present invention by the actual theoretical plate hight that records.Table 2 is listed the measurement result that several pillar posts are imitated, and its theoretical plate hight is about 0.25mm, is about 0.46mm and contain inner leg.
The specification analysis condition of several column types of table 1, analysis result
Table 2
| Column type | Conventional packed capillary column | Contain the inner core packed capillary column | The present invention | |
| Column dimension (length * interior warp) | 10m×0.25mm | 18m×0.45mm | 4m×0.50mm | |
| Carrier gas | N 2 | H 2 | H 2 | |
| Pressure before the post | 3.88ml/min | 0.2MPa | 0.25MPa | |
| Column temperature (℃) | 78 | 65 | 80 | |
| min | N-pentane | 8 | 17 | 7 |
| 1.3 butadiene | 10 | 32 | 9 | |
| Benzene | 75 | Do not report | 14 | |
| Toluene | Do not report | Do not report | 17 | |
| Column type | Post specification (length * interior warp) | Carrier gas | Carrier gas linear speed (cm/sec) | Theoretical plate hight (mm) |
| Capillary column of the present invention | 6m×0.47mm | N 2 | 6.70 | 0.25 |
| 6m×0.46mm | N 2 | 5.70 | 0.24 | |
| 6m×0.45mm | N 2 | 7.00 | 0.23 | |
| The Al that contains inner core 2O 3Packed capillary column | 16m * 0.36mm inner core 0.11mm | N 2 | 8.64 | 0.46 |
Claims (2)
1. AL
2O
3The filling glass capillary chromatographic column is by AL
2O
3Fine grained is filled the heavy wall glass tube, is drawn into type under the glass softening point temperature, it is characterized in that filling material AL
2O
3Adopt the 1.5molKCl solution impregnation, activate 4 hours down at 380-420 ℃ then, activate 5 hours at 490-520 ℃, and connect flexible quartz capillary respectively at the two ends of filling glass capillary column.
2. according to the said packed capillary column of claim 1, it is characterized in that glass capillary column and being connected by inserting silicon rubber of flexible quartzy tubule seal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94105028 CN1049735C (en) | 1994-05-12 | 1994-05-12 | Capillary chromatographic column filled with aluminum trioxide and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94105028 CN1049735C (en) | 1994-05-12 | 1994-05-12 | Capillary chromatographic column filled with aluminum trioxide and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1106139A CN1106139A (en) | 1995-08-02 |
| CN1049735C true CN1049735C (en) | 2000-02-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94105028 Expired - Fee Related CN1049735C (en) | 1994-05-12 | 1994-05-12 | Capillary chromatographic column filled with aluminum trioxide and its preparation method |
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| CN113264688A (en) * | 2021-06-21 | 2021-08-17 | 南京百赛生物色谱技术有限公司 | Sectional coating device and method for inner surface of quartz capillary column |
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